Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CHEMICALLY LINKED SILK FIBROIN COATINGS AND
METHODS OF MAKING AND USING THEREOF
FIELD
The disclosure relates to chemically linked silk fibroin coatings and methods
of
making and using thereof, for example use of such chemically linked fibroin in
coated
articles, including various fabric and leather apparel, and various fabric and
leather
products for use in home and automotive applications.
BACKGROUND
Silk is a natural polymer produced by a variety of insects and spiders, and
comprises a filament core protein, silk fibroin, and a glue-like coating
consisting of a
non-filamentous protein, sericin. Silk fibers are light weight, breathable,
and
hypoallergenic. Silk is comfortable when worn next to the skin and insulates
very well;
keeping the wearer warm in cold temperatures and is cooler than many other
fabrics in
warm temperatures.
SUMMARY
The disclosure relates to articles including one or more coated substrates,
wherein
the coatings include silk protein fragments (SPF) as defined herein, including
without
limitation silk fibroin or silk fibroin fragments, and a chemical modifier or
a physical
modifier. In some embodiments, the chemical modifier is chemically linked to
one or
more of a silk fibroin side group and a silk fibroin terminal group. In some
embodiments,
the silk fibroin side group and the silk fibroin terminal group are
independently selected
from an amine group, an amide group, a carboxyl group, a hydroxyl group, a
thiol group,
and a sulfhydryl group. In some embodiments, the chemical modifier is
chemically linked
to one or more functional groups on the substrate. In some embodiments, the
functional
group on the substrate is selected from an amine group, an amide group, a
carboxyl
group, a hydroxyl group, a thiol group, and a sulfhydryl group. In some
embodiments, the
chemical modifier includes one or more of a chemically linked functional
group, or
functional group residue, and a linker. In some embodiments, the chemical
modifier
includes one or more of -CRa2-, -CIV=CRa-, -C=C-, -alkyl-, -alkenyl-, -alkynyl-
, -aryl-,
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-heteroaryl-, -0-, -S-, -0C(0)-, -N(Ra)-, -N=N-, =N-, -C(0)-, -C(0)0-, -
0C(0)N(Ra)-, -
C(0)N(Ra)-, -N(Ra)C(0)0-, -N(Ra)C(0)-, -N(Ra)C(0)N(Ra)-, -N(Ra)c(NRa)N(Ra)_, _
N(Ra)S(0)t-, -S(0)t0-, -S(0)tN(Ra)-, -S(0)tN(Ra)C(0)-, -0P(0)(0Ra)0-, wherein
t is 1
or 2, and wherein at each independent occurrence Ra is selected from hydrogen,
alkyl,
alkenyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl,
heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl. In some embodiments,
the coating
includes one or more of low molecular weight silk fibroin or silk fibroin
fragments,
medium molecular weight silk fibroin or silk fibroin fragments and high
molecular
weight silk fibroin or silk fibroin fragments. In some embodiments, the
coating includes
SPF as defined herein, including without limitation silk fibroin or silk
fibroin fragments,
with an average weight average molecular weight from about 5 to about 144 kDa.
In
some embodiments, the coating includes SPF as defined herein, including
without
limitation silk fibroin or silk fibroin fragments, with an average weight
average molecular
weight from about 1 kDa to about 5 kDa, from about 5 kDa to about 10 kDa, from
about
6 kDa to about 17 kDa, from about 10 kDa to about 15 kDa, from about 15 kDa to
about
20 kDa, from about 17 kDa to about 39 kDa, from about 20 kDa to about 25 kDa,
from
about 25 kDa to about 30 kDa, from about 30 kDa to about 35 kDa, from about 35
kDa to
about 40 kDa, from about 39 kDa to about 80 kDa, from about 40 kDa to about 45
kDa,
from about 45 kDa to about 50 kDa, from about 60 kDa to about 100 kDa, or from
about
80 kDa to about 144 kDa. In some embodiments, the coating includes SPF as
defined
herein, including without limitation silk fibroin or silk fibroin fragments,
with a
polydispersity between 1 and about 5Ø In some embodiments, the coating
includes SPF
as defined herein, including without limitation silk fibroin or silk fibroin
fragments,
which prior to coating the substrate are stable in a solution. In some
embodiments, the
coating includes SPF as defined herein, including without limitation silk
fibroin or silk
fibroin fragments, which prior to coating the substrate do not spontaneously
or gradually
gelate and/or do not visibly change in color or turbidity when in a solution
for at least 10
days. In some embodiments, the substrate includes one or more of a fiber, a
thread, a
yarn, a fabric, a textile, a cloth, or a hide. In some embodiments, the
fabric, textile, or
cloth is woven or nonwoven. In some embodiments, the fiber, thread, or yarn
includes
one or more of polyester, recycled polyester, Mylar, cotton, nylon, recycled
nylon,
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polyester-polyurethane copolymer, rayon, acetate, aramid (aromatic polyamide),
acrylic,
ingeo (polylactide), lurex (polyamide-polyester), olefin (polyethylene-
polypropylene),
and combinations thereof In some embodiments, the fiber, thread, or yarn
includes one
or more of alpaca fiber, alpaca fleece, alpaca wool, lama fiber, lama fleece,
lama wool,
cotton, cashmere, sheep fiber, sheep fleece, sheep wool, byssus, chiengora,
qiviut, yak,
rabbit, lambswool, mohair wool, camel hair, angora wool, silkworm silk, abaca
fiber, coir
fiber, flax fiber, jute fiber, kapok fiber, kenaf fiber, raffia fiber, bamboo
fiber, hemp,
modal fiber, pina, ramie, sisal, and soy protein fiber. In some embodiments,
the fiber,
thread, or yarn includes one or more of mineral wool, mineral cotton, man-made
mineral
fiber, fiberglass, glass, glasswool, stone wool, rock wool, slagwool, glass
filaments,
asbestos fibers, and ceramic fibers.
The disclosure also relates to a method of coating a substrate with a coating
including SPF as defined herein, including without limitation silk fibroin or
silk fibroin
fragments, and a chemical modifier or a physical modifier, the method
including applying
to the substrate at least one composition including SPF as defined herein,
including
without limitation silk fibroin or silk fibroin fragments, with an average
weight average
molecular weight from about 1 kDa to about 144 kDa, and a polydispersity
between 1
and about 5Ø In some embodiments, the method further includes applying to
the
substrate a chemical modifier or a physical modifier selected from a wetting
agent, a
detergent, a sequestering or dispersing agent, an enzyme, a bleaching agent,
an
antifoaming agent, an anti-creasing agent, a dye dispersing agent, a dye
leveling agent, a
dye fixing agent, a dye special resin agent, a dye anti-reducing agent, a
pigment dye
system anti-migrating agent, a pigment dye system binder, a delave agent, a
wrinkle free
treatment, a softener, a handle modifier, a waterborne polyurethane
dispersion, a
finishing resin, an oil or water repellant, a flame retardant, a crosslinker,
an activator, a
thickener for technical finishing, or any combination thereof. In some
embodiments, the
crosslinker or the activator are independently selected from a N-
hydroxysuccinimide
ester crosslinker, an imidoester crosslinker, a sulfosuccinimidyl
aminobenzoate, a
methacrylate, a silane, a silicate, an alkyne compound, an azide compound, an
aldehyde,
a carbodiimide crosslinker, a dicyclohexyl carbodiimide activator, a
dicyclohexyl
carbodiimide crosslinker, a maleimide crosslinker, a haloacetyl crosslinker, a
pyridyl
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disulfide crosslinker, a hydrazide crosslinker, an alkoxyamine crosslinker, a
reductive
amination crosslinker, an aryl azide crosslinker, a diazirine crosslinker, an
azide-
phosphine crosslinker, a transferase crosslinker, a hydrolase crosslinker, a
transglutaminase crosslinker, a peptidase crosslinker, an oxidoreductase
crosslinker, a
tyrosinase crosslinker, a laccase crosslinker, a peroxidase crosslinker, a
lysyl oxidase
crosslinker, and combinations thereof. In some embodiments, the composition
includes
low molecular weight SPF as defined herein, including without limitation silk
fibroin or
silk fibroin fragments. In some embodiments, the composition includes medium
molecular weight SPF as defined herein, including without limitation silk
fibroin or silk
fibroin fragments. In some embodiments, the composition includes high
molecular
weight SPF as defined herein, including without limitation silk fibroin or
silk fibroin
fragments. In some embodiments, the composition includes a chemical fabric
softener. In
some embodiments, the composition includes a Bronsted acid. In some
embodiments, the
method further includes dyeing the substrate prior to applying to the
substrate the at least
one composition including SPF as defined herein, including without limitation
silk
fibroin or silk fibroin fragments. In some embodiments, the method further
includes
dyeing the substrate after applying to the substrate the at least one
composition including
SPF as defined herein, including without limitation silk fibroin or silk
fibroin fragments.
The disclosure also relates to a method of coating a substrate with a coating
including SPF as defined herein, including without limitation silk fibroin or
silk fibroin
fragments, and a chemical modifier or a physical modifier, for example a
crosslinker, the
method including applying to the substrate at least one composition including
SPF as
defined herein, including without limitation silk fibroin or silk fibroin
fragments, with an
average weight average molecular weight from about 1 kDa to about 144 kDa, and
a
polydispersity between 1 and about 5.0, wherein the chemical modifier or
physical
modifier, for example the crosslinker, is added "in-situ," i.e., at the same
time the SPF as
defined herein, including without limitation silk fibroin or silk fibroin
fragments, are
added to the substrate, for example a fabric.
The disclosure also relates to a method of coating a substrate with a coating
including SPF as defined herein, including without limitation silk fibroin or
silk fibroin
fragments, and a chemical modifier or a physical modifier, for example a
crosslinker, the
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method including applying to the substrate at least one composition including
SPF as
defined herein, including without limitation silk fibroin or silk fibroin
fragments, with an
average weight average molecular weight from about 1 kDa to about 144 kDa, and
a
polydispersity between 1 and about 5.0, wherein the chemical modifier or
physical
modifier, for example the crosslinker, is added to the SPF as defined herein,
including
without limitation silk fibroin or silk fibroin fragments, to create a
modified silk fibroin,
which is thereafter applied to the substrate, for example a fabric.
The disclosure relates to articles including one or more coated substrates,
the
articles including, but not being limited to, apparel, padding, shoes, gloves,
luggage, furs,
jewelry and bags, configured to be worn or carried on the body, that is at
least partially
surface treated with a composition, for example a solution, of pure silk
fibroin-based
protein fragments of the present disclosure so as to result in a silk coating
on the product.
In some embodiments, the solutions of silk fibroin-based proteins or fragments
thereof
may be aqueous solutions, organic solutions, or emulsions. In an embodiment,
the
product is manufactured from a textile material. In an embodiment, the product
is
manufactured from a non-textile material. In an embodiment, desired additives
can be
added to an aqueous solution of pure silk fibroin-based protein fragments of
the present
disclosure so as to result in a silk coating having desired additives.
BRIEF DESCRIPTION OF THE DRAWINGS
The presently disclosed embodiments will be further explained with reference
to
the attached drawings. The drawings shown are not necessarily to scale, with
emphasis
instead generally being placed upon illustrating the principles of the
presently disclosed
embodiments.
Fig. 1A illustrates a synthetic scheme for conjugating silk fibroin to a
reactive
linker, which is then reacted to a group on a substrate. Fig. 1B illustrates a
synthetic
scheme for chemical modification and purification of silk molecules; the pH of
the silk
solutions was 7-8 prior to addition of crosslinker; the pH dropped
significantly upon
addition of the crosslinker; the pH was then adjusted to 8.5, and the samples
were either
dialyzed against water or purified via TFF against water; the pH was adjusted
to 4-5 for
fabric coatings. Fig. 1C illustrates a synthetic scheme for in situ
modification of silk; the
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pH of the silk solutions was 6-7 prior to addition of crosslinker; the pH
dropped
significantly upon addition of the crosslinker; the solution was filtered and
used within
hours for fabric coatings without purification or pH adjustments.
Fig. 2 illustrates some examples of chemically linked Silk-Substrate
constructs,
including Silk-Linker-Substrate constructs.
Fig. 3 illustrates a synthetic scheme for conjugating a substrate to a
reactive
linker, which is then reacted to silk fibroin; several Silk-Linker-Substrate
constructs are
depicted including an amino-silane based linker.
Figs. 4A and 4B illustrate comparative vertical wicking test results for
samples
coated with chemically modified silk fibroin (STI-17100706-D001: coated with
silk-
conjugate; STI-17100706-D002: coated with silk only; STI-17100706-D003: coated
with
precursor linker only; STI-17100706: control), tested after a number (T) of
laundering
cycles (T=0, Fig. 4A; T=3 Fig. 4B; samples coated with a silk-conjugate, and
samples
coated with silk only improve wicking compared to an unfinished control
sample;
samples coated with a silk-conjugate shows better wicking than samples coated
with silk
only; unfinished control samples, and samples coated with a precursor linker
only show
almost no wicking.
Figs. 5A and 5B illustrate comparative absorbency test results for samples
coated
with chemically modified silk fibroin (STI-17100706-D001: coated with silk-
conjugate;
STI-17100706-D002: coated with silk only; STI-17100706-D003: coated with
precursor
linker only; STI-17100706: control), tested after a number (T) of laundering
cycles (T=0,
Fig. 5A; T=3 Fig. 5B); samples coated with a silk-conjugate, and samples
coated with
silk only have a significantly improved absorbency, and samples coated with a
silk-
conjugate absorb better than samples coated with silk only; unfinished control
samples
and samples coated with the precursor linker only do not absorb for T=0.
Figs. 6A and 6B illustrate comparative dry rate test results for samples
coated
with chemically modified silk fibroin (STI-17100706-D001: coated with silk-
conjugate;
STI-17100706-D002: coated with silk only; STI-17100706-D003: coated with
precursor
linker only; STI-17100706: control), tested after a number (T) of laundering
cycles (T=0,
Fig. 6A; T=3 Fig. 6B); samples coated with a silk-conjugate have an improved
dry rate
compared to the unfinished sample; samples coated with silk only have lower
dry rate
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than unfinished control samples (Fig. 6A); for T=3 samples coated with a silk-
conjugate
show significant improvements (Fig. 6B).
Figs. 7A-7D illustrate comparative vertical wicking test results for samples
coated
with chemically modified silk fibroin (control: Fig. 7A; coated with silk
only: Fig. 7B;
coated with in-situ modified silk: Fig. 7C; coated with purified silk-
conjugate: Fig. 7D),
tested after a number (T) of laundering cycles (0, 3, and 20).
Figs. 8A-8D illustrate comparative absorbency test results for samples coated
with chemically modified silk fibroin (control: Fig. 8A; coated with silk
only: Fig. 8B;
coated with in-situ modified silk: Fig. 8C; coated with purified silk-
conjugate: Fig. 8D),
tested after a number (T) of laundering cycles (0, 3, and 20).
Figs. 9A-9D illustrate comparative dry rate test results for samples coated
with
chemically modified silk fibroin (control: Fig. 9A; coated with silk only:
Fig. 9B; coated
with in-situ modified silk: Fig. 9C; coated with purified silk-conjugate: Fig.
9D), tested
after a number (T) of laundering cycles (0, 3, and 20).
Fig. 10 illustrates comparative absorbency test results for samples coated
with silk
fibroin chemically modified with natural crosslinkers (control sample, sample
coated
with silk only, sample coated with silk modified with caffeic acid, sample
coated with
silk modified with genipin).
Figs. 11A-D illustrate the data analysis by PEAKS software for the mass
spectrum obtained for functionalized silk samples: 077-027-1 (Fig. 11A), 077-
024-2 (Fig.
11B), 077-028-2 (Fig. 11C) and 077-030-1 (Fig. 11D).
Figs. 12A-B show the electrophoresis gel for silk fibroin-based protein
fragments
(Fig. 12A), and functionalized silk fibroin-based protein fragments samples
077-024-2
(Lane 3), 077-027-1 (Lane 4), 077-027-2 (Lane 5), 077-028-2 (Lane 6), and 077-
030-1
(Lane 7) (Fig. 12B). Lane 1 of Fig. 12B shows BioRad IEF Standards of
molecular
weight bands. Lane 2 of Fig. 12B shows IEF Sample buffer. Lane 8 of Fig. 12B
shows
MC-1. Lane 9 of Fig. 12B shows 5700-SP. Lane 10 of Fig. 12B shows DBr-7. Lane
11
of Fig. 12B shows Ser-1. Fig. 12A shows the electrophoresis gel from several
Activated
SilksTM, and Fig. 12B shows the electrophoresis gel for chemically modified
Activated
SilksTM.
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Fig. 13 shows the SEC-RI chromatograms of two modified Mid-MW silks (098-
29-02, and 098-30-02) compared to an unmodified Mid-MW weight silk.
Fig. 14A-B show the m/z and ms2 fragmentation patterns for two subunits: heavy
chain (Fig. 14A), light chain (Fig. 14B) in the mass spectra for the modified
Low-MW
silk (077-027-1).
Fig. 15A-C show the m/z and ms2 fragmentation patterns for all three subunits:
heavy chain (Fig. 15A), light chain (Fig. 15B), and fibrohexamerin (Fig. 15C)
in the mass
spectra for the modified Low-MW silk (077-024-2).
Fig. 16 shows the m/z and ms2 fragmentation patterns light chain in the mass
spectrum for the modified Low-MW silk (077-028-2).
Fig. 17 shows the m/z and ms2 fragmentation patterns light chain in the mass
spectrum for the modified Low-MW silk (077-030-1).
Fig. 18 is a flow chart showing various embodiments for producing pure silk
fibroin protein fragments (SPFs) of the present disclosure.
FIG. 19 is a flow chart showing various parameters that can be modified during
the process of producing a silk protein fragment solution of the present
disclosure during
the extraction and the dissolution steps.
While the above-identified drawings set forth presently disclosed embodiments,
other embodiments are also contemplated, as noted in the discussion. This
disclosure
presents illustrative embodiments by way of representation and not limitation.
Numerous
other modifications and embodiments can be devised by those skilled in the art
which fall
within the scope and spirit of the principles of the presently disclosed
embodiments.
DETAILED DESCRIPTION
SPF Definitions and Properties
As used herein, "silk protein fragments" (SPF) include one or more of: "silk
fibroin fragments" as defined herein; "recombinant silk fragments" as defined
herein;
"spider silk fragments" as defined herein; "silk fibroin-like protein
fragments" as defined
herein; and/or "chemically modified silk fragments" as defined herein. SPF may
have any
molecular weight values or ranges described herein, and any polydispersity
values or
ranges described herein. As used herein, in some embodiments the term "silk
protein
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fragment" also refers to a silk protein that comprises or consists of at least
two identical
repetitive units which each independently selected from naturally-occurring
silk
polypeptides or of variations thereof, amino acid sequences of naturally-
occurring silk
polypeptides, or of combinations of both.
SPF Molecular Weight and Polydispersity
In an embodiment, a composition of the present disclosure includes SPF having
an average weight average molecular weight ranging from 6 kDa to 17 kDa. In an
embodiment, a composition of the present disclosure includes SPF having a
weight
average molecular weight ranging from 17 kDa to 39 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an average weight
average
molecular weight ranging from 39 kDa to 80 kDa. In an embodiment, a
composition of
the present disclosure includes SPF having an average weight average molecular
weight
ranging from about 1 to about 5 kDa. In an embodiment, a composition of the
present
disclosure includes SPF having an average weight average molecular weight
ranging
from about 5 to about 10 kDa. In an embodiment, a composition of the present
disclosure
includes SPF having an average weight average molecular weight ranging from
about 10
to about 15 kDa. In an embodiment, a composition of the present disclosure
includes SPF
having an average weight average molecular weight ranging from about 15 to
about 20
kDa. In an embodiment, a composition of the present disclosure includes SPF
having an
average weight average molecular weight ranging from about 20 to about 25 kDa.
In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 25 to about 30 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 30 to about 35 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 35 to about 40 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 40 to about 45 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 45 to about 50 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
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weight average molecular weight ranging from about 50 to about 55 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 55 to about 60 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 60 to about 65 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 65 to about 70 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 70 to about 75 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 75 to about 80 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 80 to about 85 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 85 to about 90 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 90 to about 95 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 95 to about 100 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 100 to about 105 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 105 to about 110 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 110 to about 115 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 115 to about 120 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 120 to about 125 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 125 to about 130 kDa. In an
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embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 130 to about 135 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 135 to about 140 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 140 to about 145 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 145 to about 150 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 150 to about 155 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 155 to about 160 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 160 to about 165 kDa. I In
an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 165 to about 170 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 170 to about 175 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 175 to about 180 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 180 to about 185 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 185 to about 190 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 190 to about 195 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 195 to about 200 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 200 to about 205 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
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weight average molecular weight ranging from about 205 to about 210 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 210 to about 215 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 215 to about 220 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 220 to about 225 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 225 to about 230 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 230 to about 235 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 235 to about 240 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 240 to about 245 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 245 to about 250 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 250 to about 255 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 255 to about 260 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 260 to about 265 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 265 to about 270 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 270 to about 275 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 275 to about 280 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 280 to about 285 kDa. In an
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embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 285 to about 290 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 290 to about 295 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 295 to about 300 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 300 to about 305 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 305 to about 310 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 310 to about 315 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 315 to about 320 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 320 to about 325 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 325 to about 330 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 330 to about 335 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 335 to about 340 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 340 to about 345 kDa. In an
embodiment, a composition of the present disclosure includes SPF having an
average
weight average molecular weight ranging from about 345 to about 350 kDa.
In some embodiments, compositions of the present disclosure include SPF
compositions selected from compositions #1001 to #2450, having weight average
molecular weights selected from about 1 kDa to about 145 kDa, and a
polydispersity
range selected from between 1 and about 5 (including, without limitation, a
polydispersity of 1), between 1 and about 1.5 (including, without limitation,
a
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polydispersity of 1), between about 1.5 and about 2, between about 1.5 and
about 3,
between about 2 and about 2.5, between about 2.5 and about 3, between about 3
and
about 3.5, between about 3.5 and about 4, between about 4 and about 4.5, and
between
about 4.5 and about 5:
PDI
(about)
1-5 1-1.5 1.5-2 1.5-3 2-2.5 2.5-3 3-3.5 3.5-4 4-4.5 4.5-5
MW
(about)
1 kDa 1001 1002 1003 1004 1005 1006 1007 1008 1009 1010
2 kDa 1011 1012 1013 1014 1015 1016 1017 1018 1019 1020
3 kDa 1021 1022 1023 1024 1025 1026 1027 1028 1029 1030
4 kDa 1031 1032 1033 1034 1035 1036 1037 1038 1039 1040
kDa 1041 1042 1043 1044 1045 1046 1047 1048 1049 1050
6 kDa 1051 1052 1053 1054 1055 1056 1057 1058 1059 1060
7 kDa 1061 1062 1063 1064 1065 1066 1067 1068 1069 1070
8 kDa 1071 1072 1073 1074 1075 1076 1077 1078 1079 1080
9 kDa 1081 1082 1083 1084 1085 1086 1087 1088 1089 1090
kDa 1091 1092 1093 1094 1095 1096 1097 1098 1099 1100
11 kDa 1101 1102 1103 1104 1105 1106 1107 1108 1109 1110
12 kDa 1111 1112 1113 1114 1115 1116 1117 1118 1119 1120
13 kDa 1121 1122 1123 1124 1125 1126 1127 1128 1129 1130
14 kDa 1131 1132 1133 1134 1135 1136 1137 1138 1139 1140
kDa 1141 1142 1143 1144 1145 1146 1147 1148 1149 1150
16 kDa 1151 1152 1153 1154 1155 1156 1157 1158 1159 1160
17 kDa 1161 1162 1163 1164 1165 1166 1167 1168 1169 1170
18 kDa 1171 1172 1173 1174 1175 1176 1177 1178 1179 1180
19 kDa 1181 1182 1183 1184 1185 1186 1187 1188 1189 1190
kDa 1191 1192 1193 1194 1195 1196 1197 1198 1199 1200
21 kDa 1201 1202 1203 1204 1205 1206 1207 1208 1209 1210
22 kDa 1211 1212 1213 1214 1215 1216 1217 1218 1219 1220
23 kDa 1221 1222 1223 1224 1225 1226 1227 1228 1229 1230
24 kDa 1231 1232 1233 1234 1235 1236 1237 1238 1239 1240
kDa 1241 1242 1243 1244 1245 1246 1247 1248 1249 1250
26 kDa 1251 1252 1253 1254 1255 1256 1257 1258 1259 1260
27 kDa 1261 1262 1263 1264 1265 1266 1267 1268 1269 1270
28 kDa 1271 1272 1273 1274 1275 1276 1277 1278 1279 1280
29 kDa 1281 1282 1283 1284 1285 1286 1287 1288 1289 1290
kDa 1291 1292 1293 1294 1295 1296 1297 1298 1299 1300
31 kDa 1301 1302 1303 1304 1305 1306 1307 1308 1309 1310
32 kDa 1311 1312 1313 1314 1315 1316 1317 1318 1319 1320
33 kDa 1321 1322 1323 1324 1325 1326 1327 1328 1329 1330
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34 kDa 1331 1332 1333 1334 1335 1336 1337 1338 1339 1340
35 kDa 1341 1342 1343 1344 1345 1346 1347 1348 1349 1350
36 kDa 1351 1352 1353 1354 1355 1356 1357 1358 1359 1360
37 kDa 1361 1362 1363 1364 1365 1366 1367 1368 1369 1370
38 kDa 1371 1372 1373 1374 1375 1376 1377 1378 1379 1380
39 kDa 1381 1382 1383 1384 1385 1386 1387 1388 1389 1390
40 kDa 1391 1392 1393 1394 1395 1396 1397 1398 1399 1400
41 kDa 1401 1402 1403 1404 1405 1406 1407 1408 1409 1410
42 kDa 1411 1412 1413 1414 1415 1416 1417 1418 1419 1420
43 kDa 1421 1422 1423 1424 1425 1426 1427 1428 1429 1430
44 kDa 1431 1432 1433 1434 1435 1436 1437 1438 1439 1440
45 kDa 1441 1442 1443 1444 1445 1446 1447 1448 1449 1450
46 kDa 1451 1452 1453 1454 1455 1456 1457 1458 1459 1460
47 kDa 1461 1462 1463 1464 1465 1466 1467 1468 1469 1470
48 kDa 1471 1472 1473 1474 1475 1476 1477 1478 1479 1480
49 kDa 1481 1482 1483 1484 1485 1486 1487 1488 1489 1490
50 kDa 1491 1492 1493 1494 1495 1496 1497 1498 1499 1500
51 kDa 1501 1502 1503 1504 1505 1506 1507 1508 1509 1510
52 kDa 1511 1512 1513 1514 1515 1516 1517 1518 1519 1520
53 kDa 1521 1522 1523 1524 1525 1526 1527 1528 1529 1530
54 kDa 1531 1532 1533 1534 1535 1536 1537 1538 1539 1540
55 kDa 1541 1542 1543 1544 1545 1546 1547 1548 1549 1550
56 kDa 1551 1552 1553 1554 1555 1556 1557 1558 1559 1560
57 kDa 1561 1562 1563 1564 1565 1566 1567 1568 1569 1570
58 kDa 1571 1572 1573 1574 1575 1576 1577 1578 1579 1580
59 kDa 1581 1582 1583 1584 1585 1586 1587 1588 1589 1590
60 kDa 1591 1592 1593 1594 1595 1596 1597 1598 1599 1600
61 kDa 1601 1602 1603 1604 1605 1606 1607 1608 1609 1610
62 kDa 1611 1612 1613 1614 1615 1616 1617 1618 1619 1620
63 kDa 1621 1622 1623 1624 1625 1626 1627 1628 1629 1630
64 kDa 1631 1632 1633 1634 1635 1636 1637 1638 1639 1640
65 kDa 1641 1642 1643 1644 1645 1646 1647 1648 1649 1650
66 kDa 1651 1652 1653 1654 1655 1656 1657 1658 1659 1660
67 kDa 1661 1662 1663 1664 1665 1666 1667 1668 1669 1670
68 kDa 1671 1672 1673 1674 1675 1676 1677 1678 1679 1680
69 kDa 1681 1682 1683 1684 1685 1686 1687 1688 1689 1690
70 kDa 1691 1692 1693 1694 1695 1696 1697 1698 1699 1700
71 kDa 1701 1702 1703 1704 1705 1706 1707 1708 1709 1710
72 kDa 1711 1712 1713 1714 1715 1716 1717 1718 1719 1720
73 kDa 1721 1722 1723 1724 1725 1726 1727 1728 1729 1730
74 kDa 1731 1732 1733 1734 1735 1736 1737 1738 1739 1740
75 kDa 1741 1742 1743 1744 1745 1746 1747 1748 1749 1750
76 kDa 1751 1752 1753 1754 1755 1756 1757 1758 1759 1760
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77 kDa 1761 1762 1763 1764 1765 1766 1767 1768 1769 1770
78 kDa 1771 1772 1773 1774 1775 1776 1777 1778 1779 1780
79 kDa 1781 1782 1783 1784 1785 1786 1787 1788 1789 1790
80 kDa 1791 1792 1793 1794 1795 1796 1797 1798 1799 1800
81 kDa 1801 1802 1803 1804 1805 1806 1807 1808 1809 1810
82 kDa 1811 1812 1813 1814 1815 1816 1817 1818 1819 1820
83 kDa 1821 1822 1823 1824 1825 1826 1827 1828 1829 1830
84 kDa 1831 1832 1833 1834 1835 1836 1837 1838 1839 1840
85 kDa 1841 1842 1843 1844 1845 1846 1847 1848 1849 1850
86 kDa 1851 1852 1853 1854 1855 1856 1857 1858 1859 1860
87 kDa 1861 1862 1863 1864 1865 1866 1867 1868 1869 1870
88 kDa 1871 1872 1873 1874 1875 1876 1877 1878 1879 1880
89 kDa 1881 1882 1883 1884 1885 1886 1887 1888 1889 1890
90 kDa 1891 1892 1893 1894 1895 1896 1897 1898 1899 1900
91 kDa 1901 1902 1903 1904 1905 1906 1907 1908 1909 1910
92 kDa 1911 1912 1913 1914 1915 1916 1917 1918 1919 1920
93 kDa 1921 1922 1923 1924 1925 1926 1927 1928 1929 1930
94 kDa 1931 1932 1933 1934 1935 1936 1937 1938 1939 1940
95 kDa 1941 1942 1943 1944 1945 1946 1947 1948 1949 1950
96 kDa 1951 1952 1953 1954 1955 1956 1957 1958 1959 1960
97 kDa 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970
98 kDa 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980
99 kDa 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990
100 kDa 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000
101 kDa 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
102 kDa 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
103 kDa 2021 2022 2023 2024 2025 2026 2027 2028 2029 2030
104 kDa 2031 2032 2033 2034 2035 2036 2037 2038 2039 2040
105 kDa 2041 2042 2043 2044 2045 2046 2047 2048 2049 2050
106 kDa 2051 2052 2053 2054 2055 2056 2057 2058 2059 2060
107 kDa 2061 2062 2063 2064 2065 2066 2067 2068 2069 2070
108 kDa 2071 2072 2073 2074 2075 2076 2077 2078 2079 2080
109 kDa 2081 2082 2083 2084 2085 2086 2087 2088 2089 2090
110 kDa 2091 2092 2093 2094 2095 2096 2097 2098 2099 2100
111 kDa 2101 2102 2103 2104 2105 2106 2107 2108 2109 2110
112 kDa 2111 2112 2113 2114 2115 2116 2117 2118 2119 2120
113 kDa 2121 2122 2123 2124 2125 2126 2127 2128 2129 2130
114 kDa 2131 2132 2133 2134 2135 2136 2137 2138 2139 2140
115 kDa 2141 2142 2143 2144 2145 2146 2147 2148 2149 2150
116 kDa 2151 2152 2153 2154 2155 2156 2157 2158 2159 2160
117 kDa 2161 2162 2163 2164 2165 2166 2167 2168 2169 2170
118 kDa 2171 2172 2173 2174 2175 2176 2177 2178 2179 2180
119 kDa 2181 2182 2183 2184 2185 2186 2187 2188 2189 2190
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120 kDa 2191 2192 2193 2194 2195 2196 2197 2198 2199 2200
121 kDa 2201 2202 2203 2204 2205 2206 2207 2208 2209 2210
122 kDa 2211 2212 2213 2214 2215 2216 2217 2218 2219 2220
123 kDa 2221 2222 2223 2224 2225 2226 2227 2228 2229 2230
124 kDa 2231 2232 2233 2234 2235 2236 2237 2238 2239 2240
125 kDa 2241 2242 2243 2244 2245 2246 2247 2248 2249 2250
126 kDa 2251 2252 2253 2254 2255 2256 2257 2258 2259 2260
127 kDa 2261 2262 2263 2264 2265 2266 2267 2268 2269 2270
128 kDa 2271 2272 2273 2274 2275 2276 2277 2278 2279 2280
129 kDa 2281 2282 2283 2284 2285 2286 2287 2288 2289 2290
130 kDa 2291 2292 2293 2294 2295 2296 2297 2298 2299 2300
131 kDa 2301 2302 2303 2304 2305 2306 2307 2308 2309 2310
132 kDa 2311 2312 2313 2314 2315 2316 2317 2318 2319 2320
133 kDa 2321 2322 2323 2324 2325 2326 2327 2328 2329 2330
134 kDa 2331 2332 2333 2334 2335 2336 2337 2338 2339 2340
135 kDa 2341 2342 2343 2344 2345 2346 2347 2348 2349 2350
136 kDa 2351 2352 2353 2354 2355 2356 2357 2358 2359 2360
137 kDa 2361 2362 2363 2364 2365 2366 2367 2368 2369 2370
138 kDa 2371 2372 2373 2374 2375 2376 2377 2378 2379 2380
139 kDa 2381 2382 2383 2384 2385 2386 2387 2388 2389 2390
140 kDa 2391 2392 2393 2394 2395 2396 2397 2398 2399 2400
141 kDa 2401 2402 2403 2404 2405 2406 2407 2408 2409 2410
142 kDa 2411 2412 2413 2414 2415 2416 2417 2418 2419 2420
143 kDa 2421 2422 2423 2424 2425 2426 2427 2428 2429 2430
144 kDa 2431 2432 2433 2434 2435 2436 2437 2438 2439 2440
145 kDa 2441 2442 2443 2444 2445 2446 2447 2448 2449 2450
As used herein, "low molecular weight," "low MW," or "low-MW" SPF may
include SPF having a weight average molecular weight, or average weight
average
molecular weight in a range of about 5 kDa to about 30 kDa, about 14 kDa to
about 30
kDa, or about 6 kDa to about 17 kDa. In some embodiments, a target low
molecular
weight for certain SPF may be weight average molecular weight of about 5 kDa,
about 6
kDa, about 7 kDa, about 8 kDa, about 9 kDa, about 10 kDa, about 11 kDa, about
12 kDa,
about 13 kDa, about 14 kDa, about 15 kDa, about 16 kDa, about 17 kDa, about 18
kDa,
about 19 kDa, about 20 kDa, about 21 kDa, about 22 kDa, about 23 kDa, about 24
kDa,
about 25 kDa, about 26 kDa, about 27 kDa, about 28 kDa, about 29 kDa, or about
30
kDa.
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As used herein, "medium molecular weight," "medium MW," or "mid-MW" SPF
may include SPF having a weight average molecular weight, or average weight
average
molecular weight in a range of about 20 kDa to about 55 kDa, about 39 kDa to
about 54
kDa, or about 17 kDa to about 39 kDa. In some embodiments, a target medium
molecular
weight for certain SPF may be weight average molecular weight of about 17 kDa,
about
18 kDa, about 19 kDa, about 20 kDa, about 21 kDa, about 22 kDa, about 23 kDa,
about
24 kDa, about 25 kDa, about 26 kDa, about 27 kDa, about 28 kDa, about 29 kDa,
about
30 kDa, about 31 kDa, about 32 kDa, about 33 kDa, about 34 kDa, about 35 kDa,
about
36 kDa, about 37 kDa, about 38 kDa, about 39 kDa, about 40 kDa, about 41 kDa,
about
42 kDa, about 43 kDa, about 44 kDa, about 45 kDa, about 46 kDa, about 47 kDa,
about
48 kDa, about 49 kDa, about 50 kDa, about 51 kDa, about 52 kDa, about 53 kDa,
about
54 kDa, or about 55 kDa.
As used herein, "high molecular weight," "high MW," or "high-MW" SPF may
include SPF having a weight average molecular weight, or average weight
average
molecular weight that is in a range of about 55 kDa to about 150 kDa, or about
39 kDa to
about 80 kDa. In some embodiments, a target high molecular weight for certain
SPF may
be about 39 kDa, about 40 kDa, about 41 kDa, about 42 kDa, about 43 kDa, about
44
kDa, about 45 kDa, about 46 kDa, about 47 kDa, about 48 kDa, about 49 kDa,
about 50
kDa, about 51 kDa, about 52 kDa, about 53 kDa, about 54 kDa, about 55 kDa,
about 56
kDa, about 57 kDa, about 58 kDa, about 59 kDa, about 60 kDa, about 61 kDa,
about 62
kDa, about 63 kDa, about 64 kDa, about 65 kDa, about 66 kDa, about 67 kDa,
about 68
kDa, about 69 kDa, about 70 kDa, about 71 kDa, about 72 kDa, about 73 kDa,
about 74
kDa, about 75 kDa, about 76 kDa, about 77 kDa, about 78 kDa, about 79 kDa, or
about
80 kDa.
In some embodiments, the molecular weights described herein (e.g., low
molecular weight silk, medium molecular weight silk, high molecular weight
silk) may
be converted to the approximate number of amino acids contained within the
respective
SPF, as would be understood by a person having ordinary skill in the art. For
example,
the average weight of an amino acid may be about 110 daltons (i.e., 110
g/mol).
Therefore, in some embodiments, dividing the molecular weight of a linear
protein by
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110 daltons may be used to approximate the number of amino acid residues
contained
therein.
In an embodiment, SPF in a composition of the present disclosure have a
polydispersity ranging from 1 to about 5.0, including, without limitation, a
polydispersity
of 1. In an embodiment, SPF in a composition of the present disclosure have a
polydispersity ranging from about 1.5 to about 3Ø In an embodiment, SPF in a
composition of the present disclosure have a polydispersity ranging from 1 to
about 1.5,
including, without limitation, a polydispersity of 1. In an embodiment, SPF in
a
composition of the present disclosure have a polydispersity ranging from about
1.5 to
about 2Ø In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity ranging from about 2.0 to about 2.5. In an embodiment, SPF in a
composition of the present disclosure have a polydispersity ranging from about
2.5 to
about 3Ø In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity ranging from about 3.0 to about 3.5. In an embodiment, SPF in a
composition of the present disclosure have a polydispersity ranging from about
3.5 to
about 4Ø In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity ranging from about 4.0 to about 4.5. In an embodiment, SPF in a
composition of the present disclosure have a polydispersity ranging from about
4.5 to
about 5Ø
In an embodiment, SPF in a composition of the present disclosure have a
polydispersity of 1. In an embodiment, SPF in a composition of the present
disclosure
have a polydispersity of about 1.1. In an embodiment, SPF in a composition of
the
present disclosure have a polydispersity of about 1.2. In an embodiment, SPF
in a
composition of the present disclosure have a polydispersity of about 1.3. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 1.4. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 1.5. In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 1.6. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 1.7. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 1.8. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
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about 1.9. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 2Ø In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 2.1. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 2.2. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 2.3. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 2.4. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 2.5. In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 2.6. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 2.7. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 2.8. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 2.9. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 3Ø In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 3.1. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 3.2. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 3.3. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 3.4. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 3.5. In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 3.6. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 3.7. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 3.8. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 3.9. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 4Ø In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 4.1. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 4.2. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 4.3. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 4.4. In an embodiment, SPF in a composition of the present disclosure
have a
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polydispersity of about 4.5. In an embodiment, SPF in a composition of the
present
disclosure have a polydispersity of about 4.6. In an embodiment, SPF in a
composition of
the present disclosure have a polydispersity of about 4.7. In an embodiment,
SPF in a
composition of the present disclosure have a polydispersity of about 4.8. In
an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of
about 4.9. In an embodiment, SPF in a composition of the present disclosure
have a
polydispersity of about 5Ø
In some embodiments, in compositions described herein having combinations of
low, medium, and/or high molecular weight SPF, such low, medium, and/or high
molecular weight SPF may have the same or different polydispersities.
Silk Fibroin Fragments
Methods of making silk fibroin or silk fibroin protein fragments and their
applications in various fields are known and are described for example in U.S.
Patents
Nos. 9,187,538, 9,511,012, 9,517,191, 9,522,107, 9,522,108, 9,545,369, and
10,166,177,
10,287,728 and 10,301,768, all of which are incorporated herein in their
entireties. Raw
silk from silkworm Bombyx mori is composed of two primary proteins: silk
fibroin
(approximately 75%) and sericin (approximately 25%). Silk fibroin is a fibrous
protein
with a semi-crystalline structure that provides stiffness and strength. As
used herein, the
term "silk fibroin" means the fibers of the cocoon of Bombyx mori having a
weight
average molecular weight of about 370,000 Da. The crude silkworm fiber
consists of a
double thread of fibroin. The adhesive substance holding these double fibers
together is
sericin. The silk fibroin is composed of a heavy chain having a weight average
molecular
weight of about 350,000 Da (H chain), and a light chain having a weight
average
molecular weight about 25,000 Da (L chain). Silk fibroin is an amphiphilic
polymer with
large hydrophobic domains occupying the major component of the polymer, which
has a
high molecular weight. The hydrophobic regions are interrupted by small
hydrophilic
spacers, and the N- and C-termini of the chains are also highly hydrophilic.
The
hydrophobic domains of the H-chain contain a repetitive hexapeptide sequence
of Gly-
Ala-Gly-Ala-Gly-Ser and repeats of Gly-Ala/Ser/Tyr dipeptides, which can form
stable
anti-parallel-sheet crystallites. The amino acid sequence of the L-chain is
non-repetitive,
so the L-chain is more hydrophilic and relatively elastic. The hydrophilic
(Tyr, Ser) and
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hydrophobic (Gly, Ala) chain segments in silk fibroin molecules are arranged
alternatively such that allows self-assembling of silk fibroin molecules.
Provided herein are methods for producing pure and highly scalable silk
fibroin-
protein fragment mixture solutions that may be used across multiple industries
for a
variety of applications. Without wishing to be bound by any particular theory,
it is
believed that these methods are equally applicable to fragmentation of any SPF
described
herein, including without limitation recombinant silk proteins, and
fragmentation of silk-
like or fibroin-like proteins.
As used herein, the term "fibroin" includes silk worm fibroin and insect or
spider
silk protein. In an embodiment, fibroin is obtained from Bombyx mori. Raw silk
from
Bombyx mori is composed of two primary proteins: silk fibroin (approximately
75%) and
sericin (approximately 25%). Silk fibroin is a fibrous protein with a semi-
crystalline
structure that provides stiffness and strength. As used herein, the term "silk
fibroin"
means the fibers of the cocoon of Bombyx mori having a weight average
molecular
weight of about 370,000 Da. Conversion of these insoluble silk fibroin fibrils
into water-
soluble silk fibroin protein fragments requires the addition of a concentrated
neutral salt
(e.g., 8-10 M lithium bromide), which interferes with inter- and
intramolecular ionic and
hydrogen bonding that would otherwise render the fibroin protein insoluble in
water.
Methods of making silk fibroin protein fragments, and/or compositions thereof,
are
known and are described for example in U.S. Patents Nos. 9,187,538, 9,511,012,
9,517,191, 9,522,107, 9,522,108, 9,545,369, and 10,166,177.
The raw silk cocoons from the silkworm Bombyx mori was cut into pieces. The
pieces silk cocoons were processed in an aqueous solution of Na2CO3 at about
100 C for
about 60 minutes to remove sericin (degumming). The volume of the water used
equals
about 0.4 x raw silk weight and the amount of Na2CO3 is about 0.848 x the
weight of the
raw silk cocoon pieces. The resulting degummed silk cocoon pieces were rinsed
with
deionized water three times at about 60 C (20 minutes per rinse). The volume
of rinse
water for each cycle was 0.2 L x the weight of the raw silk cocoon pieces. The
excess
water from the degummed silk cocoon pieces was removed. After the DI water
washing
step, the wet degummed silk cocoon pieces were dried at room temperature. The
degummed silk cocoon pieces were mixed with a LiBr solution, and the mixture
was
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heated to about 100 C. The warmed mixture was placed in a dry oven and was
heated at
about 100 C for about 60 minutes to achieve complete dissolution of the
native silk
protein. The resulting silk fibroin solution was filtered and dialyzed using
Tangential
Flow Filtration (TFF) and a 10 kDa membrane against deionized water for 72
hours. The
resulting silk fibroin aqueous solution has a concentration of about 8.5 wt.
%. Then, 8.5
% silk solution was diluted with water to result in a 1.0 % w/v silk solution.
TFF can then
be used to further concentrate the pure silk solution to a concentration of
20.0 % w/w silk
to water.
Dialyzing the silk through a series of water changes is a manual and time
intensive process, which could be accelerated by changing certain parameters,
for
example diluting the silk solution prior to dialysis. The dialysis process
could be scaled
for manufacturing by using semi-automated equipment, for example a tangential
flow
filtration system.
In some embodiments, the silk solutions are prepared under various preparation
condition parameters such as: 90 C 30 min, 90 C 60 min, 100 C 30 min, and
100 C 60
min. Briefly, 9.3 M LiBr was prepared and allowed to sit at room temperature
for at least
30 minutes. 5 mL of LiBr solution was added to 1.25 g of silk and placed in
the 60 C
oven. Samples from each set were removed at 4, 6, 8, 12, 24, 168 and 192
hours.
In some embodiments, the silk solutions are prepared under various preparation
condition parameters such as: 90 C 30 min, 90 C 60 min, 100 C 30 min, and
100 C 60
min. Briefly, 9.3 M LiBr solution was heated to one of four temperatures: 60
C, 80 C,
100 C or boiling. 5 mL of hot LiBr solution was added to 1.25 g of silk and
placed in the
60 C oven. Samples from each set were removed at 1, 4 and 6 hours.
In some embodiments, the silk solutions are prepared under various preparation
condition parameters such as: Four different silk extraction combinations were
used: 90
C 30 min, 90 C 60 min, 100 C 30 min, and 100 C 60 min. Briefly, 9.3 M LiBr
solution was heated to one of four temperatures: 60 C, 80 C, 100 C or
boiling. 5 mL of
hot LiBr solution was added to 1.25 g of silk and placed in the oven at the
same
temperature of the LiBr. Samples from each set were removed at 1, 4 and 6
hours. 1 mL
of each sample was added to 7.5 mL of 9.3 M LiBr and refrigerated for
viscosity testing.
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In some embodiments, SPF are obtained by dissolving raw unscoured, partially
scoured, or scoured silkworm fibers with a neutral lithium bromide salt. The
raw
silkworm silks are processed under selected temperature and other conditions
in order to
remove any sericin and achieve the desired weight average molecular weight
(Mw) and
polydispersity (PD) of the fragment mixture. Selection of process parameters
may be
altered to achieve distinct final silk protein fragment characteristics
depending upon the
intended use. The resulting final fragment solution is silk fibroin protein
fragments and
water with parts per million (ppm) to non-detectable levels of process
contaminants,
levels acceptable in the pharmaceutical, medical and consumer eye care
markets. The
concentration, size and polydispersity of SPF may further be altered depending
upon the
desired use and performance requirements.
Fig. 18 is a flow chart showing various embodiments for producing pure silk
fibroin protein fragments (SPFs) of the present disclosure. It should be
understood that
not all of the steps illustrated are necessarily required to fabricate all
silk solutions of the
present disclosure. As illustrated in Fig. 18, step A, cocoons (heat-treated
or non-heat-
treated), silk fibers, silk powder, spider silk or recombinant spider silk can
be used as the
silk source. If starting from raw silk cocoons from Bombyx mori, the cocoons
can be cut
into small pieces, for example pieces of approximately equal size, step Bl.
The raw silk
is then extracted and rinsed to remove any sericin, step Cla. This results in
substantially
sericin free raw silk. In an embodiment, water is heated to a temperature
between 84 C
and 100 C (ideally boiling) and then Na2CO3 (sodium carbonate) is added to
the boiling
water until the Na2CO3 is completely dissolved. The raw silk is added to the
boiling
water/Na2CO3 (100 C) and submerged for approximately 15 - 90 minutes, where
boiling
for a longer time results in smaller silk protein fragments. In an embodiment,
the water
volume equals about 0.4 x raw silk weight and the Na2CO3 volume equals about
0.848 x
raw silk weight. In an embodiment, the water volume equals 0.1 x raw silk
weight and
the Na2CO3 volume is maintained at 2.12 g/L.
Subsequently, the water dissolved Na2CO3 solution is drained and excess
water/Na2CO3is removed from the silk fibroin fibers (e.g., ring out the
fibroin extract by
hand, spin cycle using a machine, etc.). The resulting silk fibroin extract is
rinsed with
warm to hot water to remove any remaining adsorbed sericin or contaminate,
typically at
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a temperature range of about 40 C to about 80 C, changing the volume of
water at least
once (repeated for as many times as required). The resulting silk fibroin
extract is a
substantially sericin-depleted silk fibroin. In an embodiment, the resulting
silk fibroin
extract is rinsed with water at a temperature of about 60 C. In an
embodiment, the
volume of rinse water for each cycle equals 0.1 L to 0.2 L x raw silk weight.
It may be
advantageous to agitate, turn or circulate the rinse water to maximize the
rinse effect.
After rinsing, excess water is removed from the extracted silk fibroin fibers
(e.g., ring out
fibroin extract by hand or using a machine). Alternatively, methods known to
one skilled
in the art such as pressure, temperature, or other reagents or combinations
thereof may be
used for the purpose of sericin extraction. Alternatively, the silk gland
(100% sericin free
silk protein) can be removed directly from a worm. This would result in liquid
silk
protein, without any alteration of the protein structure, free of sericin.
The extracted fibroin fibers are then allowed to dry completely. Once dry, the
extracted silk fibroin is dissolved using a solvent added to the silk fibroin
at a
temperature between ambient and boiling, step C lb. In an embodiment, the
solvent is a
solution of Lithium bromide (LiBr) (boiling for LiBr is 140 C).
Alternatively, the
extracted fibroin fibers are not dried but wet and placed in the solvent;
solvent
concentration can then be varied to achieve similar concentrations as to when
adding
dried silk to the solvent. The final concentration of LiBr solvent can range
from 0.1 M to
9.3 M. Complete dissolution of the extracted fibroin fibers can be achieved by
varying
the treatment time and temperature along with the concentration of dissolving
solvent.
Other solvents may be used including, but not limited to, phosphate phosphoric
acid,
calcium nitrate, calcium chloride solution or other concentrated aqueous
solutions of
inorganic salts. To ensure complete dissolution, the silk fibers should be
fully immersed
within the already heated solvent solution and then maintained at a
temperature ranging
from about 60 C to about 140 C for 1-168 hrs. In an embodiment, the silk
fibers should
be fully immersed within the solvent solution and then placed into a dry oven
at a
temperature of about 100 C for about 1 hour.
The temperature at which the silk fibroin extract is added to the LiBr
solution (or
vice versa) has an effect on the time required to completely dissolve the
fibroin and on
the resulting molecular weight and polydispersity of the final SPF mixture
solution. In an
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embodiment, silk solvent solution concentration is less than or equal to 20%
w/v. In
addition, agitation during introduction or dissolution may be used to
facilitate dissolution
at varying temperatures and concentrations. The temperature of the LiBr
solution will
provide control over the silk protein fragment mixture molecular weight and
polydispersity created. In an embodiment, a higher temperature will more
quickly
dissolve the silk offering enhanced process scalability and mass production of
silk
solution. In an embodiment, using a LiBr solution heated to a temperature
between 80 C
- 140 C reduces the time required in an oven in order to achieve full
dissolution. Varying
time and temperature at or above 60 C of the dissolution solvent will alter
and control
the MW and polydispersity of the SPF mixture solutions formed from the
original
molecular weight of the native silk fibroin protein.
Alternatively, whole cocoons may be placed directly into a solvent, such as
LiBr,
bypassing extraction, step B2. This requires subsequent filtration of silk
worm particles
from the silk and solvent solution and sericin removal using methods know in
the art for
separating hydrophobic and hydrophilic proteins such as a column separation
and/or
chromatography, ion exchange, chemical precipitation with salt and/or pH, and
or
enzymatic digestion and filtration or extraction, all methods are common
examples and
without limitation for standard protein separation methods, step C2. Non-heat
treated
cocoons with the silkworm removed, may alternatively be placed into a solvent
such as
LiBr, bypassing extraction. The methods described above may be used for
sericin
separation, with the advantage that non-heat treated cocoons will contain
significantly
less worm debris.
Dialysis may be used to remove the dissolution solvent from the resulting
dissolved fibroin protein fragment solution by dialyzing the solution against
a volume of
water, step El. Pre-filtration prior to dialysis is helpful to remove any
debris (i.e., silk
worm remnants) from the silk and LiBr solution, step D. In one example, a 3
p.m or 5 p.m
filter is used with a flow-rate of 200-300 mL/min to filter a 0.1% to 1.0%
silk-LiBr
solution prior to dialysis and potential concentration if desired. A method
disclosed
herein, as described above, is to use time and/or temperature to decrease the
concentration from 9.3 M LiBr to a range from 0.1 M to 9.3 M to facilitate
filtration and
downstream dialysis, particularly when considering creating a scalable process
method.
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Alternatively, without the use of additional time or temperate, a 9.3 M LiBr-
silk protein
fragment solution may be diluted with water to facilitate debris filtration
and dialysis.
The result of dissolution at the desired time and temperate filtration is a
translucent
particle-free room temperature shelf-stable silk protein fragment-LiBr
solution of a
known MW and polydispersity. It is advantageous to change the dialysis water
regularly
until the solvent has been removed (e.g., change water after 1 hour, 4 hours,
and then
every 12 hours for a total of 6 water changes). The total number of water
volume changes
may be varied based on the resulting concentration of solvent used for silk
protein
dissolution and fragmentation. After dialysis, the final silk solution maybe
further filtered
to remove any remaining debris (i.e., silk worm remnants).
Alternatively, Tangential Flow Filtration (TFF), which is a rapid and
efficient
method for the separation and purification of biomolecules, may be used to
remove the
solvent from the resulting dissolved fibroin solution, step E2. TFF offers a
highly pure
aqueous silk protein fragment solution and enables scalability of the process
in order to
produce large volumes of the solution in a controlled and repeatable manner.
The silk and
LiBr solution may be diluted prior to TFF (20% down to 0.1% silk in either
water or
LiBr). Pre-filtration as described above prior to TFF processing may maintain
filter
efficiency and potentially avoids the creation of silk gel boundary layers on
the filter's
surface as the result of the presence of debris particles. Pre-filtration
prior to TFF is also
helpful to remove any remaining debris (i.e., silk worm remnants) from the
silk and LiBr
solution that may cause spontaneous or long-term gelation of the resulting
water only
solution, step D. TFF, recirculating or single pass, may be used for the
creation of water-
silk protein fragment solutions ranging from 0.1% silk to 30.0% silk (more
preferably,
0.1% - 6.0% silk). Different cutoff size TFF membranes may be required based
upon the
desired concentration, molecular weight and polydispersity of the silk protein
fragment
mixture in solution. Membranes ranging from 1-100 kDa may be necessary for
varying
molecular weight silk solutions created for example by varying the length of
extraction
boil time or the time and temperate in dissolution solvent (e.g., LiBr). In an
embodiment,
a TFF 5 or 10 kDa membrane is used to purify the silk protein fragment mixture
solution
and to create the final desired silk-to-water ratio. As well, TFF single pass,
TFF, and
other methods known in the art, such as a falling film evaporator, may be used
to
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concentrate the solution following removal of the dissolution solvent (e.g.,
LiBr) (with
resulting desired concentration ranging from 0.1% to 30% silk). This can be
used as an
alternative to standard HFIP concentration methods known in the art to create
a water-
based solution. A larger pore membrane could also be utilized to filter out
small silk
protein fragments and to create a solution of higher molecular weight silk
with and/or
without tighter polydispersity values.
An assay for LiBr and Na2CO3 detection can be performed using an HPLC system
equipped with evaporative light scattering detector (ELSD). The calculation
was
performed by linear regression of the resulting peak areas for the analyte
plotted against
concentration. More than one sample of a number of formulations of the present
disclosure was used for sample preparation and analysis. Generally, four
samples of
different formulations were weighed directly in a 10 mL volumetric flask. The
samples
were suspended in 5 mL of 20 mM ammonium formate (pH 3.0) and kept at 2-8 C
for 2
hours with occasional shaking to extract analytes from the film. After 2 hours
the solution
was diluted with 20 mM ammonium formate (pH 3.0). The sample solution from the
volumetric flask was transferred into HPLC vials and injected into the HPLC-
ELSD
system for the estimation of sodium carbonate and lithium bromide.
The analytical method developed for the quantitation of Na2CO3 and LiBr in
silk
protein formulations was found to be linear in the range 10 - 165 pg/mL, with
RSD for
injection precision as 2% and 1% for area and 0.38% and 0.19% for retention
time for
sodium carbonate and lithium bromide respectively. The analytical method can
be
applied for the quantitative determination of sodium carbonate and lithium
bromide in
silk protein formulations.
Fig. 19 is a flow chart showing various parameters that can be modified during
the process of producing a silk protein fragment solution of the present
disclosure during
the extraction and the dissolution steps. Select method parameters may be
altered to
achieve distinct final solution characteristics depending upon the intended
use, e.g.,
molecular weight and polydispersity. It should be understood that not all of
the steps
illustrated are necessarily required to fabricate all silk solutions of the
present disclosure.
In an embodiment, silk protein fragment solutions useful for a wide variety of
applications are prepared according to the following steps: forming pieces of
silk cocoons
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from the Bombyx mori silkworm; extracting the pieces at about 100 C in a
Na2CO3water
solution for about 60 minutes, wherein a volume of the water equals about 0.4
x raw silk
weight and the amount of Na2CO3 is about 0.848 x the weight of the pieces to
form a silk
fibroin extract; triple rinsing the silk fibroin extract at about 60 C for
about 20 minutes
per rinse in a volume of rinse water, wherein the rinse water for each cycle
equals about
0.2 L x the weight of the pieces; removing excess water from the silk fibroin
extract;
drying the silk fibroin extract; dissolving the dry silk fibroin extract in a
LiBr solution,
wherein the LiBr solution is first heated to about 100 C to create a silk and
LiBr solution
and maintained; placing the silk and LiBr solution in a dry oven at about 100
C for about
60 minutes to achieve complete dissolution and further fragmentation of the
native silk
protein structure into mixture with desired molecular weight and
polydispersity; filtering
the solution to remove any remaining debris from the silkworm; diluting the
solution with
water to result in a 1.0 wt. % silk solution; and removing solvent from the
solution using
Tangential Flow Filtration (TFF). In an embodiment, a 10 kDa membrane is
utilized to
purify the silk solution and create the final desired silk-to-water ratio. TFF
can then be
used to further concentrate the silk solution to a concentration of 2.0 wt. %
silk in water.
Without wishing to be bound by any particular theory, varying extraction
(i.e.,
time and temperature), LiBr (i.e., temperature of LiBr solution when added to
silk fibroin
extract or vice versa) and dissolution (i.e., time and temperature) parameters
results in
solvent and silk solutions with different viscosities, homogeneities, and
colors. Also
without wishing to be bound by any particular theory, increasing the
temperature for
extraction, lengthening the extraction time, using a higher temperature LiBr
solution at
emersion and over time when dissolving the silk and increasing the time at
temperature
(e.g., in an oven as shown here, or an alternative heat source) all resulted
in less viscous
and more homogeneous solvent and silk solutions.
The extraction step could be completed in a larger vessel, for example an
industrial washing machine where temperatures at or in between 60 C to 100 C
can be
maintained. The rinsing step could also be completed in the industrial washing
machine,
eliminating the manual rinse cycles. Dissolution of the silk in LiBr solution
could occur
in a vessel other than a convection oven, for example a stirred tank reactor.
Dialyzing the
silk through a series of water changes is a manual and time intensive process,
which
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could be accelerated by changing certain parameters, for example diluting the
silk
solution prior to dialysis. The dialysis process could be scaled for
manufacturing by using
semi-automated equipment, for example a tangential flow filtration system.
Varying extraction (i.e., time and temperature), LiBr (i.e., temperature of
LiBr
solution when added to silk fibroin extract or vice versa) and dissolution
(i.e., time and
temperature) parameters results in solvent and silk solutions with different
viscosities,
homogeneities, and colors. Increasing the temperature for extraction,
lengthening the
extraction time, using a higher temperature LiBr solution at emersion and over
time when
dissolving the silk and increasing the time at temperature (e.g., in an oven
as shown here,
or an alternative heat source) all resulted in less viscous and more
homogeneous solvent
and silk solutions. While almost all parameters resulted in a viable silk
solution, methods
that allow complete dissolution to be achieved in fewer than 4 to 6 hours are
preferred for
process scalability.
In an embodiment, solutions of silk fibroin protein fragments having a weight
average ranging from about 6 kDa to about 17 kDa are prepared according to
following
steps: degumming a silk source by adding the silk source to a boiling (100 C)
aqueous
solution of sodium carbonate for a treatment time of between about 30 minutes
to about
60 minutes; removing sericin from the solution to produce a silk fibroin
extract
comprising non- detectable levels of sericin; draining the solution from the
silk fibroin
extract; dissolving the silk fibroin extract in a solution of lithium bromide
having a
starting temperature upon placement of the silk fibroin extract in the lithium
bromide
solution that ranges from about 60 C to about 140 C; maintaining the
solution of silk
fibroin-lithium bromide in an oven having a temperature of about 140 C for a
period of
at most 1 hour; removing the lithium bromide from the silk fibroin extract;
and producing
an aqueous solution of silk protein fragments, the aqueous solution
comprising:
fragments having a weight average molecular weight ranging from about 6 kDa to
about
17 kDa, and a polydispersity of between 1 and about 5, or between about 1.5
and about
3Ø The method may further comprise drying the silk fibroin extract prior to
the
dissolving step. The aqueous solution of silk fibroin protein fragments may
comprise
lithium bromide residuals of less than 300 ppm as measured using a high-
performance
liquid chromatography lithium bromide assay. The aqueous solution of silk
fibroin
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protein fragments may comprise sodium carbonate residuals of less than 100 ppm
as
measured using a high-performance liquid chromatography sodium carbonate
assay. The
aqueous solution of silk fibroin protein fragments may be lyophilized. In some
embodiments, the silk fibroin protein fragment solution may be further
processed into
various forms including gel, powder, and nanofiber.
In an embodiment, solutions of silk fibroin protein fragments having a weight
average molecular weight ranging from about 17 kDa to about 39 kDa are
prepared
according to the following steps: adding a silk source to a boiling (100 C)
aqueous
solution of sodium carbonate for a treatment time of between about 30 minutes
to about
60 minutes so as to result in degumming; removing sericin from the solution to
produce a
silk fibroin extract comprising non-detectable levels of sericin; draining the
solution from
the silk fibroin extract; dissolving the silk fibroin extract in a solution of
lithium bromide
having a starting temperature upon placement of the silk fibroin extract in
the lithium
bromide solution that ranges from about 80 C to about 140 C; maintaining the
solution
of silk fibroin-lithium bromide in a dry oven having a temperature in the
range between
about 60 C to about 100 C for a period of at most 1 hour; removing the
lithium bromide
from the silk fibroin extract; and producing an aqueous solution of silk
fibroin protein
fragments, wherein the aqueous solution of silk fibroin protein fragments
comprises
lithium bromide residuals of between about 10 ppm and about 300 ppm, wherein
the
aqueous solution of silk protein fragments comprises sodium carbonate
residuals of
between about 10 ppm and about 100 ppm, wherein the aqueous solution of silk
fibroin
protein fragments comprises fragments having a weight average molecular weight
ranging from about 17 kDa to about 39 kDa, and a polydispersity of between 1
and about
5, or between about 1.5 and about 3Ø The method may further comprise drying
the silk
fibroin extract prior to the dissolving step. The aqueous solution of silk
fibroin protein
fragments may comprise lithium bromide residuals of less than 300 ppm as
measured
using a high- performance liquid chromatography lithium bromide assay. The
aqueous
solution of silk fibroin protein fragments may comprise sodium carbonate
residuals of
less than 100 ppm as measured using a high-performance liquid chromatography
sodium
carbonate assay.
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In some embodiments, a method for preparing an aqueous solution of silk
fibroin
protein fragments having an average weight average molecular weight ranging
from
about 6 kDa to about 17 kDa includes the steps of: degumming a silk source by
adding
the silk source to a boiling (100 C) aqueous solution of sodium carbonate for
a treatment
time of between about 30 minutes to about 60 minutes; removing sericin from
the
solution to produce a silk fibroin extract comprising non-detectable levels of
sericin;
draining the solution from the silk fibroin extract; dissolving the silk
fibroin extract in a
solution of lithium bromide having a starting temperature upon placement of
the silk
fibroin extract in the lithium bromide solution that ranges from about 60 C
to about 140
C; maintaining the solution of silk fibroin-lithium bromide in an oven having
a
temperature of about 140 C for a period of at least 1 hour; removing the
lithium bromide
from the silk fibroin extract; and producing an aqueous solution of silk
protein fragments,
the aqueous solution comprising: fragments having an average weight average
molecular
weight ranging from about 6 kDa to about 17 kDa, and a polydispersity of
between 1 and
about 5, or between about 1.5 and about 3Ø The method may further comprise
drying
the silk fibroin extract prior to the dissolving step. The aqueous solution of
pure silk
fibroin protein fragments may comprise lithium bromide residuals of less than
300 ppm
as measured using a high-performance liquid chromatography lithium bromide
assay.
The aqueous solution of pure silk fibroin protein fragments may comprise
sodium
carbonate residuals of less than 100 ppm as measured using a high-performance
liquid
chromatography sodium carbonate assay. The method may further comprise adding
a
therapeutic agent to the aqueous solution of pure silk fibroin protein
fragments. The
method may further comprise adding a molecule selected from one of an
antioxidant or
an enzyme to the aqueous solution of pure silk fibroin protein fragments. The
method
may further comprise adding a vitamin to the aqueous solution of pure silk
fibroin protein
fragments. The vitamin may be vitamin C or a derivative thereof. The aqueous
solution of
pure silk fibroin protein fragments may be lyophilized. The method may further
comprise
adding an alpha hydroxy acid to the aqueous solution of pure silk fibroin
protein
fragments. The alpha hydroxy acid may be selected from the group consisting of
glycolic
acid, lactic acid, tartaric acid and citric acid. The method may further
comprise adding
hyaluronic acid or its salt form at a concentration of about 0.5 % to about
10.0 % to the
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aqueous solution of pure silk fibroin protein fragments. The method may
further
comprise adding at least one of zinc oxide or titanium dioxide. A film may be
fabricated
from the aqueous solution of pure silk fibroin protein fragments produced by
this method.
The film may comprise from about 1.0 wt. % to about 50,0 wt. % of vitamin C or
a
derivative thereof. The film may have a water content ranging from about 2.0
wt. % to
about 20.0 wt. %. The film may comprise from about 30.0 wt. % to about 99.5
wt. % of
pure silk fibroin protein fragments. A gel may be fabricated from the aqueous
solution of
pure silk fibroin protein fragments produced by this method. The gel may
comprise from
about 0.5 wt. % to about 20.0 wt. % of vitamin C or a derivative thereof. The
gel may
have a silk content of at least 2 % and a vitamin content of at least 20 %.
In some embodiments, a method for preparing an aqueous solution of silk
fibroin
protein fragments having an average weight average molecular weight ranging
from
about 17 kDa to about 39 kDa includes the steps of: adding a silk source to a
boiling (100
C) aqueous solution of sodium carbonate for a treatment time of between about
30
minutes to about 60 minutes so as to result in degumming; removing sericin
from the
solution to produce a silk fibroin extract comprising non-detectable levels of
sericin;
draining the solution from the silk fibroin extract; dissolving the silk
fibroin extract in a
solution of lithium bromide having a starting temperature upon placement of
the silk
fibroin extract in the lithium bromide solution that ranges from about 80 C
to about 140
C; maintaining the solution of silk fibroin-lithium bromide in a dry oven
having a
temperature in the range between about 60 C to about 100 C for a period of
at least 1
hour; removing the lithium bromide from the silk fibroin extract; and
producing an
aqueous solution of pure silk fibroin protein fragments, wherein the aqueous
solution of
pure silk fibroin protein fragments comprises lithium bromide residuals of
between about
ppm and about 300 ppm, wherein the aqueous solution of silk protein fragments
comprises sodium carbonate residuals of between about 10 ppm and about 100
ppm,
wherein the aqueous solution of pure silk fibroin protein fragments comprises
fragments
having an average weight average molecular weight ranging from about 17 kDa to
about
39 kDa, and a polydispersity of between 1 and about 5, or between about 1.5
and about
3Ø The method may further comprise drying the silk fibroin extract prior to
the
dissolving step. The aqueous solution of pure silk fibroin protein fragments
may
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comprise lithium bromide residuals of less than 300 ppm as measured using a
high-
performance liquid chromatography lithium bromide assay. The aqueous solution
of pure
silk fibroin protein fragments may comprise sodium carbonate residuals of less
than 100
ppm as measured using a high-performance liquid chromatography sodium
carbonate
assay. The method may further comprise adding a therapeutic agent to the
aqueous
solution of pure silk fibroin protein fragments. The method may further
comprise adding
a molecule selected from one of an antioxidant or an enzyme to the aqueous
solution of
pure silk fibroin protein fragments. The method may further comprise adding a
vitamin to
the aqueous solution of pure silk fibroin protein fragments. The vitamin may
be vitamin
C or a derivative thereof. The aqueous solution of pure silk fibroin protein
fragments may
be lyophilized. The method may further comprise adding an alpha hydroxy acid
to the
aqueous solution of pure silk fibroin protein fragments. The alpha hydroxy
acid may be
selected from the group consisting of glycolic acid, lactic acid, tartaric
acid and citric
acid. The method may further comprise adding hyaluronic acid or its salt form
at a
concentration of about 0.5% to about 10.0% to the aqueous solution of pure
silk fibroin
protein fragments. The method may further comprise adding at least one of zinc
oxide or
titanium dioxide. A film may be fabricated from the aqueous solution of pure
silk fibroin
protein fragments produced by this method. The film may comprise from about 1
,0 wt.
% to about 50.0 wt. % of vitamin C or a derivative thereof. The film may have
a water
content ranging from about 2.0 wt. % to about 20.0 wt. %. The film may
comprise from
about 30.0 wt. % to about 99.5 wt. % of pure silk fibroin protein fragments. A
gel may be
fabricated from the aqueous solution of pure silk fibroin protein fragments
produced by
this method. The gel may comprise from about 0.5 wt. % to about 20.0 wt. % of
vitamin
C or a derivative thereof. The gel may have a silk content of at least 2% and
a vitamin
content of at least 20%.
In an embodiment, solutions of silk fibroin protein fragments having a weight
average molecular weight ranging from about 39 kDa to about 80 kDa are
prepared
according to the following steps: adding a silk source to a boiling (100 C)
aqueous
solution of sodium carbonate for a treatment time of about 30 minutes so as to
result in
degumming; removing sericin from the solution to produce a silk fibroin
extract
comprising non-detectable levels of sericin; draining the solution from the
silk fibroin
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extract; dissolving the silk fibroin extract in a solution of lithium bromide
having a
starting temperature upon placement of the silk fibroin extract in the lithium
bromide
solution that ranges from about 80 C to about 140 C; maintaining the
solution of silk
fibroin-lithium bromide in a dry oven having a temperature in the range
between about 60
C to about 100 C for a period of at most 1 hour; removing the lithium bromide
from the
silk fibroin extract; and producing an aqueous solution of silk fibroin
protein fragments,
wherein the aqueous solution of silk fibroin protein fragments comprises
lithium bromide
residuals of between about 10 ppm and about 300 ppm, sodium carbonate
residuals of
between about 10 ppm and about 100 ppm, fragments having a weight average
molecular
weight ranging from about 39 kDa to about 80 kDa, and a polydispersity of
between 1
and about 5, or between about 1.5 and about 3Ø The method may further
comprise
drying the silk fibroin extract prior to the dissolving step. The aqueous
solution of silk
fibroin protein fragments may comprise lithium bromide residuals of less than
300 ppm
as measured using a high-performance liquid chromatography lithium bromide
assay.
The aqueous solution of silk fibroin protein fragments may comprise sodium
carbonate
residuals of less than 100 ppm as measured using a high-performance liquid
chromatography sodium carbonate assay. In some embodiments, the method may
further
comprise adding an active agent (e.g., therapeutic agent) to the aqueous
solution of pure
silk fibroin protein fragments. The method may further comprise adding an
active agent
selected from one of an antioxidant or an enzyme to the aqueous solution of
pure silk
fibroin protein fragments. The method may further comprise adding a vitamin to
the
aqueous solution of pure silk fibroin protein fragments. The vitamin may be
vitamin C or
a derivative thereof. The aqueous solution of pure silk fibroin protein
fragments may be
lyophilized. The method may further comprise adding an alpha-hydroxy acid to
the
aqueous solution of pure silk fibroin protein fragments. The alpha hydroxy
acid may be
selected from the group consisting of glycolic acid, lactic acid, tartaric
acid and citric
acid. The method may further comprise adding hyaluronic acid or its salt form
at a
concentration of about 0.5% to about 10.0% to the aqueous solution of pure
silk fibroin
protein fragments. A film may be fabricated from the aqueous solution of pure
silk
fibroin protein fragments produced by this method. The film may comprise from
about
1.0 wt. % to about 50.0 wt. % of vitamin C or a derivative thereof The film
may have a
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water content ranging from about 2.0 wt. % to about 20.0 wt. %. The film may
comprise
from about 30.0 wt. % to about 99.5 wt. % of pure silk fibroin protein
fragments. A gel
may be fabricated from the aqueous solution of pure silk fibroin protein
fragments
produced by this method. The gel may comprise from about 0.5 wt. % to about
20.0 wt.
% of vitamin C or a derivative thereof. The gel may have a silk content of at
least 2 wt. %
and a vitamin content of at least 20 wt. %.
Molecular weight of the silk protein fragments may be controlled based upon
the
specific parameters utilized during the extraction step, including extraction
time and
temperature; specific parameters utilized during the dissolution step,
including the LiBr
temperature at the time of submersion of the silk in to the lithium bromide
and time that
the solution is maintained at specific temperatures; and specific parameters
utilized
during the filtration step. By controlling process parameters using the
disclosed methods,
it is possible to create silk fibroin protein fragment solutions with
polydispersity equal to
or lower than 2.5 at a variety of different molecular weight ranging from 5
kDa to 200
kDa, or between 10 kDa and 80 kDa. By altering process parameters to achieve
silk
solutions with different molecular weights, a range of fragment mixture end
products,
with desired polydispersity of equal to or less than 2.5 may be targeted based
upon the
desired performance requirements. For example, a higher molecular weight silk
film
containing an ophthalmic drug may have a controlled slow release rate compared
to a
lower molecular weight film making it ideal for a delivery vehicle in eye care
products.
Additionally, the silk fibroin protein fragment solutions with a
polydispersity of greater
than 2.5 can be achieved. Further, two solutions with different average
molecular
weights and polydispersity can be mixed to create combination solutions.
Alternatively, a
liquid silk gland (100% sericin free silk protein) that has been removed
directly from a
worm could be used in combination with any of the silk fibroin protein
fragment
solutions of the present disclosure. Molecular weight of the pure silk fibroin
protein
fragment composition was determined using High Pressure Liquid Chromatography
(HPLC) with a Refractive Index Detector (RID). Polydispersity was calculated
using
Cirrus GPC Online GPC/SEC Software Version 3.3 (Agilent).
Differences in the processing parameters can result in regenerated silk
fibroins
that vary in molecular weight, and peptide chain size distribution
(polydispersity, PD).
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This, in turn, influences the regenerated silk fibroin performance, including
mechanical
strength, water solubility etc.
Parameters were varied during the processing of raw silk cocoons into the silk
solution. Varying these parameters affected the MW of the resulting silk
solution.
Parameters manipulated included (i) time and temperature of extraction, (ii)
temperature
of LiBr, (iii) temperature of dissolution oven, and (iv) dissolution time.
Experiments were
carried out to determine the effect of varying the extraction time. Tables A-F
summarize
the results. Below is a summary:
¨ A sericin extraction time of 30 minutes resulted in larger molecular
weight than a
sericin extraction time of 60 minutes
¨ Molecular weight decreases with time in the oven
¨ 140 C LiBr and oven resulted in the low end of the confidence interval
to be below a
molecular weight of 9500 Da
¨ 30 min extraction at the 1 hour and 4 hour time points have undigested
silk
¨ 30 min extraction at the 1 hour time point resulted in a significantly
high molecular
weight with the low end of the confidence interval being 35,000 Da
¨ The range of molecular weight reached for the high end of the confidence
interval
was 18000 to 216000 Da (important for offering solutions with specified upper
limit).
Table A. The effect of extraction time (30 min vs 60 min) on molecular weight
of silk
processed under the conditions of 100 C Extraction Temperature, 100 C
Lithium
Bromide (LiBr) and 100 C Oven Dissolution (Oven/Dissolution Time was varied).
Boil Time Oven Time Average Mw Std dev Confidence Interval PD
30 1 57247 12780 35093 93387 1.63
60 1 31520 1387 11633 85407 2.71
30 4 40973 2632 14268 117658 2.87
60 4 25082 1248 10520 59803 2.38
30 6 25604 1405 10252 63943 2.50
60 6 20980 1262 10073 43695 2.08
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Table B. The effect of extraction time (30 min vs 60 min) on molecular weight
of silk
processed under the conditions of 100 C Extraction Temperature, boiling
Lithium
Bromide (LiBr) and 60 C Oven Dissolution for 4 hr.
Sample Boil Time Average Mw Std Confidence Interval PD
dev
30 min, 4 hr 30 49656 4580 17306 142478 2.87
60 min, 4 hr 60 30042 1536 11183 80705 2.69
Table C. The effect of extraction time (30 min vs 60 min) on molecular weight
of silk
processed under the conditions of 100 C Extraction Temperature, 60 C Lithium
Bromide (LiBr) and 60 C Oven Dissolution (Oven/Dissolution Time was varied).
Sample Boil Time Oven Average Std Confidence PD
Time Mw dev Interval
30 min, 1 hr 30 1 58436 22201 153809 2.63
60 min, 1 hr 60 1 31700 11931 84224 2.66
30 min, 4 hr 30 4 61956.5 13337 21463 178847 2.89
60 min, 4 hr 60 4 25578.5 2446 9979 65564 2.56
Table D. The effect of extraction time (30 min vs 60 min) on molecular weight
of silk
processed under the conditions of 100 C Extraction Temperature, 80 C Lithium
Bromide (LiBr) and 80 C Oven Dissolution for 6 hr.
Sample Boil Time Average Std Confidence Interval PD
Mw dev
30 min, 6 hr 30 63510 18693 215775 3.40
60 min, 6 hr 60 25164 238 9637 65706 2.61
Table E. The effect of extraction time (30 min vs 60 min) on molecular weight
of silk
processed under the conditions of 100 C Extraction Temperature, 80 C Lithium
Bromide (LiBr) and 60 C Oven Dissolution (Oven/Dissolution Time was varied).
Sample Boil Time Oven Average Std dev Confidence PD
Time Mw Interval
30 min, 4 hr 30 4 59202 14028 19073 183760 3.10
60 min, 4 hr 60 4 26312.5 637 10266 67442 2.56
30 min, 6 hr 30 6 46824 18076 121293 2.59
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60 min, 6 hr 60 6 26353 10168 68302 2.59
Table F. The effect of extraction time (30 min vs 60 min) on molecular weight
of silk
processed under the conditions of 100 C Extraction Temperature, 140 C
Lithium
Bromide (LiBr) and 140 C Oven Dissolution (Oven/Dissolution Time was varied).
Sample Boil Time Oven Average Std dev Confidence PD
Time Mw Interval
30 min, 4 hr 30 4 9024.5 1102 4493 18127
2.00865
60 min, 4 hr 60 4 15548 6954 34762 2.2358
30 min, 6 hr 30 6 13021 5987 28319 2.1749
60 min, 6 hr 60 6 10888 5364 22100 2.0298
Experiments were carried out to determine the effect of varying the extraction
temperature. Table G summarizes the results. Below is a summary:
¨ Sericin extraction at 90 C resulted in higher MW than sericin extraction
at 100
C extraction
¨ Both 90 C and 100 C show decreasing MW over time in the oven
Table G. The effect of extraction temperature (90 C vs. 100 C) on molecular
weight of
silk processed under the conditions of 60 min. Extraction Temperature, 100 C
Lithium
Bromide (LiBr) and 100 C Oven Dissolution (Oven/Dissolution Time was varied).
Sample Boil Time Oven Time Average Mw Std dev Confidence Interval PD
90 C, 4 hr 60 4 37308 4204 13368 104119 2.79
100 C, 4 hr 60 4 25082 1248 10520 59804 2.38
90 C, 6 hr 60 6 34224 1135 12717 92100 2.69
100 C, 6 hr 60 6 20980 1262 10073 43694 2.08
Experiments were carried out to determine the effect of varying the Lithium
Bromide (LiBr) temperature when added to silk. Tables H-I summarize the
results.
Below is a summary:
¨ No impact on molecular weight or confidence interval (all CI ¨10500-6500
Da)
¨ Studies illustrated that the temperature of LiBr-silk dissolution, as
LiBr is added
and begins dissolving, rapidly drops below the original LiBr temperature due
to
the majority of the mass being silk at room temperature
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Table H. The effect of Lithium Bromide (LiBr) temperature on molecular weight
of silk
processed under the conditions of 60 min. Extraction Time., 100 C Extraction
Temperature and 60 C Oven Dissolution (Oven/Dissolution Time was varied).
Sample LiBr Oven Average Std dev Confidence Interval PD
Temp Time Mw
( C)
60 C LiBr, 60 1 31700 11931 84223 2.66
1 hr
100 C LiBr, 100 1 27907 200 10735 72552 2.60
1 hr
RT LiBr, RT 4 29217 1082 10789 79119 2.71
4 hr
60 C LiBr, 60 4 25578 2445 9978 65564 2.56
4 hr
80 C LiBr, 80 4 26312 637 10265 67441 2.56
4 hr
100 C LiBr, 100 4 27681 1729 11279 67931 2.45
4 hr
Boil LiBr, Boil 4 30042 1535 11183 80704 2.69
4 hr
RT LiBr, RT 6 26543 1893 10783 65332 2.46
6 hr
80 C LiBr, 80 6 26353 10167 68301 2.59
6 hr
100 C LiBr, 100 6 27150 916 11020 66889 2.46
6 hr
Table I. The effect of Lithium Bromide (LiBr) temperature on molecular weight
of silk
processed under the conditions of 30 min. Extraction Time, 100 C Extraction
Temperature and 60 C Oven Dissolution (Oven/Dissolution Time was varied).
Sample LiBr Oven Average Std dev Confidence Interval PD
Temp Time Mw
( C)
60 C LiBr, 60 4 61956 13336 21463 178847 2.89
4 hr
80 C LiBr, 80 4 59202 14027 19073 183760 3.10
4 hr
100 C LiBr, 100 4 47853 19757 115899 2.42
4 hr
80 C LiBr, 80 6 46824 18075 121292 2.59
6 hr
100 C LiBr, 100 6 55421 8991 19152 160366 2.89
6 hr
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Experiments were carried out to determine the effect of v oven/dissolution
temperature. Tables J-N summarize the results. Below is a summary:
¨ Oven temperature has less of an effect on 60 min extracted silk than 30
min
extracted silk. Without wishing to be bound by theory, it is believed that the
30
min silk is less degraded during extraction and therefore the oven temperature
has
more of an effect on the larger MW, less degraded portion of the silk.
¨ For 60 C vs. 140 C oven the 30 min extracted silk showed a very
significant
effect of lower MW at higher oven temp, while 60 min extracted silk had an
effect
but much less
¨ The 140 C oven resulted in a low end in the confidence interval at ¨6000
Da.
Table J. The effect of oven/dissolution temperature on molecular weight of
silk
processed under the conditions of 100 C Extraction Temperature, 30 min.
Extraction
Time, and 100 C Lithium Bromide (LiBr) (Oven/Dissolution Time was varied).
Boil Time Oven Temp Oven Average Std dev Confidence Interval PD
( C) Time Mw
30 60 4 47853 19758 115900 2.42
30 100 4 40973 2632 14268 117658 2.87
30 60 6 55421 8992 19153 160366 2.89
30 100 6 25604 1405 10252 63943 2.50
Table K. The effect of oven/dissolution temperature on molecular weight of
silk
processed under the conditions of 100 C Extraction Temperature, 60 min.
Extraction
Time, and 100 C Lithium Bromide (LiBr) (Oven/Dissolution Time was varied).
Boil Time Oven Temp Oven Average Std dev Confidence Interval PD
(minutes) Time Mw
60 60 1 27908 200 10735 72552 2.60
60 100 1 31520 1387 11633 85407 2.71
60 60 4 27681 1730 11279 72552 2.62
60 100 4 25082 1248 10520 59803 2.38
60 60 6 27150 916 11020 66889 2.46
60 100 6 20980 1262 10073 43695 2.08
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Table L. The effect of oven/dissolution temperature on molecular weight of
silk
processed under the conditions of 100 C Extraction Temperature, 60 min.
Extraction
Time, and 140 C Lithium Bromide (LiBr) (Oven/Dissolution Time was varied).
Boil Time Oven Oven Average Std dev Confidence Interval PD
(minutes) Temp( C) Time
60 60 4 30042 1536 11183 80705 2.69
60 140 4 15548 7255 33322 2.14
Table M. The effect of oven/dissolution temperature on molecular weight of
silk
processed under the conditions of 100 C Extraction Temperature, 30 min.
Extraction
Time, and 140 C Lithium Bromide (LiBr) (Oven/Dissolution Time was varied).
Boil Time Oven Oven Average Std dev Confidence Interval PD
(minutes) Temp Time Mw
( C)
30 60 4 49656 4580 17306 142478 2.87
30 140 4 9025
1102 4493 18127 2.01
30 60 6 59383 11640
17641 199889 3.37
30 140 6 13021 5987 28319 2.17
Table N. The effect of oven/dissolution temperature on molecular weight of
silk
processed under the conditions of 100 C Extraction Temperature, 60 min.
Extraction
Time, and 80 C Lithium Bromide (LiBr) (Oven/Dissolution Time was varied).
Boil Time Oven Temp Oven Average Std dev Confidence Interval PD
(minutes) ( C) Time Mw
60 60 4 26313 637 10266 67442 2.56
60 80 4 30308 4293 12279 74806 2.47
60 60 6 26353 10168 68302 2.59
60 80 6 25164 238 9637 65706 2.61
The raw silk cocoons from the silkworm Bombyx mori was cut into pieces. The
pieces of raw silk cocoons were boiled in an aqueous solution of Na2CO3 (about
100 C)
for a period of time between about 30 minutes to about 60 minutes to remove
sericin
(degumming). The volume of the water used equals about 0.4 x raw silk weight
and the
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amount of Na2CO3 is about 0.848 x the weight of the raw silk cocoon pieces.
The
resulting degummed silk cocoon pieces were rinsed with deionized water three
times at
about 60 C (20 minutes per rinse). The volume of rinse water for each cycle
was 0.2 L x
the weight of the raw silk cocoon pieces. The excess water from the degummed
silk
cocoon pieces was removed. After the DI water washing step, the wet degummed
silk
cocoon pieces were dried at room temperature. The degummed silk cocoon pieces
were
mixed with a LiBr solution, and the mixture was heated to about 100 C. The
warmed
mixture was placed in a dry oven and was heated at a temperature ranging from
about 60
C to about 140 C for about 60 minutes to achieve complete dissolution of the
native
silk protein. The resulting solution was allowed to cool to room temperature
and then was
dialyzed to remove LiBr salts using a 3,500 Da MWCO membrane. Multiple
exchanges
were performed in Di water until Br- ions were less than 1 ppm as determined
in the
hydrolyzed fibroin solution read on an Oakton Bromide (Br-) double-junction
ion-
selective electrode.
The resulting silk fibroin aqueous solution has a concentration of about 8.0 %
w/v
containing pure silk fibroin protein fragments having an average weight
average
molecular weight ranging from about 6 kDa to about 16 kDa, about 17 kDa to
about 39
kDa, and about 39 kDa to about 80 kDa and a polydispersity of between about
1.5 and
about 3Ø The 8.0 % w/v was diluted with DI water to provide a 1.0 % w/v, 2.0
% w/v,
3.0 % w/v, 4.0 % w/v, 5.0 % w/v by the coating solution.
A variety of % silk concentrations have been produced through the use of
Tangential Flow Filtration (TFF). In all cases a 1 % silk solution was used as
the input
feed. A range of 750-18,000 mL of 1% silk solution was used as the starting
volume.
Solution is diafiltered in the TFF to remove lithium bromide. Once below a
specified
level of residual LiBr, solution undergoes ultrafiltration to increase the
concentration
through removal of water. See examples below.
Six (6) silk solutions were utilized in standard silk structures with the
following
results:
Solution #1 is a silk concentration of 5.9 wt. %, average MW of 19.8 kDa and
2.2
PDI (made with a 60 min boil extraction, 100 C LiBr dissolution for 1 hour).
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Solution #2 is a silk concentration of 6.4 wt. % (made with a 30 min boil
extraction, 60 C LiBr dissolution for 4 hrs).
Solution #3 is a silk concentration of 6.17 wt. % (made with a 30 min boil
extraction 100 C LiBr dissolution for 1 hour).
Solution #4 is a silk concentration of 7.30 wt. %: A 7.30 % silk solution was
produced beginning with 30 minute extraction batches of 100 g silk cocoons per
batch.
Extracted silk fibers were then dissolved using 100 C 9.3 M LiBr in a 100 C
oven for 1
hour. 100 g of silk fibers were dissolved per batch to create 20% silk in
LiBr. Dissolved
silk in LiBr was then diluted to 1% silk and filtered through a 5 p.m filter
to remove large
debris. 15,500 mL of 1 %, filtered silk solution was used as the starting
volume/diafiltration volume for TFF. Once LiBr was removed, the solution was
ultrafiltered to a volume around 1300 mL. 1262 mL of 7.30 % silk was then
collected.
Water was added to the feed to help remove the remaining solution and 547 mL
of 3.91
% silk was then collected.
Solution #5 is a silk concentration of 6.44 wt. %: A 6.44 wt. % silk solution
was
produced beginning with 60 minute extraction batches of a mix of 25, 33, 50,
75 and 100
g silk cocoons per batch. Extracted silk fibers were then dissolved using 100
C 9.3 M
LiBr in a 100 C oven for 1 hour. 35, 42, 50 and 71 g per batch of silk fibers
were
dissolved to create 20 % silk in LiBr and combined. Dissolved silk in LiBr was
then
diluted to 1 % silk and filtered through a 5 p.m filter to remove large
debris. 17,000 mL
of 1 %, filtered silk solution was used as the starting volume/diafiltration
volume for
TFF. Once LiBr was removed, the solution was ultrafiltered to a volume around
3000
mL. 1490 mL of 6.44 % silk was then collected. Water was added to the feed to
help
remove the remaining solution and 1454 mL of 4.88 % silk was then collected.
Solution #6 is a silk concentration of 2.70 wt. %: A 2.70 % silk solution was
produced beginning with 60-minute extraction batches of 25 g silk cocoons per
batch.
Extracted silk fibers were then dissolved using 100 C 9.3 M LiBr in a 100 C
oven for 1
hour. 35.48 g of silk fibers were dissolved per batch to create 20 % silk in
LiBr.
Dissolved silk in LiBr was then diluted to 1% silk and filtered through a 5
p.m filter to
remove large debris. 1000 mL of 1%, filtered silk solution was used as the
starting
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volume/diafiltration volume for TFF. Once LiBr was removed, the solution was
ultrafiltered to a volume around 300 mL. 312 mL of 2.7 % silk was then
collected.
The preparation of silk fibroin solutions with higher molecular weights is
given in
Table 0.
Table 0. Preparation and properties of silk fibroin solutions.
Average
Extraction Extraction LiBr weight
Sample Oven/Sol'n average Average
Time Temp Temp
Name Temp molecular polydispersity
(mins) ( C) ( C)
weight
(kDa)
Group A
60 100 100 100 C 34.7 2.94
TFF oven
Group A
60 100 100 100 C 44.7 3.17
DIS oven
Group B
60 100 100 100 C 41.6 3.07
TFF sol'n
Group B
60 100 100 100 C 44.0 3.12
DIS sol'n
Group D 30
90 60 60 C 129.7 2.56
DIS sol'n
Group D 30
90 60 60 C 144.2 2.73
FIL sol'n
Group E 15
100 RT 60 C 108.8 2.78
DIS sol'n
Group E 15
100 RT 60 C 94.8 2.62
FIL sol'n
Silk aqueous coating composition for application to fabrics are given in
Tables P and Q
below.
Table P. Silk Solution Characteristics
Molecular Weight: 57 kDa
Polydispersity: 1.6
% Silk 5.0% 3.0%
1.0% 0.5%
Process Parameters
Extraction
Boil Time: 30 minutes
Boil Temperature: 100 C
Rinse Temperature: 60 C
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Dissolution
LiBr Temperature: 100
Oven Temperature: 100 C
Oven Time: 60 minutes
Table Q. Silk Solution Characteristics
Molecular Weight: 25 kDa
Polydispersity: 2.4
% Silk 5.0% 3.0%
1.0% 0.5%
Process Parameters
Extraction
Boil Time: 60 minutes
Boil Temperature: 100 C
Rinse Temperature: 60 C
Dissolution
LiBr Temperature: 100 C
Oven Temperature: 100 C
Oven Time: 60 minutes
Three (3) silk solutions were utilized in film making with the following
results:
Solution #1 is a silk concentration of 5.9 %, average MW of 19.8 kDa and 2.2
PD
(made with a 60 min boil extraction, 100 C LiBr dissolution for 1 hr).
Solution #2 is a silk concentration of 6.4 % (made with a 30 min boil
extraction,
60 C LiBr dissolution for 4 hrs).
Solution #3 is a silk concentration of 6.17% (made with a 30 min boil
extraction,
100 C LiBr dissolution for 1 hour).
Films were made in accordance with Rockwood et al. (Nature Protocols; Vol. 6;
No. 10; published on-line Sep. 22, 2011; doi:10.1038/nprot.2011.379). 4 mL of
1% or 2%
(wt/vol) aqueous silk solution was added into 100 mm Petri dish (Volume of
silk can be
varied for thicker or thinner films and is not critical) and allowed to dry
overnight
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uncovered. The bottom of a vacuum desiccator was filled with water. Dry films
were
placed in the desiccator and vacuum applied, allowing the films to water
anneal for 4
hours prior to removal from the dish. Films cast from solution #1 did not
result in a
structurally continuous film; the film was cracked in several pieces. These
pieces of film
dissolved in water in spite of the water annealing treatment.
Silk solutions of various molecular weights and/or combinations of molecular
weights can be optimized for gel applications. The following provides an
example of this
process but it not intended to be limiting in application or formulation.
Three (3) silk
solutions were utilized in gel making with the following results:
Solution #1 is a silk concentration of 5.9 %, average MW of 19.8 kDa and 2.2
PD
(made with a 60 min boil extraction, 100 C LiBr dissolution for 1 hr).
Solution #2 is a silk concentration of 6.4 % (made with a 30 min boil
extraction,
60 C LiBr dissolution for 4 hrs).
Solution #3 is a silk concentration of 6.17% (made with a 30 min boil
extraction,
100 C LiBr dissolution for 1 hour).
"Egel" is an electrogelation process as described in Rockwood of al. Briefly,
10
ml of aqueous silk solution is added to a 50 ml conical tube and a pair of
platinum wire
electrodes immersed into the silk solution. A 20 volt potential was applied to
the
platinum electrodes for 5 minutes, the power supply turned off and the gel
collected.
Solution #1 did not form an EGEL over the 5 minutes of applied electric
current.
Solutions #2 and #3 were gelled in accordance with the published horseradish
peroxidase (HRP) protocol. Behavior seemed typical of published solutions.
Materials and Methods: the following equipment and material are used in
determination of Silk Molecular weight: Agilent 1100 with chemstation software
ver.
10.01; Refractive Index Detector (RID); analytical balance; volumetric flasks
(1000 mL,
mL and 5 mL); HPLC grade water; ACS grade sodium chloride; ACS grade sodium
phosphate dibasic heptahydrate; phosphoric acid; dextran MW Standards-Nominal
Molecular Weights of 5 kDa, 11.6 kDa, 23.8 kDa, 48.6 kDa, and 148 kDa; 50 mL
PET or
polypropylene disposable centrifuge tubes; graduated pipettes; amber glass
HPLC vials
with Teflon caps; Phenomenex PolySep GFC P-4000 column (size: 7.8 mm x 300
mm).
Procedural Steps:
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A) Preparation of 1 L Mobile Phase (0.1 M Sodium Chloride solution in
0.0125 M
Sodium phosphate buffer)
Take a 250 mL clean and dry beaker, place it on the balance and tare the
weight.
Add about 3.3509 g of sodium phosphate dibasic heptahydrate to the beaker.
Note down
the exact weight of sodium phosphate dibasic weighed. Dissolve the weighed
sodium
phosphate by adding 100 mL of HPLC water into the beaker. Take care not to
spill any of
the content of the beaker. Transfer the solution carefully into a clean and
dry 1000 mL
volumetric flask. Rinse the beaker and transfer the rinse into the volumetric
flask. Repeat
the rinse 4-5 times. In a separate clean and dry 250 mL beaker weigh exactly
about
5.8440 g of sodium chloride. Dissolve the weighed sodium chloride in 50 mL of
water
and transfer the solution to the sodium phosphate solution in the volumetric
flask. Rinse
the beaker and transfer the rinse into the volumetric flask. Adjust the pH of
the solution to
7.0 0.2 with phosphoric acid. Make up the volume in volumetric flask with
HPLC water
to 1000 mL and shake it vigorously to homogeneously mix the solution. Filter
the
solution through 0.45 p.m polyamide membrane filter. Transfer the solution to
a clean and
dry solvent bottle and label the bottle. The volume of the solution can be
varied to the
requirement by correspondingly varying the amount of sodium phosphate dibasic
heptahydrate and sodium chloride.
B) Preparation of Dextran Molecular Weight Standard solutions
At least five different molecular weight standards are used for each batch of
samples that are run so that the expected value of the sample to be tested is
bracketed by
the value of the standard used. Label six 20 mL scintillation glass vials
respective to the
molecular weight standards. Weigh accurately about 5 mg of each of dextran
molecular
weight standards and record the weights. Dissolve the dextran molecular weight
standards
in 5 mL of mobile phase to make a 1 mg/mL standard solution.
C) Preparation of Sample solutions
When preparing sample solutions, if there are limitations on how much sample
is
available, the preparations may be scaled as long as the ratios are
maintained. Depending
on sample type and silk protein content in sample weigh enough sample in a 50
mL
disposable centrifuge tube on an analytical balance to make a 1 mg/mL sample
solution
for analysis. Dissolve the sample in equivalent volume of mobile phase make a
1 mg/mL
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solution. Tightly cap the tubes and mix the samples (in solution). Leave the
sample
solution for 30 minutes at room temperature. Gently mix the sample solution
again for 1
minute and centrifuge at 4000 RPM for 10 minutes.
D) HPLC analysis of the samples
Transfer 1.0 mL of all the standards and sample solutions into individual HPLC
vials. Inject the molecular weight standards (one injection each) and each
sample in
duplicate. Analyze all the standards and sample solutions using the following
HPLC
conditions:
Column Poly Sep GFC P-4000 (7.8 x 300 mm)
Column Temperature 25 C
Detector Refractive Index Detector (Temperature @ 35 C)
Injection Volume 25.0 !IL
Mobile Phase 0.1 M Sodium Chloride solution in 0.0125 M sodium phosphate
buffer
Flow Rate 1.0 mL/min
Run Time 20.0 min
E) Data analysis and calculations - Calculation of Average Molecular Weight
using
Cirrus Software
Upload the chromatography data files of the standards and the analytical
samples
into Cirrus SEC data collection and molecular weight analysis software.
Calculate the
weight average molecular weight (Mw), number average molecular weight (Mn),
peak
average molecular weight (Me), and polydispersity for each injection of the
sample.
Spider Silk Fragments
Spider silks are natural polymers that consist of three domains: a repetitive
middle
core domain that dominates the protein chain, and non-repetitive N-terminal
and C-
terminal domains. The large core domain is organized in a block copolymer-like
arrangement, in which two basic sequences, crystalline [poly(A) or poly(GA)]
and less
crystalline (GGX or GPGXX) polypeptides alternate. Dragline silk is the
protein complex
composed of major ampullate dragline silk protein 1 (MaSpl) and major
ampullate
dragline silk protein 2 (MaSp2). Both silks are approximately 3500 amino acid
long.
MaSpl can be found in the fibre core and the periphery, whereas MaSp2 forms
clusters in
certain core areas. The large central domains of MaSp 1 and MaSp2 are
organized in
block copolymer-like arrangements, in which two basic sequences, crystalline
[poly(A)
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or poly(GA)] and less crystalline (GGX or GPGXX) polypeptides alternate in
core
domain. Specific secondary structures have been assigned to poly(A)/(GA), GGX
and
GPGXX motifs including 13-sheet, a-helix and 0-spiral respectively. The
primary
sequence, composition and secondary structural elements of the repetitive core
domain
are responsible for mechanical properties of spider silks; whereas, non-
repetitive N- and
C-terminal domains are essential for the storage of liquid silk dope in a
lumen and fibre
formation in a spinning duct.
The main difference between MaSpl and MaSp2 is the presence of proline (P)
residues accounting for 15% of the total amino acid content in MaSp2, whereas
MaSpl is
proline-free. By calculating the number of proline residues in N. clavipes
dragline silk, it
is possible to estimate the presence of the two proteins in fibres; 81% MaSpl
and 19%
MaSp2. Different spiders have different ratios ofMaSpl and MaSp2. For example,
a
dragline silk fibre from the orb weaver Argiope aurantia contains 41% MaSpl
and 59%
MaSp2. Such changes in the ratios of major ampullate silks can dictate the
performance
of the silk fibre.
At least seven different types of silk proteins are known for one orb-weaver
species of spider. Silks differ in primary sequence, physical properties and
functions. For
example, dragline silks used to build frames, radii and lifelines are known
for outstanding
mechanical properties including strength, toughness and elasticity. On an
equal weight
basis, spider silk has a higher toughness than steel and Kevlar. Flageliform
silk found in
capture spirals has extensibility of up to 500%. Minor ampullate silk, which
is found in
auxiliary spirals of the orb-web and in prey wrapping, possesses high
toughness and
strength almost similar to major ampullate silks, but does not supercontract
in water.
Spider silks are known for their high tensile strength and toughness. The
recombinant silk proteins also confer advantageous properties to cosmetic or
dermatological compositions, in particular to be able to improve the hydrating
or
softening action, good film forming property and low surface density. Diverse
and unique
biomechanical properties together with biocompatibility and a slow rate of
degradation
make spider silks excellent candidates as biomaterials for tissue engineering,
guided
tissue repair and drug delivery, for cosmetic products (e.g. nail and hair
strengthener, skin
care products), and industrial materials (e.g. nanowires, nanofibers, surface
coatings).
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In an embodiment, a silk protein may include a polypeptide derived from
natural
spider silk proteins. The polypeptide is not limited particularly as long as
it is derived
from natural spider silk proteins, and examples of the polypeptide include
natural spider
silk proteins and recombinant spider silk proteins such as variants, analogs,
derivatives or
the like of the natural spider silk proteins. In terms of excellent tenacity,
the polypeptide
may be derived from major dragline silk proteins produced in major ampullate
glands of
spiders. Examples of the major dragline silk proteins include major ampullate
spidroin
MaSpl and MaSp2 from Nephila clavipes, and ADF3 and ADF4 from Araneus
diadematus, etc. Examples of the polypeptide derived from major dragline silk
proteins
include variants, analogs, derivatives or the like of the major dragline silk
proteins.
Further, the polypeptide may be derived from flagelliform silk proteins
produced in
flagelliform glands of spiders. Examples of the flagelliform silk proteins
include
flagelliform silk proteins derived from Nephila clavipes, etc.
Examples of the polypeptide derived from major dragline silk proteins include
a
polypeptide containing two or more units of an amino acid sequence represented
by the
formula 1: REP1-REP2 (1), preferably a polypeptide containing five or more
units
thereof, and more preferably a polypeptide containing ten or more units
thereof.
Alternatively, the polypeptide derived from major dragline silk proteins may
be a
polypeptide that contains units of the amino acid sequence represented by the
formula 1:
REP1-REP2 (1) and that has, at a C-terminal, an amino acid sequence
represented by any
of SEQ ID NOS: 1 to 3 of U.S. Patent No. 9,051,453 or an amino acid sequence
having a
homology of 90% or more with the amino acid sequence represented by any of SEQ
ID
NOS: 1 to 3 of U.S. Patent No. 9,051,453. In the polypeptide derived from
major dragline
silk proteins, units of the amino acid sequence represented by the formula 1:
REP1-REP2
(1) may be the same or may be different from each other. In the case of
producing a
recombinant protein using a microbe such as Escherichia colt as a host, the
molecular
weight of the polypeptide derived from major dragline silk proteins is 500 kDa
or less, or
300 kDa or less, or 200 kDa or less, in terms of productivity.
In the formula (1), the REP1 indicates polyalanine. In the REP1, the number of
alanine residues arranged in succession is preferably 2 or more, more
preferably 3 or
more, further preferably 4 or more, and particularly preferably 5 or more.
Further, in the
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REP1, the number of alanine residues arranged in succession is preferably 20
or less,
more preferably 16 or less, further preferably 12 or less, and particularly
preferably 10 or
less. In the formula (1), the REP2 is an amino acid sequence composed of 10 to
200
amino acid residues. The total number of glycine, serine, glutamine and
alanine residues
contained in the amino acid sequence is 40% or more, preferably 60% or more,
and more
preferably 70% or more with respect to the total number of amino acid residues
contained
therein.
In the major dragline silk, the REP1 corresponds to a crystal region in a
fiber
where a crystal 0 sheet is formed, and the REP2 corresponds to an amorphous
region in a
fiber where most of the parts lack regular configurations and that has more
flexibility.
Further, the [REP1-REP2] corresponds to a repetitious region (repetitive
sequence)
composed of the crystal region and the amorphous region, which is a
characteristic
sequence of dragline silk proteins.
Recombinant Silk Fragments
In some embodiments, the recombinant silk protein refers to recombinant spider
silk polypeptides, recombinant insect silk polypeptides, or recombinant mussel
silk
polypeptides. In some embodiments, the recombinant silk protein fragment
disclosed
herein include recombinant spider silk polypeptides of Araneidae or Araneoids,
or
recombinant insect silk polypeptides of Bombyx mori. In some embodiments, the
recombinant silk protein fragment disclosed herein include recombinant spider
silk
polypeptides of Araneidae or Araneoids. In some embodiments, the recombinant
silk
protein fragment disclosed herein include block copolymer having repetitive
units
derived from natural spider silk polypeptides of Araneidae or Araneoids. In
some
embodiments, the recombinant silk protein fragment disclosed herein include
block
copolymer having synthetic repetitive units derived from spider silk
polypeptides of
Araneidae or Araneoids and non-repetitive units derived from natural
repetitive units of
spider silk polypeptides of Araneidae or Araneoids.
Recent advances in genetic engineering have provided a route to produce
various
types of recombinant silk proteins. Recombinant DNA technology has been used
to
provide a more practical source of silk proteins. As used herein "recombinant
silk
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protein" refers to synthetic proteins produced heterologously in prokaryotic
or eukaryotic
expression systems using genetic engineering methods.
Various methods for synthesizing recombinant silk peptides are known and have
been described by Ausubel et al., Current Protocols in Molecular Biology 8
(John
Wiley & Sons 1987, (1990)), incorporated herein by reference. A gram-negative,
rod-
shaped bacterium E. coil is a well-established host for industrial scale
production of
proteins. Therefore, the majority of recombinant silks have been produced in
E. coil. E.
coil which is easy to manipulate, has a short generation time, is relatively
low cost and
can be scaled up for larger amounts protein production.
The recombinant silk proteins can be produced by transformed prokaryotic or
eukaryotic systems containing the cDNA coding for a silk protein, for a
fragment of this
protein or for an analog of such a protein. The recombinant DNA approach
enables the
production of recombinant silks with programmed sequences, secondary
structures,
architectures and precise molecular weight. There are four main steps in the
process: (i)
design and assembly of synthetic silk-like genes into genetic 'cassettes',
(ii) insertion of
this segment into a DNA recombinant vector, (iii) transformation of this
recombinant
DNA molecule into a host cell and (iv) expression and purification of the
selected clones.
The term "recombinant vectors", as used herein, includes any vectors known to
the skilled person including plasmid vectors, cosmid vectors, phage vectors
such as
lambda phage, viral vectors such as adenoviral or baculoviral vectors, or
artificial
chromosome vectors such as bacterial artificial chromosomes (BAC), yeast
artificial
chromosomes (YAC), or P1 artificial chromosomes (PAC). Said vectors include
expression as well as cloning vectors. Expression vectors comprise plasmids as
well as
viral vectors and generally contain a desired coding sequence and appropriate
DNA
sequences necessary for the expression of the operably linked coding sequence
in a
particular host organism (e.g., bacteria, yeast, or plant) or in in vitro
expression systems.
Cloning vectors are generally used to engineer and amplify a certain desired
DNA
fragment and may lack functional sequences needed for expression of the
desired DNA
fragments.
The prokaryotic systems include Gram-negative bacteria or Gram-positive
bacteria. The prokaryotic expression vectors can include an origin of
replication which
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can be recognized by the host organism, a homologous or heterologous promoter
which is
functional in the said host, the DNA sequence coding for the spider silk
protein, for a
fragment of this protein or for an analogous protein. Nonlimiting examples of
prokaryotic
expression organisms are Escherichia coil, Bacillus subtilis, Bacillus
megaterium,
Corynebacterium glutamicum, Anabaena, Caulobacter, Gluconobacter, Rhodobacter,
Pseudomonas, Para coccus, Bacillus (e.g. Bacillus subtilis) Brevi bacterium,
Corynebacterium, Rhizobium (Sinorhizobium), Flavobacterium, Klebsiella,
Enterobacter,
Lactobacillus, Lactococcus, Methylobacterium, Prop/on/bacterium,
Staphylococcus or
Streptomyces cells.
The eukaryotic systems include yeasts and insect, mammalian or plant cells. In
this case, the expression vectors can include a yeast plasmid origin of
replication or an
autonomous replication sequence, a promoter, a DNA sequence coding for a
spider silk
protein, for a fragment or for an analogous protein, a polyadenylation
sequence, a
transcription termination site and, lastly, a selection gene. Nonlimiting
examples of
eukaryotic expression organisms include yeasts, such as Saccharomyces
cerevisiae,
Pichia pastoris, basidiosporogenous, ascosporogenous, filamentous fungi, such
as
Aspergillus niger, Aspergillus oryzae, Aspergillus nidulans, Trichoderma
reesei,
Acremonium chrysogenum, Candida, Hansenula, Kluyveromyces, Saccharomyces (e.g.
Saccharomyces cerevisiae), Schizosaccharomyces, Pichia (e.g. Pichia pastoris)
or
Yarrowia cells etc., mammalian cells, such as HeLa cells, COS cells, CHO cells
etc.,
insect cells, such as Sf9 cells, MEL cells, etc., "insect host cells" such as
Spodoptera
frupperda or Trichoplusia ni cells. SF9 cells, SF-21 cells or High-Five cells,
wherein
SF-9 and SF-21 are ovarian cells from Spodoptera frupperda, and High-Five
cells are
egg cells from Trichoplusia ni., "plant host cells", such as tobacco, potato
or pea cells.
A variety of heterologous host systems have been explored to produce different
types of recombinant silks. Recombinant partial spidroins as well as
engineered silks
have been cloned and expressed in bacteria (Escherichia coli), yeast (Pichia
pastoris),
insects (silkworm larvae), plants (tobacco, soybean, potato, Arabidopsis),
mammalian
cell lines (BHT/hamster) and transgenic animals (mice, goats). Most of the
silk proteins
are produced with an N- or C-terminal His-tags to make purification simple and
produce
enough amounts of the protein.
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In some embodiments, the host suitable for expressing the recombinant spider
silk
protein using heterogeneous system may include transgenic animals and plants.
In some
embodiments, the host suitable for expressing the recombinant spider silk
protein using
heterogeneous system comprises bacteria, yeasts, mammalian cell lines. In some
embodiments, the host suitable for expressing the recombinant spider silk
protein using
heterogeneous system comprises E. coil. In some embodiments, the host suitable
for
expressing the recombinant spider silk protein using heterogeneous system
comprises
transgenic B. mori silkworm generated using genome editing technologies (e.g.
CRISPR).
The recombinant silk protein in this disclosure comprises synthetic proteins
which
are based on repeat units of natural silk proteins. Besides the synthetic
repetitive silk
protein sequences, these can additionally comprise one or more natural
nonrepetitive silk
protein sequences.
In some embodiments, "recombinant silk protein" refers to recombinant silkworm
silk protein or fragments thereof. The recombinant production of silk fibroin
and silk
sericin has been reported. A variety of hosts are used for the production
including E. coil,
Sacchromyces cerevisiae, Pseudomonas sp., Rhodopseudomonas sp., Bacillus sp.,
and
Strepomyces. See EP 0230702, which is incorporate by reference herein by its
entirety.
Provided herein also include design and biological-synthesis of silk fibroin
protein-like multiblock polymer comprising GAGAGX hexapeptide (X is A, Y, V or
S)
derived from the repetitive domain of B. mori silk heavy chain (H chain)
In some embodiments, this disclosure provides silk protein-like multiblock
polymers derived from the repetitive domain of B. mori silk heavy chain (H
chain)
comprising the GAGAGS hexapeptide repeating units. The GAGAGS hexapeptide is
the
core unit of H-chain and plays an important role in the formation of
crystalline domains.
The silk protein-like multiblock polymers containing the GAGAGS hexapeptide
repeating units spontaneously aggregate into 13-sheet structures, similar to
natural silk
fibroin protein, where in the silk protein-like multiblock polymers having any
weight
average molecular weight described herein.
In some embodiments, this disclosure provides silk-peptide like multiblock
copolymers composed of the GAGAGS hexapeptide repetitive fragment derived from
H
chain of B. mori silk heavy chain and mammalian elastin VPGVG motif produced
by E.
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coil. In some embodiments, this disclosure provides fusion silk fibroin
proteins composed
of the GAGAGS hexapeptide repetitive fragment derived from H chain of B. mori
silk
heavy chain and GVGVP produced by E. coil, where in the silk protein-like
multiblock
polymers having any weight average molecular weight described herein.
In some embodiments, this disclosure provides B. mori silkworm recombinant
proteins composed of the (GAGAGS)16 repetitive fragment. In some embodiments,
this
disclosure provides recombinant proteins composed of the (GAGAGS)16 repetitive
fragment and the non-repetitive (GAGAGS)16¨F-COOH, (GAGAGS)16¨F-F-COOH,
(GAGAGS)16¨F-F-F-COOH, (GAGAGS)16¨F-F-F-F-COOH, (GAGAGS)16¨F-F-F-F-
F-F-F-F-COOH, (GAGAGS)16¨F-F-F-F¨F-F-F-F-F-F-F-F-COOH produced by E. coil,
where F has the following amino acid sequence
SGFGPVANGGSGEASSESDFGSSGFGPVANASSGEASSESDFAG, and where in the
silk protein-like multiblock polymers having any weight average molecular
weight
described herein.
In some embodiments, "recombinant silk protein" refers to recombinant spider
silk protein or fragments thereof. The productions of recombinant spider silk
proteins
based on a partial cDNA clone have been reported. The recombinant spider silk
proteins
produced as such comprise a portion of the repetitive sequence derived from a
dragline
spider silk protein, Spidroin /, from the spider Nephila clavipes. see Xu et
al. (Proc. Natl.
Acad. Sci. U.S.A., 87:7120-7124 (1990). cDNA clone encoding a portion of the
repeating sequence of a second fibroin protein, Spidroin 2, from dragline silk
of Nephila
clavipes and the recombinant synthesis thereof is described in I Biol. Chem.,
1992,
volume 267, pp. 19320-19324. The recombinant synthesis of spider silk proteins
including protein fragments and variants of Nephila clavipes from transformed
E. coil is
described in U.S. Pat. Nos. 5,728,810 and 5,989,894. cDNA clones encoding
minor
ampullate spider silk proteins and the expression thereof is described in U.S.
Pat. Nos.
5,733,771 and 5,756,677. cDNA clone encoding the flagelliform silk protein
from an orb-
web spinning spider is described in U.S. Pat. No. 5,994,099. U.S. Pat. No.
6,268,169
describes the recombinant synthesis of spider silk like proteins derived from
the repeating
peptide sequence found in the natural spider dragline of Nephila clavipes by
E. coil,
Bacillus subtilis, and Pichia pastoris recombinant expression systems. WO
03/020916
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describes the cDNA clone encoding and recombinant production of spider spider
silk
proteins having repeative sequences derived from the major ampullate glands of
Nephila
madagascariensis, Nephila senegalensis, Tetragnatha kauaiensis, Tetragnatha
versicolor, Argiope aurantia, Argiope trifasciata, Gasteracantha mammosa, and
Latrodectus geometricus, the flagelliform glands of Argiope trifasciata, the
ampullate
glands of Dolomedes tenebrosus, two sets of silk glands from Plectreurys
tristis, and the
silk glands of the mygalomorph Euagrus chisoseus. Each of the above reference
is
incorporated herein by reference in its entirety.
In some embodiments, the recombinant spider silk protein is a hybrid protein
of a
spider silk protein and an insect silk protein, a spider silk protein and
collagen, a spider
silk protein and resilin, or a spider silk protein and keratin. The spider
silk repetitive unit
comprises or consists of an amino acid sequence of a region that comprises or
consists of
at least one peptide motif that repetitively occurs within a naturally
occurring major
ampullate gland polypeptide, such as a dragline spider silk polypeptide, a
minor
ampullate gland polypeptide, a flagelliform polypeptide, an aggregate spider
silk
polypeptide, an aciniform spider silk polypeptide or a pyriform spider silk
polypeptide.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises synthetic spider silk proteins derived from repetitive units of
natural spider silk
proteins, consensus sequence, and optionally one or more natural non-
repetitive spider
silk protein sequences. The repeated units of natural spider silk polypeptide
may include
dragline spider silk polypeptides or flagelliform spider silk polypeptides of
Araneidae or
Araneoids.
As used herein, the spider silk "repetitive unit" comprises or consists of at
least
one peptide motif that repetitively occurs within a naturally occurring major
ampullate
gland polypeptide, such as a dragline spider silk polypeptide, a minor
ampullate gland
polypeptide, a flagelliform polypeptide, an aggregate spider silk polypeptide,
an
aciniform spider silk polypeptide or a pyriform spider silk polypeptide. A
"repetitive
unit" refers to a region which corresponds in amino acid sequence to a region
that
comprises or consists of at least one peptide motif (e.g. AAAAAA) or GPGQQ)
that
repetitively occurs within a naturally occurring silk polypeptide (e.g. MaSpI,
ADF-3,
ADF-4, or Flag) (i.e. identical amino acid sequence) or to an amino acid
sequence
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substantially similar thereto (i.e. variational amino acid sequence). A
"repetitive unit"
having an amino acid sequence which is "substantially similar" to a
corresponding amino
acid sequence within a naturally occurring silk polypeptide (i.e. wild-type
repetitive unit)
is also similar with respect to its properties, e.g. a silk protein comprising
the
"substantially similar repetitive unit" is still insoluble and retains its
insolubility. A
"repetitive unit" having an amino acid sequence which is "identical" to the
amino acid
sequence of a naturally occurring silk polypeptide, for example, can be a
portion of a silk
polypeptide corresponding to one or more peptide motifs of MaSpI, MaSpII, ADF-
3
and/or ADF-4. A "repetitive unit" having an amino acid sequence which is
"substantially
similar" to the amino acid sequence of a naturally occurring silk polypeptide,
for
example, can be a portion of a silk polypeptide corresponding to one or more
peptide
motifs of MaSpI, MaSpII, ADF-3 and/or ADF-4, but having one or more amino acid
substitution at specific amino acid positions.
As used herein, the term "consensus peptide sequence" refers to an amino acid
sequence which contains amino acids which frequently occur in a certain
position (e.g.
"G") and wherein, other amino acids which are not further determined are
replaced by the
place holder "X". In some embodiments, the consensus sequence is at least one
of (i)
GPGXX, wherein X is an amino acid selected from A, S, G, Y, P and Q; (ii) GGX,
wherein X is an amino acid selected from Y, P, R, S, A, T, N and Q, preferably
Y, P and
Q; (iii) Ax, wherein x is an integer from 5 to 10.
The consensus peptide sequences GPGXX and GGX, i.e. glycine rich motifs,
provide flexibility to the silk polypeptide and thus, to the thread formed
from the silk
protein containing said motifs. In detail, the iterated GPGXX motif forms turn
spiral
structures, which imparts elasticity to the silk polypeptide. Major ampullate
and
flagelliform silks both have a GPGXX motif The iterated GGX motif is
associated with a
helical structure having three amino acids per turn and is found in most
spider silks. The
GGX motif may provide additional elastic properties to the silk. The iterated
polyalanine
Ax (peptide) motif forms a crystalline 13-sheet structure that provides
strength to the silk
polypeptide, as described for example in WO 03/057727.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises two identical repetitive units each comprising at least one,
preferably one,
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amino acid sequence selected from the group consisting of: GGRPSDTYG and
GGRPSSSYG derived from Resilin. Resilin is an elastomeric protein found in
most
arthropods that provides low stiffness and high strength.
As used herein, "non-repetitive units" refers to an amino acid sequence which
is
"substantially similar" to a corresponding non-repetitive (carboxy terminal)
amino acid
sequence within a naturally occurring dragline polypeptide (i.e. wild-type non-
repetitive
(carboxy terminal) unit), preferably within ADF-3 (SEQ ID NO:1), ADF-4 (SEQ ID
NO:2), NR3 (SEQ ID NO:41), NR4 (SEQ ID NO:42), ADF-4 of the spider Araneus
diadematus as described in U.S. Pat. No. 8,367,803, C16 peptide (spider silk
protein
eADF4, molecular weight of 47.7 kDa, AMSilk) comprising the 16 repeats of the
sequence GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP, an amino acid
sequence adapted from the natural sequence of ADF4 from A. diadematus. Non-
repetitive
ADF-4 and variants thereof display efficient assembly behavior.
Among the synthetic spider silk proteins, the recombinant silk protein in this
disclosure comprises in some embodiments the C16-protein having the
polypeptide
sequence SEQ ID NO: 1 as described in U.S. Patent No. 8288512. Besides the
polypeptide sequence shown in SEQ ID NO:1, particularly functional
equivalents,
functional derivatives and salts of this sequence are also included.
As used herein, "functional equivalents" refers to mutant which, in at least
one
sequence position of the abovementioned amino acid sequences, have an amino
acid
other than that specifically mentioned.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises, in an effective amount, at least one natural or recombinant silk
protein
including spider silk protein, corresponding to Spidroin major 1 described by
Xu et al.,
PNAS, USA, 87, 7120, (1990), Spidroin major 2 described by Hinman and Lewis,
J.
Biol. Chem., 267, 19320, (1922), recombinant spider silk protein as described
in U.S.
Patent Application No. 2016/0222174 and U.S. Patent Nos. 9,051,453, 9,617,315,
9,689,089, 8,173,772, 8,642,734, 8,367,803 8,097,583, 8,030,024, 7,754,851,
7,148,039,
7,060,260, or alternatively the minor Spidroins described in patent
application WO
95/25165. Each of the above-cited references is incorporated herein by
reference in its
entirety. Additional recombinant spider silk proteins suitable for the
recombinant RSPF
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of this disclosure include ADF3 and ADF4 from the "Major Ampullate" gland of
Araneus diadematus.
Recombinant silk is also described in other patents and patent applications,
incorporated by reference herein: US 2004590196, US 7,754,851, US 2007654470,
US
7,951,908, US 2010785960, US 8,034,897, US 20090263430, US 2008226854, US
20090123967, US 2005712095, US 2007991037, US 20090162896, US 200885266, US
8,372,436, US 2007989907, US 2009267596, US 2010319542, US 2009265344, US
2012684607, US 2004583227, US 8,030,024, US 2006643569, US 7,868,146, US
2007991916, US 8,097,583, US 2006643200, US 8,729,238, US 8,877,903, US
20190062557, US 20160280960, US 20110201783, US 2008991916, US 2011986662,
US 2012697729, US 20150328363, US 9,034,816, US 20130172478, US 9,217,017, US
20170202995, US 8,721,991, US 2008227498, US 9,233,067, US 8,288,512, US
2008161364, US 7,148,039, US 1999247806, US 2001861597, US 2004887100, US
9,481,719, US 8,765,688, US 200880705, US 2010809102, US 8,367,803, US
2010664902, US 7,569,660, US 1999138833, US 2000591632, US 20120065126, US
20100278882, US 2008161352, US 20100015070, US 2009513709, US 20090194317,
US 2004559286, US 200589551, US 2008187824, US 20050266242, US 20050227322,
and US 20044418.
Recombinant silk is also described in other patents and patent applications,
incorporated by reference herein: US 20190062557, US 20150284565, US
20130225476,
US 20130172478, US 20130136779, US 20130109762, US 20120252294, US
20110230911, US 20110201783, US 20100298877, US 10,478,520,U5 10,253,213,U5
10,072,152, US 9,233,067, US 9,217,017, US 9,034,816, US 8,877,903, US
8,729,238,
US 8,721,991, US 8,097,583, US 8,034,897, US 8,030,024, US 7,951,908, US
7,868,146,
and US 7,754,851.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises or consists of 2 to 80 repetitive units, each independently selected
from
GPGXX, GGX and Ax as defined herein.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises or consists of repetitive units each independently selected from
selected from
the group consisting of GPGAS, GPGSG, GPGGY, GPGGP, GPGGA, GPGQQ,
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GPGGG, GPGQG, GPGGS, GGY, GGP, GGA, GGR, GGS, GGT, GGN, GGQ,
AAAAA, AAAAAA, AAAAAAA, AAAAAAAA, AAAAAAAAA, AAAAAAAAAA,
GGRPSDTYG and GGRPSSSYG, (i) GPYGPGASAAAAAAGGYGPGSGQQ, (ii)
GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP, (iii)
GPGQQGPGQQGPGQQGPGQQ: (iv) GPGGAGGPYGPGGAGGPYGPGGAGGPY,
(v) GGTTIIEDLDITIDGADGPITISEELTI, (vi)
PGSSAAAAAAAASGPGQGQGQGQGQGGRPSDTYG, (vii)
SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG, (viii)
GGAGGAGGAGGSGGAGGS (SEQ ID NO: 27), (ix)
GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY, (x)
GPYGPGASAAAAAAGGYGPGCGQQ, (xi) GPYGPGASAAAAAAGGYGPGKGQQ,
(xii) GSSAAAAAAAASGPGGYGPENQGPCGPGGYGPGGP, (xiii)
GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP, (xiv)
GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP, or variants thereof as
described in U.S. Pat. No. 8,877,903, for example, a synthetic spider peptide
having
sequential order of GPGAS, GGY, GPGSG in the peptide chain, or sequential
order of
AAAAAAAA, GPGGY, GPGGP in the peptide chain, sequential order of AAAAAAAA,
GPGQG, GGR in the peptide chain.
In some embodiments, this disclosure provides silk protein-like multiblock
peptides that imitate the repeating units of amino acids derived from natural
spider silk
proteins such as Spidroin major 1 domain, Spidroin major 2 domain or Spidroin
minor 1
domain and the profile of variation between the repeating units without
modifying their
three-dimensional conformation, wherein these silk protein-like multiblock
peptides
comprise a repeating unit of amino acids corresponding to one of the sequences
(I), (II),
(III) and/or (IV) below.
[(XGG)w(XGA)(GXG)x(AGA)y(G)zAG]p Formula (I) in which: X corresponds to
tyrosine or to glutamine, w is an integer equal to 2 or 3, x is an integer
from 1 to 3, y is an
integer from 5 to 7, z is an integer equal to 1 or 2, and p is an integer and
having any
weight average molecular weight described herein, and/or
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[(GP G2YGP GQ2)a(X' )2S (A)b]p Formula (II) in which: X' corresponds to the
amino acid sequence GPS or GPG, a is equal to 2 or 3, b is an integer from 7
to 10, and p
is an integer and having any weight average molecular weight described herein,
and/or
[(GR)(GA)1(A)m(GGX)n(GA)1(A)ndp Formula (III) and/or [(GGX)n(GA)m(A)dp
Formula (IV) in which: X" corresponds to tyrosine, glutamine or alanine, 1 is
an integer
from 1 to 6, m is an integer from 0 to 4, n is an integer from 1 to 4, and p
is an integer.
In some embodiments, the recombinant spider silk protein or an analog of a
spider
silk protein comprising an amino acid repeating unit of sequence (V):
[(Xaa Gly Gly)w(Xaa Gly Ala)(Gly Xaa Gly)x(Ala Gly Ala)y(Gly)zAla Gly]p
Formula (V), wherein Xaa is tyrosine or glutamine, w is an integer equal to 2
or 3, x is an
integer from 1 to 3, y is an integer from 5 to 7, z is an integer equal to 1
or 2, and p is an
integer.
In some embodiments, the recombinant spider silk protein in this disclosure is
selected from the group consisting of ADF-3 or variants thereof, ADF-4 or
variants
thereof, MaSpI (SEQ ID NO: 43) or variants thereof, MaSpII (SEQ ID NO: 44) or
variants thereof as described in U.S. Pat. No. 8,367,803.
In some embodiments, this disclosure provides water soluble recombinant spider
silk proteins produced in mammalian cells. The solubility of the spider silk
proteins
produced in mammalian cells was attributed to the presence of the COOH-
terminus in
these proteins, which makes them more hydrophilic. These COOH-terminal amino
acids
are absent in spider silk proteins expressed in microbial hosts.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises water soluble recombinant spider silk protein C16 modified with an
amino or
carboxyl terminal selected from the amino acid sequences consisting of:
GCGGGGGG,
GKGGGGGG, GCGGSGGGGSGGGG, GKGGGGGGSGGGG, and
GCGGGGGGSGGGG. In some embodiments, the recombinant spider silk protein in
this
disclosure comprises C16NR4, C32NR4, C 1 6, C32, NR4C16NR4, NR4C32NR4,
NR3 C 16NR3 , or NR3 C32NR3 such that the molecular weight of the protein
ranges as
described herein.
In some embodiments, the recombinant spider silk protein in this disclosure
comprises recombinant spider silk protein having a synthetic repetitive
peptide segments
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and an amino acid sequence adapted from the natural sequence of ADF4 from A.
diadematus as described in U.S. Pat. No. 8,877,903. In some embodiments, the
RSPF in
this disclosure comprises the recombinant spider silk proteins having
repeating peptide
units derived from natural spider silk proteins such as Spidroin major 1
domain, Spidroin
major 2 domain or Spidroin minor 1 domain, wherein the repeating peptide
sequence is
GSSAAAAAAAASGPGQGQGQGQGQGGRPSDTYG or
SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG, as described in U.S.
Pat. No. 8,367,803.
In some embodiments, this disclosure provides recombinant spider proteins
composed of the GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY repetitive fragment
and having a molecular weight as described herein.
As used herein, the term "recombinant silk" refers to recombinant spider
and/or
silkworm silk protein or fragments thereof. In an embodiment, the spider silk
protein is
selected from the group consisting of swathing silk (Achniform gland silk),
egg sac silk
(Cylindriform gland silk), egg case silk (Tubuliform silk), non-sticky
dragline silk
(Ampullate gland silk), attaching thread silk (Pyriform gland silk), sticky
silk core fibers
(Flagelliform gland silk), and sticky silk outer fibers (Aggregate gland
silk). For example,
recombinant spider silk protein, as described herein, includes the proteins
described in
U.S. Patent Application No. 2016/0222174 and U.S. Patent Nos. 9,051,453,
9,617,315,
9,689,089, 8,173,772, and 8,642,734.
Some organisms make multiple silk fibers with unique sequences, structural
elements, and mechanical properties. For example, orb weaving spiders have six
unique
types of glands that produce different silk polypeptide sequences that are
polymerized
into fibers tailored to fit an environmental or lifecycle niche. The fibers
are named for the
gland they originate from and the polypeptides are labeled with the gland
abbreviation
(e.g. "Ma") and "Sp" for spidroin (short for spider fibroin). In orb weavers,
these types
include Major Ampullate (MaSp, also called dragline), Minor Ampullate (MiSp),
Flagelliform (Flag), Aciniform (AcSp), Tubuliform (TuSp), and Pyriform (PySp).
This
combination of polypeptide sequences across fiber types, domains, and
variation amongst
different genus and species of organisms leads to a vast array of potential
properties that
can be harnessed by commercial production of the recombinant fibers. To date,
the vast
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majority of the work with recombinant silks has focused on the Major Ampullate
Spidroins (MaSp).
Aciniform (AcSp) silks tend to have high toughness, a result of moderately
high
strength coupled with moderately high extensibility. AcSp silks are
characterized by large
block ("ensemble repeat") sizes that often incorporate motifs of poly serine
and GPX.
Tubuliform (TuSp or Cylindrical) silks tend to have large diameters, with
modest
strength and high extensibility. TuSp silks are characterized by their poly
serine and poly
threonine content, and short tracts of poly alanine. Major Ampullate (MaSp)
silks tend to
have high strength and modest extensibility. MaSp silks can be one of two
subtypes:
MaSpl and MaSp2. MaSpl silks are generally less extensible than MaSp2 silks,
and are
characterized by poly alanine, GX, and GGX motifs. MaSp2 silks are
characterized by
poly alanine, GGX, and GPX motifs. Minor Ampullate (MiSp) silks tend to have
modest
strength and modest extensibility. MiSp silks are characterized by GGX, GA,
and poly A
motifs, and often contain spacer elements of approximately 100 amino acids.
Flagelliform (Flag) silks tend to have very high extensibility and modest
strength. Flag
silks are usually characterized by GPG, GGX, and short spacer motifs.
Silk polypeptides are characteristically composed of a repeat domain (REP)
flanked by non-repetitive regions (e.g., C-terminal and N-terminal domains).
In an
embodiment, both the C-terminal and N-terminal domains are between 75-350
amino
acids in length. The repeat domain exhibits a hierarchical architecture. The
repeat domain
comprises a series of blocks (also called repeat units). The blocks are
repeated,
sometimes perfectly and sometimes imperfectly (making up a quasi-repeat
domain),
throughout the silk repeat domain. The length and composition of blocks varies
among
different silk types and across different species. Table 1 of U.S. Published
Application
No. 2016/0222174, the entirety of which is incorporated herein, lists examples
of block
sequences from selected species and silk types, with further examples
presented in
Rising, A. et al., Spider silk proteins: recent advances in recombinant
production,
structure-function relationships and biomedical applications, Cell Mol. Life
Sc., 68:2, pg
169-184 (2011); and Gatesy, J. et al., Extreme diversity, conservation, and
convergence
of spider silk fibroin sequences, Science, 291:5513, pg. 2603-2605 (2001). In
some cases,
blocks may be arranged in a regular pattern, forming larger macro-repeats that
appear
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multiple times (usually 2-8) in the repeat domain of the silk sequence.
Repeated blocks
inside a repeat domain or macro-repeat, and repeated macro-repeats within the
repeat
domain, may be separated by spacing elements.
The construction of certain spider silk block copolymer polypeptides from the
blocks and/or macro-repeat domains, according to certain embodiments of the
disclosure,
is illustrated in U.S. Published Patent Application No. 2016/0222174.
The recombinant block copolymer polypeptides based on spider silk sequences
produced by gene expression in a recombinant prokaryotic or eukaryotic system
can be
purified according to methods known in the art. In a preferred embodiment, a
commercially available expression/secretion system can be used, whereby the
recombinant polypeptide is expressed and thereafter secreted from the host
cell, to be
easily purified from the surrounding medium. If expression/secretion vectors
are not
used, an alternative approach involves purifying the recombinant block
copolymer
polypeptide from cell lysates (remains of cells following disruption of
cellular integrity)
derived from prokaryotic or eukaryotic cells in which a polypeptide was
expressed.
Methods for generation of such cell lysates are known to those of skill in the
art. In some
embodiments, recombinant block copolymer polypeptides are isolated from cell
culture
supernatant.
Recombinant block copolymer polypeptide may be purified by affinity
separation,
such as by immunological interaction with antibodies that bind specifically to
the
recombinant polypeptide or nickel columns for isolation of recombinant
polypeptides
tagged with 6-8 histidine residues at their N-terminus or C-terminus
Alternative tags may
comprise the FLAG epitope or the hemagglutinin epitope. Such methods are
commonly
used by skilled practitioners.
A solution of such polypeptides (i.e., recombinant silk protein) may then be
prepared and used as described herein.
In another embodiment, recombinant silk protein may be prepared according to
the methods described in U.S. Patent No. 8,642,734, the entirety of which is
incorporated
herein, and used as described herein.
In an embodiment, a recombinant spider silk protein is provided. The spider
silk
protein typically consists of from 170 to 760 amino acid residues, such as
from 170 to
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600 amino acid residues, preferably from 280 to 600 amino acid residues, such
as from
300 to 400 amino acid residues, more preferably from 340 to 380 amino acid
residues.
The small size is advantageous because longer spider silk proteins tend to
form
amorphous aggregates, which require use of harsh solvents for solubilization
and
polymerization. The recombinant spider silk protein may contain more than 760
residues,
in particular in cases where the spider silk protein contains more than two
fragments
derived from the N-terminal part of a spider silk protein, The spider silk
protein
comprises an N-terminal fragment consisting of at least one fragment (NT)
derived from
the corresponding part of a spider silk protein, and a repetitive fragment
(REP) derived
from the corresponding internal fragment of a spider silk protein. Optionally,
the spider
silk protein comprises a C-terminal fragment (CT) derived from the
corresponding
fragment of a spider silk protein. The spider silk protein comprises typically
a single
fragment (NT) derived from the N-terminal part of a spider silk protein, but
in preferred
embodiments, the N-terminal fragment include at least two, such as two
fragments (NT)
derived from the N-terminal part of a spider silk protein. Thus, the spidroin
can
schematically be represented by the formula NT-REP, and alternatively NT-REP-
CT,
where m is an integer that is 1 or higher, such as 2 or higher, preferably in
the ranges of
1-2, 1-4, 1-6, 2-4 or 2-6. Preferred spidroins can schematically be
represented by the
formulas NT2-REP or NT-REP, and alternatively NT2-REP-CT or NT-REP-CT. The
protein fragments are covalently coupled, typically via a peptide bond. In one
embodiment, the spider silk protein consists of the NT fragment(s) coupled to
the REP
fragment, which REP fragment is optionally coupled to the CT fragment.
In one embodiment, the first step of the method of producing polymers of an
isolated spider silk protein involves expression of a polynucleic acid
molecule which
encodes the spider silk protein in a suitable host, such as Escherichia coil.
The thus
obtained protein is isolated using standard procedures. Optionally,
lipopolysaccharides
and other pyrogens are actively removed at this stage.
In the second step of the method of producing polymers of an isolated spider
silk
protein, a solution of the spider silk protein in a liquid medium is provided.
By the terms
"soluble" and "in solution" is meant that the protein is not visibly
aggregated and does
not precipitate from the solvent at 60,000x g. The liquid medium can be any
suitable
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medium, such as an aqueous medium, preferably a physiological medium,
typically a
buffered aqueous medium, such as a 10-50 mM Tris-HC1 buffer or phosphate
buffer. The
liquid medium has a pH of 6.4 or higher and/or an ion composition that
prevents
polymerization of the spider silk protein. That is, the liquid medium has
either a pH of
6.4 or higher or an ion composition that prevents polymerization of the spider
silk
protein, or both.
Ion compositions that prevent polymerization of the spider silk protein can
readily
be prepared by the skilled person utilizing the methods disclosed herein. A
preferred ion
composition that prevents polymerization of the spider silk protein has an
ionic strength
of more than 300 mM. Specific examples of ion compositions that prevent
polymerization of the spider silk protein include above 300 mM NaCl, 100 mM
phosphate and combinations of these ions having desired preventive effect on
the
polymerization of the spider silk protein, e.g. a combination of 10 mM
phosphate and 300
mM NaCl.
The presence of an NT fragment improves the stability of the solution and
prevents polymer formation under these conditions. This can be advantageous
when
immediate polymerization may be undesirable, e.g. during protein purification,
in
preparation of large batches, or when other conditions need to be optimized.
It is
preferred that the pH of the liquid medium is adjusted to 6.7 or higher, such
as 7.0 or
higher, or even 8.0 or higher, such as up to 10.5, to achieve high solubility
of the spider
silk protein. It can also be advantageous that the pH of the liquid medium is
adjusted to
the range of 6.4-6.8, which provides sufficient solubility of the spider silk
protein but
facilitates subsequent pH adjustment to 6.3 or lower.
In the third step, the properties of the liquid medium are adjusted to a pH of
6.3 or
lower and ion composition that allows polymerization. That is, if the liquid
medium
wherein the spider silk protein is dissolved has a pH of 6.4 or higher, the pH
is decreased
to 6.3 or lower. The skilled person is well aware of various ways of achieving
this,
typically involving addition of a strong or weak acid. If the liquid medium
wherein the
spider silk protein is dissolved has an ion composition that prevents
polymerization, the
ion composition is changed so as to allow polymerization. The skilled person
is well
aware of various ways of achieving this, e.g. dilution, dialysis or gel
filtration. If
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required, this step involves both decreasing the pH of the liquid medium to
6.3 or lower
and changing the ion composition so as to allow polymerization. It is
preferred that the
pH of the liquid medium is adjusted to 6.2 or lower, such as 6.0 or lower. In
particular, it
may be advantageous from a practical point of view to limit the pH drop from
6.4 or 6.4-
6.8 in the preceding step to 6.3 or 6.0-6.3, e.g. 6.2 in this step. In a
preferred embodiment,
the pH of the liquid medium of this step is 3 or higher, such as 4.2 or
higher. The
resulting pH range, e.g. 4.2-6.3 promotes rapid polymerization,
In the fourth step, the spider silk protein is allowed to polymerize in the
liquid
medium having pH of 6.3 or lower and an ion composition that allows
polymerization of
the spider silk protein. Although the presence of the NT fragment improves
solubility of
the spider silk protein at a pH of 6.4 or higher and/or an ion composition
that prevents
polymerization of the spider silk protein, it accelerates polymer formation at
a pH of 6.3
or lower when the ion composition allows polymerization of the spider silk
protein. The
resulting polymers are preferably solid and macroscopic, and they are formed
in the
liquid medium having a pH of 6.3 or lower and an ion composition that allows
polymerization of the spider silk protein. In a preferred embodiment, the pH
of the liquid
medium of this step is 3 or higher, such as 4.2 or higher. The resulting pH
range, e.g. 4.2-
6.3 promotes rapid polymerization, Resulting polymer may be provided at the
molecular
weights described herein and prepared as a solution form that may be used as
necessary
for article coatings.
Ion compositions that allow polymerization of the spider silk protein can
readily
be prepared by the skilled person utilizing the methods disclosed herein. A
preferred ion
composition that allows polymerization of the spider silk protein has an ionic
strength of
less than 300 mM. Specific examples of ion compositions that allow
polymerization of
the spider silk protein include 150 mM NaCl, 10 mM phosphate, 20 mM phosphate
and
combinations of these ions lacking preventive effect on the polymerization of
the spider
silk protein, e.g. a combination of 10 mM phosphate or 20 mM phosphate and 150
mM
NaCl. It is preferred that the ionic strength of this liquid medium is
adjusted to the range
of 1-250 mM.
Without desiring to be limited to any specific theory, it is envisaged that
the NT
fragments have oppositely charged poles, and that environmental changes in pH
affects
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the charge balance on the surface of the protein followed by polymerization,
whereas salt
inhibits the same event.
At neutral pH, the energetic cost of burying the excess negative charge of the
acidic pole may be expected to prevent polymerization. However, as the dimer
approaches its isoelectric point at lower pH, attractive electrostatic forces
will eventually
become dominant, explaining the observed salt and pH-dependent polymerization
behavior of NT and NT-containing minispidroins. It is proposed that, in some
embodiments, pH-induced NT polymerization, and increased efficiency of fiber
assembly
of NT-minispidroins, are due to surface electrostatic potential changes, and
that
clustering of acidic residues at one pole of NT shifts its charge balance such
that the
polymerization transition occurs at pH values of 6.3 or lower.
In a fifth step, the resulting, preferably solid spider silk protein polymers
are
isolated from said liquid medium. Optionally, this step involves actively
removing
lipopolysaccharides and other pyrogens from the spidroin polymers.
Without desiring to be limited to any specific theory, it has been observed
that
formation of spidroin polymers progresses via formation of water-soluble
spidroin
dimers. The present disclosure thus also provides a method of producing dimers
of an
isolated spider silk protein, wherein the first two method steps are as
described above.
The spider silk proteins are present as dimers in a liquid medium at a pH of
6.4 or higher
and/or an ion composition that prevents polymerization of said spider silk
protein. The
third step involves isolating the dimers obtained in the second step, and
optionally
removal of lipopolysaccharides and other pyrogens. In a preferred embodiment,
the
spider silk protein polymer of the disclosure consists of polymerized protein
dimers. The
present disclosure thus provides a novel use of a spider silk protein,
preferably those
disclosed herein, for producing dimers of the spider silk protein.
According to another aspect, the disclosure provides a polymer of a spider
silk
protein as disclosed herein. In an embodiment, the polymer of this protein is
obtainable
by any one of the methods therefor according to the disclosure. Thus, the
disclosure
provides various uses of recombinant spider silk protein, preferably those
disclosed
herein, for producing polymers of the spider silk protein as recombinant silk
based
coatings. According to one embodiment, the present disclosure provides a novel
use of a
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dimer of a spider silk protein, preferably those disclosed herein, for
producing polymers
of the isolated spider silk protein as recombinant silk based coatings. In
these uses, it is
preferred that the polymers are produced in a liquid medium having a pH of 6.3
or lower
and an ion composition that allows polymerization of said spider silk protein.
In an
embodiment, the pH of the liquid medium is 3 or higher, such as 4.2 or higher.
The
resulting pH range, e.g. 4.2-6.3 promotes rapid polymerization,
Using the method(s) of the present disclosure, it is possible to control the
polymerization process, and this allows for optimization of parameters for
obtaining silk
polymers with desirable properties and shapes.
In an embodiment, the recombinant silk proteins described herein, include
those
described in U.S. patent No. 8,642,734, the entirety of which is incorporated
by
reference.
In another embodiment, the recombinant silk proteins described herein may be
prepared according to the methods described in U.S. Patent No. 9,051,453, the
entirety of
which is incorporated herein by reference.
An amino acid sequence represented by SEQ ID NO: 1 of U.S. Patent No.
9,051,453 is identical to an amino acid sequence that is composed of 50 amino
acid
residues of an amino acid sequence of ADF3 at the C-terminal (NCBI Accession
No.:
AAC47010, GI: 1263287). An amino acid sequence represented by SEQ ID NO: 2 of
U.S. Patent No. 9,051,453 is identical to an amino acid sequence represented
by SEQ ID
NO: 1 of U.S. Patent No. 9,051,453 from which 20 residues have been removed
from the
C-terminal. An amino acid sequence represented by SEQ ID NO: 3 of U.S. Patent
No.
9,051,453 is identical to an amino acid sequence represented by SEQ ID NO: 1
from
which 29 residues have been removed from the C-terminal.
An example of the polypeptide that contains units of the amino acid sequence
represented by the formula 1: REP1-REP2 (1) and that has, at a C-terminal, an
amino
acid sequence represented by any of SEQ ID NOS: 1 to 3 or an amino acid
sequence
having a homology of 90% or more with the amino acid sequence represented by
any of
SEQ ID NOS: 1 to 3 of U.S. Patent No. 9,051,453 is a polypeptide having an
amino acid
sequence represented by SEQ ID NO: 8 of U.S. Patent No. 9,051,453. The
polypeptide
having the amino acid sequence represented by SEQ ID NO: 8 of U.S. Patent No.
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9,051,453 is obtained by the following mutation: in an amino acid sequence of
ADF3
(NCBI Accession No.: AAC47010, GI: 1263287) to the N-terminal of which has
been
added an amino acid sequence (SEQ ID NO: 5 of U.S. Patent No. 9,051,453)
composed
of a start codon, His 10 tags and an HRV3C Protease (Human rhinovirus 3C
Protease)
recognition site, istto 13th repetitive regions are about doubled and the
translation ends at
the 1154th amino acid residue. In the polypeptide having the amino acid
sequence
represented by SEQ ID NO: 8 of U.S. Patent No. 9,051,453, the C-terminal
sequence is
identical to the amino acid sequence represented by SEQ ID NO: 3.
Further, the polypeptide that contains units of the amino acid sequence
represented by the formula 1: REP1-REP2 (1) and that has, at a C-terminal, an
amino
acid sequence represented by any of SEQ ID NOS: 1 to 3 of U.S. Patent No.
9,051,453 or
an amino acid sequence having a homology of 90% or more with the amino acid
sequence represented by any of SEQ ID NOS: 1 to 3 of U.S. Patent No. 9,051,453
may
be a protein that has an amino acid sequence represented by SEQ ID NO: 8 of
U.S. Patent
No. 9,051,453 in which one or a plurality of amino acids have been
substituted, deleted,
inserted and/or added and that has a repetitious region composed of a crystal
region and
an amorphous region.
Further, an example of the polypeptide containing two or more units of the
amino
acid sequence represented by the formula 1: REP1-REP2 (1) is a recombinant
protein
derived from ADF4 having an amino acid sequence represented by SEQ ID NO: 15
of
U.S. Patent No. 9,051,453. The amino acid sequence represented by SEQ ID NO:
15 of
U.S. Patent No. 9,051,453 is an amino acid sequence obtained by adding the
amino acid
sequence (SEQ ID NO: 5 of U.S. Patent No. 9,051,453) composed of a start
codon, His
tags and an HRV3C Protease (Human rhinovirus 3C Protease) recognition site, to
the
N-terminal of a partial amino acid sequence of ADF4 obtained from the NCBI
database
(NCBI Accession No.: AAC47011, GI: 1263289). Further, the polypeptide
containing
two or more units of the amino acid sequence represented by the formula 1:
REP1-REP2
(1) may be a polypeptide that has an amino acid sequence represented by SEQ ID
NO: 15
of U.S. Patent No. 9,051,453 in which one or a plurality of amino acids have
been
substituted, deleted, inserted and/or added and that has a repetitious region
composed of a
crystal region and an amorphous region. Further, an example of the polypeptide
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containing two or more units of the amino acid sequence represented by the
formula 1:
REP1-REP2 (1) is a recombinant protein derived from MaSp2 that has an amino
acid
sequence represented by SEQ ID NO: 17 of U.S. Patent No. 9,051,453. The amino
acid
sequence represented by SEQ ID NO: 17 of U.S. Patent No. 9,051,453 is an amino
acid
sequence obtained by adding the amino acid sequence (SEQ ID NO: 5 of U.S.
Patent No.
9,051,453) composed of a start codon, His 10 tags and an HRV3C Protease (Human
rhinovirus 3C Protease) recognition site, to the N-terminal of a partial
sequence of
MaSp2 obtained from the NCBI web database (NCBI Accession No.: AAT75313, GI:
50363147). Furthermore, the polypeptide containing two or more units of the
amino acid
sequence represented by the formula 1: REP1-REP2 (1) may be a polypeptide that
has an
amino acid sequence represented by SEQ ID NO: 17 of U.S. Patent No. 9,051,453
in
which one or a plurality of amino acids have been substituted, deleted,
inserted and/or
added and that has a repetitious region composed of a crystal region and an
amorphous
region.
Examples of the polypeptide derived from flagelliform silk proteins include a
polypeptide containing 10 or more units of an amino acid sequence represented
by the
formula 2: REP3 (2), preferably a polypeptide containing 20 or more units
thereof, and
more preferably a polypeptide containing 30 or more units thereof In the case
of
producing a recombinant protein using a microbe such as Escherichia coil as a
host, the
molecular weight of the polypeptide derived from flagelliform silk proteins is
preferably
500 kDa or less, more preferably 300 kDa or less, and further preferably 200
kDa or less,
in terms of productivity.
In the formula (2), the REP 3 indicates an amino acid sequence composed of Gly-
Pro-Gly-Gly-X, where X indicates an amino acid selected from the group
consisting of
Ala, Ser, Tyr and Val.
A major characteristic of the spider silk is that the flagelliform silk does
not have
a crystal region, but has a repetitious region composed of an amorphous
region. Since the
major dragline silk and the like have a repetitious region composed of a
crystal region
and an amorphous region, they are expected to have both high stress and
stretchability.
Meanwhile, as to the flagelliform silk, although the stress is inferior to
that of the major
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dragline silk, the stretchability is high. The reason for this is considered
to be that most of
the flagelliform silk is composed of amorphous regions.
An example of the polypeptide containing 10 or more units of the amino acid
sequence represented by the formula 2: REP3 (2) is a recombinant protein
derived from
flagelliform silk proteins having an amino acid sequence represented by SEQ ID
NO: 19
of U.S. Patent No. 9,051,453. The amino acid sequence represented by SEQ ID
NO: 19
of U.S. Patent No. 9,051,453 is an amino acid sequence obtained by combining a
partial
sequence of flagelliform silk protein of Nephila clavipes obtained from the
NCBI
database (NCBI Accession No.: AAF36090, GI: 7106224), specifically, an amino
acid
sequence thereof from the 1220th residue to the 1659th residue from the N-
terminal that
corresponds to repetitive sections and motifs (referred to as a PR1 sequence),
with a
partial sequence of flagelliform silk protein of Nephila clavipes obtained
from the NCBI
database (NCBI Accession No.: AAC38847, GI: 2833649), specifically, a C-
terminal
amino acid sequence thereof from the 816th residue to the 907th residue from
the C-
terminal, and thereafter adding the amino acid sequence (SEQ ID NO: 5 of U.S.
Patent
No. 9,051,453) composed of a start codon, His 10 tags and an HRV3C Protease
recognition site, to the N-terminal of the combined sequence. Further, the
polypeptide
containing 10 or more units of the amino acid sequence represented by the
formula 2:
REP3 (2) may be a polypeptide that has an amino acid sequence represented by
SEQ ID
NO: 19 of U.S. Patent No. 9,051,453 in which one or a plurality of amino acids
have
been substituted, deleted, inserted and/or added and that has a repetitious
region
composed of an amorphous region.
The polypeptide can be produced using a host that has been transformed by an
expression vector containing a gene encoding a polypeptide. A method for
producing a
gene is not limited particularly, and it may be produced by amplifying a gene
encoding a
natural spider silk protein from a cell derived from spiders by a polymerase
chain
reaction (PCR), etc., and cloning it, or may be synthesized chemically. Also,
a method for
chemically synthesizing a gene is not limited particularly, and it can be
synthesized as
follows, for example: based on information of amino acid sequences of natural
spider silk
proteins obtained from the NCBI web database, etc., oligonucleotides that have
been
synthesized automatically with AKTA oligopilot plus 10/100 (GE Healthcare
Japan
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Corporation) are linked by PCR, etc. At this time, in order to facilitate the
purification
and observation of protein, it is possible to synthesize a gene that encodes a
protein
having an amino acid sequence of the above-described amino acid sequence to
the N-
terminal of which has been added an amino acid sequence composed of a start
codon and
His 10 tags.
Examples of the expression vector include a plasmid, a phage, a virus, and the
like that can express protein based on a DNA sequence. The plasmid-type
expression
vector is not limited particularly as long as it allows a target gene to be
expressed in a
host cell and it can amplify itself. For example, in the case of using
Escherichia coil
Rosetta (DE3) as a host, a pET22b(+) plasmid vector, a pCold plasmid vector,
and the
like can be used. Among these, in terms of productivity of protein, it is
preferable to use
the pET22b(+) plasmid vector. Examples of the host include animal cells, plant
cells,
microbes, etc.
The polypeptide used in the present disclosure is preferably a polypeptide
derived
from ADF3, which is one of two principal dragline silk proteins of Araneus
diadematus.
This polypeptide has advantages of basically having high strength-elongation
and
toughness and of being synthesized easily.
Accordingly, the recombinant silk protein (e.g., the recombinant spider silk-
based
protein) used in accordance with the embodiments, articles, and/or methods
described
herein, may include one or more recombinant silk proteins described above or
recited in
U.S. Patent Nos. 8,173,772, 8,278,416, 8,618,255, 8,642,734, 8,691,581,
8,729,235,
9,115,204, 9,157,070, 9,309,299, 9,644,012, 9,708,376, 9,051,453, 9,617,315,
9,968,682,
9,689,089, 9,732,125, 9,856,308, 9,926,348, 10,065,997, 10,316,069, and
10,329,332;
and U.S. Patent Publication Nos. 2009/0226969, 2011/0281273, 2012/0041177,
2013/0065278, 2013/0115698, 2013/0316376, 2014/0058066, 2014/0079674,
2014/0245923, 2015/0087046, 2015/0119554, 2015/0141618, 2015/0291673,
2015/0291674, 2015/0239587, 2015/0344542, 2015/0361144, 2015/0374833,
2015/0376247, 2016/0024464, 2017/0066804, 2017/0066805, 2015/0293076,
2016/0222174, 2017/0283474, 2017/0088675, 2019/0135880, 2015/0329587,
2019/0040109, 2019/0135881, 2019/0177363, 2019/0225646, 2019/0233481,
2019/0031842, 2018/0355120, 2019/0186050, 2019/0002644, 2020/0031887,
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2018/0273590, 20191/094403, 2019/0031843, 2018/0251501, 2017/0066805,
2018/0127553, 2019/0329526, 2020/0031886, 2018/0080147, 2019/0352349,
2020/0043085, 2019/0144819, 2019/0228449, 2019/0340666, 2020/0000091,
2019/0194710, 2019/0151505, 2018/0265555, 2019/0352330, 2019/0248847, and
2019/0378191, the entirety of which are incorporated herein by reference.
Silk Fibroin-like Protein Fragments
The recombinant silk protein in this disclosure comprises synthetic proteins
which
are based on repeat units of natural silk proteins. Besides the synthetic
repetitive silk
protein sequences, these can additionally comprise one or more natural
nonrepetitive silk
protein sequences. As used herein, "silk fibroin-like protein fragments" refer
to protein
fragments having a molecular weight and polydispersity as defined herein, and
a certain
degree of homology to a protein selected from native silk protein, fibroin
heavy chain,
fibroin light chain, or any protein comprising one or more GAGAGS hexa amino
acid
repeating units. In some embodiments, a degree of homology is selected from
about 99%,
about 98%, about 97%, about 96%, about 95%, about 94%, about 93%, about 92%,
about
91%, about 90%, about 89%, about 88%, about 87%, about 86%, about 85%, about
84%,
about 83%, about 82%, about 81%, about 80%, about 79%, about 78%, about 77%,
about
76%, about 75%, or less than 75%.
As described herein, a protein such as native silk protein, fibroin heavy
chain,
fibroin light chain, or any protein comprising one or more GAGAGS hexa amino
acid
repeating units includes between about 9% and about 45% glycine, or about 9%
glycine,
or about 10% glycine, about 43% glycine, about 44% glycine, about 45% glycine,
or
about 46% glycine. As described herein, a protein such as native silk protein,
fibroin
heavy chain, fibroin light chain, or any protein comprising one or more GAGAGS
hexa
amino acid repeating units includes between about 13% and about 30% alanine,
or about
13% alanine, or about 28% alanine, or about 29% alanine, or about 30% alanine,
or about
31% alanine. As described herein, a protein such as native silk protein,
fibroin heavy
chain, fibroin light chain, or any protein comprising one or more GAGAGS hexa
amino
acid repeating units includes between 9% and about 12% serine, or about 9%
serine, or
about 10% serine, or about 11% serine, or about 12% serine.
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In some embodiments, a silk fibroin-like protein described herein includes
about
5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%,
about
13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about
20%,
about 21%, about 22%, about 23 %, about 24%, about 25%, about 26%, about 27%,
about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%,
about
35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about
42%,
about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%,
about
50%, about 51%, about 52%, about 53%, about 54%, or about 55% glycine. In some
embodiments, a silk fibroin-like protein described herein includes about 13%,
about 14%,
about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%,
about
22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about
29%,
about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%,
about
37%, about 38%, or about 39% alanine. In some embodiments, a silk fibroin-like
protein
described herein includes about 2%, about 3%, about 4%, about 5%, about 6%,
about 7%,
about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%,
about
15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, or
about
22% serine. In some embodiments, a silk fibroin-like protein described herein
may
include independently any amino acid known to be included in natural fibroin.
In some
embodiments, a silk fibroin-like protein described herein may exclude
independently any
amino acid known to be included in natural fibroin. In some embodiments, on
average 2
out of 6 amino acids, 3 out of 6 amino acids, or 4 out of 6 amino acids in a
silk fibroin-
like protein described herein is glycine. In some embodiments, on average 1
out of 6
amino acids, 2 out of 6 amino acids, or 3 out of 6 amino acids in a silk
fibroin-like
protein described herein is alanine. In some embodiments, on average none out
of 6
amino acids, 1 out of 6 amino acids, or 2 out of 6 amino acids in a silk
fibroin-like
protein described herein is serine.
Other Properties of SPF
Compositions of the present disclosure are "biocompatible" or otherwise
exhibit
"biocompatibility" meaning that the compositions are compatible with living
tissue or a
living system by not being toxic, injurious, or physiologically reactive and
not causing
immunological rejection or an inflammatory response. Such biocompatibility can
be
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evidenced by participants topically applying compositions of the present
disclosure on
their skin for an extended period of time. In an embodiment, the extended
period of time
is about 3 days. In an embodiment, the extended period of time is about 7
days. In an
embodiment, the extended period of time is about 14 days. In an embodiment,
the
extended period of time is about 21 days. In an embodiment, the extended
period of time
is about 30 days. In an embodiment, the extended period of time is selected
from the
group consisting of about 1 month, about 2 months, about 3 months, about 4
months,
about 5 months, about 6 months, about 7 months, about 8 months, about 9
months, about
months, about 11 months, about 12 months, and indefinitely. For example, in
some
embodiments, the coatings described herein are biocompatible coatings.
In some embodiments, compositions described herein, which may be
biocompatible compositions (e.g., biocompatible coatings that include silk),
may be
evaluated and comply with International Standard ISO 10993-1, titled the
"Biological
evaluation of medical devices ¨ Part 1: Evaluation and testing within a risk
management
process." In some embodiments, compositions described herein, which may be
biocompatible compositions, may be evaluated under ISO 106993-1 for one or
more of
cytotoxicity, sensitization, hemocompatibility, pyrogenicity, implantation,
genotoxicity,
carcinogenicity, reproductive and developmental toxicity, and degradation.
Compositions of the present disclosure are "hypoallergenic" meaning that they
are
relatively unlikely to cause an allergic reaction. Such hypoallergenicity can
be evidenced
by participants topically applying compositions of the present disclosure on
their skin for
an extended period of time. In an embodiment, the extended period of time is
about 3
days. In an embodiment, the extended period of time is about 7 days. In an
embodiment,
the extended period of time is about 14 days. In an embodiment, the extended
period of
time is about 21 days. In an embodiment, the extended period of time is about
30 days. In
an embodiment, the extended period of time is selected from the group
consisting of
about 1 month, about 2 months, about 3 months, about 4 months, about 5 months,
about 6
months, about 7 months, about 8 months, about 9 months, about 10 months, about
11
months, about 12 months, and indefinitely.
In an embodiment, the stability of a composition of the present disclosure is
about
1 day. In an embodiment, the stability of a composition of the present
disclosure is about
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2 days. In an embodiment, the stability of a composition of the present
disclosure is about
3 days. In an embodiment, the stability of a composition of the present
disclosure is about
4 days. In an embodiment, the stability of a composition of the present
disclosure is about
days. In an embodiment, the stability of a composition of the present
disclosure is about
6 days. In an embodiment, the stability of a composition of the present
disclosure is about
7 days. In an embodiment, the stability of a composition of the present
disclosure is about
8 days. In an embodiment, the stability of a composition of the present
disclosure is about
9 days. In an embodiment, the stability of a composition of the present
disclosure is about
days.
In an embodiment, the stability of a composition of the present disclosure is
about
11 days, about 12 days, about 13 days, about 14 days, about 15 days, about 16
days,
about 17 days, about 18 days, about 19 days, about 20 days, about 21 days,
about 22
days, about 23 days, about 24 days, about 25 days, about 26 days, about 27
days, about
28 days, about 29 days, or about 30 days.
In an embodiment, the stability of a composition of the present disclosure is
10
days to 6 months. In an embodiment, the stability of a composition of the
present
disclosure is 6 months to 12 months. In an embodiment, the stability of a
composition of
the present disclosure is 12 months to 18 months. In an embodiment, the
stability of a
composition of the present disclosure is 18 months to 24 months. In an
embodiment, the
stability of a composition of the present disclosure is 24 months to 30
months. In an
embodiment, the stability of a composition of the present disclosure is 30
months to 36
months. In an embodiment, the stability of a composition of the present
disclosure is 36
months to 48 months. In an embodiment, the stability of a composition of the
present
disclosure is 48 months to 60 months.
In an embodiment, a SPF composition of the present disclosure is not soluble
in
an aqueous solution due to the crystallinity of the protein. In an embodiment,
a SPF
composition of the present disclosure is soluble in an aqueous solution. In an
embodiment, the SPF of a composition of the present disclosure include a
crystalline
portion of about two-thirds and an amorphous region of about one-third. In an
embodiment, the SPF of a composition of the present disclosure include a
crystalline
portion of about one-half and an amorphous region of about one-half In an
embodiment,
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the SPF of a composition of the present disclosure include a 99% crystalline
portion and
a 1% amorphous region. In an embodiment, the SPF of a composition of the
present
disclosure include a 95% crystalline portion and a 5% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure include a 90%
crystalline
portion and a 10% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 85% crystalline portion and a 15% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 80%
crystalline
portion and a 20% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 75% crystalline portion and a 25% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 70%
crystalline
portion and a 30% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 65% crystalline portion and a 35% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 60%
crystalline
portion and a 40% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 50% crystalline portion and a 50% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 40%
crystalline
portion and a 60% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 35% crystalline portion and a 65% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 30%
crystalline
portion and a 70% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 25% crystalline portion and a 75% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 20%
crystalline
portion and a 80% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 15% crystalline portion and a 85% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 10%
crystalline
portion and a 90% amorphous region. In an embodiment, the SPF of a composition
of the
present disclosure include a 5% crystalline portion and a 90% amorphous
region. In an
embodiment, the SPF of a composition of the present disclosure include a 1%
crystalline
portion and a 99% amorphous region.
As used herein, the term "substantially free of inorganic residuals" means
that the
composition exhibits residuals of 0.1 % (w/w) or less. In an embodiment,
substantially
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free of inorganic residuals refers to a composition that exhibits residuals of
0.05% (w/w)
or less. In an embodiment, substantially free of inorganic residuals refers to
a
composition that exhibits residuals of 0.01 % (w/w) or less. In an embodiment,
the
amount of inorganic residuals is between 0 ppm ("non-detectable" or "ND") and
1000
ppm. In an embodiment, the amount of inorganic residuals is ND to about 500
ppm. In
an embodiment, the amount of inorganic residuals is ND to about 400 ppm. In an
embodiment, the amount of inorganic residuals is ND to about 300 ppm. In an
embodiment, the amount of inorganic residuals is ND to about 200 ppm. In an
embodiment, the amount of inorganic residuals is ND to about 100 ppm. In an
embodiment, the amount of inorganic residuals is between 10 ppm and 1000 ppm.
As used herein, the term "substantially free of organic residuals" means that
the
composition exhibits residuals of 0.1 % (w/w) or less, in an embodiment,
substantially
free of organic residuals refers to a composition that exhibits residuals of
0.05% (w/w) or
less. In an embodiment, substantially free of organic residuals refers to a
composition that
exhibits residuals of 0.01% (w/w) or less. In an embodiment, the amount of
organic
residuals is between 0 ppm ("non-detectable" or "ND") and 1000 ppm. In an
embodiment, the amount of organic residuals is ND to about 500 ppm. In an
embodiment, the amount of organic residuals is ND to about 400 ppm. In an
embodiment, the amount of organic residuals is ND to about 300 ppm. In an
embodiment, the amount of organic residuals is ND to about 200 ppm. In an
embodiment, the amount of organic residuals is ND to about 100 ppm. In an
embodiment, the amount of organic residuals is between 10 ppm and 1000 ppm.
Compositions of the present disclosure exhibit "biocompatibility" meaning that
the compositions are compatible with living tissue or a living system by not
being toxic,
injurious, or physiologically reactive and not causing immunological
rejection. Such
biocompatibility can be evidenced by participants topically applying
compositions of the
present disclosure on their skin for an extended period of time. In an
embodiment, the
extended period of time is about 3 days. In an embodiment, the extended period
of time is
about 7 days, in an embodiment, the extended period of time is about 14 days,
in an
embodiment, the extended period of time is about 21 days. In an embodiment,
the
extended period of time is about 30 days. In an embodiment, the extended
period of time
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is selected from the group consisting of about I month, about 2 months, about
3 months,
about 4 months, about 5 months, about 6 months, about 7 months, about 8
months, about
9 months, about 10 months, about 11 months, about 12 months, and indefinitely.
Compositions of the present disclosure are "hypoallergenic" meaning that they
are
relatively unlikely to cause an allergic reaction. Such hypoallergenicity can
be evidenced
by participants topically applying compositions of the present disclosure on
their skin for
an extended period of time. In an embodiment, the extended period of time is
about 3
days. In an embodiment, the extended period of time is about 7 days. In an
embodiment,
the extended period of time is about 14 days. In an embodiment, the extended
period of
time is about 21 days. In an embodiment, the extended period of time is about
30 days. In
an embodiment, the extended period of time is selected from the group
consisting of
about 1 month, about 2 months, about 3 months, about 4 months, about 5 months,
about 6
months, about 7 months, about 8 months, about 9 months, about 10 months, about
11
months, about 12 months, and indefinitely.
Following are non-limiting examples of suitable ranges for various parameters
in
and for preparation of the silk solutions of the present disclosure. The silk
solutions of the
present disclosure may include one or more, but not necessarily all, of these
parameters
and may be prepared using various combinations of ranges of such parameters.
In an embodiment, the percent SPF in the solution is less than 30.0 wt. %. In
an
embodiment, the percent SPF in the solution is less than 25.0 wt. %. In an
embodiment,
the percent SPF in the solution is less than 20.0 wt. %. In an embodiment, the
percent
SPF in the solution is less than 19.0 wt. %. In an embodiment, the percent SPF
in the
solution is less than 18.0 wt. %. In an embodiment, the percent SPF in the
solution is less
than 17.0 wt. %. In an embodiment, the percent SPF in the solution is less
than 16.0 wt.
%. In an embodiment, the percent SPF in the solution is less than 15.0 wt. %.
In an
embodiment, the percent SPF in the solution is less than 14.0 wt. %. In an
embodiment,
the percent SPF in the solution is less than 13.0 wt. %. In an embodiment, the
percent
SPF in the solution is less than 12.0 wt. %. In an embodiment, the percent SPF
in the
solution is less than 11.0 wt. %. In an embodiment, the percent SPF in the
solution is less
than 10.0 wt. %. In an embodiment, the percent SPF in the solution is less
than 9.0 wt. %.
In an embodiment, the percent SPF in the solution is less than 8.0 wt. %. In
an
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embodiment, the percent SPF in the solution is less than 7.0 wt. %. In an
embodiment,
the percent SPF in the solution is less than 6.0 wt. %. In an embodiment, the
percent SPF
in the solution is less than 5.0 wt. %. In an embodiment, the percent SPF in
the solution is
less than 4.0 wt. %. In an embodiment, the percent SPF in the solution is less
than 3.0 wt.
%. In an embodiment, the percent SPF in the solution is less than 2.0 wt. %.
In an
embodiment, the percent SPF in the solution is less than 1.0 wt. %. In an
embodiment,
the percent SPF in the solution is less than 0.9 wt. %. In an embodiment, the
percent SPF
in the solution is less than 0.8 wt. %. In an embodiment, the percent SPF in
the solution is
less than 0.7 wt. %. In an embodiment, the percent SPF in the solution is less
than 0.6 wt.
%. In an embodiment, the percent SPF in the solution is less than 0.5 wt. %.
In an
embodiment, the percent SPF in the solution is less than 0.4 wt. %. In an
embodiment,
the percent SPF in the solution is less than 0.3 wt. %. In an embodiment, the
percent SPF
in the solution is less than 0.2 wt. %. In an embodiment, the percent SPF in
the solution is
less than 0.1 wt. %.
In an embodiment, the percent SPF in the solution is greater than 0.1 wt. %.
In an
embodiment, the percent SPF in the solution is greater than 0.2 wt. %. In an
embodiment,
the percent SPF in the solution is greater than 0.3 wt. %. In an embodiment,
the percent
SPF in the solution is greater than 0.4 wt. %. In an embodiment, the percent
SPF in the
solution is greater than 0.5 wt. %. In an embodiment, the percent SPF in the
solution is
greater than 0.6 wt. %. In an embodiment, the percent SPF in the solution is
greater than
0.7 wt. %. In an embodiment, the percent SPF in the solution is greater than
0.8 wt. %. In
an embodiment, the percent SPF in the solution is greater than 0.9 wt. %. In
an
embodiment, the percent SPF in the solution is greater than 1.0 wt. %. In an
embodiment,
the percent SPF in the solution is greater than 2.0 wt. %. In an embodiment,
the percent
SPF in the solution is greater than 3.0 wt. %. In an embodiment, the percent
SPF in the
solution is greater than 4.0 wt. %. In an embodiment, the percent SPF in the
solution is
greater than 5.0 wt. %. In an embodiment, the percent SPF in the solution is
greater than
6.0 wt. %. In an embodiment, the percent SPF in the solution is greater than
7.0 wt. %. In
an embodiment, the percent SPF in the solution is greater than 8.0 wt. %. In
an
embodiment, the percent SPF in the solution is greater than 9.0 wt. %. In an
embodiment,
the percent SPF in the solution is greater than 10.0 wt. %. In an embodiment,
the percent
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SPF in the solution is greater than 11.0 wt. %. In an embodiment, the percent
SPF in the
solution is greater than 12.0 wt. %. In an embodiment, the percent SPF in the
solution is
greater than 13.0 wt. %. In an embodiment, the percent SPF in the solution is
greater than
14.0 wt. %. In an embodiment, the percent SPF in the solution is greater than
15.0 wt. %.
In an embodiment, the percent SPF in the solution is greater than 16.0 wt. %.
In an
embodiment, the percent SPF in the solution is greater than 17.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 18.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 19.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 20.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 25.0 wt. %.
In an embodiment, the percent SPF in the solution ranges from about 0.1 wt. %
to
about 30.0 wt. %. In an embodiment, the percent SPF in the solution ranges
from about
0.1 wt. % to about 25.0 wt. %. In an embodiment, the percent SPF in the
solution ranges
from about 0.1 wt. % to about 20.0 wt. %. In an embodiment, the percent SPF in
the
solution ranges from about 0.1 wt. % to about 15.0 wt. %. In an embodiment,
the percent
SPF in the solution ranges from about 0.1 wt. % to about 10.0 wt. %. In an
embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to about 9.0 wt.
%. In an
embodiment, the percent SPF in the solution ranges from about 0.1 wt. % to
about 8.0 wt.
%. In an embodiment, the percent SPF in the solution ranges from about 0.1 wt.
% to
about 7.0 wt. %. In an embodiment, the percent SPF in the solution ranges from
about 0.1
wt. % to about 6.5 wt. %. In an embodiment, the percent SPF in the solution
ranges from
about 0.1 wt. % to about 6.0 wt. %. In an embodiment, the percent SPF in the
solution
ranges from about 0.1 wt. % to about 5.5 wt. %. In an embodiment, the percent
SPF in
the solution ranges from about 0.1 wt. % to about 5.0 wt. %. In an embodiment,
the
percent SPF in the solution ranges from about 0.1 wt. % to about 4.5 wt. %. In
an
embodiment, the percent SPF in the solution ranges from about 0.1 wt. % to
about 4.0 wt.
%. In an embodiment, the percent SPF in the solution ranges from about 0.1 wt.
% to
about 3.5 wt. %. In an embodiment, the percent SPF in the solution ranges from
about 0.1
wt. % to about 3.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from
about 0.1 wt. % to about 2.5 wt. %. In an embodiment, the percent SPF in the
solution
ranges from about 0.1 wt. % to about 2.0 wt. %. In an embodiment, the percent
SPF in
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the solution ranges from about 0.1 wt. % to about 2.4 wt. %. In an embodiment,
the
percent SPF in the solution ranges from about 0.5 wt. % to about 5.0 wt. %. In
an
embodiment, the percent SPF in the solution ranges from about 0.5 wt. % to
about 4.5 wt.
%. In an embodiment, the percent SPF in the solution ranges from about 0.5 wt.
% to
about 4.0 wt. %. In an embodiment, the percent SPF in the solution ranges from
about 0.5
wt. % to about 3.5 wt. %. In an embodiment, the percent SPF in the solution
ranges from
about 0.5 wt. % to about 3.0 wt. %. In an embodiment, the percent SPF in the
solution
ranges from about 0.5 wt. % to about 2.5 wt. %. In an embodiment, the percent
SPF in
the solution ranges from about 1.0 wt. % to about 4.0 wt. %. In an embodiment,
the
percent SPF in the solution ranges from about 1.0 wt. % to about 3.5 wt. %. In
an
embodiment, the percent SPF in the solution ranges from about 1.0 wt. % to
about 3.0 wt.
%. In an embodiment, the percent SPF in the solution ranges from about 1.0 wt.
% to
about 2.5 wt. %. In an embodiment, the percent SPF in the solution ranges from
about 1.0
wt. % to about 2.4 wt. %. In an embodiment, the percent SPF in the solution
ranges from
about 1.0 wt. % to about 2.0 wt. %.
In an embodiment, the percent SPF in the solution ranges from about 20.0 wt. %
to about 30.0 wt. %. In an embodiment, the percent SPF in the solution ranges
from about
0.1 wt. % to about 10.0 wt. %. In an embodiment, the percent SPF in the
solution ranges
from about 1.0 wt. % to about 10.0 wt. %. In an embodiment, the percent SPF in
the
solution ranges from about 2 wt. % to about 10.0 wt. %. In an embodiment, the
percent
SPF in the solution ranges from about 0.1 wt. % to about 6.0 wt. %. In an
embodiment,
the percent SPF in the solution ranges from about 6.0 wt. % to about 10.0 wt.
%. In an
embodiment, the percent SPF in the solution ranges from about 6.0 wt. % to
about 8.0 wt.
%. In an embodiment, the percent SPF in the solution ranges from about 6.0 wt.
% to
about 9.0 wt. %. In an embodiment, the percent SPF in the solution ranges from
about
10.0 wt. % to about 20.0 wt. %. In an embodiment, the percent SPF in the
solution ranges
from about 11.0 wt. % to about 19.0 wt. %. In an embodiment, the percent SPF
in the
solution ranges from about 12.0 wt. % to about 18.0 wt. %. In an embodiment,
the
percent SPF in the solution ranges from about 13.0 wt. % to about 17.0 wt. %.
In an
embodiment, the percent SPF in the solution ranges from about 14.0 wt. % to
about 16.0
wt. %. In an embodiment, the percent SPF in the solution is about 1.0 wt. %.
In an
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embodiment, the percent SPF in the solution is about 1.5 wt. %. In an
embodiment, the
percent SPF in the solution is about 2.0 wt.%. In an embodiment, the percent
SPF in the
solution is about 2.4 wt. %. In an embodiment, the percent SPF in the solution
is 3.0 wt.
%. In an embodiment, the percent SPF in the solution is 3.5 wt. %. In an
embodiment, the
percent SPF in the solution is about 4.0 wt. %. In an embodiment, the percent
SPF in the
solution is about 4.5 wt. %. In an embodiment, the percent SPF in the solution
is about
5.0 wt. %. In an embodiment, the percent SPF in the solution is about 5.5 wt.
%. In an
embodiment the percent SPF in the solution is about 6.0 wt. %. In an
embodiment, the
percent SPF in the solution is about 6.5 wt. %. In an embodiment, the percent
SPF in the
solution is about 7.0 wt. %. In an embodiment, the percent SPF in the solution
is about
7.5 wt. %. In an embodiment, the percent SPF in the solution is about 8.0 wt.
%. In an
embodiment, the percent SPF in the solution is about 8.5 wt. %. In an
embodiment, the
percent SPF in the solution is about 9.0 wt. %. In an embodiment, the percent
SPF in the
solution is about 9.5 wt. %. In an embodiment, the percent SPF in the solution
is about
10.0 wt. %.
In an embodiment, the percent sericin in the solution is non-detectable to
25.0 wt.
%. In an embodiment, the percent sericin in the solution is non-detectable to
5.0 wt. %. In
an embodiment, the percent sericin in the solution is 1.0 wt. %. In an
embodiment, the
percent sericin in the solution is 2.0 wt. %. In an embodiment, the percent
sericin in the
solution is 3.0 wt. %. In an embodiment, the percent sericin in the solution
is 4.0 wt. %.
In an embodiment, the percent sericin in the solution is 5.0 wt. %. In an
embodiment, the
percent sericin in the solution is 10.0 wt. %. In an embodiment, the percent
sericin in the
solution is 25.0 wt. %.
In some embodiments, the silk fibroin protein fragments of the present
disclosure
are shelf stable (they will not slowly or spontaneously gel when stored in an
aqueous
solution and there is no aggregation of fragments and therefore no increase in
molecular
weight over time), from 10 days to 3 years depending on storage conditions,
percent SPF,
and number of shipments and shipment conditions. Additionally, pH may be
altered to
extend shelf life and/or support shipping conditions by preventing premature
folding and
aggregation of the silk. In an embodiment, the stability of the LiBr-silk
fragment solution
is 0 to 1 year. In an embodiment, the stability of the LiBr-silk fragment
solution is 0 to 2
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years. In an embodiment, the stability of the LiBr-silk fragment solution is 0
to 3 years.
In an embodiment, the stability of the LiBr-silk fragment solution is 0 to 4
years. In an
embodiment, the stability of the LiBr-silk fragment solution is 0 to 5 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 1 to 2 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 1 to 3 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 1 to 4 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 1 to 5 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 2 to 3 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 2 to 4 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 2 to 5 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 3 to 4 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 3 to 5 years.
In an
embodiment, the stability of the LiBr-silk fragment solution is 4 to 5 years.
In an embodiment, the stability of a composition of the present disclosure is
10
days to 6 months. In an embodiment, the stability of a composition of the
present
disclosure is 6 months to 12 months. In an embodiment, the stability of a
composition of
the present disclosure is 12 months to 18 months. In an embodiment, the
stability of a
composition of the present disclosure is 18 months to 24 months. In an
embodiment, the
stability of a composition of the present disclosure is 24 months to 30
months. In an
embodiment, the stability of a composition of the present disclosure is 30
months to 36
months. In an embodiment, the stability of a composition of the present
disclosure is 36
months to 48 months. In an embodiment, the stability of a composition of the
present
disclosure is 48 months to 60 months.
In an embodiment, a composition of the present disclosure having SPF has non-
detectable levels of LiBr residuals. In an embodiment, the amount of the LiBr
residuals in
a composition of the present disclosure is between 10 ppm and 1000 ppm. In an
embodiment, the amount of the LiBr residuals in a composition of the present
disclosure
is between 10 ppm and 300 ppm. In an embodiment, the amount of the LiBr
residuals in a
composition of the present disclosure is less than 25 ppm. In an embodiment,
the amount
of the Li Br residuals in a composition of the present disclosure is less than
50 ppm. In an
embodiment, the amount of the LiBr residuals in a composition of the present
disclosure
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is less than 75 ppm. In an embodiment, the amount of the LiBr residuals in a
composition
of the present disclosure is less than 100 ppm. In an embodiment, the amount
of the LiBr
residuals in a composition of the present disclosure is less than 200 ppm. In
an
embodiment, the amount of the LiBr residuals in a composition of the present
disclosure
is less than 300 ppm. In an embodiment, the amount of the LiBr residuals in a
composition of the present disclosure is less than 400 ppm. In an embodiment,
the
amount of the LiBr residuals in a composition of the present disclosure is
less than 500
ppm. In an embodiment, the amount of the LiBr residuals in a composition of
the present
disclosure is less than 600 ppm. In an embodiment, the amount of the LiBr
residuals in a
composition of the present disclosure is less than 700 ppm. In an embodiment,
the
amount of the LiBr residuals in a composition of the present disclosure is
less than 800
ppm. In an embodiment, the amount of the LiBr residuals in a composition of
the present
disclosure is less than 900 ppm. In an embodiment, the amount of the LiBr
residuals in a
composition of the present disclosure is less than 1000 ppm. In an embodiment,
the
amount of the LiBr residuals in a composition of the present disclosure is non-
detectable
to 500 ppm. In an embodiment, the amount of the LiBr residuals in a
composition of the
present disclosure is non-detectable to 450 ppm. In an embodiment, the amount
of the
LiBr residue in a composition of the present disclosure is non-detectable to
400 ppm. In
an embodiment, the amount of the LiBr residuals in a composition of the
present
disclosure is non-detectable to 350 ppm. In an embodiment, the amount of the
LiBr
residuals in a composition of the present disclosure is non-detectable to 300
ppm. In an
embodiment, the amount of the LiBr residuals in a composition of the present
disclosure
is non-detectable to 250 ppm. In an embodiment, the amount of the LiBr
residuals in a
composition of the present disclosure is non-detectable to 200 ppm. In an
embodiment,
the amount of the LiBr residuals in a composition of the present disclosure is
non-
detectable to 150 ppm. In an embodiment, the amount of the LiBr residuals in a
composition of the present disclosure is non-detectable to 100 ppm. In an
embodiment,
the amount of the LiBr residuals in a composition of the present disclosure is
100 ppm to
200 ppm. In an embodiment, the amount of the LiBr residuals in a composition
of the
present disclosure is 200 ppm to 300 ppm. In an embodiment, the amount of the
LiBr
residuals in a composition of the present disclosure is 300 ppm to 400 ppm. In
an
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embodiment, the amount of the LiBr residuals in a composition of the present
disclosure
is 400 ppm to 500 ppm.
In an embodiment, a composition of the present disclosure having SPF, has non-
detectable levels of Na2CO3 residuals. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is less than 100 ppm. In
an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is less than 200 ppm. In an embodiment, the amount of the Na2CO3
residuals
in a composition of the present disclosure is less than 300 ppm. In an
embodiment, the
amount of the Na2CO3 residuals in a composition of the present disclosure is
less than
400 ppm. In an embodiment, the amount of the Na2CO3 residuals in a composition
of the
present disclosure is less than 500 ppm. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is less than 600 ppm. In
an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is less than 700 ppm. In an embodiment, the amount of the Na2CO3
residuals
in a composition of the present disclosure is less than 800 ppm. In an
embodiment, the
amount of the Na2CO3 residuals in a composition of the present disclosure is
less than
900 ppm. In an embodiment, the amount of the Na2CO3 residuals in a composition
of the
present disclosure is less than 1000 ppm. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is non-detectable to 500
ppm. In an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is non-detectable to 450 ppm. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is non-detectable to 400
ppm. In an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is non-detectable to 350 ppm. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is non-detectable to 300
ppm. In an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is non-detectable to 250 ppm. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is non-detectable to 200
ppm. In an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is non-detectable to 150 ppm. In an embodiment, the amount of the
Na2CO3
residuals in a composition of the present disclosure is non-detectable to 100
ppm. In an
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embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is 100 ppm to 200 ppm. In an embodiment, the amount of the Na2CO3
residuals in a composition of the present disclosure is 200 ppm to 300 ppm. In
an
embodiment, the amount of the Na2CO3 residuals in a composition of the present
disclosure is 300 ppm to 400 ppm. In an embodiment, the amount of the Na2CO3
residuals in a composition of the present disclosure is 400 ppm to 500 ppm.
A unique feature of the SPF compositions of the present disclosure are shelf
stability (they will not slowly or spontaneously gel when stored in an aqueous
solution
and there is no aggregation of fragments and therefore no increase in
molecular weight
over time), from 10 days to 3 years depending on storage conditions, percent
silk, and
number of shipments and shipment conditions. Additionally pH may be altered to
extend
shelf-life and/or support shipping conditions by preventing premature folding
and
aggregation of the silk. In an embodiment, a SPF solution composition of the
present
disclosure has a shelf stability for up to 2 weeks at room temperature (RT).
In an
embodiment, a SPF solution composition of the present disclosure has a shelf
stability for
up to 4 weeks at RT. In an embodiment, a SPF solution composition of the
present
disclosure has a shelf stability for up to 6 weeks at RT. In an embodiment, a
SPF solution
composition of the present disclosure has a shelf stability for up to 8 weeks
at RT. In an
embodiment, a SPF solution composition of the present disclosure has a shelf
stability for
up to 10 weeks at RT. In an embodiment, a SPF solution composition of the
present
disclosure has a shelf stability for up to 12 weeks at RT. In an embodiment, a
SPF
solution composition of the present disclosure has a shelf stability ranging
from about 4
weeks to about 52 weeks at RT. Table R below shows shelf stability test
results for
embodiments of SPF compositions of the present disclosure.
Table R. Shelf Stability of SPF Compositions of the Present Disclosure
Time to Gelation
% Silk Temperature
2 RT 4 weeks
2 4 C >9 weeks
4 RT 4 weeks
4 4 C >9 weeks
6 RT 2 weeks
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6 4 C >9 weeks
In some embodiments, the water solubility of the silk film derived from silk
fibroin protein fragments as described herein can be modified by solvent
annealing (water
annealing or methanol annealing), chemical crosslinking, enzyme crosslinking
and heat
treatment.
In some embodiments, the process of annealing may involve inducing beta-sheet
formation in the silk fibroin protein fragment solutions used as a coating
material.
Techniques of annealing (e.g., increase crystallinity) or otherwise promoting
"molecular
packing" of silk fibroin-protein based fragments have been described. In some
embodiments, the amorphous silk film is annealed to introduce beta-sheet in
the presence
of a solvent selected from the group of water or organic solvent. In some
embodiments,
the amorphous silk film is annealed to introduce beta-sheet in the presence of
water
(water annealing process). In some embodiments, the amorphous silk fibroin
protein
fragment film is annealed to introduce beta-sheet in the presence of methanol.
In some
embodiments, annealing (e.g., the beta sheet formation) is induced by addition
of an
organic solvent. Suitable organic solvents include, but are not limited to
methanol,
ethanol, acetone, isopropanol, or combination thereof.
In some embodiments, annealing is carried out by so-called "water-annealing"
or
"water vapor annealing" in which water vapor is used as an intermediate
plasticizing
agent or catalyst to promote the packing of beta-sheets. In some embodiments,
the
process of water annealing may be performed under vacuum. Suitable such
methods have
been described in Jin H-J et al. (2005), Water-stable Silk Films with Reduced
Beta-Sheet
Content, Advanced Functional Materials, 15: 1241-1247; Xiao H. et al. (2011),
Regulation of Silk Material Structure by Temperature-Controlled Water Vapor
Annealing, Biomacromolecules, 12(5): 1686-1696.
The important feature of the water annealing process is to drive the formation
of
crystalline beta-sheet in the silk fibroin protein fragment peptide chain to
allow the silk
fibroin self-assembling into a continuous film. In some embodiments, the
crystallinity of
the silk fibroin protein fragment film is controlled by controlling the
temperature of water
vapor and duration of the annealing. In some embodiments, the annealing is
performed at
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a temperature ranging from about 65 C to about 110 C. In some embodiments,
the
temperature of the water is maintained at about 80 C. In some embodiments,
annealing
is performed at a temperature selected from the group of about 65 C, about 70
C, about
75 C, about 80 C, about 85 C, about 90 C, about 95 C, about 100 C, about
105 C,
and about 110 C.
In some embodiments, the annealing process lasts a period of time selected
from
the group of about 1 minute to about 40 minutes, about 1 minute to about 50
minutes,
about 1 minute to about 60 minutes, about 1 minute to about 70 minutes, about
1 minute
to about 80 minutes, about 1 minute to about 90 minutes, about 1 minute to
about 100
minutes, about 1 minute to about 110 minutes, about 1 minute to about 120
minutes,
about 1 minute to about 130 minutes, about 5 minutes to about 40 minutes,
about 5
minutes to about 50 minutes, about 5 minutes to about 60 minutes, about 5
minutes to
about 70 minutes, about 5 minutes to about 80 minutes, about 5 minutes to
about 90
minutes, about 5 minutes to about 100 minutes, about 5 minutes to about 110
minutes,
about 5 minutes to about 120 minutes, about 5 minutes to about 130 minutes,
about 10
minutes to about 40 minutes, about 10 minutes to about 50 minutes, about 10
minutes to
about 60 minutes, about 10 minutes to about 70 minutes, about 10 minutes to
about 80
minutes, about 10 minutes to about 90 minutes, about 10 minutes to about 100
minutes,
about 10 minutes to about 110 minutes, about 10 minutes to about 120 minutes,
about
minutes to about 130 minutes, about 15 minutes to about 40 minutes, about 15
minutes to about 50 minutes, about 15 minutes to about 60 minutes, about 15
minutes to
about 70 minutes, about 15 minutes to about 80 minutes, about 15 minutes to
about 90
minutes, about 15 minutes to about 100 minutes, about 15 minutes to about 110
minutes,
about 15 minutes to about 120 minutes, about 15 minutes to about 130 minutes,
about 20
minutes to about 40 minutes, about 20 minutes to about 50 minutes, about 20
minutes to
about 60 minutes, about 20 minutes to about 70 minutes, about 20 minutes to
about 80
minutes, about 20 minutes to about 90 minutes, about 20 minutes to about 100
minutes,
about 20 minutes to about 110 minutes, about 20 minutes to about 120 minutes,
about
minutes to about 130 minutes, about 25 minutes to about 40 minutes, about 25
minutes to about 50 minutes, about 25 minutes to about 60 minutes, about 25
minutes to
about 70 minutes, about 25 minutes to about 80 minutes, about 25 minutes to
about 90
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minutes, about 25 minutes to about 100 minutes, about 25 minutes to about 110
minutes,
about 25 minutes to about 120 minutes, about 25 minutes to about 130 minutes,
about 30
minutes to about 40 minutes, about 30 minutes to about 50 minutes, about 30
minutes to
about 60 minutes, about 30 minutes to about 70 minutes, about 30 minutes to
about 80
minutes, about 30 minutes to about 90 minutes, about 30 minutes to about 100
minutes,
about 30 minutes to about 110 minutes, about 30 minutes to about 120 minutes,
about 30
minutes to about 130 minutes, about 35 minutes to about 40 minutes, about 35
minutes
to about 50 minutes, about 35 minutes to about 60 minutes, about 35 minutes to
about
70 minutes, about 35 minutes to about 80 minutes, about 35 minutes to about 90
minutes, about 35 minutes to about 100 minutes, about 35 minutes to about 110
minutes,
about 35 minutes to about 120 minutes, about 35 minutes to about 130 minutes,
about 40
minutes to about 50 minutes, about 40 minutes to about 60 minutes, about 40
minutes to
about 70 minutes, about 40 minutes to about 80 minutes, about 40 minutes to
about 90
minutes, about 40 minutes to about 100 minutes, about 40 minutes to about 110
minutes,
about 40 minutes to about 120 minutes, about 40 minutes to about 130 minutes,
about 45
minutes to about 50 minutes, about 45 minutes to about 60 minutes, about 45
minutes to
about 70 minutes, about 45 minutes to about 80 minutes, about 45 minutes to
about 90
minutes, about 45 minutes to about 100 minutes, about 45 minutes to about 110
minutes,
about 45 minutes to about 120 minutes, and about 45 minutes to about 130
minutes. In
some embodiments, the annealing process lasts a period of time ranging from
about 1
minute to about 60 minutes. In some embodiments, the annealing process lasts a
period of
time ranging from about 45 minutes to about 60 minutes. The longer water
annealing
post-processing corresponded an increased crystallinity of silk fibroin
protein fragments.
In some embodiments, the annealed silk fibroin protein fragment film is
immersing the wet silk fibroin protein fragment film in 100 % methanol for 60
minutes at
room temperature. The methanol annealing changed the composition of silk
fibroin
protein fragment film from predominantly amorphous random coil to crystalline
antiparallel beta-sheet structure.
In some embodiments, the SPF as described herein can be used to prepare SPF
microparticles by precipitation with methanol. Alternative flash drying, fluid-
bed drying,
spray drying or vacuum drying can be applied to remove water from the silk
solution.
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The SPF powder can then be stored and handled without refrigeration or other
special
handling procedures. In some embodiments, the SPF powders comprise low
molecular
weight silk fibroin protein fragments. In some embodiments, the SPF powders
comprise
mid-molecular weight silk fibroin protein fragments. In some embodiments, the
SPF
powders comprise a mixture of low molecular weight silk fibroin protein
fragments and
mid-molecular weight silk fibroin protein fragment.
In an embodiment, the water solubility of pure silk fibroin protein fragments
of
the present disclosure is 50 to 100%. In an embodiment, the water solubility
of pure silk
fibroin protein fragments of the present disclosure is 60 to 100%. In an
embodiment, the
water solubility of pure silk fibroin protein fragments of the present
disclosure is 70 to
100%. In an embodiment, the water solubility of pure silk fibroin protein
fragments of the
present disclosure is 80 to 100%. In an embodiment, the water solubility is 90
to 100%.
In an embodiment, the silk fibroin fragments of the present disclosure are non-
soluble in
aqueous solutions.
In an embodiment, the solubility of pure silk fibroin protein fragments of the
present disclosure in organic solutions is 50 to 100%. In an embodiment, the
solubility of
pure silk fibroin protein fragments of the present disclosure in organic
solutions is 60 to
100%. In an embodiment, the solubility of pure silk fibroin protein fragments
of the
present disclosure in organic solutions is 70 to 100%. In an embodiment, the
solubility of
pure silk fibroin protein fragments of the present disclosure in organic
solutions is 80 to
100%. In an embodiment, the solubility of pure silk fibroin protein fragments
of the
present disclosure in organic solutions is 90 to 100%. In an embodiment, the
silk fibroin
fragments of the present disclosure are non- soluble in organic solutions.
In some embodiments, the silk fibroin protein fragments comprise cationic
quaternized amino acid residue (cationic quaternized silk fibroin) with fatty
alkyl groups,
wherein the silk fibroin protein fragments having any weight average molecular
weight
and polydispersity described herein. In some embodiments, the fatty alkyl
group for
quaternization of amine groups of the silk fibroin protein fragment is
selected from the
group of cocodimonium hydroxypropyl, hydroxypropyltrimonium, lauryidimonium
hydroxypropyl, steardimonium hydroxypropyl, quaternium-79, and combinations
thereof.
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Silk Fibroin-Based Protein Fragments and Solutions Thereof
Provided herein are methods for producing pure and highly scalable SPF as
defined herein, including without limitation silk fibroin or silk fibroin
fragments, mixture
compositions, for example solutions, that may be used to coat at least a
portion of a
substrate, or may be formed into usable fibers for weaving into yarn, in
particular to be
used with a chemical modifier, or a physical modifier. Methods of making silk
fibroin or
silk fibroin fragments are known and are described for example in U.S. Patents
Nos.
9,187,538, 9,511,012, 9,517,191, 9,522,107, 9,522,108, 9,545,369, and
10,166,177, all of
which are incorporated herein in their entireties. Methods of using silk
fibroin or silk
fibroin fragments in coating applications are known and are described for
example in
U.S. Patent Application Publications Nos. 20160222579, and 20160281294.
In some embodiments, the SPF as defined herein, including without limitation
silk
fibroin or silk fibroin fragments, have an average weight average molecular
weight from
about 1 kDa to about 5 kDa, from about 5 kDa to about 10 kDa, from about 6 kDa
to
about 17 kDa, from about 10 kDa to about 15 kDa, from about 15 kDa to about 20
kDa,
from about 17 kDa to about 39 kDa, from about 20 kDa to about 25 kDa, from
about 25
kDa to about 30 kDa, from about 30 kDa to about 35 kDa, from about 35 kDa to
about 40
kDa, from about 39 kDa to about 80 kDa, from about 40 kDa to about 45 kDa,
from
about 45 kDa to about 50 kDa, from about 60 kDa to about 100 kDa, or from
about 80
kDa to about 144 kDa, wherein the SPF and/or silk fibroin or silk fibroin
fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin or silk fibroin fragments are chemically
linked to a
substrate through the linker. In some embodiments, the SPF as defined herein,
including
without limitation silk fibroin or silk fibroin fragments, have a
polydispersity between 1
and about 5.0, wherein the SPF and/or silk fibroin or silk fibroin fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the SPF and/or silk fibroin or silk fibroin fragments are
chemically
linked to a substrate through the linker.
As used herein, "average weight average molecular weight" refers to an average
of two or more values of weight average molecular weight of silk fibroin or
fragments
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thereof of the same compositions, the two or more values determined by two or
more
separate experimental readings.
As used herein, the terms "substantially sericin free" or "substantially
devoid of
sericin" refer to silk fibers in which a majority of the sericin protein has
been removed. In
an embodiment, silk fibroin that is substantially devoid of sericin refers to
silk fibroin
having between about 0.01% (w/w) and about 10.0% (w/w) sericin. In an
embodiment,
silk fibroin that is substantially devoid of sericin refers to silk fibroin
having between
about 0.01% (w/w) and about 9.0% (w/w) sericin. In an embodiment, silk fibroin
that is
substantially devoid of sericin refers to silk fibroin having between about
0.01% (w/w)
and about 8.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid
of sericin refers to silk fibroin having between about 0.01% (w/w) and about
7.0% (w/w)
sericin. In an embodiment, silk fibroin that is substantially devoid of
sericin refers to silk
fibroin having between about 0.01% (w/w) and about 6.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin refers to
silk fibroin
having between about 0.01% (w/w) and about 5.0% (w/w) sericin. In an
embodiment,
silk fibroin that is substantially devoid of sericin refers to silk fibroin
having between
about 0% (w/w) and about 4.0% (w/w) sericin. In an embodiment, silk fibroin
that is
substantially devoid of sericin refers to silk fibroin having between about
0.05% (w/w)
and about 4.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid
of sericin refers to silk fibroin having between about 0.1% (w/w) and about
4.0% (w/w)
sericin. In an embodiment, silk fibroin that is substantially devoid of
sericin refers to silk
fibroin having between about 0.5% (w/w) and about 4.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin refers to
silk fibroin
having between about 1.0% (w/w) and about 4.0% (w/w) sericin. In an
embodiment, silk
fibroin that is substantially devoid of sericin refers to silk fibroin having
between about
1.5% (w/w) and about 4.0% (w/w) sericin. In an embodiment, silk fibroin that
is
substantially devoid of sericin refers to silk fibroin having between about
2.0% (w/w) and
about 4.0% (w/w) sericin. In an embodiment, silk fibroin that is substantially
devoid of
sericin refers to silk fibroin having between about 2.5% (w/w) and about 4.0%
(w/w)
sericin. In an embodiment, silk fibroin that is substantially devoid of
sericin refers to silk
fibroin having a sericin content between about 0.01% (w/w) and about 0.1 %
(w/w). In an
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embodiment, silk fibroin that is substantially devoid of sericin refers to
silk fibroin
having a sericin content below about 0.1 % (w/w). In an embodiment, silk
fibroin that is
substantially devoid of sericin refers to silk fibroin having a sericin
content below about
0.05 % (w/w). In an embodiment, when a silk source is added to a boiling (100
C)
aqueous solution of sodium carbonate for a treatment time of between about 30
minutes
to about 60 minutes, a degumming loss of about 26 wt. % to about 31 wt.% is
obtained.
As used herein, the term "substantially homogeneous" may refer to pure silk
fibroin-based protein fragments that are distributed in a normal distribution
about an
identified molecular weight. As used herein, the term "substantially
homogeneous" may
refer to an even distribution of additive, for example vitamin C, throughout a
composition
of the present disclosure.
Textiles and Leathers Coated with Silk Fibroin-Based Protein Fragments
As used herein, the term "washable" and "exhibiting washability" means that a
silk coated fabric of the present disclosure is capable of being washed
without shrinking,
fading, or the like.
As used herein, the term "textile" refers to a flexible woven or non-woven
material consisting of a network of natural or artificial fibers often
referred to as fabric,
thread, or yarn. In an embodiment, textiles can be used to fabricate clothing,
shoes and
bags. In an embodiment, textiles can be used to fabricate carpeting,
upholstered
furnishings, window shades, towels, and coverings for tables, beds, and other
flat
surfaces. In an embodiment, textiles can be used to fabricate flags,
backpacks, tents, nets,
handkerchiefs, balloons, kites, sails, and parachutes.
As used herein, the term "leather" refers to natural leather and synthetic
leather.
Natural leather includes chrome-tanned leather (e.g., tanned using chromium
sulfate and
other chromium salts), vegetable-tanned leather (e.g., tanned using tannins),
aldehyde-
tanned leather (also known as wet-white leather, e.g., tanned using
glutaraldehyde or
oxazolidine compounds), brain-tanned leather, formaldehyde-tanned leather,
Chamois
leather (e.g., tanned using cod oils), rose-tanned leather (e.g., tanned using
rose otto oils),
synthetic-tanned leather (e.g., tanned using aromatic polymers), alum-tanned
leather,
patent leather, Vachetta leather, nubuck leather, and rawhide leather. Natural
leather also
includes split leather, full-grain leather, top-grain leather, and corrected-
grain leather, the
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properties and preparation of which are known to those of skill in the art.
Synthetic
leather includes poromeric imitation leathers (e.g., polyurethane on
polyester), vinyl and
polyamide felt fibers, polyurethane, polyvinyl chloride, polyethylene (PE),
polypropylene
(PP), vinyl acetate copolymer (EVA), polyamide, polyester, recycled polyester,
textile-
polymer composite microfibers, corfan, koskin, leatherette, BIOTHANE ,
BIRKIBUC , BIRKO-FLOR , CLARINO , ECOLORICA , KYDEX , LORICA ,
NAUGAHYDE , REXINE , VEGETAN , FABRIKOID , or combinations thereof.
As used herein, the term "hand" refers to the feel of a fabric, which may be
further described as the feeling of softness, crispness, dryness, silkiness,
and
combinations thereof. Fabric hand is also referred to as "drape." A fabric
with a hard
hand is coarse, rough, and generally less comfortable for the wearer. A fabric
with a soft
hand is fluid and smooth, such as fine silk or wool, and generally more
comfortable for
the wearer. Fabric hand can be determined by comparison to collections of
fabric
samples, or by use of methods such as the Kawabata Evaluation System (KES) or
the
Fabric Assurance by Simple Testing (FAST) methods. Behera and Hari, Ind. I
Fibre &
Textile Res., 1994, 19, 168-71.
As used herein, the term "yarn" refers to a single or multi-fiber construct.
As used herein, the term "bath coating" encompasses coating a fabric in a
batch,
immersing a fabric in a bath, and submerging a fabric in a bath. Concepts of
bath coating
are set forth in U.S. Patent No. 4,521,458, the entirety of which is
incorporated by
reference.
In an embodiment, the disclosure provides a textile or leather product coated
with
silk fibroin-based proteins or fragments thereof, in particular wherein the
coating includes
one or more chemical modifiers and/or physical modifiers. Silk fibroin coated
articles
have been described in U.S. Patent Application Publications Nos. 20160222579,
20160281294, and 20190003113, all of which are incorporated herein in their
entireties.
In some embodiments, the article includes one or more substrates, the
substrates
including one or more of a fiber, a thread, a yarn, a fabric, a textile, a
cloth, or a hide. In
some embodiments, the fabric, textile, or cloth is woven or nonwoven. In some
embodiments, the fiber, thread, or yarn includes one or more of polyester,
recycled
polyester, Mylar, cotton, nylon, recycled nylon, polyester-polyurethane
copolymer,
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rayon, acetate, aramid (aromatic polyamide), acrylic, ingeo (polylactide),
lurex
(polyamide-polyester), olefin (polyethylene-polypropylene), and combinations
thereof In
some embodiments, the fiber, thread, or yarn includes one or more of alpaca
fiber, alpaca
fleece, alpaca wool, lama fiber, lama fleece, lama wool, cotton, cashmere,
sheep fiber,
sheep fleece, sheep wool, byssus, chiengora, qiviut, yak, rabbit, lambswool,
mohair wool,
camel hair, angora wool, silkworm silk, abaca fiber, coir fiber, flax fiber,
jute fiber,
kapok fiber, kenaf fiber, raffia fiber, bamboo fiber, hemp, modal fiber, pina,
ramie, sisal,
and soy protein fiber. In some embodiments, the fiber, thread, or yarn
includes one or
more of mineral wool, mineral cotton, man-made mineral fiber, fiberglass,
glass,
glasswool, stone wool, rock wool, slagwool, glass filaments, asbestos fibers,
and ceramic
fibers.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the SPF and/or
silk
based proteins or fragments are chemically modified with a precursor linker to
form a
silk-conjugate, and wherein in some embodiments the silk based proteins or
fragments
thereof are chemically linked to the fiber or yarn through the linker, wherein
the article is
a fabric, wherein the fabric exhibits an improved property, wherein the
improved
property is an accumulative one-way moisture transport index selected from the
group
consisting of greater than 40 %, greater than 60 %, greater than 80 %, greater
than 100 %,
greater than 120 %, greater than 140 %, greater than 160 %, and greater than
180%. In an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
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molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the fabric exhibits an improved property, wherein the improved
property is an
accumulative one way transport capability increase relative to uncoated fabric
selected
from the group consisting of 1.2 fold, 1.5 fold, 2.0 fold, 3.0 fold, 4.0 fold,
5.0 fold, and 10
fold. In an embodiment, the foregoing improved property is determined after a
period of
machine washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved property, or
any other
improved property described herein, is determined after a period of machine
washing
(e.g., by home laundering machine washing) cycles selected from the group
consisting of
0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9
cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the fabric exhibits an improved property, wherein the improved
property is an
overall moisture management capability selected from the group consisting of
greater
than 0.05, greater than 0.10, greater than 0.15, greater than 0.20, greater
than 0.25, greater
than 0.30, greater than 0.35, greater than 0.40, greater than 0.50, greater
than 0.60, greater
than 0.70, and greater than 0.80. In an embodiment, the foregoing improved
property is
determined after a period of machine washing cycles selected from the group
consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment, the
foregoing
improved property, or any other improved property described herein, is
determined after
a period of machine washing (e.g., by home laundering machine washing) cycles
selected
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from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles,
5 cycles, 6
cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13
cycles, 14 cycles,
15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles,
and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the fabric exhibits substantially no increase in microbial growth
after a
number of machine washing cycles selected from the group consisting of 5
cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or
any other improved property described herein, is determined after a period of
machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the fabric exhibits substantially no increase in microbial growth
after a number
of machine washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25
cycles, and 50 cycles, and wherein the microbial growth is microbial growth of
a microbe
selected from the group consisting of Staphylococcus aureus, Klebisiella
pneumoniae,
and combinations thereof. In an embodiment, the foregoing improved property,
or any
other improved property described herein, is determined after a period of
machine
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washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the fabric exhibits substantially no increase in microbial growth
after a number
of machine washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25
cycles, and 50 cycles, and wherein the microbial growth is microbial growth of
a microbe
selected from the group consisting of Staphylococcus aureus, Klebisiella
pneumoniae,
and combinations thereof
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the fabric exhibits substantially no increase in microbial growth
after a number
of machine washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25
cycles, and 50 cycles, wherein the microbial growth is microbial growth of a
microbe
selected from the group consisting of Staphylococcus aureus, Klebisiella
pneumoniae,
and combinations thereof, wherein the microbial growth is reduced by a
percentage
selected from the group consisting of 50%, 100%, 500%, 1000%, 2000%, and 3000%
compared to an uncoated fabric.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the coating is applied to the fabric at the fiber level prior to
forming the
fabric.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the coating is applied to the fabric at the fabric level or
garment level (e.g.,
after manufacture of a garment from fabrics, leathers, and/or other
materials).
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level or garment
level, and
wherein the fabric is bath coated.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level or garment
level, and
wherein the fabric is spray coated.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level or garment
level, and
wherein the fabric is coated with a stencil.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level or garment
level, and
wherein the coating is applied to at least one side of the fabric using a
method selected
from the group consisting of a bath coating process, a spray coating process,
a stencil
(i.e., screen) process, a silk-foam based process, a roller-based process, a
magnetic roller
process, a knife process, a transfer process, a foam process, a lacquering
process, and a
printing process.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level, and wherein
the coating is
applied to both sides of the fabric using a method selected from the group
consisting of a
bath coating process, a spray coating process, a stencil (i.e., screen)
process, a silk-foam
based process, a roller-based process, a magnetic roller process, a knife
process, a
transfer process, a foam process, a lacquering process, and a printing
process.
In any of the foregoing embodiment, the coating may be applied at the fabric
garment level by any of the methods disclosed herein to recondition fabrics or
garments.
For example, such reconditioning using a coating comprising silk based
proteins or
fragments thereof may be performed as part of washing or cleaning a fabric or
garment.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, and wherein the
coating has a
thickness of about one nanolayer.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, and wherein the
coating has a
thickness selected from the group consisting of about 5 nm, about 10 nm, about
15 nm,
about 20 nm, about 25 nm, about 50 nm, about 100 nm, about 200 nm, about 500
nm,
about 1 m, about 5 m, about 10 m, and about 20 m.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the coating is adsorbed on the fabric.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the coating is attached to the fabric through chemical, enzymatic,
thermal, or
irradiative cross-linking.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level, and wherein
the hand of the
coated fabric is improved relative to an uncoated fabric.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
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and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level, and wherein
the hand of the
coated fabric is improved relative to an uncoated fabric, wherein the hand of
the coated
fabric that is improved is selected from the group consisting of softness,
crispness,
dryness, silkiness, and combinations thereof.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is applied to the fabric at the fabric level, and wherein
the pilling of
the fabric is improved relative to an uncoated fabric.
In an embodiment, the silk coating is applied using a bath process, a screen
(or
stencil) process, a spray process, a silk-foam based process, a roller based
process, a
tenter frame process, or a pad-dry-cure process.
In an embodiment, a fiber or a yarn comprises a synthetic fiber or yarn,
including
polyester, recycled polyester, Mylar, cotton, nylon, recycled nylon, polyester-
polyurethane copolymer, rayon, acetate, aramid (aromatic polyamide), acrylic,
ingeo
(polylactide), lurex (polyamide-polyester), olefin (polyethylene-
polypropylene), and
combinations thereof
In an embodiment, a fiber or a yarn comprises a natural fiber or yarn (e.g.,
from
animal or plant sources), including alpaca fiber, alpaca fleece, alpaca wool,
lama fiber,
lama fleece, lama wool, cotton, cashmere and sheep fiber, sheep fleece, sheep
wool,
byssus, chiengora, qiviut, yak, rabbit, lambswool, mohair wool, camel hair,
angora wool,
silkworm silk, abaca fiber, coir fiber, flax fiber, jute fiber, kapok fiber,
kenaf fiber, raffia
fiber, bamboo fiber, hemp, modal fiber, pina, ramie, sisal, and soy protein
fiber.
In an embodiment, a fiber or a yarn comprises a mineral fiber, also known as
mineral wool, mineral cotton, or man-made mineral fiber, including fiberglass,
glass,
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glasswool, stone wool, rock wool, slagwool, glass filaments, asbestos fibers,
and ceramic
fibers.
In an embodiment, a water-soluble silk coating may be used as an adhesive or
binder for binding particles to fabrics or for binding fabrics, wherein the
silk based
proteins or fragments in the water-soluble silk coating are chemically
modified with a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
based proteins or fragments thereof are chemically linked to the fiber or yarn
through the
linker. In an embodiment, an article comprises a fabric bound to another
fabric using a
silk coating. In an embodiment, an article comprises a fabric with particles
bound to the
fabric using a silk adhesive.
In an embodiment, the coating is applied to an article including a fabric at
the
yarn level. In an embodiment, the coating is applied at the fabric level. In
an
embodiment, the coating has a thickness selected from the group consisting of
about 5
nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 50 nm, about 100
nm,
about 200 nm, about 500 nm, about 1 m, about 5 m, about 10 m, and about 20
m. In
an embodiment, the coating has a thickness range selected from the group
consisting of
about 5 nm to about 100 nm, about 100 nm to about 200 nm, about 200 nm to
about 500
nm, about 1 p.m to about 2 m, about 2 p.m to about 5 m, about 5 p.m to about
10 m,
and about 10 p.m to about 20 m.
In an embodiment, a fiber or a yarn is treated with a polymer, such as
polyglycolide (PGA), polyethylene glycols, copolymers of glycolide,
glycolide/L-lactide
copolymers (PGA/PLLA), glycolide/trimethylene carbonate copolymers (PGA/TMC),
polylactides (PLA), stereocopolymers of PLA, poly-L-lactide (PLLA), poly-DL-
lactide
(PDLLA), L-lactide/DL-lactide copolymers, co-polymers of PLA,
lactide/tetramethylglycolide copolymers, lactide/trimethylene carbonate
copolymers,
lactide/6-valerolactone copolymers, lactide/c-caprolactone copolymers,
polydepsipeptides, PLA/polyethylene oxide copolymers, unsymmetrically 3,6-
substituted
poly-1,4-dioxane-2,5-diones, poly-P-hydroxybutyrate (PHBA), PHBA/P-
hydroxyvalerate
copolymers (PHBA/HVA), poly-P-hydroxypropionate (PHPA), poly-p-dioxanone (PD
S),
poly-6-valerolactone, poly-c-caprolactone, methylmethacrylate-N-vinyl
pyrrolidine
copolymers, polyesteramides, polyesters of oxalic acid, polydihydropyrans,
polyalky1-2-
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cyanoacrylates, polyurethanes (PU), polyvinylalcohols (PVA), polypeptides,
poly-0-
malic acid (PMLA), poly-P-alkanoic acids, polyvinylalcohol (PVA),
polyethyleneoxide
(PEO), chitine polymers, polyethylene, polypropylene, polyasetal, polyamides,
polyesters, recycled polyesters, polysulphone, polyether ether ketone,
polyethylene
terephthalate, polycarbonate, polyaryl ether ketone, and polyether ketone
ketone.
In an embodiment, the silk coating surface can be modified silk crystals that
range
in size from nm to m.
The criterion for "visibility" is satisfied by any one of the following: a
change in
the surface character of the textile; the silk coating fills the interstices
where the yarns
intersect; or the silk coating blurs or obscures the weave.
In an embodiment, a SPF as defined herein, for example, and without
limitation,
silk based protein or fragment solution may be utilized to coat at least a
portion of a
fabric which can be used to create a textile. In an embodiment, a silk based
protein or
fragment solution may be weaved into yarn that can be used as a fabric in a
textile. In an
embodiment, a silk based protein or fragment solution may be used to coat a
fiber. In an
embodiment, the disclosure provides an article comprising a silk based protein
or
fragment solution coating at least a portion of a fabric or a textile. In an
embodiment, the
disclosure provides an article comprising a silk based protein or fragment
solution
coating a yarn. In an embodiment, the disclosure provides an article
comprising a silk
based protein or fragment solution coating a fiber, wherein the silk based
proteins or
fragments are chemically modified with a precursor linker to form a silk-
conjugate, and
wherein in some embodiments the silk based proteins or fragments thereof are
chemically
linked to the fiber or yarn through the linker.
There is disclosed a textile that is at least partially surface treated with
an aqueous
solution of SPF as defined herein, for example, and without limitation, silk
fibroin-based
protein fragments of the present disclosure so as to result in a silk coating
on the textile,
wherein the silk based proteins or fragments are chemically modified with a
precursor
linker to form a silk-conjugate, and wherein in some embodiments the silk
based proteins
or fragments thereof are chemically linked to the fiber or yarn through the
linker. In an
embodiment, the silk coating of the present disclosure is available in a spray
can and can
be sprayed on any textile by a consumer. In an embodiment, a textile
comprising a silk
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coating of the present disclosure is sold to a consumer. In an embodiment, a
textile of the
present disclosure is used in constructing action sportswear/apparel. In an
embodiment, a
silk coating of the present disclosure is positioned on the underlining of
apparel. In an
embodiment, a silk coating of the present disclosure is positioned on the
shell, the lining,
or the interlining of apparel. In an embodiment, apparel is partially made
from a silk
coated textile of the present disclosure and partially made from an uncoated
textile. In an
embodiment, apparel partially made from a silk coated textile and partially
made from an
uncoated textile combines an uncoated inert synthetic material with a silk
coated inert
synthetic material. Examples of inert synthetic material include, but are not
limited to,
polyester, recycled polyester, polyamide, polyaramid, polytetrafluoroethylene,
polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane
and
polyethyleneglycol, ultrahigh molecular weight polyethylene, high-performance
polyethylene, and mixtures thereof. In an embodiment, apparel partially made
from a silk
coated textile and partially made from an uncoated textile combines an
elastomeric
material at least partially covered with a silk coating of the present
disclosure. In an
embodiment, the percentage of silk to elastomeric material can be varied to
achieve
desired shrink or wrinkle resistant properties.
In an embodiment, a silk coating of the present disclosure is visible. In an
embodiment, a silk coating of the present disclosure positioned on apparel
helps control
skin temperature. In an embodiment, a silk coating of the present disclosure
positioned on
apparel helps control fluid transfer away from the skin. In an embodiment, a
silk coating
of the present disclosure positioned on apparel has a soft feel against the
skin decreasing
abrasions from fabric on skin. In an embodiment, a silk coating of the present
disclosure
positioned on a textile has properties that confer at least one of wrinkle
resistance,
shrinkage resistance, or machine washability to the textile. In an embodiment,
a silk
coated textile of the present disclosure is 100% machine washable and dry
cleanable. In
an embodiment, a silk coated textile of the present disclosure is 100%
waterproof. In an
embodiment, a silk coated textile of the present disclosure is wrinkle
resistant. In an
embodiment, a silk coated textile of the present disclosure is shrink
resistant. In an
embodiment, a silk coated textile of the present disclosure has the qualities
of being
waterproof, breathable, and elastic and possess a number of other qualities
which are
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highly desirable in action sportswear. in an embodiment, a silk coated textile
of the
present disclosure manufactured from a silk fabric of the present disclosure
further
includes LYCRA brand spandex fibers.
In an embodiment, a textile at least partially coated with an aqueous solution
of
SPF as defined herein, for example, and without limitation, silk fibroin-based
protein
fragments of the present disclosure is a breathable fabric. In an embodiment,
a textile at
least partially coated with an aqueous solution of SPF as defined herein, for
example, and
without limitation, silk fibroin-based protein fragments of the present
disclosure is a
water-resistant fabric. In an embodiment, a textile at least partially coated
with an
aqueous solution of SPF as defined herein, for example, and without
limitation, silk
fibroin-based protein fragments of the present disclosure is a shrink-
resistant fabric. In an
embodiment, a textile at least partially coated with an aqueous solution of
SPF as defined
herein, for example, and without limitation, silk fibroin-based protein
fragments of the
present disclosure is a machine-washable fabric. In an embodiment, a textile
at least
partially coated with an aqueous solution of SPF as defined herein, for
example, and
without limitation, silk fibroin-based protein fragments of the present
disclosure is a
wrinkle resistant fabric. In an embodiment, textile at least partially coated
with an
aqueous solution of SPF as defined herein, for example, and without
limitation, silk
fibroin-based protein fragments of the present disclosure provides moisture
and vitamins
to the skin.
In an embodiment, an aqueous solution of SPF as defined herein, for example,
and without limitation, silk fibroin-based protein fragments of the present
disclosure is
used to coat a textile or leather, wherein the silk based proteins or
fragments are
chemically modified with a precursor linker to form a silk-conjugate. In an
embodiment,
the concentration of silk in the solution ranges from about 0.1% to about
20.0%. In an
embodiment, the concentration of silk in the solution ranges from about 0.1%
to about
15.0%. In an embodiment, the concentration of silk in the solution ranges from
about
0.5% to about 10.0%. In an embodiment, the concentration of silk in the
solution ranges
from about 1.0% to about 5.0%. In an embodiment, an aqueous solution of pure
silk
fibroin-based protein fragments of the present disclosure is applied directly
to a fabric.
Alternatively, silk microsphere and any additives may be used for coating a
fabric. In an
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embodiment, additives can be added to an aqueous solution of pure silk fibroin-
based
protein fragments of the present disclosure before coating (e.g., alcohols) to
further
enhance material properties. In an embodiment, a silk coating of the present
disclosure
can have a pattern to optimize properties of the silk on the fabric. In an
embodiment, a
coating is applied to a fabric under tension and/or lax to vary penetration in
to the fabric.
In an embodiment, a silk coating of the present disclosure can be applied at
the
yarn level, followed by creation of a fabric once the yarn is coated. In an
embodiment, an
aqueous solution of pure silk fibroin-based protein fragments of the present
disclosure
can be spun into fibers to make a silk fabric and/or silk fabric blend with
other materials
known in the apparel industry.
Uses of Textiles and Leathers Coated with Silk Fibroin-Based Protein Fragments
in
Apparel and Garment Applications
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
exhibits an
improved color retention property. Without being bound by any specific theory,
it is
postulated that the coating prevents the article from color degradation by
separating the
fiber or yarn from air or from detergents during washing.
Methods of testing the color retention property of an article are well within
the
knowledge of one skilled in the art. A specific method of testing of the color
retention
property of a fabric is described in U.S. Patent No. 5,142,292, which is
incorporated
herein by reference in its entirety.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
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and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits an improved color retention property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article exhibits an
improved
color retention property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article exhibits an improved color retention
property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article exhibits an improved
color
retention property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article exhibits an improved color retention property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article exhibits an
improved
color retention property.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article
exhibits an improved color retention property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article exhibits
an
improved color retention property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
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wherein the article exhibits an improved color retention property. In an
embodiment, the
foregoing color retention property of the fabric is determined after a period
of machine
washing cycles selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and
50 cycles. In an embodiment, the foregoing improved property, or any other
improved
property described herein, is determined after a period of machine washing
(e.g., by
home laundering machine washing) cycles selected from the group consisting of
0 cycles,
1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles,
9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30
cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits an
improved color retention property. In an embodiment, the foregoing improved
color
retention property of the textile is determined after a period of machine
washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is resistant to
microbial (including bacterial and fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is resistant to microbial (including bacterial and fungal)
growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is resistant
to
microbial (including bacterial and fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is resistant to microbial (including
bacterial and
fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
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chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is resistant to
microbial (including
bacterial and fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is resistant to microbial (including bacterial and fungal)
growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
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or fragments comprise silk and a copolymer, wherein the article is resistant
to microbial
(including bacterial and fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is
resistant to microbial (including bacterial and fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article is
resistant to
microbial (including bacterial and fungal) growth.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
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and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is resistant to microbial (including bacterial and fungal)
growth. In an
embodiment, the foregoing resistant to microbial (including bacterial and
fungal) growth
property of the fabric is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
resistant
to microbial (including bacterial and fungal) growth property. In an
embodiment, the
foregoing resistant to microbial (including bacterial and fungal) growth
property of the
textile is determined after a period of machine washing cycles selected from
the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is resistant to
the buildup of static electrical charge.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is resistant to the buildup of static electrical charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is resistant
to the
buildup of static electrical charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is resistant to the buildup of
static electrical
charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
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without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is resistant to the
buildup of static
electrical charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is resistant to the buildup of static electrical charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
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molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article is resistant
to the buildup
of static electrical charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is
resistant to the buildup of static electrical charge.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article is
resistant to the
buildup of static electrical charge.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is resistant to the buildup of static electrical charge.
In an
embodiment, the foregoing resistant to the buildup of static electrical charge
property of
the fabric is determined after a period of machine washing cycles selected
from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
resistant
to the buildup of static electrical charge property. In an embodiment, the
foregoing
resistant to the buildup of static electrical charge property of the textile
is determined
after a period of machine washing cycles selected from the group consisting of
5 cycles,
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property,
or any other improved property described herein, is determined after a period
of machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is mildew
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
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without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is mildew resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is mildew
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is mildew resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
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chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is mildew resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is mildew resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article is mildew
resistant.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is
mildew resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article is
mildew
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
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wherein the article is mildew resistant. In an embodiment, the foregoing
mildew resistant
property of the fabric is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
mildew
resistant property. In an embodiment, the foregoing mildew resistant property
of the
textile is determined after a period of machine washing cycles selected from
the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the coating
is
transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the coating
is
transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the coating is
transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the coating is transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the coating is transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the coating is transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the coating is
transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
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without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
coating is
transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the coating is
transparent.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating is transparent. In an embodiment, the foregoing
transparent property
of the coating is determined after a period of machine washing cycles selected
from the
group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the
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foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather comprises a silk coating of the present
disclosure, wherein the silk coating is transparent. In an embodiment, the
foregoing
transparent property of the coating is determined after a period of machine
washing
cycles selected from the group consisting of 5 cycles, 10 cycles, 25 cycles,
and 50 cycles.
In an embodiment, the foregoing improved property, or any other improved
property
described herein, is determined after a period of machine washing (e.g., by
home
laundering machine washing) cycles selected from the group consisting of 0
cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9
cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30
cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is resistant to
freeze-thaw cycle damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
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chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is resistant to freeze-thaw cycle damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is resistant
to freeze-
thaw cycle damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is resistant to freeze-thaw cycle
damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
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combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is resistant to freeze-
thaw cycle
damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is resistant to freeze-thaw cycle damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article is resistant
to freeze-
thaw cycle damage.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is
resistant to freeze-thaw cycle damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article is
resistant to
freeze-thaw cycle damage.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
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wherein the article is resistant to freeze-thaw cycle damage. In an
embodiment, the
foregoing resistant to freeze-thaw cycle damage property of the fabric is
determined after
a period of machine washing cycles selected from the group consisting of 5
cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or
any other improved property described herein, is determined after a period of
machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
resistant
to freeze-thaw cycle damage. In an embodiment, the foregoing resistant to
freeze-thaw
cycle damage property of the textile is determined after a period of machine
washing
cycles selected from the group consisting of 5 cycles, 10 cycles, 25 cycles,
and 50 cycles.
In an embodiment, the foregoing improved property, or any other improved
property
described herein, is determined after a period of machine washing (e.g., by
home
laundering machine washing) cycles selected from the group consisting of 0
cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9
cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30
cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the coating
provides
protection from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
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chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating provides protection from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the coating provides
protection
from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the coating provides protection from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
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combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the coating provides protection
from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the coating provides protection from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the coating provides
protection
from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
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without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
coating
provides protection from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the coating provides
protection from abrasion.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the coating provides protection from abrasion. In an embodiment, the
foregoing
abrasion resistant property of the fabric is determined after a period of
machine washing
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cycles selected from the group consisting of 5 cycles, 10 cycles, 25 cycles,
and 50 cycles.
In an embodiment, the foregoing improved property, or any other improved
property
described herein, is determined after a period of machine washing (e.g., by
home
laundering machine washing) cycles selected from the group consisting of 0
cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9
cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30
cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
abrasion
resistant. In an embodiment, the foregoing abrasion resistant property of the
textile is
determined after a period of machine washing cycles selected from the group
consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment, the
foregoing
improved property, or any other improved property described herein, is
determined after
a period of machine washing (e.g., by home laundering machine washing) cycles
selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles,
5 cycles, 6
cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13
cycles, 14 cycles,
15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles,
and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
exhibits the
property of blocking ultraviolet (UV) radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
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chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits the property of blocking ultraviolet (UV)
radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article exhibits the
property
of blocking ultraviolet (UV) radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article exhibits the property of blocking
ultraviolet
(UV) radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article exhibits the property
of blocking
ultraviolet (UV) radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article exhibits the property of blocking ultraviolet (UV)
radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article exhibits the
property of
blocking ultraviolet (UV) radiation.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article
exhibits the property of blocking ultraviolet (UV) radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article exhibits
the
property of blocking ultraviolet (UV) radiation.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
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wherein the article exhibits the property of blocking ultraviolet (UV)
radiation. In an
embodiment, the foregoing UV blocking property of the fabric is determined
after a
period of machine washing cycles selected from the group consisting of 5
cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or
any other improved property described herein, is determined after a period of
machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits UV
blocking property. In an embodiment, the foregoing UV blocking property of the
textile
is determined after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the garment
regulates
the body temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the garment regulates the body temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the garment regulates
the body
temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the garment regulates the body temperature of a
wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
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or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the garment regulates the body
temperature of
a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the garment regulates the body temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
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or fragments comprise silk and a copolymer, wherein the garment regulates the
body
temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
garment
regulates the body temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the garment
regulates the
body temperature of a wearer.
In an embodiment, the disclosure provides a garment comprising a fiber or yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
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and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the garment regulates the body temperature of a wearer. In an
embodiment, the
foregoing temperature regulation property of the fabric is determined after a
period of
machine washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved property, or
any other
improved property described herein, is determined after a period of machine
washing
(e.g., by home laundering machine washing) cycles selected from the group
consisting of
0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9
cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits a
temperature regulation property. In an embodiment, the foregoing temperature
regulation
property of the textile is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, and wherein the
article is tear
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
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without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the article is tear resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, and wherein the article is tear
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, and wherein the article is tear resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
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chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, and wherein the article is tear resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
and wherein the article is tear resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, and wherein the article is tear
resistant.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, and wherein the
article is
tear resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, and wherein the article is
tear
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
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and wherein the article is tear resistant. In an embodiment, the foregoing
tear resistant
property of the fabric is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits a
tear
resistant property. In an embodiment, the foregoing tear resistant property of
the textile is
determined after a period of machine washing cycles selected from the group
consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment, the
foregoing
improved property, or any other improved property described herein, is
determined after
a period of machine washing (e.g., by home laundering machine washing) cycles
selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles,
5 cycles, 6
cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13
cycles, 14 cycles,
15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles,
and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the
elasticity of the
article is improved.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
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and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the
elasticity of the
article is reduced.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the elasticity of the
article is
improved.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the elasticity of the
article is
reduced.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
exhibits a
rebound dampening property. Without being bound by any specific theory, it is
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postulated that the coating prevents the article from returning to the
original shape or
orientation, and results in the rebound dampening property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits a rebound dampening property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article exhibits a
rebound
dampening property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article exhibits a rebound dampening
property.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article exhibits a rebound
dampening
property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article exhibits a rebound dampening property.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article exhibits a
rebound
dampening property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article
exhibits a rebound dampening property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
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polyurethane copolymer, and combinations thereof, wherein the article exhibits
a rebound
dampening property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits a rebound dampening property. In an embodiment,
the
foregoing rebound dampening property of the fabric is determined after a
period of
machine washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved property, or
any other
improved property described herein, is determined after a period of machine
washing
(e.g., by home laundering machine washing) cycles selected from the group
consisting of
0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9
cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits a
rebound
dampening property. In an embodiment, the foregoing rebound dampening property
of
the textile is determined after a period of machine washing cycles selected
from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
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molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
exhibits an
anti-itch property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits an anti-itch property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article exhibits an
anti-itch
property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article exhibits an anti-itch property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article exhibits an anti-itch
property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article exhibits an anti-itch property.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article exhibits an
anti-itch
property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article
exhibits an anti-itch property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
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polyurethane copolymer, and combinations thereof, wherein the article exhibits
an anti-
itch property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits an anti-itch property. In an embodiment, the
foregoing anti-
itch property of the fabric is determined after a period of machine washing
cycles
selected from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits an
anti-
itch property. In an embodiment, the foregoing anti-itch property of the
textile is
determined after a period of machine washing cycles selected from the group
consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment, the
foregoing
improved property, or any other improved property described herein, is
determined after
a period of machine washing (e.g., by home laundering machine washing) cycles
selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles,
5 cycles, 6
cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13
cycles, 14 cycles,
15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles,
and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
exhibits an
improved insulation/warmth property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits an improved insulation/warmth property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article exhibits an
improved
insulation/warmth property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
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combinations thereof, wherein the article exhibits an improved
insulation/warmth
property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article exhibits an improved
insulation/warmth property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
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proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article exhibits an improved insulation/warmth property.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article exhibits an improved insulation/warmth property. In an
embodiment,
the foregoing improved insulation/warmth property of the fabric is determined
after a
period of machine washing cycles selected from the group consisting of 5
cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or
any other improved property described herein, is determined after a period of
machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
improved
an insulation/warmth property. In an embodiment, the foregoing improved
insulation/warmth property of the textile is determined after a period of
machine washing
cycles selected from the group consisting of 5 cycles, 10 cycles, 25 cycles,
and 50 cycles.
In an embodiment, the foregoing improved property, or any other improved
property
described herein, is determined after a period of machine washing (e.g., by
home
laundering machine washing) cycles selected from the group consisting of 0
cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9
cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30
cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
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molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is wrinkle
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is wrinkle resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is wrinkle
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is wrinkle resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is wrinkle resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is wrinkle resistant.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article is wrinkle
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is
wrinkle resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
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polyurethane copolymer, and combinations thereof, wherein the article is
wrinkle
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is wrinkle resistant. In an embodiment, the foregoing
wrinkle resistant
property of the fabric is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
wrinkle
resistant property. In an embodiment, the foregoing wrinkle resistant property
of the
textile is determined after a period of machine washing cycles selected from
the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
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molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is stain
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is stain resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is stain
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is stain resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is stain resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is stain resistant.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article is stain
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is stain
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article is stain
resistant.
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In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is stain resistant. In an embodiment, the foregoing stain
resistant
property of the fabric is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
stain
resistant property. In an embodiment, the foregoing stain resistant property
of the textile
is determined after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
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and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is sticky.
Without being bound to any specific theory, it is postulated that the coating
provides
stickiness and maintains stickiness.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is sticky.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is sticky.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is sticky. In an embodiment, the foregoing sticky property
of the
fabric is determined after a period of machine washing cycles selected from
the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the
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foregoing improved property, or any other improved property described herein,
is
determined after a period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1 cycle, 2
cycles, 3
cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles,
11 cycles, 12
cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35
cycles, 40
cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure exhibits
sticky
property. In an embodiment, the foregoing sticky property of the textile is
determined
after a period of machine washing cycles selected from the group consisting of
5 cycles,
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property,
or any other improved property described herein, is determined after a period
of machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides an article comprising a textile or
leather coated with silk fibroin-based proteins or fragments thereof, wherein
the silk
based proteins or fragments are chemically modified with a precursor linker to
form a
silk-conjugate, and wherein in some embodiments the silk based proteins or
fragments
thereof are chemically linked to the fiber or yarn through the linker, wherein
the article
exhibits improved flame resistance relative to an uncoated textile. In an
embodiment, the
disclosure provides an article comprising a textile or leather coated with
silk fibroin-
based proteins or fragments thereof, wherein the silk based proteins or
fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk based proteins or fragments thereof are chemically
linked to
the fiber or yarn through the linker, wherein the article exhibits equal flame
resistance
relative to an uncoated textile or leather. In an embodiment, the disclosure
provides an
article comprising a textile or leather coated with silk fibroin-based
proteins or fragments
thereof, wherein the silk based proteins or fragments are chemically modified
with a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
based proteins or fragments thereof are chemically linked to the fiber or yarn
through the
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linker, wherein the article exhibits equal flame resistance relative to an
uncoated textile or
leather, wherein an alternative textile or leather coating exhibits reduced
flame resistance.
In an embodiment, the disclosure provides an article comprising a textile or
leather
coated with silk fibroin-based proteins or fragments thereof, wherein the silk
based
proteins or fragments are chemically modified with a precursor linker to form
a silk-
conjugate, and wherein in some embodiments the silk based proteins or
fragments thereof
are chemically linked to the fiber or yarn through the linker, wherein the
article exhibits
improved resistance to fire relative to an uncoated textile or leather,
wherein the
improved resistance to fire is determined by a flammability test. In an
embodiment, the
flammability test measures afterflame time, afterglow time, char length, and
the
observation of fabric melting or dripping.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is flame
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the article is flame resistant.
In an embodiment, the disclosure provides an article comprising a polyester
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
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or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is flame
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof comprise silk fibroin-based proteins or protein fragments
having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article is flame
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the article is flame resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
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or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the article is flame resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments thereof are selected from the group consisting of natural silk
based proteins
or fragments thereof, recombinant silk based proteins or fragments thereof,
and
combinations thereof, wherein the silk based proteins or fragments thereof are
natural silk
based proteins or fragments thereof that are selected from the group
consisting of spider
silk based proteins or fragments thereof, silkworm silk based proteins or
fragments
thereof, and combinations thereof, wherein the natural silk based proteins or
fragments
are silkworm silk based proteins or fragments thereof, and the silkworm silk
based
proteins or fragments thereof is Bombyx mori silk based proteins or fragments
thereof,
wherein the article is flame resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the silk
based proteins
or fragments comprise silk and a copolymer, wherein the article is flame
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
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without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or yarn
selected from the
group consisting of cotton, alpaca fleece, alpaca wool, lama fleece, lama
wool, cotton,
cashmere, sheep fleece, sheep wool, and combinations thereof, wherein the
article is
flame resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the fiber
or yarn is
selected from the group consisting of natural fiber or yarn, synthetic fiber
or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber or yarn
selected from
the group consisting of polyester, recycled polyester, nylon, recycled nylon,
polyester-
polyurethane copolymer, and combinations thereof, wherein the article is flame
resistant.
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
wherein the fabric is flame resistant. In an embodiment, the foregoing flame
resistant
property of the fabric is determined after a period of machine washing cycles
selected
from the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In
an
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embodiment, the foregoing improved property, or any other improved property
described
herein, is determined after a period of machine washing (e.g., by home
laundering
machine washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2
cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles,
10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30
cycles, 35
cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, a textile or leather of the present disclosure is flame
resistant.
In an embodiment, the foregoing flame resistant property of the textile is
determined after
a period of machine washing cycles selected from the group consisting of 5
cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or
any other improved property described herein, is determined after a period of
machine
washing (e.g., by home laundering machine washing) cycles selected from the
group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6
cycles, 7 cycles, 8
cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15
cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles.
In an embodiment, the disclosure provides a leather coated with coating,
wherein
the coating comprises SPF as defined herein, for example, and without
limitation, silk
based proteins or fragments thereof having a weight average molecular weight
range of
about 5 kDa to about 144 kDa, wherein the silk based proteins or fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk based proteins or fragments thereof are chemically
linked to
the fiber or yarn through the linker, wherein the leather exhibits an property
selected from
the group consisting of an improved color retention property, improved mildew
resistance, improved resistance to freeze-thaw cycle damage, improved
resistance to
abrasion, improved blocking of ultraviolet (UV) radiation, improved regulation
of the
body temperature of a wearer, improved tear resistance, improved elasticity,
improved
rebound dampening, improved anti-itch properties, improved insulation,
improved
wrinkle resistance, improved stain resistance, and improved stickiness. In an
embodiment, the disclosure provides a leather coated with coating, wherein the
coating
comprises SPF as defined herein, for example, and without limitation, silk
based proteins
or fragments thereof having a weight average molecular weight range of about 5
kDa to
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about 144 kDa, wherein the silk based proteins or fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk based proteins or fragments thereof are chemically linked to the fiber or
yarn through
the linker, wherein the coating is transparent.
In any of the foregoing embodiments, at least one property of the article is
improved, wherein the property that is improved is selected from the group
consisting of
color retention, resistance to microbial growth, resistance to bacterial
growth, resistance
to fungal growth, resistance to the buildup of static electrical charge,
resistance to the
growth of mildew, transparency of the coating, resistance to freeze-thaw cycle
damage,
resistance from abrasion, blocking of ultraviolet (UV) radiation, regulation
of the body
temperature of a wearer, resistance to tearing, elasticity of the article,
rebound
dampening, tendency to cause itching in the wearer, thermal insulation of the
wearer,
wrinkle resistance, stain resistance, stickiness to skin, and flame
resistance, and wherein
the property is improved by an amount relative to an uncoated article selected
from the
group consisting of at least 5%, at least 10%, at least 15%, at least 20%, at
least 25%, at
least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least
55%, at least
60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at
least 90%, at
least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at
least 300%, at
least 400%, and at least 500%.
In any of the foregoing embodiments, the silk based proteins or protein
fragments
thereof have an average weight average molecular weight range selected from
the group
consisting of about 5 to about 10 kDa, about 6 kDa to about 16 kDa, about 17
kDa to
about 38 kDa, about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and
about 80
kDa to about 144 kDa, wherein the silk based proteins or fragments thereof
have a
polydispersity of between about 1.5 and about 3.0, wherein the silk based
proteins or
fragments are chemically modified with a precursor linker to form a silk-
conjugate, and
wherein in some embodiments the silk based proteins or fragments thereof are
chemically
linked to a fiber or yarn through the linker, and optionally wherein the
proteins or protein
fragments, prior to coating the fabric, do not spontaneously or gradually
gelate and do not
visibly change in color or turbidity when in a solution for at least 10 days.
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Additional Agents for Use with Textiles Coated with Silk Fibroin-Based Protein
Fragments
In an embodiment, the disclosure provides an article comprising a fiber or
yarn
having a coating, wherein the coating comprises SPF as defined herein, for
example, and
without limitation, silk based proteins or fragments thereof having a weight
average
molecular weight range of about 5 kDa to about 144 kDa, wherein the silk based
proteins
or fragments are chemically modified with a precursor linker to form a silk-
conjugate,
and wherein in some embodiments the silk based proteins or fragments thereof
are
chemically linked to the fiber or yarn through the linker, wherein the article
is a fabric,
and wherein the fabric is pretreated with various additional agents.
Additional agents are
described in U.S. Patent Application Publications Nos. 20160222579,
20160281294, and
20190003113, all of which are incorporated herein in their entireties.
Other Materials Coated with Silk Fibroin-Based Protein Fragments
In an embodiment, the disclosure provides a material coated with silk fibroin-
based proteins or fragments thereof The material may be any material suitable
for
coating, including plastics (e.g., vinyl), foams (e.g., for use in padding and
cushioning),
and various natural or synthetic products.
In an embodiment, the disclosure provides an automobile component coated with
silk fibroin-based proteins or fragments thereof having a weight average
molecular
weight range of about 5 kDa to about 144 kDa, wherein the silk based proteins
or
fragments are chemically modified with a precursor linker to form a silk-
conjugate, and
wherein in some embodiments the silk based proteins or fragments thereof are
chemically
linked to the component through the linker,. In an embodiment, the disclosure
provides
an automobile component coated with silk fibroin-based proteins or fragments
thereof
having a weight average molecular weight range selected from the group
consisting of
about 5 to about 10 kDa, about 6 kDa to about 16 kDa, about 17 kDa to about 38
kDa,
about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and about 80 kDa to
about
144 kDa, wherein the silk based proteins or fragments thereof have a
polydispersity of
between about 1.5 and about 3.0, wherein the silk based proteins or fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk based proteins or fragments thereof are chemically
linked to
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the component through the linker, and optionally wherein the proteins or
protein
fragments, prior to coating the fabric, do not spontaneously or gradually
gelate and do not
visibly change in color or turbidity when in a solution for at least 10 days.
In an
embodiment, the disclosure provides an automobile component coated with silk
fibroin-
based proteins or fragments thereof, wherein the silk based proteins or
fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk based proteins or fragments thereof are chemically
linked to
the component through the linker, wherein the automobile component exhibits an
improved property relative to an uncoated automobile component. In an
embodiment, the
disclosure provides an automobile component coated with silk fibroin-based
proteins or
fragments thereof, wherein the silk based proteins or fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk based proteins or fragments thereof are chemically linked to the
component through
the linker, wherein the automobile component exhibits an improved property
relative to
an uncoated automobile component, and wherein the automobile component is
selected
from the group consisting of an upholstery fabric, a headliner, a seat, a
headrest, a
transmission control, a floor mat, a carpet fabric, a dashboard, a steering
wheel, a trim, a
wiring harness, an airbag cover, an airbag, a sunvisor, a seat belt, a
headrest, an armrest,
and a children's car seat. In an embodiment, the disclosure provides an
electrical
component insulated with a coating comprising silk fibroin-based proteins or
fragments
thereof, wherein the silk based proteins or fragments are chemically modified
with a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
based proteins or fragments thereof are chemically linked to the component
through the
linker,.
In an embodiment, the disclosure provides a foam coated with silk fibroin-
based
proteins or fragments thereof having a weight average molecular weight range
of about 5
kDa to about 144 kDa, wherein the silk based proteins or fragments are
chemically
modified with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk based proteins or fragments thereof are chemically linked
to the
foam through the linker. In an embodiment, the disclosure provides a foam
coated with
silk fibroin-based proteins or fragments thereof having a weight average
molecular
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weight range selected from the group consisting of about 5 to about 10 kDa,
about 6 kDa
to about 16 kDa, about 17 kDa to about 38 kDa, about 39 kDa to about 80 kDa,
about 60
to about 100 kDa, and about 80 kDa to about 144 kDa, wherein the silk based
proteins or
fragments thereof have a polydispersity of between about 1.5 and about 3.0,
wherein the
silk based proteins or fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk based proteins or
fragments
thereof are chemically linked to the foam through the linker, and optionally
wherein the
proteins or protein fragments, prior to coating the foam, do not spontaneously
or
gradually gelate and do not visibly change in color or turbidity when in a
solution for at
least 10 days. In an embodiment, the disclosure provides a foam coated with
silk fibroin-
based proteins or fragments thereof, wherein the silk based proteins or
fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk based proteins or fragments thereof are chemically
linked to
the foam through the linker, wherein the foam exhibits an improved property
relative to
an uncoated foam, and wherein the foam is selected from the group consisting
of a
polyurethane foam, an ethylene-vinyl acetate copolymer foam, a low density
polyethylene foam, a low density polyethylene foam, a high density
polyethylene foam, a
polypropylene copolymer foam, a linear low density polyethylene foam, a
natural rubber
foam, a latex foam, and combinations thereof.
In any of the foregoing embodiments, the material coating comprises SPF as
defined herein, for example, and without limitation, silk based proteins or
fragments
thereof having a weight average molecular weight range of about 5 kDa to about
144
kDa. In any of the foregoing embodiments, the material coating comprises SPF
as
defined herein, for example, and without limitation, silk based proteins or
fragments
thereof having a weight average molecular weight range of about 6 kDa to about
16 kDa.
In any of the foregoing embodiments, the material coating comprises SPF as
defined
herein, for example, and without limitation, silk based proteins or fragments
thereof
having a weight average molecular weight range of about 17 kDa to about 38
kDa. In any
of the foregoing embodiments, the material coating comprises SPF as defined
herein, for
example, and without limitation, silk based proteins or fragments thereof
having a weight
average molecular weight range of about 39 kDa to about 80 kDa. In any of the
foregoing
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embodiments, the silk based proteins or fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
based proteins or fragments thereof are chemically linked to a substrate
through the
linker.
In any of the foregoing embodiments, the silk based proteins or protein
fragments
thereof have an average weight average molecular weight range selected from
the group
consisting of about 5 to about 10 kDa, about 6 kDa to about 16 kDa, about 17
kDa to
about 38 kDa, about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and
about 80
kDa to about 144 kDa, wherein the silk based proteins or fragments thereof
have a
polydispersity of between about 1.5 and about 3.0, the silk based proteins or
fragments
are chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk based proteins or fragments thereof are chemically
linked to a
substrate through the linker, and wherein the proteins or protein fragments,
prior to
coating the fabric, do not spontaneously or gradually gelate and do not
visibly change in
color or turbidity when in a solution for at least 10 days.
Processes for Coating Textiles and Leathers with Silk Fibroin-Based Protein
Fragments
In an embodiment, a method for silk coating a textile, leather, or other
material
(such as a foam) includes immersion of the textile, leather, or other material
in any of the
aqueous solutions of pure silk fibroin-based protein fragments of the present
disclosure.
Such methods are described in U.S. Patent Application Publications Nos.
20160222579,
20160281294, and 20190003113, all of which are incorporated herein in their
entireties.
In some embodiments, the disclosure relates to such methods including the use
of
chemical modifiers and/or physical modifiers. In an embodiment, a method for
silk
coating a textile, leather, or other material (such as a foam) includes
chemically
modifying silk based proteins or fragments with a precursor linker to form a
silk-
conjugate, and optionally chemically linking the silk based proteins or
fragments thereof
to a substrate through the linker.
Additives for Silk Fibroin-Based Protein Fragments and Solutions Thereof
In an embodiment, a solution of the present disclosure is contacted with an
additive,
such as a therapeutic agent and/or an additive molecule. U.S. Patent
Application
Publications Nos. 20160222579, 20160281294, and 20190003113, all of which are
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incorporated herein in their entireties. The present disclosure relates in
particular to the use
of such solutions, therapeutic agents, and/or additive molecules in
conjunction with a
chemical modifier and/or physical modifier.
Processes for Production of Silk Fibroin-Based Protein Fragments and Solutions
Thereof
As used herein, the term "fibroin" includes silkworm fibroin and insect or
spider
silk protein. In an embodiment, fibroin is obtained from Bombyx mori. In an
embodiment,
the spider silk protein is selected from the group consisting of swathing silk
(Achniform
gland silk), egg sac silk (Cylindriform gland silk), egg case silk (Tubuliform
silk), non-
sticky dragline silk (Ampullate gland silk), attaching thread silk (Pyriform
gland silk),
sticky silk core fibers (Flagelliform gland silk), and sticky silk outer
fibers (Aggregate
gland silk). Methods of making silk fibroin or silk fibroin fragments are
known and are
described for example in U.S. Patents Nos. 9,187,538, 9,511,012, 9,517,191,
9,522,107,
9,522,108, 9,545,369, and 10,166,177, and U.S. Patent Application Publications
Nos.
20160222579, 20160281294, and 20190003113, all of which are incorporated
herein in
their entireties.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 6 kDa to about 17 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 17 kDa to about 39 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 39 kDa to about 80 kDa, wherein
the silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker.
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In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 1 kDa to about 5 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 5 kDa to about 10 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 10 kDa to about 15 kDa, wherein
the silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 15 kDa to about 20
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
20
kDa to about 25 kDa, wherein the silk fibroin-based protein fragments are
chemically
modified with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk fibroin-based protein fragments are chemically linked to
a substrate
through the linker. In an embodiment, a coating of the present disclosure
includes silk
fibroin-based protein fragments having an average weight average molecular
weight
ranging from about 25 kDa to about 30 kDa, wherein the silk fibroin-based
protein
fragments are chemically modified with a precursor linker to form a silk-
conjugate, and
wherein in some embodiments the silk fibroin-based protein fragments are
chemically
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linked to a substrate through the linker. In an embodiment, a coating of the
present
disclosure includes silk fibroin-based protein fragments having an average
weight
average molecular weight ranging from about 30 kDa to about 35 kDa, wherein
the silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 35 to about 40 kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
40 to
about 45 kDa. In an embodiment, a coating of the present disclosure includes
silk fibroin-
based protein fragments having an average weight average molecular weight
ranging
from about 45 to about 50 kDa, wherein the silk fibroin-based protein
fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 50 to about 55 kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 55 to about 60 kDa, wherein the silk
fibroin-based
protein fragments are chemically modified with a precursor linker to form a
silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
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average molecular weight ranging from about 60 to about 65 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 65 to about 70 kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
70 to
about 75 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker. In an embodiment, a coating of the present disclosure includes silk
fibroin-based
protein fragments having an average weight average molecular weight ranging
from
about 75 to about 80 kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 80 to about 85 kDa, wherein the silk
fibroin-based
protein fragments are chemically modified with a precursor linker to form a
silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 85 to about 90 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
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average weight average molecular weight ranging from about 90 to about 95 kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
95 to
about 100 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 100 to about 105 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 105 to about 110 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 110 to about 115 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 115 to about 120
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
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an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
120 to
about 125 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker. In an embodiment, a coating of the present disclosure includes silk
fibroin-based
protein fragments having an average weight average molecular weight ranging
from
about 125 to about 130 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 130 to about 135 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 135 to about 140 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 140 to about 145
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
145 to
about 150 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
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silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 150 to about 155 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 155 to about 160 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 160 to about 165 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 165 to about 170
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
170 to
about 175 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker. In an embodiment, a coating of the present disclosure includes silk
fibroin-based
protein fragments having an average weight average molecular weight ranging
from
about 175 to about 180 kDa, wherein the silk fibroin-based protein fragments
are
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chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 180 to about 185 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 185 to about 190 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 190 to about 195
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
195 to
about 200 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 200 to about 205 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
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molecular weight ranging from about 205 to about 210 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 210 to about 215 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 215 to about 220
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
220 to
about 225 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker. In an embodiment, a coating of the present disclosure includes silk
fibroin-based
protein fragments having an average weight average molecular weight ranging
from
about 225 to about 230 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 230 to about 235 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
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average molecular weight ranging from about 235 to about 240 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 240 to about 245
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
245 to
about 250 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 250 to about 255 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 255 to about 260 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 260 to about 265 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
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coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 265 to about 270
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
270 to
about 275 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker. In an embodiment, a coating of the present disclosure includes silk
fibroin-based
protein fragments having an average weight average molecular weight ranging
from
about 275 to about 280 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 280 to about 285 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 285 to about 290 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 290 to about 295
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
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an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
295 to
about 300 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker.
In an embodiment, a coating of the present disclosure includes silk fibroin-
based
protein fragments having an average weight average molecular weight ranging
from
about 300 to about 305 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 305 to about 310 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 310 to about 315 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 315 to about 320
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
320 to
about 325 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
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silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker. In an embodiment, a coating of the present disclosure includes silk
fibroin-based
protein fragments having an average weight average molecular weight ranging
from
about 325 to about 330 kDa, wherein the silk fibroin-based protein fragments
are
chemically modified with a precursor linker to form a silk-conjugate, and
wherein in
some embodiments the silk fibroin-based protein fragments are chemically
linked to a
substrate through the linker. In an embodiment, a coating of the present
disclosure
includes silk fibroin-based protein fragments having an average weight average
molecular weight ranging from about 330 to about 335 kDa, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
coating of the
present disclosure includes silk fibroin-based protein fragments having an
average weight
average molecular weight ranging from about 335 to about 340 kDa, wherein the
silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker. In an
embodiment, a
coating of the present disclosure includes silk fibroin-based protein
fragments having an
average weight average molecular weight ranging from about 340 to about 345
kDa,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a coating of the present disclosure includes silk fibroin-based
protein
fragments having an average weight average molecular weight ranging from about
345 to
about 350 kDa, wherein the silk fibroin-based protein fragments are chemically
modified
with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the
silk fibroin-based protein fragments are chemically linked to a substrate
through the
linker.
In an embodiment, a composition of the present disclosure, for example a
coating
or a composition used to make such coating, includes silk fibroin-based
protein fragments
having a polydispersity ranging from about 1 to about 5.0, wherein the silk
fibroin-based
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protein fragments are chemically modified with a precursor linker to form a
silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
composition of
the present disclosure, for example a coating or a composition used to make
such coating,
includes silk fibroin-based protein fragments having a polydispersity ranging
from about
1.5 to about 3.0, wherein the silk fibroin-based protein fragments are
chemically
modified with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk fibroin-based protein fragments are chemically linked to
a substrate
through the linker. In an embodiment, a composition of the present disclosure,
for
example a coating or a composition used to make such coating, includes silk
fibroin-
based protein fragments having a polydispersity ranging from about 1 to about
1.5,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
an embodiment, a composition of the present disclosure, for example a coating
or a
composition used to make such coating, includes silk fibroin-based protein
fragments
having a polydispersity ranging from about 1.5 to about 2.0, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker. In an embodiment, a
composition of
the present disclosure, for example a coating or a composition used to make
such coating,
includes silk fibroin-based protein fragments having a polydispersity ranging
from about
2.0 to about 2.5, wherein the silk fibroin-based protein fragments are
chemically
modified with a precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk fibroin-based protein fragments are chemically linked to
a substrate
through the linker. In an embodiment, a composition of the present disclosure,
for
example a coating or a composition used to make such coating, includes silk
fibroin-
based protein fragments having a polydispersity ranging from about 2.0 to
about 3.0,
wherein the silk fibroin-based protein fragments are chemically modified with
a
precursor linker to form a silk-conjugate, and wherein in some embodiments the
silk
fibroin-based protein fragments are chemically linked to a substrate through
the linker. In
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an embodiment, a composition of the present disclosure, for example a coating
or a
composition used to make such coating, includes silk fibroin-based protein
fragments
having a polydispersity ranging from about 2.5 to about 3.0, wherein the silk
fibroin-
based protein fragments are chemically modified with a precursor linker to
form a silk-
conjugate, and wherein in some embodiments the silk fibroin-based protein
fragments are
chemically linked to a substrate through the linker.
Chemical Modification of Silk Fibroin
The disclosure relates to articles including one or more coated substrates,
wherein
the coatings include silk fibroin or silk fibroin fragments and a chemical
modifier or a
physical modifier. In some embodiments, the chemical modifier is chemically
linked to
one or more of a silk fibroin side group and a silk fibroin terminal group. In
some
embodiments, the silk fibroin side group and the silk fibroin terminal group
are
independently selected from an amine group, an amide group, a carboxyl group,
a
hydroxyl group, a thiol group, and a sulfhydryl group. In some embodiments,
the
chemical modifier is chemically linked to one or more functional groups on the
substrate.
In some embodiments, the functional group on the substrate is selected from an
amine
group, an amide group, a carboxyl group, a hydroxyl group, a thiol group, and
a
sulfhydryl group. In some embodiments, the chemical modifier includes one or
more of a
chemically linked functional group, or functional group residue, and a linker.
In some
embodiments, the chemical modifier includes one or more of -CRa2-, -CRa=CRa-, -
C=C-
, -alkyl-, -alkenyl-, -alkynyl-, -aryl-, -heteroaryl-, -0-, -S-, -0C(0)-, -
N(Ra)-, -N=N-, =N-,
-C(0)-, -C(0)0-, -0C(0)N(Ra)-, -C(0)N(Ra)-, -N(Ra)C(0)0-, -N(Ra)C(0)-
, -N(Ra)C(0)N(Ra)_, _N(ta)c(NRa)N(Ra)_,
)S(0)t-, -S(0)t0-, -S(0)tN(Ra)-, -
S(0)tN(Ra)C(0)-, -0P(0)(0Ra)0-, wherein t is 1 or 2, and wherein at each
independent
occurrence Ra is selected from hydrogen, alkyl, alkenyl, fluoroalkyl,
carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl,
heteroaryl, or
heteroarylalkyl.
In some embodiments, any SPF described herein, including silk fibroin or silk
fibroin-based protein fragments are chemically modified with a precursor
linker to form
silk conjugates. Precursor linkers can be selected from any of the following
crosslinkers:
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Example of
chemical
Class of Crosslinker Example
group
reactivity
Succinimidyl Amine
k 0 a
Bis[Sulfosuccinimidyl] gIutarate
Carbodiimide Carboxyls
1EDC
I-Efti,:s.-110ialeftkmt::::ix4083,13r0000#0
MW
Itmos
Acyl chloride Amines/Hydro 0
xyis
CI )LN1 Br
Br
2,3-Dibromopropionyl chloride
Carbonyldiimidazole Amine/Hydrox 0
yls
N N
N,N1-Carbonyldiimidazote
NHS-maleirnide crosslinking, Thiot o0 0
çfNO'r
0 0
Succinimidy1-4-[N-
maIeimidomethyl]cyclohexane-1-
carboxylate
Imidoester crossIinking Amine
"
DMP
dimethyl pimetimidate
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dicyciohexyi carbodiimide Amines
crosslinking
Q Q
NI--:--C=N
NHS-haioacetyi crosslinking Amine
,,,,,,:.
Suifo-SIAB (suifosuccinimidyi Na+ o - Ca , is.k 1 8 .
..,...,
(4-iodoacetyi)-aminohenzoate)
(--
-0
Methacrylate
Epoxide Hydroxyi/amin
es
Silanes Hydroxyls H:30 pHs,
...si.,
0¨
\
H3d CH.-3
TEOS Tetraethyl orthosilicate
Alkyne- Click Chemistry Azide
Azide-click Chemistry- Alkyne
Aldehyde Amines
Formaldehyde Amines
Thioester Thiols, mines,.
hydroxyls.
Photo-crossiinker Amines N'
H
N '
N
0, crN
_..... . ..õ. . .. 0
.._.õ
NaOai
N-Sulfosuccinimidyi-6-PV-azido-2-
nitrophenytaminoi hexanoate
pyridyl. thiol.,: Amines and Q
s41µ Cl )11,õ ...,0, . õe%,õ ".õ õ=-=-, ,k,..,,======:.õ,
suifosuccinimidyi 6[3'(2- sullhydryl 04._ .N 1 ^,'" ¨ N ==
pyii.dyklithio)propionamido]he s,
0 \--k 0
..a H
..
xanoate
hydrazide Aldehydes,
carbohydrates
ekoxyamine Aldehydes
reductive amination Amine
aryl azi.de Alkyne-
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Diazirine, NHS diazirine, Amine 0 NN
,O. )/
suecinimidyi (through NHS
i3
azipentanoate group) to , 0
amine (UV 0
350 nm)
azide-phosphine
Aryl halide, 1,5-Difluoro-2,4- Primary
02N,
dinitrobenzen.e amines
NO
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Chemical Structure
0
HN-Low-MW silk-000H
¨N¨ OH
0 \
1-1N-Mid-MW silk-COOH
¨N¨ OH
\
=,( OH
HN-Low-MW
siIk-
0
b0
0 HNNH2
,µ
HN-Low-MW
0
0
HN NH2
0 /
HN-Low-MW
siIk-
HO
/pi
/ X
HN-Mid-MW silk¨COOH
Structure
)).r0H
NiLow-MW sill COOH
0
0
0
HVIL-Thr Low-MW
0
0
H 0
n
NN'11\/[--Isli,Low-MW
0
HN-Mid-MW silk¨COOH
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OH
HO 0I
N..---......õ-N.,
silk H
OH
HO sN.---........./....õ...--
H
silk
Modified SPF Chemical Structure
0
/ HN-SPF COOH
¨N¨ OH
0 \
0
1
/ç HN¨SPF COOH
¨N¨ OH
0 \
0
0 / OH
, HN SPF
HN H2N,....,......õ..-,......õ....õ.." 0
b0
õ---.....,.........-..........
0\ / l<
> HN HN NH2
SPF
HN 0
õ.....,,,.....................,-,
H2N
0
0\
HNNH2
)/
' HN-SPF µ
HO 0
/ / -\HN-SPF COOH
Modified SPF Structure
H
)(01 N
i SPF )COOH
0
H
SPF il-COOH
0
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0
HO
)=r SPF }CO OH
0
0
0
SPF
0
HN-SPF-COOH
OH
HO
N
SPF
OH
HO io
SPF
Precursor linkers can be selected from any of the following natural
crosslinkers:
caffeic acid, tannic acid, genipin, proanthocyanidin, and the like. Precursor
crosslinking
can be selected from any of the following enzymatic crosslinking:
transglutaminase
transferase crosslinking, hydrolase crosslinking, peptidase crosslinking
(e.g., sortase SrtA
from Staphylococcus aureus), oxidoreductase crosslinking, tyrosinase
crosslinking, laccase
crosslinking, peroxidase crosslinking (e.g., horseradish peroxidase), lysyl
oxidase
crosslinking, peptide ligases (e.g., butelase 1, peptiligase, subtiligase,
etc.), and the like.
In some embodiments, silk fibroin or silk fibroin-based protein fragments are
chemically modified with a precursor linker to form silk conjugates with a
crosslinker or
an activator independently selected from a N-hydroxysuccinimide ester
crosslinker, an
imidoester crosslinker, a sulfosuccinimidyl aminobenzoate, a methacrylate, a
silane, a
silicate, an alkyne compound, an azide compound, an aldehyde, a carbodiimide
crosslinker, a dicyclohexyl carbodiimide activator, a dicyclohexyl
carbodiimide
crosslinker, a maleimide crosslinker, a haloacetyl crosslinker, a pyridyl
disulfide
crosslinker, a hydrazide crosslinker, an alkoxyamine crosslinker, a reductive
amination
crosslinker, an aryl azide crosslinker, a diazirine crosslinker, an azide-
phosphine
crosslinker, a transferase crosslinker, a hydrolase crosslinker, a
transglutaminase
crosslinker, a peptidase crosslinker, an oxidoreductase crosslinker, a
tyrosinase
crosslinker, a laccase crosslinker, a peroxidase crosslinker, a lysyl oxidase
crosslinker,
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and any combinations thereof Some chemically modified silk fibroin has been
described
in J Mater Chem. 2009, June 23, 19(36), 6443-6450, including cyanuric chloride-
activated coupling, carbodiimide coupling, arginine masking, chlorosulfonic
acid
reaction, diazonium coupling, tyrosinase-catalyzed grafting, and
poly(methacrylate)
grafting.
Compositions and Processes Including Silk Fibroin-Based Coatings
In an embodiment, the disclosure may include textiles, such as fibers, yarns,
fabrics, or other materials and combinations thereof, that may be coated with
an SPF
mixture solution (i.e., silk fibroin solution (SFS)) as described herein to
produce a coated
article, wherein the silk fibroin is chemically modified with a precursor
linker to form a
silk-conjugate, and wherein in some embodiments the silk fibroin is chemically
linked to
a substrate through the linker. In an embodiment, the coated articles
described herein may
be treated with additional chemical agents that may enhance the properties of
the coated
article. In an embodiment, the SFS may include one or more chemical agents
that may
enhance the properties of the coated article.
In an embodiment, textiles may be flexible materials (woven or non-woven) that
include a network of natural and/or man-made fibers, thread, yarn, or a
combination
thereof. SFS may be applied at any stage of textile processing from individual
fibers, to
yarn, to fabric, to thread, or a combination thereof
In an embodiment, fibers may be natural fibers that may include a natural
fiber
cellulose base, wherein the natural fiber cellulose base may include one or
more of: (1) a
baste such as flax, hemp, kenaf, jute, linen, and/or ramie; (2) a leaf such as
flax, hemp,
sisal, abaca, banana, henequen, ramie, sunn, and/or coir; and (3) seed hair
such as cotton
and/or kapok. In an embodiment, fibers may be natural fibers that may include
a natural
fiber protein base, wherein the natural fiber protein base may include one or
more of: (1)
hair such as alpaca, camel, cashmere, llama, mohair, and/or vicuna; (2) wool
such as
sheep; (3) filament such as silk. In an embodiment, fibers may be natural
fibers that may
include a natural fiber mineral base, including asbestos. In an embodiment,
fibers may be
man-made fibers that may include a man-made fiber organic natural polymer
base, which
may include one or more of: (1) a cellulose base such as bamboo, rayon,
lyocell, acetate,
and/or triacetate; (2) a protein base such as azlon; (3) an alginate; and (4)
rubber. In an
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embodiment, fibers may be man-made fibers that may include a man-made fiber
organic
synthetic base, which may include one ore more of acrylic, anidex, aramid,
fluorocarbon,
modacrylic, novoloid, nylon, recycled nylon, nytril, olefin, PBI,
polycarbonate, polyester,
recycled polyester, rubber, saran, spandex, vinal vinvon. In an embodiment,
fibers may
be man-made fibers that may include a man-made fiber inorganic base, which may
include one ore more of a glass material, metallic material, and carbon
material.
In an embodiment, yarn may include natural fibers that may include a natural
fiber cellulose base, wherein the natural fiber cellulose base may be from:
(1) a baste
such as flax, hemp, kenaf, jute, linen, and/or ramie; (2) a leaf such as flax,
hemp, sisal,
abaca, banana, henequen, ramie, sunn, and/or coir; or (3) seed hair such as
cotton and/or
kapok. In an embodiment, yarn may include natural fibers that may include a
natural fiber
protein base, wherein the natural fiber protein base may be from: (1) hair
such as alpaca,
camel, cashmere, llama, mohair, and/or vicuna; (2) wool such as sheep; or (3)
filament
such as silk. In an embodiment, yarn may include natural fibers that may
include a
natural fiber mineral base, including asbestos. In an embodiment, yarn may
include man-
made fibers that may include a man-made fiber organic natural polymer base,
which may
include: (1) a cellulose base such as bamboo, rayon, lyocell, acetate, and/or
triacetate; (2)
a protein base such as azlon; (3) an alginate; or (4) rubber. In an
embodiment, yarn may
include man-made fibers that may include a man-made fiber organic synthetic
base,
which may include acrylic, anidex, aramid, fluorocarbon, modacrylic, novoloid,
nylon,
recycled nylon, nytril, olefin, PBI, polycarbonate, polyester, recycled
polyester, rubber,
saran, spandex, vinal and/or vinvon. In an embodiment, yarn may include man-
made
fibers that may include a man-made fiber inorganic base, which may include a
glass
material, metallic material, carbon material, and/or specialty material.
In an embodiment, fabrics may include natural fibers and/or yarn that may
include
a natural fiber cellulose base, wherein the natural fiber cellulose base may
be from: (1) a
baste such as flax, hemp, kenaf, jute, linen, and/or ramie; (2) a leaf such as
flax, hemp,
sisal, abaca, banana, henequen, ramie, sunn, and/or coir; or (3) seed hair
such as cotton
and/or kapok. In an embodiment, fabric may include natural fibers and/or yarn
that may
include a natural fiber protein base, wherein the natural fiber protein base
may be from:
(1) hair such as alpaca, camel, cashmere, llama, mohair, and/or vicuna; (2)
wool such as
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sheep; or (3) filament such as silk. In an embodiment, fabric may include
natural fibers
and/or yarn that may include a natural fiber mineral base, including asbestos.
In an
embodiment, fabric may include man-made fibers and/or yarn that may include a
man-
made fiber organic natural polymer base, which may include: (1) a cellulose
base such as
bamboo, rayon, lyocell, acetate, and/or triacetate; (2) a protein base such as
azlon; (3) an
alginate; or (4) rubber. In an embodiment, fabric may include man-made fibers
and/or
yarn that may include a man-made fiber organic synthetic base, which may
include
acrylic, anidex, aramid, fluorocarbon, modacrylic, novoloid, nylon, recycled
nylon, nytril,
olefin, PBI, polycarbonate, polyester, recycled polyester, rubber, saran,
spandex, vinal
and/or vinvon. In an embodiment, fabric may include man-made fibers and/or
yarn that
may include a man-made fiber inorganic base, which may include a glass
material,
metallic material, carbon material, and/or specialty material.
In an embodiment, textiles may be manufactured via one or more of the
following
processes weaving processes, knitting processes, and non-woven processes. In
an
embodiment, weaving processes may include plain weaving, twill weaving, and/or
satin
weaving. In an embodiment, knitting processes may include weft knitting (e.g.,
circular,
flat bed, and/or full fashioned) and/or warp knitting (e.g., tricot, Raschel,
and/or crochet).
In an embodiment, non-woven processes may include stable fiber (e.g., dry laid
and/or
wet laid) and/or continuous filament (e.g., spun laid and/or melt blown).
In some embodiments, silk fibroin fragments may be applied to fibers and/or
yarn
having a diameter of less than about 100 nm, or less than about 200 nm, or
less than
about 300 nm, or less than about 400 nm, or less than about 500 nm, or less
than about
600 nm, or less than about 700 nm, or less than about 800 nm, or less than
about 900 nm,
or less than about 1000 nm, or less than about 2 p.m, or less than about 5
p.m, or less than
about 10 p.m, or less than about 20 p.m, or less than about 30 pm, or less
than about 40
p.m, or less than about 50 p.m, or less than about 60 p.m, or less than about
70 p.m, or less
than about 80 p.m, or less than about 90 p.m, or less than about 100 p.m, or
less than about
200 m, or less than about 300 p.m, or less than about 400 p.m, or less than
about 500 p.m,
or less than about 600 p.m, or less than about 700 p.m, or less than about 800
p.m, or less
than about 900 p.m, or less than about 1000 p.m, or less than about 2 mm, or
less than
about 3 mm, or less than about 4 mm, or less than about 5 mm, 6 mm, or less
than about
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7 mm, or less than about 8 mm, or less than about 9 mm, or less than about 10
mm, or
less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or
less than
about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than
about 80
mm, or less than about 90 mm, or less than about 100 mm, or less than about
200 mm, or
less than about 300 mm, or less than about 400 mm, or less than about 500 mm,
or less
than about 600 mm, or less than about 700 mm, or less than about 800 mm, or
less than
about 900 mm, or less than about 1000 mm.
In some embodiments, silk fibroin fragments may be applied to fibers and/or
yarn
haying a diameter of greater than about 100 nm, or greater than about 200 nm,
or greater
than about 300 nm, or greater than about 400 nm, or greater than about 500 nm,
or greater
than about 600 nm, or greater than about 700 nm, or greater than about 800 nm,
or greater
than about 900 nm, or greater than about 1000 nm, or greater than about 2 p.m,
or greater
than about 5 p.m, or greater than about 10 p.m, or greater than about 20 p.m,
or greater
than about 30 p.m, or greater than about 40 p.m, or greater than about 50 p.m,
or greater
than about 60 p.m, or greater than about 70 p.m, or greater than about 80 p.m,
or greater
than about 90 p.m, or greater than about 100 p.m, or greater than about 200
p.m, or greater
than about 300 p.m, or greater than about 400 p.m, or greater than about 500
p.m, or
greater than about 600 p.m, or greater than about 700 p.m, or greater than
about 800 p.m,
or greater than about 900 p.m, or greater than about 1000 p.m, or greater than
about 2 mm,
or greater than about 3 mm, or greater than about 4 mm, or greater than about
5 mm, 6
mm, or greater than about 7 mm, or greater than about 8 mm, or greater than
about 9 mm,
or greater than about 10 mm, or greater than about 20 mm, or greater than
about 30 mm,
or greater than about 40 mm, or greater than about 50 mm, or greater than
about 60 mm,
or greater than about 70 mm, or greater than about 80 mm, or greater than
about 90 mm,
or greater than about 100 mm, or greater than about 200 mm, or greater than
about 300
mm, or greater than about 400 mm, or greater than about 500 mm, or greater
than about
600 mm, or greater than about 700 mm, or greater than about 800 mm, or greater
than
about 900 mm, or greater than about 1000 mm.
In some embodiments, silk fibroin fragments may be applied to fibers and/or
yarn
haying a length of less than about 100 nm, or less than about 200 nm, or less
than about
300 nm, or less than about 400 nm, or less than about 500 nm, or less than
about 600 nm,
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or less than about 700 nm, or less than about 800 nm, or less than about 900
nm, or less
than about 1000 nm, or less than about 2 pm, or less than about 5 pm, or less
than about
pm, or less than about 20 pm, or less than about 30 pm, or less than about 40
pm, or
less than about 50 pm, or less than about 60 pm, or less than about 70 pm, or
less than
about 80 pm, or less than about 90 pm, or less than about 100 pm, or less than
about 200
pm, or less than about 300 pm, or less than about 400 pm, or less than about
500 pm, or
less than about 600 pm, or less than about 700 pm, or less than about 800 pm,
or less
than about 900 pm, or less than about 1000 pm, or less than about 2 mm, or
less than
about 3 mm, or less than about 4 mm, or less than about 5 mm, 6 mm, or less
than about
7 mm, or less than about 8 mm, or less than about 9 mm, or less than about 10
mm, or
less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or
less than
about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than
about 80
mm, or less than about 90 mm, or less than about 100 mm, or less than about
200 mm, or
less than about 300 mm, or less than about 400 mm, or less than about 500 mm,
or less
than about 600 mm, or less than about 700 mm, or less than about 800 mm, or
less than
about 900 mm, or less than about 1000 mm.
In some embodiments, silk fibroin fragments may be applied to fibers and/or
yarn
haying a length of greater than about 100 nm, or greater than about 200 nm, or
greater
than about 300 nm, or greater than about 400 nm, or greater than about 500 nm,
or greater
than about 600 nm, or greater than about 700 nm, or greater than about 800 nm,
or greater
than about 900 nm, or greater than about 1000 nm, or greater than about 2 pm,
or greater
than about 5 pm, or greater than about 10 pm, or greater than about 20 pm, or
greater
than about 30 pm, or greater than about 40 pm, or greater than about 50 pm, or
greater
than about 60 pm, or greater than about 70 pm, or greater than about 80 pm, or
greater
than about 90 pm, or greater than about 100 pm, or greater than about 200 pm,
or greater
than about 300 pm, or greater than about 400 pm, or greater than about 500 pm,
or
greater than about 600 pm, or greater than about 700 pm, or greater than about
800 pm,
or greater than about 900 pm, or greater than about 1000 pm, or greater than
about 2 mm,
or greater than about 3 mm, or greater than about 4 mm, or greater than about
5 mm, 6
mm, or greater than about 7 mm, or greater than about 8 mm, or greater than
about 9 mm,
or greater than about 10 mm, or greater than about 20 mm, or greater than
about 30 mm,
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or greater than about 40 mm, or greater than about 50 mm, or greater than
about 60 mm,
or greater than about 70 mm, or greater than about 80 mm, or greater than
about 90 mm,
or greater than about 100 mm, or greater than about 200 mm, or greater than
about 300
mm, or greater than about 400 mm, or greater than about 500 mm, or greater
than about
600 mm, or greater than about 700 mm, or greater than about 800 mm, or greater
than
about 900 mm, or greater than about 1000 mm.
In some embodiments, silk fibroin fragments may be applied to fibers and/or
yarn
haying a weight (g/m2) of less than about 1 g/m2, or less than about 2 g/m2,
or less than
about 3 g/m2, or less than about 4 g/m2, or less than about 5 g/m2, or less
than about 6
g/m2, or less than about 7 g/m2, or less than about 8 g/m2, or less than about
9 g/m2, or
less than about 10 g/m2, or less than about 20 g/m2, or less than about 30
g/m2, or less
than about 40 g/m2, or less than about 50 g/m2, or less than about 60 g/m2, or
less than
about 70 g/m2, or less than about 80 g/m2, or less than about 90 g/m2, or less
than about
100 g/m2, or less than about 200 g/m2, or less than about 300 g/m2, or less
than about 400
g/m2, or less than about 500 g/m2.
In some embodiments, silk fibroin fragments may be applied to fibers and/or
yarn
haying a weight (g/m2) of at greater than about 1 g/m2, or greater than about
2 g/m2, or
greater than about 3 g/m2, or greater than about 4 g/m2, or greater than about
5 g/m2, or
greater than about 6 g/m2, or greater than about 7 g/m2, or greater than about
8 g/m2, or
greater than about 9 g/m2, or greater than about 10 g/m2, or greater than
about 20 g/m2, or
greater than about 30 g/m2, or greater than about 40 g/m2, or greater than
about 50 g/m2,
or greater than about 60 g/m2, or greater than about 70 g/m2, or greater than
about 80
g/m2, or greater than about 90 g/m2, or greater than about 100 g/m2, or
greater than about
200 g/m2, or greater than about 300 g/m2, or greater than about 400 g/m2, or
greater than
about 500 g/m2.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
thickness of less than about 100 nm, or less than about 200 nm, or less than
about 300
nm, or less than about 400 nm, or less than about 500 nm, or less than about
600 nm, or
less than about 700 nm, or less than about 800 nm, or less than about 900 nm,
or less than
about 1000 nm, or less than about 2 p.m, or less than about 5 p.m, or less
than about 10
p.m, or less than about 20 p.m, or less than about 30 p.m, or less than about
40 p.m, or less
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than about 50 p.m, or less than about 60 p.m, or less than about 70 p.m, or
less than about
80 p.m, or less than about 90 p.m, or less than about 100 p.m, or less than
about 200 p.m,
or less than about 300 p.m, or less than about 400 p.m, or less than about 500
p.m, or less
than about 600 p.m, or less than about 700 p.m, or less than about 800 p.m, or
less than
about 900 p.m, or less than about 1000 p.m, or less than about 2 mm, or less
than about 3
mm, or less than about 4 mm, or less than about 5 mm, 6 mm, or less than about
7 mm, or
less than about 8 mm, or less than about 9 mm, or less than about 10 mm.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
thickness of greater than about 100 nm, or greater than about 200 nm, or
greater than
about 300 nm, or greater than about 400 nm, or greater than about 500 nm, or
greater than
about 600 nm, or greater than about 700 nm, or greater than about 800 nm, or
greater than
about 900 nm, or greater than about 1000 nm, or greater than about 2 p.m, or
greater than
about 5 p.m, or greater than about 10 p.m, or greater than about 20 p.m, or
greater than
about 30 p.m, or greater than about 40 p.m, or greater than about 50 p.m, or
greater than
about 60 p.m, or greater than about 70 p.m, or greater than about 80 p.m, or
greater than
about 90 p.m, or greater than about 100 p.m, or greater than about 200 p.m, or
greater than
about 300 p.m, or greater than about 400 p.m, or greater than about 500 p.m,
or greater
than about 600 p.m, or greater than about 700 p.m, or greater than about 800
p.m, or
greater than about 900 p.m, or greater than about 1000 p.m, or greater than
about 2 mm, or
greater than about 3 mm, or greater than about 4 mm, or greater than about 5
mm, 6 mm,
or greater than about 7 mm, or greater than about 8 mm, or greater than about
9 mm, or
greater than about 10 mm.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
width of less than about 100 nm, or less than about 200 nm, or less than about
300 nm, or
less than about 400 nm, or less than about 500 nm, or less than about 600 nm,
or less than
about 700 nm, or less than about 800 nm, or less than about 900 nm, or less
than about
1000 nm, or less than about 2 p.m, or less than about 5 p.m, or less than
about 10 p.m, or
less than about 20 p.m, or less than about 30 p.m, or less than about 40 p.m,
or less than
about 50 p.m, or less than about 60 p.m, or less than about 70 p.m, or less
than about 80
p.m, or less than about 90 p.m, or less than about 100 p.m, or less than about
200 p.m, or
less than about 300 p.m, or less than about 400 p.m, or less than about 500
p.m, or less
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than about 600 p.m, or less than about 700 p.m, or less than about 800 p.m, or
less than
about 900 p.m, or less than about 1000 p.m, or less than about 2 mm, or less
than about 3
mm, or less than about 4 mm, or less than about 5 mm, 6 mm, or less than about
7 mm, or
less than about 8 mm, or less than about 9 mm, or less than about 10 mm, or
less than
about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than
about 50
mm, or less than about 60 mm, or less than about 70 mm, or less than about 80
mm, or
less than about 90 mm, or less than about 100 mm, or less than about 200 mm,
or less
than about 300 mm, or less than about 400 mm, or less than about 500 mm, or
less than
about 600 mm, or less than about 700 mm, or less than about 800 mm, or less
than about
900 mm, or less than about 1000 mm, or less than about 2 m, or less than about
3 m, or
less than about 4 m, or less than about 5 m.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
width of greater than about 100 nm, or greater than about 200 nm, or greater
than about
300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater
than about
600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater
than about
900 nm, or greater than about 1000 nm, or greater than about 2 p.m, or greater
than about
p.m, or greater than about 10 p.m, or greater than about 20 p.m, or greater
than about 30
p.m, or greater than about 40 p.m, or greater than about 50 p.m, or greater
than about 60
p.m, or greater than about 70 p.m, or greater than about 80 p.m, or greater
than about 90
p.m, or greater than about 100 p.m, or greater than about 200 p.m, or greater
than about
300 p.m, or greater than about 400 p.m, or greater than about 500 p.m, or
greater than
about 600 p.m, or greater than about 700 p.m, or greater than about 800 p.m,
or greater
than about 900 p.m, or greater than about 1000 p.m, or greater than about 2
mm, or greater
than about 3 mm, or greater than about 4 mm, or greater than about 5 mm, 6 mm,
or
greater than about 7 mm, or greater than about 8 mm, or greater than about 9
mm, or
greater than about 10 mm, or greater than about 20 mm, or greater than about
30 mm, or
greater than about 40 mm, or greater than about 50 mm, or greater than about
60 mm, or
greater than about 70 mm, or greater than about 80 mm, or greater than about
90 mm, or
greater than about 100 mm, or greater than about 200 mm, or greater than about
300 mm,
or greater than about 400 mm, or greater than about 500 mm, or greater than
about 600
mm, or greater than about 700 mm, or greater than about 800 mm, or greater
than about
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900 mm, or greater than about 1000 mm, or greater than about 2 m, or greater
than about
3 m, or greater than about 4 m, or greater than about 5 m.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
length of less than about 100 nm, or less than about 200 nm, or less than
about 300 nm, or
less than about 400 nm, or less than about 500 nm, or less than about 600 nm,
or less than
about 700 nm, or less than about 800 nm, or less than about 900 nm, or less
than about
1000 nm, or less than about 2 p.m, or less than about 5 p.m, or less than
about 10 p.m, or
less than about 20 p.m, or less than about 30 p.m, or less than about 40 p.m,
or less than
about 50 p.m, or less than about 60 p.m, or less than about 70 p.m, or less
than about 80
p.m, or less than about 90 p.m, or less than about 100 p.m, or less than about
200 p.m, or
less than about 300 p.m, or less than about 400 p.m, or less than about 500
p.m, or less
than about 600 p.m, or less than about 700 p.m, or less than about 800 p.m, or
less than
about 900 p.m, or less than about 1000 p.m, or less than about 2 mm, or less
than about 3
mm, or less than about 4 mm, or less than about 5 mm, 6 mm, or less than about
7 mm, or
less than about 8 mm, or less than about 9 mm, or less than about 10 mm, or
less than
about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than
about 50
mm, or less than about 60 mm, or less than about 70 mm, or less than about 80
mm, or
less than about 90 mm, or less than about 100 mm, or less than about 200 mm,
or less
than about 300 mm, or less than about 400 mm, or less than about 500 mm, or
less than
about 600 mm, or less than about 700 mm, or less than about 800 mm, or less
than about
900 mm, or less than about 1000 mm.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
length of greater than about 100 nm, or greater than about 200 nm, or greater
than about
300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater
than about
600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater
than about
900 nm, or greater than about 1000 nm, or greater than about 2 p.m, or greater
than about
p.m, or greater than about 10 p.m, or greater than about 20 p.m, or greater
than about 30
p.m, or greater than about 40 p.m, or greater than about 50 p.m, or greater
than about 60
p.m, or greater than about 70 p.m, or greater than about 80 p.m, or greater
than about 90
p.m, or greater than about 100 p.m, or greater than about 200 p.m, or greater
than about
300 p.m, or greater than about 400 p.m, or greater than about 500 p.m, or
greater than
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about 600 p.m, or greater than about 700 p.m, or greater than about 800 p.m,
or greater
than about 900 p.m, or greater than about 1000 p.m, or greater than about 2
mm, or greater
than about 3 mm, or greater than about 4 mm, or greater than about 5 mm, 6 mm,
or
greater than about 7 mm, or greater than about 8 mm, or greater than about 9
mm, or
greater than about 10 mm, or greater than about 20 mm, or greater than about
30 mm, or
greater than about 40 mm, or greater than about 50 mm, or greater than about
60 mm, or
greater than about 70 mm, or greater than about 80 mm, or greater than about
90 mm, or
greater than about 100 mm, or greater than about 200 mm, or greater than about
300 mm,
or greater than about 400 mm, or greater than about 500 mm, or greater than
about 600
mm, or greater than about 700 mm, or greater than about 800 mm, or greater
than about
900 mm, or greater than about 1000 mm.
In some embodiments, silk fibroin fragments may be applied to fabric having a
stretch percentage of less than about 1 %, or less than about 2 %, or less
than about 3 %,
or less than about 4 %, or less than about 5 %, or less than about 6 %, or
less than about 7
%, or less than about 8 %, or less than about 9 %, or less than about 10 %, or
less than
about 20 %, or less than about 30 %, or less than about 40 %, or less than
about 50 %, or
less than about 60 %, or less than about 70 %, or less than about 80 %, or
less than about
90 %, or less than about 100, or less than about 110 %, or less than about 120
%, or less
than about 130 %, or less than about 140 %, or less than about 150 %, or less
than about
160 %, or less than about 170 %, or less than about 180 %, or less than about
190 %, or
less than about 200 %. Stretch percentage may be determined for a fabric
having an
unstretched width and stretching the fabric to a stretched width, then
subtracting the
unstretched width from the stretched width to yield the net stretched width,
then dividing
the net stretched width and multiplying the quotient by 100 to find the
stretch percentage
(%):
(Stretched Width ¨ Unstretched Width)
Stretch Percentage = _______________________________________ * 100
Unstretched Width
In some embodiments, silk fibroin fragments may be applied to fabric having a
stretch percentage of greater than about 1 %, or greater than about 2 %, or
greater than
about 3 %, or greater than about 4 %, or greater than about 5 %, or greater
than about 6
%, or greater than about 7 %, or greater than about 8 %, or greater than about
9 %, or
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greater than about 10 %, or greater than about 20 %, or greater than about 30
%, or
greater than about 40 %, or greater than about 50 %, or greater than about 60
%, or
greater than about 70 %, or greater than about 80 %, or greater than about 90
%, or
greater than about 100, or greater than about 110 %, or greater than about 120
%, or
greater than about 130 %, or greater than about 140 %, or greater than about
150 %, or
greater than about 160 %, or greater than about 170 %, or greater than about
180 %, or
greater than about 190 %, or greater than about 200 %
In some embodiments, silk fibroin fragments may be applied to fabric haying a
tensile energy (N/cm2) of less than about 1 cN/cm2, or less than about 2
cN/cm2, or less
than about 3 cN/cm2, or less than about 4 cN/cm2, or less than about 5 cN/cm2,
or less
than about 5 cN/cm2, or less than about 6 cN/cm2, or less than about 7 cN/cm2,
or less
than about 8 cN/cm2, or less than about 9 cN/cm2, or less than about 10
cN/cm2, or less
than about 20 cN/cm2, or less than about 30 cN/cm2, or less than about 40
cN/cm2, or less
than about 50 cN/cm2, or less than about 60 cN/cm2, or less than about 70
cN/cm2, or less
than about 80 cN/cm2, or less than about 90 cN/cm2, or less than about 100
cN/cm2, or
less than about 2 N/cm2, or less than about 3 N/cm2, or less than about 4
N/cm2, or less
than about 5 N/cm2, or less than about 6 N/cm2, or less than about 7 N/cm2, or
less than
about 8 N/cm2, or less than about 9 N/cm2, or less than about 10 N/cm2, or
less than about
20 N/cm2, or less than about 30 N/cm2, or less than about 40 N/cm2, or less
than about 50
N/cm2, or less than about 60 N/cm2, or less than about 70 N/cm2, or less than
about 80
N/cm2, or less than about 90 N/cm2, or less than about 100 N/cm2, or less than
about 150
N/cm2, or less than about 200 N/cm2.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
tensile energy (N/cm2) of greater than about 1 cN/cm2, or greater than about 2
cN/cm2, or
greater than about 3 cN/cm2, or greater than about 4 cN/cm2, or greater than
about 5
cN/cm2, or greater than about 5 cN/cm2, or greater than about 6 cN/cm2, or
greater than
about 7 cN/cm2, or greater than about 8 cN/cm2, or greater than about 9
cN/cm2, or
greater than about 10 cN/cm2, or greater than about 20 cN/cm2, or greater than
about 30
cN/cm2, or greater than about 40 cN/cm2, or greater than about 50 cN/cm2, or
greater than
about 60 cN/cm2, or greater than about 70 cN/cm2, or greater than about 80
cN/cm2, or
greater than about 90 cN/cm2, or greater than about 100 cN/cm2, or greater
than about 2
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N/cm2, or greater than about 3 N/cm2, or greater than about 4 N/cm2, or
greater than
about 5 N/cm2, or greater than about 6 N/cm2, or greater than about 7 N/cm2,
or greater
than about 8 N/cm2, or greater than about 9 N/cm2, or greater than about 10
N/cm2, or
greater than about 20 N/cm2, or greater than about 30 N/cm2, or greater than
about 40
N/cm2, or greater than about 50 N/cm2, or greater than about 60 N/cm2, or
greater than
about 70 N/cm2, or greater than about 80 N/cm2, or greater than about 90
N/cm2, or
greater than about 100 N/cm2, or greater than about 150 N/cm2, or greater than
about 200
N/cm2.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
shear rigidity (N/cm-degree) of less than about 1 cN/cm-degree, or less than
about 2
cN/cm-degree, or less than about 3 cN/cm-degree, or less than about 4 cN/cm-
degree, or
less than about 5 cN/cm-degree, or less than about 5 cN/cm-degree, or less
than about 6
cN/cm-degree, or less than about 7 cN/cm-degree, or less than about 8 cN/cm-
degree, or
less than about 9 cN/cm-degree, or less than about 10 cN/cm-degree, or less
than about
20 cN/cm-degree, or less than about 30 cN/cm-degree, or less than about 40
cN/cm-
degree, or less than about 50 cN/cm-degree, or less than about 60 cN/cm-
degree, or less
than about 70 cN/cm-degree, or less than about 80 cN/cm-degree, or less than
about 90
cN/cm-degree, or less than about 100 cN/cm-degree, or less than about 2 N/cm-
degree, or
less than about 3 N/cm-degree, or less than about 4 N/cm-degree, or less than
about 5
N/cm-degree, or less than about 6 N/cm-degree, or less than about 7 N/cm-
degree, or less
than about 8 N/cm-degree, or less than about 9 N/cm-degree, or less than about
10 N/cm-
degree, or less than about 20 N/cm-degree, or less than about 30 N/cm-degree,
or less
than about 40 N/cm-degree, or less than about 50 N/cm-degree, or less than
about 60
N/cm-degree, or less than about 70 N/cm-degree, or less than about 80 N/cm-
degree, or
less than about 90 N/cm-degree, or less than about 100 N/cm-degree, or less
than about
150 N/cm-degree, or less than about 200 N/cm-degree.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
shear rigidity (N/cm-degree) of greater than about 1 cN/cm-degree, or greater
than about
2 cN/cm-degree, or greater than about 3 cN/cm-degree, or greater than about 4
cN/cm-
degree, or greater than about 5 cN/cm-degree, or greater than about 5 cN/cm-
degree, or
greater than about 6 cN/cm-degree, or greater than about 7 cN/cm-degree, or
greater than
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about 8 cN/cm-degree, or greater than about 9 cN/cm-degree, or greater than
about 10
cN/cm-degree, or greater than about 20 cN/cm-degree, or greater than about 30
cN/cm-
degree, or greater than about 40 cN/cm-degree, or greater than about 50 cN/cm-
degree, or
greater than about 60 cN/cm-degree, or greater than about 70 cN/cm-degree, or
greater
than about 80 cN/cm-degree, or greater than about 90 cN/cm-degree, or greater
than
about 100 cN/cm-degree, or greater than about 2 N/cm-degree, or greater than
about 3
N/cm-degree, or greater than about 4 N/cm-degree, or greater than about 5 N/cm-
degree,
or greater than about 6 N/cm-degree, or greater than about 7 N/cm-degree, or
greater than
about 8 N/cm-degree, or greater than about 9 N/cm-degree, or greater than
about 10
N/cm-degree, or greater than about 20 N/cm-degree, or greater than about 30
N/cm-
degree, or greater than about 40 N/cm-degree, or greater than about 50 N/cm-
degree, or
greater than about 60 N/cm-degree, or greater than about 70 N/cm-degree, or
greater than
about 80 N/cm-degree, or greater than about 90 N/cm-degree, or greater than
about 100
N/cm-degree, or greater than about 150 N/cm-degree, or greater than about 200
N/cm-
degree.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
bending rigidity (N=cm2/cm) of less than about 1 cN=cm2/cm, or less than about
2
cN=cm2/cm, or less than about 3 cN=cm2/cm, or less than about 4 cN=cm2/cm, or
less than
about 5 cN=cm2/cm, or less than about 5 cN=cm2/cm, or less than about 6
cN=cm2/cm, or
less than about 7 cN=cm2/cm, or less than about 8 cN=cm2/cm, or less than
about 9
cN=cm2/cm, or less than about 10 cN=cm2/cm, or less than about 20 cN=cm2/cm,
or less
than about 30 cN=cm2/cm, or less than about 40 cN=cm2/cm, or less than about
50
cN=cm2/cm, or less than about 60 cN=cm2/cm, or less than about 70 cN=cm2/cm,
or less
than about 80 cN=cm2/cm, or less than about 90 cN=cm2/cm, or less than about
100
cN=cm2/cm, or less than about 2 N=cm2/cm, or less than about 3 N=cm2/cm, or
less than
about 4 N=cm2/cm, or less than about 5 N=cm2/cm, or less than about 6
N=cm2/cm, or less
than about 7 N=cm2/cm, or less than about 8 N=cm2/cm, or less than about 9
N=cm2/cm, or
less than about 10 N=cm2/cm, or less than about 20 N=cm2/cm, or less than
about 30
N=cm2/cm, or less than about 40 N=cm2/cm, or less than about 50 N=cm2/cm, or
less than
about 60 N=cm2/cm, or less than about 70 N=cm2/cm, or less than about 80
N=cm2/cm, or
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less than about 90 N=cm2/cm, or less than about 100 N=cm2/cm, or less than
about 150
N=cm2/cm, or less than about 200 N=cm2/cm.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
bending rigidity (N=cm2/cm) of greater than about 1 cN=cm2/cm, or greater than
about 2
cN=cm2/cm, or greater than about 3 cN=cm2/cm, or greater than about 4
cN=cm2/cm, or
greater than about 5 cN=cm2/cm, or greater than about 5 cN=cm2/cm, or greater
than about
6 cN=cm2/cm, or greater than about 7 cN=cm2/cm, or greater than about 8
cN=cm2/cm, or
greater than about 9 cN=cm2/cm, or greater than about 10 cN=cm2/cm, or greater
than
about 20 cN=cm2/cm, or greater than about 30 cN=cm2/cm, or greater than about
40
cN=cm2/cm, or greater than about 50 cN=cm2/cm, or greater than about 60
cN=cm2/cm, or
greater than about 70 cN=cm2/cm, or greater than about 80 cN=cm2/cm, or
greater than
about 90 cN=cm2/cm, or greater than about 100 cN=cm2/cm, or greater than about
2
N=cm2/cm, or greater than about 3 N=cm2/cm, or greater than about 4 N=cm2/cm,
or
greater than about 5 N=cm2/cm, or greater than about 6 N=cm2/cm, or greater
than about 7
N=cm2/cm, or greater than about 8 N=cm2/cm, or greater than about 9 N=cm2/cm,
or
greater than about 10 N=cm2/cm, or greater than about 20 N=cm2/cm, or greater
than
about 30 N=cm2/cm, or greater than about 40 N=cm2/cm, or greater than about 50
N=cm2/cm, or greater than about 60 N=cm2/cm, or greater than about 70
N=cm2/cm, or
greater than about 80 N=cm2/cm, or greater than about 90 N=cm2/cm, or greater
than
about 100 N=cm2/cm, or greater than about 150 N=cm2/cm, or greater than about
200
N=cm2/cm.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
compression energy (N=cm/cm2) of less than about 1 cN=cm/cm2, or less than
about 2
cN=cm/cm2, or less than about 3 cN=cm/cm2, or less than about 4 cN=cm/cm2, or
less than
about 5 c N=cm/cm2, or less than about 5 cN=cm/cm2, or less than about 6
cN=cm/cm2, or
less than about 7 cN=cm/cm2, or less than about 8 cN=cm/cm2, or less than
about 9
cN=cm/cm2, or less than about 10 cN=cm/cm2, or less than about 20 cN=cm/cm2,
or less
than about 30 cN=cm/cm2, or less than about 40 cN=cm/cm2, or less than about
50
cN=cm/cm2, or less than about 60 cN=cm/cm2, or less than about 70 cN=cm/cm2,
or less
than about 80 cN=cm/cm2, or less than about 90 cN=cm/cm2, or less than about
100
cN=cm/cm2, or less than about 2 N=cm/cm2, or less than about 3 N=cm/cm2, or
less than
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about 4 N=cm/cm2, or less than about 5 N=cm/cm2, or less than about 6
N=cm/cm2, or less
than about 7 N=cm/cm2, or less than about 8 N=cm/cm2, or less than about 9
N=cm/cm2, or
less than about 10 N=cm/cm2, or less than about 20 N=cm/cm2, or less than
about 30
N=cm/cm2, or less than about 40 N=cm/cm2, or less than about 50 N=cm/cm2, or
less than
about 60 N=cm/cm2, or less than about 70 N=cm/cm2, or less than about 80
N=cm/cm2, or
less than about 90 N=cm/cm2, or less than about 100 N=cm/cm2, or less than
about 150
N=cm/cm2, or less than about 200 N=cm/cm2.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
compression energy (N=cm/cm2) of greater than about 1 cl\T=cm/cm2, or greater
than about
2 cl\T=cm/cm2, or greater than about 3 cl\T=cm/cm2, or greater than about 4
cl\T=cm/cm2, or
greater than about 5 cl\T=cm/cm2, or greater than about 5 cl\T=cm/cm2, or
greater than about
6 cl\T=cm/cm2, or greater than about 7 cl\T=cm/cm2, or greater than about 8
cl\T=cm/cm2, or
greater than about 9 cl\T=cm/cm2, or greater than about 10 cl\T=cm/cm2, or
greater than
about 20 cl\T=cm/cm2, or greater than about 30 cl\T=cm/cm2, or greater than
about 40
cl\T=cm/cm2, or greater than about 50 cl\T=cm/cm2, or greater than about 60
cl\T=cm/cm2, or
greater than about 70 cl\T=cm/cm2, or greater than about 80 cl\T=cm/cm2, or
greater than
about 90 cl\T=cm/cm2, or greater than about 100 cl\T=cm/cm2, or greater than
about 2
N=cm/cm2, or greater than about 3 N=cm/cm2, or greater than about 4 N=cm/cm2,
or
greater than about 5 N=cm/cm2, or greater than about 6 N=cm/cm2, or greater
than about 7
N=cm/cm2, or greater than about 8 N=cm/cm2, or greater than about 9 N=cm/cm2,
or
greater than about 10 N=cm/cm2, or greater than about 20 N=cm/cm2, or greater
than
about 30 N=cm/cm2, or greater than about 40 N=cm/cm2, or greater than about 50
N=cm/cm2, or greater than about 60 N=cm/cm2, or greater than about 70
N=cm/cm2, or
greater than about 80 N=cm/cm2, or greater than about 90 N=cm/cm2, or greater
than
about 100 N=cm/cm2, or greater than about 150 N=cm/cm2, or greater than about
200
N=cm/cm2.
In some embodiments, silk fibroin fragments may be applied to fabric haying a
coefficient of friction of less than about 0.04, or less than about 0.05, or
less than about
0.06, or less than about 0.07, or less than about 0.08, or less than about
0.09, or less than
about 0.10, or less than about 0.10, or less than about 0.15, or less than
about 0.20, or less
than about 0.25, or less than about 0.30, or less than about 0.35, or less
than about 0.40,
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or less than about 0.45, or less than about 0.50, or less than about 0.55, or
less than about
0.60, or less than about 0.65, or less than about 0.70, or less than about
0.75, or less than
about 0.80, or less than about 0.85, or less than about 0.90, or less than
about 0.95, or less
than about 1.00, or less than about 1.05.
In some embodiments, silk fibroin fragments may be applied to fabric having a
coefficient of friction of greater than about 0.04, or greater than about
0.05, or greater
than about 0.06, or greater than about 0.07, or greater than about 0.08, or
greater than
about 0.09, or greater than about 0.10, or greater than about 0.10, or greater
than about
0.15, or greater than about 0.20, or greater than about 0.25, or greater than
about 0.30, or
greater than about 0.35, or greater than about 0.40, or greater than about
0.45, or greater
than about 0.50, or greater than about 0.55, or greater than about 0.60, or
greater than
about 0.65, or greater than about 0.70, or greater than about 0.75, or greater
than about
0.80, or greater than about 0.85, or greater than about 0.90, or greater than
about 0.95, or
greater than about 1.00, or greater than about 1.05.
In some embodiments, chemical finishes may be applied to textiles before or
after
such textiles are coated with SFS. In an embodiment, chemical finishing may be
intended
as the application of chemical agents and/or SFS to textiles, including
fibers, yarn, and
fabric, or to garments that are prepared by such fibers, yarn, and fabric to
modify the
original textile's or garment's properties and achieve properties in the
textile or garment
that would be otherwise absent. With chemical finishes, textiles treated with
such
chemical finishes may act as surface treatments and/or the treatments may
modify the
elemental analysis of treated textile base polymers.
In an embodiment, a type of chemical finishing may include the application of
certain silk-fibroin based solutions to textiles. For example, SFS may be
applied to a
fabric after it is dyed, but there are also scenarios that may require the
application of SFS
during processing, during dyeing, or after a garment is assembled from a
selected textile
or fabric, thread, or yarn. In some embodiments, after its application, SFS
may be dried
with the use of heat. SFS may then be fixed to the surface of the textile in a
processing
step called curing.
In some embodiments, silk fibroin fragments may be supplied in a concentrated
form suspended in water. In some embodiments, silk fibroin fragments may have
a
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concentration by weight (% w/w or % w/v) or by volume (v/v) of less than about
50 %,
or less than about 45%, or less than about 40%, or less than about 35%, or
less than about
30%, or less than about 25%, or less than about 20%, or less than about 15%,
or less than
about 10%, or less than about 5%, or less than about 4%, or less than about
3%, or less
than about 2%, or less than about 1%, or less than about 0.1%, or less than
about 0.01%,
or less than about 0.001%, or less than about 0.0001%, or less than about
0.00001%. In
some embodiments, SFS may have a concentration by weight (% w/w or % w/v) or
by
volume (v/v) of greater than about 50 %, or greater than about 45%, or greater
than about
40%, or greater than about 35%, or greater than about 30%, or greater than
about 25%, or
greater than about 20%, or greater than about 15%, or greater than about 10%,
or greater
than about 5%, or greater than about 4%, or greater than about 3%, or greater
than about
2%, or greater than about 1%, or greater than about 0.1%, or greater than
about 0.01%, or
greater than about 0.001%, or greater than about 0.0001%, or greater than
about
0.00001%.
In some embodiments, the solution concentration and the wet pick of the
material
determines the amount of silk fibroin solution, which may include silk-based
proteins or
fragments thereof, that may be fixed or otherwise adhered to the textile being
coated. The
wet pick up may be expressed by the following formula:
weight of SFS applied x100
wet pick up(%) =
weight of dry textile material
The total amount of silk fibroin fragments added to the textile material may
be
expressed by the following formula:
SFS added (%) = weight of dry SFS coated textile material x 100
weight of dry textile material before coating
Regarding methods for applying silk fibroin fragments to textiles more
broadly,
silk fibroin fragments may be applied to textiles by methods known in the art,
for
example methods described in U.S. Patent Application Publications Nos.
20160222579,
20160281294, and 20190003113.
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In an embodiment, "substantially modifying" silk fibroin coating performance
may be a decrease in a selected property of silk fibroin coating, such as
wetting time,
absorption rate, spreading speed, accumulative one-way transport, or overall
moisture
management capability as compared to a control silk fibroin coating that was
not
subjected to the selected temperature for drying, curing, wash cycling, and/or
heat setting
purposes, where such decrease is less than about a 1% decrease, or less than
about a 2 %
decrease, or less than about a 3 % decrease, or less than about a 4 %
decrease, or less than
about a 5 % decrease, or less than about a 6 % decrease, or less than about a
7 %
decrease, or less than about an 8 % decrease, or less than about a 9 %
decrease, or less
than about a 10 % decrease, or less than about a 15 % decrease, or less than
about a 20 %
decrease, or less than about a 25 % decrease, or less than about a 30 %
decrease, or less
than about a 35 % decrease, or less than about a 40 % decrease, or less than
about a 45 %
decrease, or less than about a 50 % decrease, or less than about a 60%
decrease, or less
than about a 70 % decrease, or less than about a 80 % decrease, or less than
about a 90 %
decrease, or less than about 100 % decrease in wetting time, absorption rate,
spreading
speed, accumulative one-way transport, or overall moisture management
capability as
compared to a control silk fibroin coating that was not subjected to the
selected
temperature for drying, curing, wash cycling, and/or heat setting purposes. In
some
embodiments, "wash cycling" may refer to at least one wash cycle, or at least
two wash
cycles, or at least three wash cycles, or at least four wash cycles, or at
least five wash
cycles.
In an embodiment, "substantially modifying" silk fibroin coating performance
may be an increase in a selected property of silk fibroin coating, such as
wetting time,
absorption rate, spreading speed, accumulative one-way transport, or overall
moisture
management capability as compared to a control silk fibroin coating that was
not
subjected to the selected temperature for drying, curing, wash cycling, and/or
heat setting
purposes, where such increase is less than about a 1% increase, or less than
about a 2 %
increase, or less than about a 3 % increase, or less than about a 4 %
increase, or less than
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about a 5 % increase, or less than about a 6 % increase, or less than about a
7 % increase,
or less than about an 8 % increase, or less than about a 9 % increase, or less
than about a
% increase, or less than about a 15 % increase, or less than about a 20 %
increase, or
less than about a 25 % increase, or less than about a 30 % increase, or less
than about a
35 % increase, or less than about a 40 % increase, or less than about a 45 %
increase, or
less than about a 50 % increase, or less than about a 60% increase, or less
than about a 70
% increase, or less than about a 80 % increase, or less than about a 90 %
increase, or less
than about 100 % increase in wetting time, absorption rate, spreading speed,
accumulative one-way transport, or overall moisture management capability as
compared
to a control silk fibroin coating that was not subjected to the selected
temperature for
drying, curing, wash cycling, and/or heat setting purposes. In some
embodiments, "wash
cycling" may refer to at least one wash cycle, or at least two wash cycles, or
at least three
wash cycles, or at least four wash cycles, or at least five wash cycles.
In some embodiments, silk fibroin fragments may be used in combination with
chemical agents. In some embodiments, silk fibroin fragments may be applied in
conjunction with a chemical agent, for example a chemical modifier and/or a
physical
modifier. In some embodiments, the chemical modifier is chemically linked to
one or
more of a silk fibroin side group and a silk fibroin terminal group. In some
embodiments,
the silk fibroin side group and the silk fibroin terminal group are
independently selected
from an amine group, an amide group, a carboxyl group, a hydroxyl group, a
thiol group,
and a sulfhydryl group. In some embodiments, the chemical modifier is
chemically linked
to one or more functional groups on the substrate. n some embodiments, the
functional
group on the substrate is selected from an amine group, an amide group, a
carboxyl
group, a hydroxyl group, a thiol group, and a sulfhydryl group. In some
embodiments, the
chemical modifier includes one or more of a chemically linked functional
group, or
functional group residue, and a linker. In some embodiments, the chemical
modifier
includes one or more of -CIV2-, -C=C-, -
alkyl-, -alkenyl-, -alkynyl-, -aryl-,
-heteroaryl-, -0-, -S-, -0C(0)-, -N=N-,
=N-, -C(0)-, -C(0)0-, -0C(0)N(Ita)-, -
C(0)N(Ita)-, -N(Ita)C(0)0-, -N(Ita)C(0)-, -N(Ita)C(0)N(Ita)-, -
N(Ita)C(NIV)N(Ita)-, -
N(Ita)S(0)t-, -S(0)t0-, -S(0)tN(Ita)-, -S(0)tN(Ita)C(0)-, -0P(0)(01V)0-,
wherein t is 1
or 2, and wherein at each independent occurrence IV is selected from hydrogen,
alkyl,
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alkenyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl,
heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl.
"Alkyl" refers to a straight or branched hydrocarbon chain radical consisting
solely of carbon and hydrogen atoms, containing no unsaturation, having from
one to ten
carbon atoms (e.g., (Ct-to)alkyl or Ci-to alkyl). Whenever it appears herein,
a numerical
range such as "1 to 10" refers to each integer in the given range - e.g.,"1 to
10 carbon
atoms" means that the alkyl group may consist of 1 carbon atom, 2 carbon
atoms, 3
carbon atoms, etc., up to and including 10 carbon atoms, although the
definition is also
intended to cover the occurrence of the term "alkyl" where no numerical range
is
specifically designated. Typical alkyl groups include, but are in no way
limited to,
methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl isobutyl,
tertiary butyl,
pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl and decyl. The alkyl
moiety may
be attached to the rest of the molecule by a single bond, such as for example,
methyl
(Me), ethyl (Et), n-propyl (Pr), 1-methylethyl (isopropyl), n-butyl, n-pentyl,
1,1-
dimethylethyl (t-butyl) and 3-methylhexyl. Unless stated otherwise
specifically in the
specification, an alkyl group is optionally substituted by one or more of
substituents
which are independently heteroalkyl, alkenyl, alkynyl, cycloalkyl,
heterocycloalkyl, aryl,
arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, -0Ra, -SRa, -0C(0)-Ra, -N(Ra)2, -
C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2
where each Ra
is independently hydrogen, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Alkylaryl" refers to an -(alkyl)aryl radical where aryl and alkyl are as
disclosed
herein and which are optionally substituted by one or more of the substituents
described
as suitable substituents for aryl and alkyl respectively.
"Alkylhetaryl" refers to an -(alkyl)hetaryl radical where hetaryl and alkyl
are as
disclosed herein and which are optionally substituted by one or more of the
substituents
described as suitable substituents for aryl and alkyl respectively.
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"Alkylheterocycloalkyl" refers to an -(alkyl) heterocyclyl radical where alkyl
and
heterocycloalkyl are as disclosed herein and which are optionally substituted
by one or
more of the substituents described as suitable substituents for
heterocycloalkyl and alkyl
respectively.
An "alkene" moiety refers to a group consisting of at least two carbon atoms
and
at least one carbon-carbon double bond, and an "alkyne" moiety refers to a
group
consisting of at least two carbon atoms and at least one carbon-carbon triple
bond. The
alkyl moiety, whether saturated or unsaturated, may be branched, straight
chain, or
cyclic.
"Alkenyl" refers to a straight or branched hydrocarbon chain radical group
consisting solely of carbon and hydrogen atoms, containing at least one double
bond, and
having from two to ten carbon atoms (i.e., (C2-io)alkenyl or C2-io alkenyl).
Whenever it
appears herein, a numerical range such as "2 to 10" refers to each integer in
the given
range - e.g., "2 to 10 carbon atoms" means that the alkenyl group may consist
of 2 carbon
atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms. The alkenyl
moiety
may be attached to the rest of the molecule by a single bond, such as for
example, ethenyl
(i.e., vinyl), prop-l-enyl (i.e., allyl), but-l-enyl, pent-l-enyl and penta-
1,4-dienyl. Unless
stated otherwise specifically in the specification, an alkenyl group is
optionally
substituted by one or more substituents which are independently alkyl,
heteroalkyl,
alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl,
hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro,
trimethylsilanyl, -OR', -
SR', -0C(0)-Ra, -N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -
N(Ra)C(0)0Ra, -N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa
(where t is 1 or 2), -S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1
or 2), or
P03(Ra)2, where each IV is independently hydrogen, alkyl, fluoroalkyl,
carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl,
heteroaryl or
heteroarylalkyl.
"Alkenyl-cycloalkyl" refers to an -(alkenyl)cycloalkyl radical where alkenyl
and
cycloalkyl are as disclosed herein and which are optionally substituted by one
or more of
the substituents described as suitable substituents for alkenyl and cycloalkyl
respectively.
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"Alkynyl" refers to a straight or branched hydrocarbon chain radical group
consisting solely of carbon and hydrogen atoms, containing at least one triple
bond,
having from two to ten carbon atoms (i.e., (C2-io)alkynyl or C2-io alkynyl).
Whenever it
appears herein, a numerical range such as "2 to 10" refers to each integer in
the given
range - e.g., "2 to 10 carbon atoms" means that the alkynyl group may consist
of 2 carbon
atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms. The alkynyl
may be
attached to the rest of the molecule by a single bond, for example, ethynyl,
propynyl,
butynyl, pentynyl and hexynyl. Unless stated otherwise specifically in the
specification,
an alkynyl group is optionally substituted by one or more substituents which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl,
heterocycloalkyl, aryl,
arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, -0Ra, -SRa, -0C(0)-Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each Ra
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Alkynyl-cycloalkyl" refers to an -(alkynyl)cycloalkyl radical where alkynyl
and
cycloalkyl are as disclosed herein and which are optionally substituted by one
or more of
the substituents described as suitable substituents for alkynyl and cycloalkyl
respectively.
"Carboxaldehyde" refers to a -(C=0)H radical.
"Carboxyl" refers to a -(C=0)0H radical.
"Cyano" refers to a -CN radical.
"Cycloalkyl" refers to a monocyclic or polycyclic radical that contains only
carbon and hydrogen, and may be saturated, or partially unsaturated.
Cycloalkyl groups
include groups having from 3 to 10 ring atoms (i.e. (C3-io)cycloalkyl or C3-10
cycloalkyl).
Whenever it appears herein, a numerical range such as "3 to 10" refers to each
integer in
the given range - e.g., "3 to 10 carbon atoms" means that the cycloalkyl group
may
consist of 3 carbon atoms, etc., up to and including 10 carbon atoms.
Illustrative
examples of cycloalkyl groups include, but are not limited to the following
moieties:
cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,
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cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, and the like.
Unless stated
otherwise specifically in the specification, a cycloalkyl group is optionally
substituted by
one or more substituents which independently are: alkyl, heteroalkyl, alkenyl,
alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl,
hydroxy, halo,
cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR', -SR',
-0C(0)-Ra,
-N(Ra)2, -C(0)Ra, -C(0)01V, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)01ta, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tOlta (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each Ra
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Cycloalkyl-alkenyl" refers to a -(cycloalkyl)alkenyl radical where cycloalkyl
and
alkenyl are as disclosed herein and which are optionally substituted by one or
more of the
substituents described as suitable substituents for cycloalkyl and alkenyl,
respectively.
"Cycloalkyl-heterocycloalkyl" refers to a -(cycloalkyl)heterocycloalkyl
radical
where cycloalkyl and heterocycloalkyl are as disclosed herein and which are
optionally
substituted by one or more of the substituents described as suitable
substituents for
cycloalkyl and heterocycloalkyl, respectively.
"Cycloalkyl-heteroaryl" refers to a -(cycloalkyl)heteroaryl radical where
cycloalkyl and heteroaryl are as disclosed herein and which are optionally
substituted by
one or more of the substituents described as suitable substituents for
cycloalkyl and
heteroaryl, respectively.
The term "alkoxy" refers to the group -0-alkyl, including from 1 to 8 carbon
atoms of a straight, branched, cyclic configuration and combinations thereof
attached to
the parent structure through an oxygen. Examples include, but are not limited
to,
methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy and cyclohexyloxy. "Lower
alkoxy" refers to alkoxy groups containing one to six carbons.
The term "substituted alkoxy" refers to alkoxy wherein the alkyl constituent
is
substituted (i.e -0-(substituted alkyl)). Unless stated otherwise specifically
in the
specification, the alkyl moiety of an alkoxy group is optionally substituted
by one or
more substituents which independently are: alkyl, heteroalkyl, alkenyl,
alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl,
hydroxy, halo,
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cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR', -SR',
-0C(0)-Ra,
-N(Ra)2, -C(0)Ra, -C(0)01V, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)01ta, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-8(0)tOlta (where t is 1 or 2), -8(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each IV
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
The term "alkoxycarbonyl" refers to a group of the formula (alkoxy)(C=0)-
attached through the carbonyl carbon wherein the alkoxy group has the
indicated number
of carbon atoms. Thus a (C1-6)alkoxycarbonyl group is an alkoxy group having
from 1 to
6 carbon atoms attached through its oxygen to a carbonyl linker. "Lower
alkoxycarbonyl"
refers to an alkoxycarbonyl group wherein the alkoxy group is a lower alkoxy
group.
The term "substituted alkoxycarbonyl" refers to the group (substituted alkyl)-
0-
C(0)- wherein the group is attached to the parent structure through the
carbonyl
functionality. Unless stated otherwise specifically in the specification, the
alkyl moiety of
an alkoxycarbonyl group is optionally substituted by one or more substituents
which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl,
heterocycloalkyl, aryl,
arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, ORa,-SR', -0C(0)-Ra, -
N(Ra)2, -C(0)Ra, -C(0)01V, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)01ta, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-8(0)tOlta (where t is 1 or 2), -8(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each IV
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Acyl" refers to the groups (alkyl)-C(0)-, (aryl)-C(0)-, (heteroaryl)-C(0)-,
(heteroalkyl)-C(0)- and (heterocycloalkyl)-C(0)-, wherein the group is
attached to the
parent structure through the carbonyl functionality. If the R radical is
heteroaryl or
heterocycloalkyl, the hetero ring or chain atoms contribute to the total
number of chain or
ring atoms. Unless stated otherwise specifically in the specification, the
alkyl, aryl or
heteroaryl moiety of the acyl group is optionally substituted by one or more
substituents
which are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl,
heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo,
cyano,
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trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -0Ra, -SRa, -0C(0)-
Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tOlta (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each IV
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Acyloxy" refers to a R(C=0)0- radical wherein R is alkyl, aryl, heteroaryl,
heteroalkyl or heterocycloalkyl, which are as described herein. If the R
radical is
heteroaryl or heterocycloalkyl, the hetero ring or chain atoms contribute to
the total
number of chain or ring atoms. Unless stated otherwise specifically in the
specification,
the R of an acyloxy group is optionally substituted by one or more
substituents which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl,
heterocycloalkyl, aryl,
arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, -0Ra, -SRa, -0C(0)-Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tOlta (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each Ra
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Acylsulfonamide" refers a -S(0)2-N(Ra)-C(=0)- radical, where Ra is hydrogen,
alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl,
heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl or heteroarylalkyl. Unless stated otherwise
specifically
in the specification, an acylsulfonamide group is optionally substituted by
one or more
substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl,
heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo,
cyano,
trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -0Ra, -SRa, -0C(0)-
Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each Ra
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
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"Amino" or "amine" refers to a -N(Ra)2 radical group, where each IV is
independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl, unless
stated
otherwise specifically in the specification. When a -N(Ra)2 group has two IV
substituents
other than hydrogen, they can be combined with the nitrogen atom to form a 4-,
5-, 6- or
7-membered ring. For example, -N(Ra)2 is intended to include, but is not
limited to, 1-
pyrrolidinyl and 4-morpholinyl. Unless stated otherwise specifically in the
specification,
an amino group is optionally substituted by one or more substituents which
independently
are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl,
arylalkyl,
heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy,
nitro, trimethylsilanyl, -0Ra, SRa,-0C(0)-Ra, -N(Ra)2, -C(0)Ra, -C(0)0Ra, -
0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2,
N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1 or 2), -S(0)tORa (where t is 1
or
2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2, where each IV is
independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
The term "substituted amino" also refers to N-oxides of the groups -NHRa, and
NRalta each as described above. N-oxides can be prepared by treatment of the
corresponding amino group with, for example, hydrogen peroxide or m-
chloroperoxybenzoic acid.
"Amide" or "amido" refers to a chemical moiety with formula -C(0)N(R)2
or -NHC(0)R, where R is selected from the group consisting of hydrogen, alkyl,
cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and
heteroalicyclic (bonded
through a ring carbon), each of which moiety may itself be optionally
substituted. The R2
of -N(R)2 of the amide may optionally be taken together with the nitrogen to
which it is
attached to form a 4-, 5-, 6- or 7-membered ring. Unless stated otherwise
specifically in
the specification, an amido group is optionally substituted independently by
one or more
of the substituents as described herein for alkyl, cycloalkyl, aryl,
heteroaryl, or
heterocycloalkyl. An amide may be an amino acid or a peptide molecule attached
to a
compound disclosed herein, thereby forming a prodrug. The procedures and
specific
groups to make such amides are known to those of skill in the art and can
readily be
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found in seminal sources such as Greene and Wuts, Protective Groups in Organic
Synthesis, 3rd Ed., John Wiley & Sons, New York, N.Y., 1999, which is
incorporated
herein by reference in its entirety.
"Aromatic" or "aryl" or "Ar" refers to an aromatic radical with six to ten
ring
atoms (e.g., C6-Cio aromatic or C6-Cio aryl) which has at least one ring
having a
conjugated pi electron system which is carbocyclic (e.g., phenyl, fluorenyl,
and
naphthyl). Bivalent radicals formed from substituted benzene derivatives and
having the
free valences at ring atoms are named as substituted phenylene radicals.
Bivalent radicals
derived from univalent polycyclic hydrocarbon radicals whose names end in "-
y1" by
removal of one hydrogen atom from the carbon atom with the free valence are
named by
adding "-idene" to the name of the corresponding univalent radical, e.g., a
naphthyl group
with two points of attachment is termed naphthylidene. Whenever it appears
herein, a
numerical range such as "6 to 10" refers to each integer in the given range;
e.g., "6 to 10
ring atoms" means that the aryl group may consist of 6 ring atoms, 7 ring
atoms, etc., up
to and including 10 ring atoms. The term includes monocyclic or fused-ring
polycyclic
(i.e., rings which share adjacent pairs of ring atoms) groups. Unless stated
otherwise
specifically in the specification, an aryl moiety is optionally substituted by
one or more
substituents which are independently alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl,
heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo,
cyano,
trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, ORa,-SRa, -0C(0)-
Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each IV
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
The term "aryloxy" refers to the group -0-aryl.
The term "substituted aryloxy" refers to aryloxy wherein the aryl substituent
is
substituted (i.e -0-(substituted aryl)). Unless stated otherwise specifically
in the
specification, the aryl moiety of an aryloxy group is optionally substituted
by one or more
substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl,
heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo,
cyano,
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trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, ORa,-SRa, -0C(0)-
Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2,
where each IV
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Aralkyl" or "arylalkyl" refers to an (aryl)alkyl-radical where aryl and alkyl
are as
disclosed herein and which are optionally substituted by one or more of the
substituents
described as suitable substituents for aryl and alkyl respectively.
"Ester" refers to a chemical radical of formula -COOR, where R is selected
from
the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a
ring carbon)
and heteroalicyclic (bonded through a ring carbon). The procedures and
specific groups
to make esters are known to those of skill in the art and can readily be found
in seminal
sources such as Greene and Wuts, Protective Groups in Organic Synthesis, 3rd
Ed., John
Wiley & Sons, New York, N.Y., 1999, which is incorporated herein by reference
in its
entirety. Unless stated otherwise specifically in the specification, an ester
group is
optionally substituted by one or more substituents which independently are:
alkyl,
heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl,
heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy,
nitro,
trimethylsilanyl, -OR', -SR', -0C(0)-Ra, -N(Ra)2, -C(0)Ra, -C(0)0Ra, -
0C(0)N(Ra)2, -
C(0)N(Ra)2, -N(Ra)C(0)0Ra, -N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -
N(Ra)S(0)tRa (where t is 1 or 2), -S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2
(where t is 1
or 2), or P03(Ra)2, where each IV is independently hydrogen, alkyl,
fluoroalkyl,
carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl,
heterocycloalkylalkyl,
heteroaryl or heteroarylalkyl.
"Fluoroalkyl" refers to an alkyl radical, as defined above, that is
substituted by
one or more fluoro radicals, as defined above, for example, trifluoromethyl,
difluoromethyl, 2,2,2-trifluoroethyl, 1-fluoromethy1-2-fluoroethyl, and the
like. The alkyl
part of the fluoroalkyl radical may be optionally substituted as defined above
for an alkyl
group.
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"Halo," "halide," or, alternatively, "halogen" is intended to mean fluoro,
chloro,
bromo or iodo. The terms "haloalkyl," "haloalkenyl," "haloalkynyl," and
"haloalkoxy"
include alkyl, alkenyl, alkynyl and alkoxy structures that are substituted
with one or more
halo groups or with combinations thereof. For example, the terms "fluoroalkyl"
and
"fluoroalkoxy" include haloalkyl and haloalkoxy groups, respectively, in which
the halo
is fluorine.
"Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" refer to optionally
substituted alkyl, alkenyl and alkynyl radicals and which have one or more
skeletal chain
atoms selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur,
phosphorus
or combinations thereof A numerical range may be given - e.g., Ci-C4
heteroalkyl which
refers to the chain length in total, which in this example is 4 atoms long. A
heteroalkyl
group may be substituted with one or more substituents which independently
are: alkyl,
heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl,
heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -
0Ra, -SRa, -
OC(0)-Ra, -N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -
N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each Ra
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
"Heteroalkylaryl" refers to an -(heteroalkyl)aryl radical where heteroalkyl
and
aryl are as disclosed herein and which are optionally substituted by one or
more of the
substituents described as suitable substituents for heteroalkyl and aryl,
respectively.
"Heteroalkylheteroaryl" refers to an -(heteroalkyl)heteroaryl radical where
heteroalkyl and heteroaryl are as disclosed herein and which are optionally
substituted by
one or more of the substituents described as suitable substituents for
heteroalkyl and
heteroaryl, respectively.
"Heteroalkylheterocycloalkyl" refers to an -(heteroalkyl)heterocycloalkyl
radical
where heteroalkyl and heterocycloalkyl are as disclosed herein and which are
optionally
substituted by one or more of the substituents described as suitable
substituents for
heteroalkyl and heterocycloalkyl, respectively.
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"Heteroalkylcycloalkyl" refers to an -(heteroalkyl)cycloalkyl radical where
heteroalkyl and cycloalkyl are as disclosed herein and which are optionally
substituted by
one or more of the substituents described as suitable substituents for
heteroalkyl and
cycloalkyl, respectively.
"Heteroaryl" or "heteroaromatic" or "HetAr" refers to a 5- to 18-membered
aromatic radical (e.g., C5-C13 heteroaryl) that includes one or more ring
heteroatoms
selected from nitrogen, oxygen and sulfur, and which may be a monocyclic,
bicyclic,
tricyclic or tetracyclic ring system. Whenever it appears herein, a numerical
range such as
"5 to 18" refers to each integer in the given range - e.g., "5 to 18 ring
atoms" means that
the heteroaryl group may consist of 5 ring atoms, 6 ring atoms, etc., up to
and including
18 ring atoms. Bivalent radicals derived from univalent heteroaryl radicals
whose names
end in "-y1" by removal of one hydrogen atom from the atom with the free
valence are
named by adding "-idene" to the name of the corresponding univalent radical -
e.g., a
pyridyl group with two points of attachment is a pyridylidene. A N-containing
"heteroaromatic" or "heteroaryl" moiety refers to an aromatic group in which
at least one
of the skeletal atoms of the ring is a nitrogen atom. The polycyclic
heteroaryl group may
be fused or non-fused. The heteroatom(s) in the heteroaryl radical are
optionally
oxidized. One or more nitrogen atoms, if present, are optionally quaternized.
The
heteroaryl may be attached to the rest of the molecule through any atom of the
ring(s).
Examples of heteroaryls include, but are not limited to, azepinyl, acridinyl,
benzimidazolyl, benzindolyl, 1,3-benzodioxolyl, benzofuranyl, benzooxazolyl,
benzo[d]thiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepinyl,
benzo[b][1,4]oxazinyl,
1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl,
benzodioxinyl,
benzoxazolyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl,
benzofurazanyl, benzothiazolyl, benzothienyl(benzothiophenyl), benzothieno[3,2-
d]pyrimidinyl, benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyridinyl, carbazolyl,
cinnolinyl,
cyclopenta[d]pyrimidinyl, 6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-
d]pyrimidinyl, 5,6-
dihydrobenzo[h]quinazolinyl, 5,6-dihydrobenzo[h]cinnolinyl, 6,7-dihydro-5H-
benzo[6,7]cyclohepta[1,2-c]pyridazinyl, dibenzofuranyl, dibenzothiophenyl,
furanyl,
furazanyl, furanonyl, furo[3,2-c]pyridinyl, 5,6,7,8,9,10-
hexahydrocycloocta[d]pyrimidinyl, 5,6,7,8,9,10-
hexahydrocycloocta[d]pyridazinyl,
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5,6,7,8,9,10-hexahydrocycloocta[d]pyridinyl, isothiazolyl, imidazolyl,
indazolyl, indolyl,
indazolyl, isoindolyl, indolinyl, isoindolinyl, isoquinolyl, indolizinyl,
isoxazolyl, 5,8-
methano-5,6,7,8-tetrahydroquinazolinyl, naphthyridinyl, 1,6-naphthyridinonyl,
oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 5,6,6a,7,8,9,10,10a-
octahydrobenzo[h]quinazolinyl, 1-pheny1-1H-pyrrolyl, phenazinyl,
phenothiazinyl,
phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrrolyl, pyrazolyl,
pyrazolo[3,4-d]pyrimidinyl, pyridinyl, pyrido[3,2-d]pyrimidinyl, pyrido[3,4-
d]pyrimidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrrolyl, quinazolinyl,
quinoxalinyl,
quinolinyl, isoquinolinyl, tetrahydroquinolinyl, 5,6,7,8-
tetrahydroquinazolinyl, 5,6,7,8-
tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidinyl, 6,7,8,9-tetrahydro-5H-
cyclohepta[4,5]thieno[2,3-d]pyrimidinyl, 5,6,7,8-tetrahydropyrido[4,5-
c]pyridazinyl,
thiazolyl, thiadiazolyl, thiapyranyl, triazolyl, tetrazolyl, triazinyl,
thieno[2,3-
d]pyrimidinyl, thieno[3,2-d]pyrimidinyl, thieno[2,3-c]pyridinyl, and
thiophenyl (i.e.,
thienyl). Unless stated otherwise specifically in the specification, a
heteroaryl moiety is
optionally substituted by one or more substituents which are independently:
alkyl,
heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl,
heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -
OR', -
OC(0)-Ra, -N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -
N(Ra)C(0)0Ra, -
N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa (where t is 1
or 2),
-S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1 or 2), or P03(Ra)2,
where each IV
is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl,
aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
Substituted heteroaryl also includes ring systems substituted with one or more
oxide (-0-) substituents, such as, for example, pyridinyl N-oxides.
"Heteroarylalkyl" refers to a moiety having an aryl moiety, as described
herein,
connected to an alkylene moiety, as described herein, wherein the connection
to the
remainder of the molecule is through the alkylene group.
"Heterocycloalkyl" refers to a stable 3- to 18-membered non-aromatic ring
radical
that comprises two to twelve carbon atoms and from one to six heteroatoms
selected from
nitrogen, oxygen and sulfur. Whenever it appears herein, a numerical range
such as "3 to
18" refers to each integer in the given range - e.g., "3 to 18 ring atoms"
means that the
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heterocycloalkyl group may consist of 3 ring atoms, 4 ring atoms, etc., up to
and
including 18 ring atoms. Unless stated otherwise specifically in the
specification, the
heterocycloalkyl radical is a monocyclic, bicyclic, tricyclic or tetracyclic
ring system,
which may include fused or bridged ring systems. The heteroatoms in the
heterocycloalkyl radical may be optionally oxidized. One or more nitrogen
atoms, if
present, are optionally quaternized. The heterocycloalkyl radical is partially
or fully
saturated. The heterocycloalkyl may be attached to the rest of the molecule
through any
atom of the ring(s). Examples of such heterocycloalkyl radicals include, but
are not
limited to, dioxolanyl, thienyl[1,3]dithianyl, decahydroisoquinolyl,
imidazolinyl,
imidazolidinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl,
octahydroindolyl,
octahydroisoindolyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl,
oxazolidinyl,
piperidinyl, piperazinyl, 4-piperidonyl, pyrrolidinyl, pyrazolidinyl,
quinuclidinyl,
thiazolidinyl, tetrahydrofuryl, trithianyl, tetrahydropyranyl,
thiomorpholinyl,
thiamorpholinyl, 1-oxo-thiomorpholinyl, and 1,1-dioxo-thiomorpholinyl. Unless
stated
otherwise specifically in the specification, a heterocycloalkyl moiety is
optionally
substituted by one or more substituents which independently are: alkyl,
heteroalkyl,
alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl,
hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -0Ra, -SRa, -0C(0)-
Ra, -
N(Ra)2, -C(0)Ra, -C(0)0Ra, -0C(0)N(Ra)2, -C(0)N(Ra)2, -
N(Ra)C(0)0Ra, -N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(0)tRa
(where t is 1 or 2), -S(0)tORa (where t is 1 or 2), -S(0)tN(Ra)2 (where t is 1
or 2), or
P03(Ra)2, where each Ra is independently hydrogen, alkyl, fluoroalkyl,
carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl,
heteroaryl or
heteroarylalkyl.
"Heterocycloalkyl" also includes bicyclic ring systems wherein one non-
aromatic
ring, usually with 3 to 7 ring atoms, contains at least 2 carbon atoms in
addition to 1-3
heteroatoms independently selected from oxygen, sulfur, and nitrogen, as well
as
combinations comprising at least one of the foregoing heteroatoms; and the
other ring,
usually with 3 to 7 ring atoms, optionally contains 1-3 heteroatoms
independently
selected from oxygen, sulfur, and nitrogen and is not aromatic.
"Nitro" refers to the -NO2 radical.
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"Oxa" refers to the -0- radical.
"Oxo" refers to the =0 radical.
"Isomers" are different compounds that have the same molecular formula.
"Stereoisomers" are isomers that differ only in the way the atoms are arranged
in space -
i.e., having a different stereochemical configuration. "Enantiomers" are a
pair of
stereoisomers that are non-superimposable mirror images of each other. A 1:1
mixture of
a pair of enantiomers is a "racemic" mixture. The term "( )" is used to
designate a
racemic mixture where appropriate. "Diastereoisomers" are stereoisomers that
have at
least two asymmetric atoms, but which are not mirror-images of each other. The
absolute
stereochemistry is specified according to the Cahn-Ingold-Prelog R-S system.
When a
compound is a pure enantiomer the stereochemistry at each chiral carbon can be
specified
by either (R) or (9. Resolved compounds whose absolute configuration is
unknown can
be designated (+) or (-) depending on the direction (dextro- or levorotatory)
which they
rotate plane polarized light at the wavelength of the sodium D line. Certain
of the
compounds described herein contain one or more asymmetric centers and can thus
give
rise to enantiomers, diastereomers, and other stereoisomeric forms that can be
defined, in
terms of absolute stereochemistry, as (R) or (9. The present chemical
entities,
pharmaceutical compositions and methods are meant to include all such possible
isomers,
including racemic mixtures, optically pure forms and intermediate mixtures.
Optically
active (R)- and (9-isomers can be prepared using chiral synthons or chiral
reagents, or
resolved using conventional techniques. When the compounds described herein
contain
olefinic double bonds or other centers of geometric asymmetry, and unless
specified
otherwise, it is intended that the compounds include both E and Z geometric
isomers.
"Substituted" means that the referenced group may have attached one or more
additional
groups, radicals or moieties individually and independently selected from, for
example,
acyl, alkyl, alkylaryl, cycloalkyl, aralkyl, aryl, carbohydrate, carbonate,
heteroaryl,
heterocycloalkyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio,
cyano, halo,
carbonyl, ester, thiocarbonyl, isocyanato, thiocyanato, isothiocyanato, nitro,
oxo,
perhaloalkyl, perfluoroalkyl, phosphate, silyl, sulfinyl, sulfonyl,
sulfonamidyl, sulfoxyl,
sulfonate, urea, and amino, including mono- and di-substituted amino groups,
and
protected derivatives thereof. The substituents themselves may be substituted,
for
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example, a cycloalkyl substituent may itself have a halide substituent at one
or more of its
ring carbons. The term "optionally substituted" means optional substitution
with the
specified groups, radicals or moieties.
"Sulfanyl" refers to groups that include -S-(optionally substituted alkyl), -S-
(optionally substituted aryl), -S-(optionally substituted heteroaryl) and -S-
(optionally
substituted heterocycloalkyl).
"Sulfinyl" refers to groups that include -S(0)-H, -S(0)-(optionally
substituted
alkyl), -S(0)-(optionally substituted amino), -S(0)-(optionally substituted
aryl), -S(0)-
(optionally substituted heteroaryl) and -S(0)-(optionally substituted
heterocycloalkyl).
"Sulfonyl" refers to groups that include -S(02)-H, -S(02)-(optionally
substituted
alkyl), -S(02)-(optionally substituted amino), -S(02)-(optionally substituted
aryl), -S(02)-
(optionally substituted heteroaryl), and -S(02)-(optionally substituted
heterocycloalkyl).
"Sulfonamidyl" or "sulfonamido" refers to a -S(=0)2-NRR radical, where each R
is selected independently from the group consisting of hydrogen, alkyl,
cycloalkyl, aryl,
heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through
a ring
carbon). The R groups in -NRR of the -S(=0)2-NRR radical may be taken together
with
the nitrogen to which it is attached to form a 4-, 5-, 6- or 7-membered ring.
A
sulfonamido group is optionally substituted by one or more of the substituents
described
for alkyl, cycloalkyl, aryl, heteroaryl, respectively.
"Sulfoxyl" refers to a -S(=0)20H radical.
"Sulfonate" refers to a -S(=0)2-OR radical, where R is selected from the group
consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring
carbon) and
heteroalicyclic (bonded through a ring carbon). A sulfonate group is
optionally
substituted on R by one or more of the substituents described for alkyl,
cycloalkyl, aryl,
heteroaryl, respectively.
In some embodiments, a chemical agent may be applied to a textile to be coated
prior to providing a silk fibroin fragments coating. In some embodiments, a
chemical
agent may be applied to a textile after such textile has been coated with a
silk fibroin
fragments coating. One or more chemical agents may be applied, as set forth
above, and
may include a first chemical agent, second chemical agent, third chemical
agent, and the
like, where the chemical agents may be the same or a combination of two or
more of the
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chemical agents described herein. In some embodiments, chemical agents may
provide
selected properties to coated textile (e.g., fabric) including, but not
limited to, an
antimicrobial property, a water repellant property, an oil repellant property,
a coloring
property, a flame retardant property, a fabric softening property, a pH
adjusting property,
an anticrocking property, an antipilling property, and/or an antifelting
property. Such
chemical agents may include, but are not limited to, softeners (e.g.,
silicone), acidic
agents, antimicrobials, finishing agents including monomers such as melted
polyester, or
combinations thereof. Chemical agents have been described in U.S. Patent
Application
Publications Nos. 20160222579, 20160281294, and 20190003113, all of which are
incorporated herein in their entireties. Any chemical agent described herein
may act as a
precursor linker. In some embodiments, a precursor linker reacts with a
substrate, and
then fibroin can react with the linker. In some embodiments, a precursor
linker reacts
with silk fibroin, and then the substrate can react with the linker.
In some embodiments, the chemical agent may include one or more of a silicone,
an acidic agent, a dyeing agent, a pigment dye, a traditional finishing agent,
and a
technical finishing agent. The dyeing agent may include one or more of a
dispersing
agent, a levelling agent, a fixing agent, a special resin, an antireducing
agent, and an
anticreasing agent. The pigment dye may include one or more of an
antimigrating agent,
a binding agent, an all in one agent, and a delave agent. The traditional
finishing agent
may include one or more of a wrinkle free treatment, a softener, a handle
modifier, a
waterborne polyurethanes dispersion, and other resins. The technical finishing
agent may
include one or more of a waterborne polyurethanes dispersion, an oil
repellant, a water
repellant, a crosslinker, and a thickener.
In some embodiments, the chemical agent may include an acidic agent. In some
embodiments, an acidic agent may be a Bronsted acid. In an embodiment, the
acidic
agent includes one or more of citric acid and acetic acid. In an embodiment,
the acidic
agent aids the deposition and coating of silk fibroin fragments mixtures on
the textile to
be coated as compared to the absence of such acidic agent. In an embodiment,
the acidic
agent improves crystallization of the SPF mixtures at the textile to be
coated.
In an embodiment, the acidic agent is added at a concentration by weight (%
w/w
or % w/v) or by volume (v/v) of greater than about 0.001 %, or greater than
about 0.002
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%, or greater than about 0.003 %, or greater than about 0.004 %, or greater
than about
0.005 %, or greater than about 0.006 %, or greater than about 0.007 %, or
greater than
about 0.008 %, or greater than about 0.009 %, or greater than about 0.01 %, or
greater
than about 0.02 %, or greater than about 0.03 %, or greater than about 0.04 %,
or greater
than about 0.05 %, or greater than about 0.06 %, or greater than about 0.07 %,
or greater
than about 0.08 %, or greater than about 0.09 %, or greater than about 0.1 %,
or greater
than about 0.2 %, or greater than about 0.3 %, or greater than about 0.4 %, or
greater than
about 0.5 %, or greater than about 0.6 %, or greater than about 0.7 %, or
greater than
about 0.8 %, or greater than about 0.9 %, or greater than about 1.0 % or
greater than
about 2.0 %, or greater than about 3.0 %, or greater than about 4.0 %, or
greater than
about 5.0%.
In an embodiment, the acidic agent is added at a concentration by weight (%
w/w
or % w/v) or by volume (v/v) of less than about 0.001 %, or less than about
0.002 %, or
less than about 0.003 %, or less than about 0.004 %, or less than about 0.005
%, or less
than about 0.006 %, or less than about 0.007 %, or less than about 0.008 %, or
less than
about 0.009 %, or less than about 0.01 %, or less than about 0.02 %, or less
than about
0.03 %, or less than about 0.04 %, or less than about 0.05 %, or less than
about 0.06 %, or
less than about 0.07 %, or less than about 0.08 %, or less than about 0.09 %,
or less than
about 0.1 %, or less than about 0.2 %, or less than about 0.3 %, or less than
about 0.4 %,
or less than about 0.5 %, or less than about 0.6%, or less than about 0.7 %,
or less than
about 0.8 %, or less than about 0.9 %, or less than about 1.0 % or less than
about 2.0 %,
or less than about 3.0 %, or less than about 4.0 %, or less than about 5.0 %.
In some embodiments, a composition including silk fibroin fragments may have a
pH of less than about 9, or less than about 8.5, or less than about 8, or less
than about 7.5,
or less than about 7, or less than about 6.5, or less than about 6, or less
than about 5.5, or
less than about 5, or less than about 4.5, or less than about 4, or greater
than about 3.5, or
greater than about 4, or greater than about 4.5, or greater than about 5, or
greater than
about 5.5, or greater than about 6, or greater than about 6.5, or greater than
about 7, or
greater than about 7.5, or greater than about 8, or greater than about 8.5.
In some embodiments, a composition including silk fibroin fragments may
include an acidic agent, and may have a pH of less than about 9, or less than
about 8.5, or
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less than about 8, or less than about 7.5, or less than about 7, or less than
about 6.5, or
less than about 6, or less than about 5.5, or less than about 5, or less than
about 4.5, or
less than about 4, or greater than about 3.5, or greater than about 4, or
greater than about
4.5, or greater than about 5, or greater than about 5.5, or greater than about
6, or greater
than about 6.5, or greater than about 7, or greater than about 7.5, or greater
than about 8,
or greater than about 8.5.
In an embodiment, the chemical agent may include silicone. In some
embodiments, a SFS may include silicone. In some embodiments, silicone may
include a
silicone emulsion. The term "silicone," may generally refer to a broad family
of synthetic
polymers, mixtures of polymers, and/or emulsions thereof, that have a
repeating silicon-
oxygen backbone including, but not limited to, polysiloxanes. For example, a
silicone
may include ULTRATEX CSP, which is a commercially available (Huntsman
International LLC) silicone emulsion that may be used as a softening agent and
which
may also increase fabric resilience, elasticity of knitted fabrics, and fiber
lubrication and
also improve sewability. A silicone may also include ULTRATEX CI, which is a
commercially available silicone composition (Huntsman International LLC) that
may be
used as a fabric softening agent.
In some embodiments, a composition including silk fibroin fragments may
include silicone in a concentration by weight (% w/w or % w/v) or by volume
(v/v) of
less than about 25 %, or less than about 20%, or less than about 15 %, or less
than about
%, or less than about 9 %, or less than about 8 %, or less than about 7 %, or
less than
about 6 %, or less than about 5 %, or less than about 4 %, or less than about
3 %, or less
than about 2 %, or less than about 1 %, or less than about 0.9 %, or less than
about 0.8%,
or less than about 0.7%, or less than about 0.6 %, or less than about 0.5%, or
less than
about 0.4%, or less than about 0.3%, or less than about 0.2%, or less than
about 0.1%, or
less than about 0.01%, or less than about 0.001 %.
In some embodiments, a composition including silk fibroin fragments may
include silicone in a concentration by weight (% w/w or % w/v) or by volume
(v/v) of
greater than about 25 %, or greater than about 20 %, or greater than about 15
%, or
greater than about 10 %, or greater than about 9 %, or greater than about 8 %,
or greater
than about 7 %, or greater than about 6 %, or greater than about 5 %, or
greater than
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about 4 %, or greater than about 3 %, or greater than about 2 %, or greater
than about 1
%, or greater than about 0.9 %, or greater than about 0.8%, or greater than
about 0.7%, or
greater than about 0.6 %, or greater than about 0.5%, or greater than about
0.4%, or
greater than about 0.3%, or greater than about 0.2%, or greater than about
0.1%, or
greater than about 0.01%, or greater than about 0.001 %.
In some embodiments, a composition including silk fibroin fragments may be
supplied in a concentrated form suspended in water. In some embodiments, a
composition including silk fibroin fragments may have a concentration by
weight (% w/w
or % w/v) or by volume (v/v) of less than about 50 %, or less than about 45%,
or less
than about 40%, or less than about 35%, or less than about 30%, or less than
about 25%,
or less than about 20%, or less than about 15%, or less than about 10%, or
less than about
5%, or less than about 4%, or less than about 3%, or less than about 2%, or
less than
about 1%, or less than about 0.1%, or less than about 0.01%, or less than
about 0.001%,
or less than about 0.0001%, or less than about 0.00001%. In some embodiments,
a
composition including silk fibroin fragments may have a concentration by
weight (% w/w
or % w/v) or by volume (v/v) of greater than about 50 %, or greater than about
45%, or
greater than about 40%, or greater than about 35%, or greater than about 30%,
or greater
than about 25%, or greater than about 20%, or greater than about 15%, or
greater than
about 10%, or greater than about 5%, or greater than about 4%, or greater than
about 3%,
or greater than about 2%, or greater than about 1%, or greater than about
0.1%, or greater
than about 0.01%, or greater than about 0.001%, or greater than about 0.0001%,
or
greater than about 0.00001%.
In some embodiments, the coating processes of the disclosure may include a
finishing step for the resulting coated textiles. In some embodiments, the
finishing or
final finishing of the textiles (e.g., fabrics) that are coated with a
composition including
silk fibroin fragments under the processes disclosed herein may include
sueding,
steaming, brushing, polishing, compacting, raising, tigering, shearing,
heatsetting,
waxing, air jet, calendaring, pressing, shrinking, treatment with polymerizer,
coating,
lamination, and/or laser etching. In some embodiments, finishing of the silk
fibroin
fragments coated textiles may include treatment of the textiles with an AIRO
24 dryer
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that may be used for continuous and open-width tumbling treatments of woven,
non-
woven, and knitted fabrics.
In some embodiments, the coated textiles (e.g., fabrics) described herein may
meet
or exceed requirements established by the following Test Methods:
Test Description Test Method Requirements
Dimensional Stability to AATCC 135 Maximum, Length: -3%,
Laundering Width: -3%
Maximum, Length: -3%,
Width: -5%, for twoway
Stretch Fabrics
Maximum, Length: -5%,
Width: -5%, for fourway
Stretch Fabrics
No Growth
Dimensional Stability to AATCC 158 Maximum, Length: -3%,
Dry Cleaning Width: -3%
Maximum, Length: -3%,
Width: -5%, for twoway
Stretch Fabrics
Maximum, Length: -5%,
Width: -5%, for fourway
Stretch Fabrics
No Growth
Pilling Resistance ASTM D 3512 Minimum 3.0
Abrasion Resistance ASTM D 4966 No rupture to 10,000 cycles
(plain fabrics up to 7.5
oz/yd2; or no rupture to
15,000 cycles (plain fabrics
over 7.5 oz/yd2)
Tearing Strength ASTM D 1424 Shorts, Pants, Jeans,
Jackets, All Plus Size
Styles: 2.5 Lbs Minimum;
or
Blouse, Skirt Dress, Lining,
excluding plus size styles:
1.5 Lbs Minimum; or
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Intimate:
<3 oz/yd2: Minimum
1.51bs;
3-6oz/yd2: Minimum
2. Olb s
>6 oz/yd2: Minimum 2.51bs
Colorfastness to AATCC 61, 2A Color Change: Minimum
Laundering/Colorfastness to 4.0
Washing Staining: Minimum 3.0
Colorfastness to Dry AATCC 132 Color Change: Minimum
Cleaning 4.0
Staining: Minimum 3.0
Colorfastness to AATCC 8 All except below - Dry:
Crocking/Colorfastness to Minimum 4.0; Wet:
Rubbing Minimum 3.0; or
Dark Shades (black, red,
navy) - Dry: Minimum 4.0;
Wet: Minimum 2.5; or
Indigos - Dry: Minimum
3.0; Wet: Minimum 2.0; or
Pigments - Dry: Minimum
3.5; Wet: Minimum 2.5.
Colorfastness to Water AATCC 107 Color Change: Minimum
4.0; Staining: Minimum 3.0
Colorfastness to AATCC 15 Color Change: Minimum
Perspiration 4.0; Staining: Minimum 3
Colorfastness to Light AATCC 16/20 AFU Color Change: Minimum
AATCC 16/5 AFU 4.0
pH Value AATCC 81 4.0 ¨ 8.5 or 4.0-7.5
(children < 36 months)
Antimicrobial AATCC 147 Original: 0% Bacterial
Growth 20 Washes: 0%
Bacterial Growth
AATCC 100 Minimum 99.9%
Reduction
ASTM E 2149
Original: Minimum 99.9%
Reduction
20 Washes: Minimum 80%
Reduction
Wicking AATCC 79 1.0 second or less
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Water Repellency ¨ Spray AATCC 22 Original: 100 Rating
Test After 3x Washes:
Minimum 70 Rating
Water Resistance ¨ Rain AATCC 35 Maximum 1 gram on
Test original and after 3 x
washes
Dimensional Stability to AATCC 150 Maximum, Length= - 3%,
Laundering (Yoga Garment) Width= -3%
Maximum, Length= -3%,
Width= -5% for two-way
Stretch Fabrics
Maximum, Length= -5%,
Width= -5% for four-way
Stretch fabrics
No Distortion Between
Components
No Growth
Dimensional Stability to AATCC 158 Maximum, Length= -3%,
Dry Cleaning (Yoga Width= -3%
Garment)
Maximum, Length= -3%,
Width= -5%, for two-way
Stretch Fabrics
Maximum, Length= -5%,
Width= -5%, for four-way
Stretch Fabrics
No Distortion Between
Components
No Growth
Pilling Resistance (Yoga ASM D 3512 Minimum 3.0
Garment)
Colorfastness to AATCC 61, 2A Color Change: Minimum
Laundering/Colorfastness to 4.0
Washing (Yoga Garment) Staining: Minimum 3.0
Colorfastness AATCC 8 General: Dry: Minimum
Crocking/Colorfastness to 4.0 ; Wet: Minimum 3.0;
Rubbing (Yoga Garment)
For Dark Colors (Black,
Red, Navy): Wet:
Minimum 2.5
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Pigment: Dry: Minimum
3.5 ; Wet: Minimum 2.5
Indigos: Dry: Minimum
3.0; Wet: Minimum 2.0
Colorfastness to Water AATCC 107 Color Change: Minimum
(Yoga Garment) 4.0
Staining: Minimum 3.0
Colorfastness to AATCC 15 Color Change: 4.0 or better
Perspiration (Yoga Staining: 3.0 or better
Garment)
Colorfastness to Light AATCC 16, 20 AFU/5 Minimum 4.0, All, Except
(Yoga Garment) AFU Silk/ Minimum 4.0, Silk
pH Value (Yoga Garment) AATCC 81 Children (>36 months) &
Adults: 4.0 ¨ 8.5
Children (< 36 months): 4.0
¨ 7.5
In some embodiments, the coated textiles (e.g., fabrics) described herein may
meet requirements established by the foregoing Test Methods. In some
embodiments, the
coated textiles (e.g., fabrics) described herein may exceed the requirements
established
by the foregoing Test Methods.
In some embodiments, the coated textiles (e.g., fabrics) may have
antimicrobial
(e.g., antifungal and/or antibacterial activity) due to the silk fibroin
fragments coating. In
an embodiment, antibacterial activity may be determined by the ability of
bacteria on the
coated textile's surface to be washed away from the coated textile surface
following one
or more wash cycles, or two or more wash cycles, or three or more wash cycles,
or four
or more wash cycles, or five or more wash cycles, where the bacteria do not
adhere to the
surface of the coated textile. In an embodiment, antibacterial activity may be
determined
by the ability of the coating to reduce the quantity of the bacteria deposited
on a surface
of the coated textile, wherein the coating may reduce the quantity of the
bacteria by
greater than about 1%, or greater than about 2%, or greater than about 3%, or
greater than
about 4%, or greater than about 5%, or greater than about 10%, or greater than
about
20%, or greater than about 30%, or greater than about 40%, or greater than
about 50%, or
greater than about 60%, or greater than about 70%, or greater than about 80%,
or greater
than about 90%, or greater than about 95%, or greater than about 96%, or
greater than
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about 97%, or greater than about 98%, or greater than about 99%, or by about
100%. In
an embodiment, antibacterial activity of the coating on the coated textile may
be
determined by fluorescent activity (see, e.g., U.S. Patent Nos. 5,089,395 and
5,968,762,
the entirety of which are incorporated herein by reference). In an embodiment,
antibacterial activity for a coating may be determined by the ability of the
coating on a
coated textile to break up colonies of bacteria that may be deposited on a
surface of the
coated textile. In an embodiment, antibacterial activity for a coating may be
determined
by the ability of the coating on a coated textile to: (a) prevent the
formation of a bacterial
biofilm on the coated textile; and/or (b) reduce the size of a bacterial
biofilm on the
coated textile.
EXAMPLES
The following examples are put forth so as to provide those of ordinary skill
in the
art with a complete disclosure and description of how to make and use the
described
embodiments, and are not intended to limit the scope of what the inventors
regard as their
disclosure nor are they intended to represent that the experiments below are
all or the only
experiments performed. Efforts have been made to ensure accuracy with respect
to
numbers used (e.g., amounts, temperature, etc.) but some experimental errors
and
deviations should be accounted for. Unless indicated otherwise, parts are
parts by weight,
molecular weight is weight average molecular weight, temperature is in degrees
Centigrade, and pressure is at or near atmospheric.
The compositions of this disclosure may be made by various methods known in
the art. Such methods include those of the following examples, as well as the
methods
specifically exemplified below. As used herein in the working examples, "low
molecular
weight," "low MW," or "low-MW" silk fibroin fragments include fragments with a
molecular weight between about 14 and about 30 kDa. As used herein in the
working
examples, "medium molecular weight," "medium MW," or "mid-MW" silk fibroin
fragments include fragments with a molecular weight between about 39 and about
54
kDa.
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Example 1: Tangential Flow Filtration (TFF) to Remove Solvent from Dissolved
Silk
Solutions
A variety of % silk concentrations have been produced through the use of
Tangential Flow Filtration (TFF). In all cases a 1% silk solution was used as
the input
feed. A range of 750-18,000 mL of 1% silk solution was used as the starting
volume.
Solution is diafiltered in the TFF to remove lithium bromide. Once below a
specified
level of residual LiBr, solution undergoes ultrafiltration to increase the
concentration
through removal of water. See examples below.
7.30% Silk Solution: A 7.30% silk solution was produced beginning with 30
minute extraction batches of 100 g silk cocoons per batch. Extracted silk
fibers were then
dissolved using 100 C 9.3 M LiBr in a 100 C oven for 1 hour. 100 g of silk
fibers were
dissolved per batch to create 20% silk in LiBr. Dissolved silk in LiBr was
then diluted to
1% silk and filtered through a 5 um filter to remove large debris. 15,500 mL
of 1%,
filtered silk solution was used as the starting volume/diafiltration volume
for TFF. Once
LiBr was removed, the solution was ultrafiltered to a volume around 1300 mL.
1262 mL
of 7.30% silk was then collected. Water was added to the feed to help remove
the
remaining solution and 547 mL of 3.91% silk was then collected.
6.44% Silk Solution: A 6.44% silk solution was produced beginning with 60
minute extraction batches of a mix of 25, 33, 50,75 and 100 g silk cocoons per
batch.
Extracted silk fibers were then dissolved using 100 C 9.3 M LiBr in a 100 C
oven for 1
hour. 35, 42, 50 and 71 g per batch of silk fibers were dissolved to create
20% silk in
LiBr and combined. Dissolved silk in LiBr was then diluted to 1% silk and
filtered
through a 5 um filter to remove large debris. 17,000 mL of 1%, filtered silk
solution was
used as the starting volume/diafiltration volume for TFF. Once LiBr was
removed, the
solution was ultrafiltered to a volume around 3000 mL. 1490 mL of 6.44% silk
was then
collected. Water was added to the feed to help remove the remaining solution
and 1454
mL of 4.88% silk was then collected
2.70% Silk Solution: A 2.70% silk solution was produced beginning with 60
minute extraction batches of 25 g silk cocoons per batch. Extracted silk
fibers were then
dissolved using 100 C 9.3 M LiBr in a 100 C oven for 1 hour. 35.48 g of silk
fibers
were dissolved per batch to create 20% silk in LiBr. Dissolved silk in LiBr
was then
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diluted to 1% silk and filtered through a 5 um filter to remove large debris.
1000 mL of
1%, filtered silk solution was used as the starting volume/diafiltration
volume for TFF.
Once LiBr was removed, the solution was ultrafiltered to a volume around 300
mL. 312
mL of 2.7% silk was then collected.
Example 2: Silk fibroin chemically linked to Nylon
Synthesis of chemically modified silk fibroin: 6% Low silk: 100 mL, was
reacted
with 2,3-Dibromopropionyl chloride (7.2 g=0.028 mol), as shown in Fig. 1, to
afford a
silk-conjugate construct. Further application of this construct to a substrate
including
reactive groups, results in substrate coated with silk, wherein the silk is
chemically linked
to the substrate. As shown in Fig. 2, this disclosure is not limited to any
particular linker,
but rather discloses any suitable linker capable to chemically link silk to a
substrate.
Example 3: Coating Substrates with a Silk-conjugate
Exhaustion: Nylon fabric: 300 g, LR: 1=13, temperature: 100 C, time: 45 min,
rinse, air dry. Nylon fabric (300g) is placed in a container with coating
solution in a
liquor ratio (LR) of 1:13. The container is closed, and the container is
heated to 100 C
for 45 min. The container is cooled once the exhaustion process is completed.
The fabric
is rinsed with water, spinned to removed excess liquid, and allowed to air
dry.
Samples used in various performance experiments:
Sample ID Solution
STI-17100706 Control
STI-17100706-D001 Silk-Conjugate
STI-17100706-D002 Silk only
STI-17100706-D003 Precursor linker only
Comparative vertical wicking test results for nylon samples are shown in Figs.
4A
and 4B (STI-17100706-D001: samples coated with silk-conjugate; STI-17100706-
D002:
samples coated with silk only; STI-17100706-D003: samples coated with
precursor linker
only; STI-17100706: control samples), at T=0 (Fig. 4A), and at T=3 (Fig. 4B).
The higher
the value the more water is absorbed by capillary action through the fabric,
which results
in better performing fabric. Samples coated with a silk-conjugate, and samples
coated
with silk only improve wicking compared to an unfinished control sample;
samples
coated with a silk-conjugate shows better wicking than samples coated with
silk only;
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unfinished control samples, and samples coated with a precursor linker only
show almost
no wicking.
Comparative absorbency test results for nylon samples coated with chemically
modified silk fibroin are shown in Figs. 5A and 5B (STI-17100706-D001: samples
coated with silk-conjugate; STI-17100706-D002: samples coated with silk only;
STI-
17100706-D003: samples coated with precursor linker only; STI-17100706:
control
samples), at T=0 (Fig. 5A), and at T=3 (Fig. 5B). Absorbency is measured in
seconds.
DNA: does not absorb the water drop, the test is stopped at 60 seconds. The
lower the
number, the faster the fabric absorbs, and therefore performance is better for
moisture
management. Samples coated with a silk-conjugate, and samples coated with silk
only
have a significantly improved absorbency, and samples coated with a silk-
conjugate
absorb better than samples coated with silk only; unfinished control samples
and samples
coated with the precursor linker only do not absorb at T=0.
Comparative dry rate test results for nylon samples coated with chemically
modified silk fibroin are shown in Figs. 6A and 6B (STI-17100706-D001: coated
with
silk-conjugate; STI-17100706-D002: coated with silk only; STI-17100706-D003:
coated
with precursor linker only; STI-17100706: control), at T=0 (Fig. 6A), and at
T=3 (Fig.
6B). Dry rate (mL/h) is how long the fabric takes to dry, a higher number
means better
performance. Samples coated with a silk-conjugate have an improved dry rate
compared
to the unfinished sample; samples coated with silk only have lower dry rate
than
unfinished control samples (Fig. 6A); at T=3 samples coated with a silk-
conjugate show
significant improvements (Fig. 6B).
Additional comparative vertical wicking test results for nylon samples are
shown
in Figs. 7A-7D (control: Fig. 7A; coated with silk only: Fig. 7B; coated with
in-situ
modified silk: Fig. 7C; coated with purified silk-conjugate: Fig. 7D), tested
after a
number (T) of laundering cycles (0, 3, and 20).
Additional comparative absorbency test results for nylon samples coated with
chemically modified silk fibroin are shown in Figs. 8A-8D (control: Fig. 8A;
coated with
silk only: Fig. 8B; coated with in-situ modified silk: Fig. 8C; coated with
purified silk-
conjugate: Fig. 8D), tested after a number (T) of laundering cycles (0, 3, and
20).
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Additional comparative dry rate test results for nylon samples coated with
chemically modified silk fibroin are shown in Figs. 9A-9D (control: Fig. 9A;
coated with
silk only: Fig. 9B; coated with in-situ modified silk: Fig. 9C; coated with
purified silk-
conjugate: Fig. 9D), tested after a number (T) of laundering cycles (0, 3, and
20).
Comparative absorbency test results for nylon samples coated with silk fibroin
chemically modified with natural crosslinkers are shown in Fig. 10 (control
sample,
sample coated with silk only, sample coated with silk modified with caffeic
acid, sample
coated with silk modified with genipin).
Example 4; Functionalized Silk
Functionalize
Chemical Structure
d Silk
(Low-MW- 0
098-02-01)
HN¨Low-MW silk-000H
¨N¨ OH
\
(Mid-MW- 0
098-02-02)
HN¨Mid-MW silk¨COOH
¨N¨ OH
\
Hexamine 0
(098-10-2) 0\ /
HN¨Low-MW silk¨µOH
0
0 / HN NH2
HN¨Low-MW silk¨µ
0
0
0 HN N H2
\ /
HN¨Low-MW
siIk¨
HO 0
(Mid-MW- 0
098-08-02)
HN¨Mid-MW silk¨COOH
As used herein the symbols and conventions used in these processes, schemes
and
examples are consistent with those used in the contemporary scientific
literature, for
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example, the Journal of the American Chemical Society or the Journal of
Biological
Chemistry.
Unless otherwise indicated, all temperatures are expressed in C (degrees
Centigrade). All reactions conducted under an inert atmosphere at room
temperature unless
otherwise noted. Reagents employed without synthetic details are commercially
available
or made according to literature procedures.
HPLC/Mass spectra were obtained on Dyonex series 3000 HPLC coupled with Q
ExactiveTM Hybrid Quadrupole-OrbitrapTM Mass Spectrometer. Detection is by MS,
UV
at 214 nM using either Atmospheric Chemical Ionization (APCI) or Electrospray
Ionization (ESI) and an evaporative light-scattering detectior (ELSD). The
data was
acquired using Thermo ScientificTM XcaliburTM Software. Data analysis was
performed
using PEAKS software.
Silk fibroin is secreted in the form of a 2.3 MDa protein complex which
consists of
six sets of heavy chain-light chain heterodimer and one molecule of
fibrohexamerin (P25).
Covalent modification of silk fibroin was confirmed for different subunits
(heavy chain,
light chain, and/or fibrohexamerin) based on m/z and ms2 fragmentation
patterns.
Prior to HPLC/MS, the functionalized silk synthesized was subjected to
protease
digestion according to the procedures below. In general, the functionalized
silk in each
sample were denatured with 6M guanidine HC1 and reduced with DTT at 60 C for
30
minutes followed by alkylation with iodoacetamide at room temperature in the
dark. The
alkylation reaction was quenched by the addition of excess DTT and the
reaction was
allowed to proceed for another 30 minutes at room temperature. Chymotrypsin
digestion
was carried out at 37 C overnight at a protein to protease ratio of 1:50.
Attenuated Total Reflection was conducted on lyophilized functionalized silk
samples using Nicolet i550 FTIR Spectrometer.
The functionalized silk prepared according to the experimental procedures
described below are summarized below:.
Sample ID Structure
Characterization
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OH
077-027-1 ))..r MS, IEFa
11
077-024-2-HLow-MWMS, IEF
077-028-2 i MS, IEF Low-MW
siliCOOH
077-030-1 N/''N)1\/-r-111¨(Low-MW SilN MS, IEF
098-08-02 FTIR
= HN-Mid-MW silk¨COOH
OH
098-29-02 HO SEC-RI, FTIR
silk
OH
HO
098-30-02 s SEC-RI, FTIR
silk
a. IEF stands for isoelectric focus.
Functionalized SPF:
Structure
OH
SPF 1COOH
0
SPF
0
Ho g)Hr SPF }COOH
0
H is
SPF
0
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HN-SPF-COOH
OH
HO s
SPF
OH
HO
NW
SPF
Functionalized SPF:
Chemical Structure
HN¨SPF COOH
-N- OH
e
i/o
HN¨SPF COOH
-N- OH
e
/o
O N/
\\ OH
7 HN¨SPF
H 0
2N zHN
j/0
0\\ HNNH2
HN¨SPF
0
H2N
//0 NH2
0 HN
HN¨SPF
HO
0
HN¨SPF COOH
OLLiLow-MW siliCOOH
0
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Low MW silk was placed on an ice bath and stirred at 300 rpm. The pH of the
solution was adjusted to 9.5 and then glycidyl methacrylate was added in 3
portions, over
3 hours. After the addition, the ice bath was removed, and the mixture was
allowed to
warm up to room temperature (RT). The mixture was allowed to react at RT for
30
minutes. The reaction mixture was purified by dialysis against water using a
10 kDa
MWCO dialysis tubing.
Covalent modification of Low-MW silk fibroin was confirmed for all three
subunits
(heavy chain, light chain, and fibrohexamerin) based on m/z and ms2
fragmentation
patterns from the mass spectrum obtained in HPLC/MS analysis (See FIG. 9A and
FIGs.
12A-B).
siliCOOH
0
Low MW silk was placed on an ice bath and stirred at 300 rpm. Acetic anhydride
was added in 3 portions, over 1 hour. After each portion the pH was adjusted
to 8.5-9.5
with sodium hydroxide. After the last succinic acid addition, the ice bath was
removed,
and the reaction was allowed to warm up to room temperature. The mixture was
allowed
to react at RT for 30 minutes. The reaction mixture was purified by dialysis
against water
using a 10 kDa MWCO dialysis tubing.
Covalent modification of Low-MW silk fibroin was confirmed for all three
subunits (heavy chain, light chain, and fibrohexamerin) based on m/z and ms2
fragmentation patterns from the mass spectrum obtained in HPLC/MS analysis
(See FIG.
9B and FIGs. 13A-C).
0
H0j*L1 iLow-MW
0
Low MW silk was placed on an ice bath and stirred at 300 rpm. Succinic
anhydride was added in 3 portions, over 1 hour. After each portion the pH was
adjusted
to 8.5-9.5 with sodium hydroxide. After the last succinic acid addition, the
ice bath was
removed, and the reaction was allowed to warm up to room temperature. The
mixture
was allowed to react at RT for 30 minutes. The reaction mixture was purified
by dialysis
against water using a 10 kDa MWCO dialysis tubing.
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Covalent modification of Low-MW silk fibroin was confirmed for all three
subunits (heavy chain, light chain, and fibrohexamerin) based on m/z and ms2
fragmentation patterns from the mass spectrum obtained in HPLC/MS analysis
(See FIG.
9C and FIG. 14).
0
0
H _________________________________________ //
/\N
0
Covalent modification of Low-MW silk fibroin was confirmed for all three
subunits (heavy chain, light chain, and fibrohexamerin) based on m/z and ms2
fragmentation patterns from the mass spectrum obtained in HPLC/MS analysis
(See FIG.
9D and FIG. 15)
H\N-Mid-MW silk¨COOH
Mid MW silk was adjusted to pH 7.2 with phosphate buffer and heated to 37 C.
Hexanal was then added, followed by hydrogen peroxide and the solution was
allowed to
react with stirring 24 hr. The solution was then cooled to room temperature
and purified by
dialysis against water using a 10 kDa MWCO dialysis tubing.
OH
HO
silk
Mid MW silk was adjusted to pH 6.5 in phosphate buffer and heated to 35 C.
Mushroom Tyrosinase was added and the solution was allowed to stir for 2 hr.
The
solution was then heated to 85 C for 10 min to deactivate the tyrosinase
enzyme, then
the temperature was reduced to 60 C and N,N-dimethylethylenediamine was
added. The
reaction mixture was allowed to react for 2 hr. The solution was then cooled
to room
temperature and purified by dialysis against water using a membrane with MWCO
of 10
kDa.
OH
HO 40
N
silk
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Mid MW silk was adjusted to pH 6.5 in phosphate buffer and heated to 35 C.
Mushroom Tyrosinase was added and the solution was allowed to stir for 2 hr.
The
solution was then heated to 85 C for 10 min to deactivate the tyrosinase
enzyme, then
the temperature was reduced to 60 C and 1-aminopentane was added. The
reaction
mixture was allowed to react for 2 hr. The solution was then cooled to room
temperature
and purified by dialysis against water using a membrane with MWCO of 10 kDa.
The molecular weight bands of the functionalized silk samples was obtained by
gel electrophoresis using Novex precast 3-10 IEF gels. The gel electrophoresis
experiments were run according to ThermoFisher Novex "Pre-Cast Gel
Electrophoresis
Guide" Version B, January 27, 2003 IM-1002. In general, functionalized silk
samples
were diluted to 14.7 mg/ml protein concentration in 3-10 IEF sample buffer
before
loading and BioRad 4.45-9.6 IEF electrophoresis standards were used. The gels
were
focused at 100 constant volts for 1 hour, 200 constant volts for 1 hour, and
500 constant
volts for 30 minutes. The gels were fixed in 12% TCA for 1/2 hour; stained in
Coomassie
Brilliant Blue R-250, stained in 10% acetic acid, and dried between cellophane
sheets.
FIGs. 12A-B show the results for the electrophoresis gel experiments performed
on
the functionalized silk synthesized in Examples 10 above and the controls.
FIG. 12A shows
the electrophoresis gel from a few typical Activated SilksTM, and FIG. 10B
shows the
electrophoresis gel for chemically modified Activated SilksTM.
The mid-molecular weight Activated SilksTM have two isoelectric point ranges,
one between pH 4-5 and a second one between pH 7-8. In contrast, low molecular
weight
Activated SilksTM have only one isoelectric point, in the range of pH 4-5.
Upon chemical
modification the isoelectric points of acetylated (sample 077-024-2) and
methacrylated
(sample 077-027-1) silks are unchanged. However, succinylation (sample 077-028-
2)
moves the isoelectric point to lower values (pH < 4.65), while amination
(sample 077-
030-1) move the isoelectric point to a higher value (pH 5.1-6) and give rise
to an
additional isoelectric point (pH 7-8).
Sample description for the gel electrophoresis samples shown in FIG. 10B
Lane Sample jig load iI Load
1 BioRad IEF Stds 6
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2 IEF Sample Buffer 7.35
3 077-024-2 100 7.35
4 077-027-1 100 7.35
077-027-2 100 7.35
6 077-028-2 100 7.35
7 077-030-1 100 7.35
8 MC-1 100 7.35
9 5700-SP 100 7.35
DBr-7 100 7.35
11 Ser-1 100 7.35
12
Molecular weight distribution for the functionalized silk samples was obtained
by
the size exclusion chromatography analysis. In general, sample solutions of
the
functionalized silk were analyzed on an Agilent 1100 HPLC equipped with a
PolySep GFC
P-4000 (7.8x300 mm) size exclusion column and a refractive index detector. The
instrument was operated at a flow rate of 1 mL/min using a mobile phase
containing 100
mM sodium chloride + 12.5 mM sodium phosphate buffer (pH 7), for a sample run
time of
minutes. The molecular weight distribution was calculated relative to Dextran
standards
using the Cirrus software package.
FIG. 13 shows the chromatograms of two modified mid molecular weight silks
compared to a typical mid molecular silk. The two modified silks have higher
molecular
weight compared to the standard (evidenced by the shift towards early elution
times).
All patents, patent applications, and published references cited herein are
hereby
incorporated by reference in their entirety. While the methods of the present
disclosure
have been described in connection with the specific embodiments thereof, it
will be
understood that it is capable of further modification. Further, this
application is intended to
cover any variations, uses, or adaptations of the methods of the present
disclosure,
including such departures from the present disclosure as come within known or
customary
practice in the art to which the methods of the present disclosure pertain.
258
