Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 93/1067:.PCr/US92/065X9
2 ~
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CROSS-REFERENCE TO RELATED FAT FOODS
SThis application is a continuation-in-part
ofU.S. application Serial No. 07/79&,292, filed
November 26, 1991, the disclosure of which is
~; ~ incorporated herein by reference.
10FIELD OF THE INVENTION
This invention relates to food for mulations in
which at least a portion of the fat and/or oil is replaced
by a ca rbohyd rate .
15BACKGROUND OF THE INVENTION
U . S . ~ Patent No . 4, 510,166 ~ Lench ;n et al . )
d;scloses converted- starches having a DE less than 5 and
certain paste and ;gel characteristics whicl- are used as a
fat~ and/or oi5~ replacement in various foods, including ice
20~ cream and ~mayonnaise. Th? ~ converted starches are
descr~bed~ as~ dextrins,~ acid-converted starches (fluidity
; ;starches) ,~ enzyme-converted starches and ox;dized
starches. ~lt ~is ~also disclosed that ;f the converted
starches~ ~are ~not~ ~ rendered ~ cold-water soluble by the
25 conversion,-~ ~they~ are pregelatinized~ pr;or to use or
cooked during use.
A ~product bullet;n ent;tled "Paselli SA2; The
~, ~Natural Alternative to Fats and Oils" (AVEBE b . a .,
Foxhol, Holland,~ ~Ref. No. 05.12.31.167 EF) d;scloses the
30 use of a low-DE-hydrolysate (DE ~less than 3) made from
potato starch~ as ~a replacement for fifty percent of the
fat with an amount o f the low-DE-potato starch
hydrolysate plus water ~starch hydrolysate at 28% dry
solids) equal to t~e amount of fat replaced.
WO 93/1067~ PCI/US92/06589
_3 ~ d~ ~,
U.S. Patent Nos. 3,962,465 (Richter et al. )
and 3,986,890 ~Richter et al. ) disclose the use of
thermoreversible gels of a starch hydrolysate (formed by
enzymatic hydrolysis) as a substitute for fat in a variety
of foods, including cake creams and fillings, mayonnaise
and remoulades, cream cheeses and other cheese
preparations, bread~ spreads, pastes, meat and sausage
products, and whipped cream.
U.S. Patent No. 4,971,723 (Chiu) discloses
10 ~ partially debranched starch prepared by enzymatic
hydro!ysis of~ the ~a-1,6-D-glucosidic bonds of the starch,
compris;ng amylopectin, partially debranched amylopectin
and up to; 80-O ~ by ~ weight, short chain amylose and that
the; partially~ debra~nched starch is useful in a variety of
5~ ways~ depending upon the degree of debranching. It ;s
disclosed ~ that~ a ~ waxy maize starch ~or other waxy
starch)~ can ~be~ partially debranched (~.e. to~ 25go to 70gO
short chaini ~amylose) to y;eld suff;c;ent short cha;n
amyiose~to form~a thermaily~reversible gèl in an aqueous
20~ starch~ suspension.~ ~ 1t is further ~disclosed that the same
degree~ of~ deb;~ranching of waxy starches is preferred for
bnd~ng ~ a ~ fat-like, ~ lubricat~ng ~texture to an aqueous
starch ~dispersion . ~
PGT~Pub~!ication ~ No.~ ~ WO 91/07106, published
25~ May~ 30,~: 1991, ~ d~scloses a ;~method of ~ ~preparing a food
grade, ~ nsol~uble ~bulking ~agent ~ from~ ~starch that is also
disclosed to~ be~us;eful as a bulking or texturizing agent
in low-fat food~ formulations. The method of preparing
; the starch~ compri~ses a retrogradation process followed
30~ by enzymatic ~(e.~g.,~ a-amylasel ~or chemical (e.g., acid)
hydrolysis of ~ amorphous ~ reglons in the retrograded
product. ~ l~n ~this~ process, amylose is allowed to
. .... . ... . .......... . ..
WO g3/1067~ PCl /US92/Q658~
2~S~
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retrograde from a solution of gelatinized starch. The
hydrolysis is t~en undertakèn to reduce or eliminate
amorphous regions in the retrograded product.
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WO 93/1067~ PCI /US~2/~6589
21L~ ''i.f'.i
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SUMMARY OF THE INVENTION
I n one aspect, this invention relates to a food
form'ulation having a reduced level of fat and/or oil
comprising a mixture of a foodstuff and a particle gel as
5 a replacement for at least a substantial portion of the fat
' and/or oil of said foodstuff, said particle gel comprising
a minor amount of a f ragmented, a-amylase hydrolyzed
`~ ~ amylose precipitate and a major amount of an aqueous
' ~ liquid.
~; 10 In another aspect, this invention relates to a
method of formulating a food containing a fat and/or oil
ingredient comprising replacing at léast a substantial
portion of said fat and/or oil ingredient Witt1 a particle
gel as a replacement for at least a substantial portion of
15 the fat and/or oil of said foodstuff, said particle gel
comprising a minor; amount of a fragmented, a-amylase
hydrolyzed amyiose precipitate and a major amount of an
aqueous liquid. ~
By "fragmented, a-amylase hydrolyzed amylose
20~ precipitate" Is ~ meant a starch material comprised of
amylose which has~ ~been subjected to precipitation of the
amylose followed ~by hydrolysis by a-amylase enzyme and
then mechan;cal ~ disintegration of the hydrolyzed
precipitate~ ~ into fragments.~ The ~ hydrolysis and
25 ~ disintegration will ibe sufficient to p~roduce a precipitate
which will form~ an aqueous - dispersion having the
characteristics of a particle gel.
I n ,another aspect, this invention r elates to a
method of making` ~a composition of matter useful in
30 replacing fat and/or' oil ;n a food formulation comprising
physically fragmenting; a minor~ amount of an a-amylase
hydrolyzed amylose~ ~precipitate in a major amount of an
aqueous liquid, the degree o~ said physically fragmenting
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WO 93/1067:` PCl`~US92/06589
--6-
being sufficient to form a particle gel of said
compos ition .
In another aspect, this invention relates to an
aqueous dispersion useful as a replacement for fats
5 and/or oils comprising a major amount by weight of water
; ~ and a minor amount by weight of a fragmented,
a-amylase hydrolyzed amylose precipitate, the degree of
~ ~ hydrolysis and fragmentation of said precipitate being
;~ ; sufficient to form a particle gel of said dispersion.
The terms ~ "foodstuff" and "food", as used
herein, are intended to broadly cover nutritional and/or
functional materials that are ingested by humans in the
course of consuming edible fare. The term "fats and/or
~, .
oils" is intendedl ~to broadly cover edible lip;ds in
15 general, specifically the fatty acid triglycerides commonly
found in foods~. The terms thus include solid fats~
plastic~ shortenings, fluid oils (and fully or partially
hydrogenated ~oils)~, and the like. Common fatty acid
triglycerides i nclude cottonseed oil, soybean oil, corn
`20 ~ oil, peanut ~o~ canola oil, sesame oil, palm oil, palm
kernel~ oil, menhaden oil, whale oil, lard, and tallow.
The~ technology ~of ~fats and/or ~o;ls ;s described generally
by T ~ H~ Applewhite, "Fats and Fatty Oils",
EncYclopedia of Chemical Technolo~Y, Vol. 9, pp.
25 ~ 795~ (Klrk-Othmer, eds.,~John Wiley ~ Sons, Inc.,
N ew York, ~ New~ York~, 3d ed.~,- 1980)~, the disclosure of
which is incorporated by reference.
The use ~ of the terms "major" and "minor" in
context togethe;r; ;ln this specification is meant to imply
30 that the major ~cam~ponent is p~esent in a greater amount
by weight than~ the~ minor component, and no more nor
less should be ~inferred therefrom unless expressly noted
otherwise in; context.
WO 93/1067:~ PC~/US92/06589
211~J1f1
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BRIEF DESCRIPTION OF T~IE DRAWINGS
Figure 1 shows the results of duplicate
analyses of the dynamic elastic modulus (G') in kilo
5 pascals as a function of strain (m) for a particle gel of
fragmented a-amylase hydrolyzed amylose precipitate at
10% precipitate solids.
- 10 DETAILED DESCRIPTION OF THE INVENTION
The fragmented, a-amylase hydrolyzed amylose
precipitate is made by the sequential steps of
precipitation, enzymatic hydrolysis, and f ragmentation of
a stàrch material containing amylose. ~tarcl1 is ~eneraliy
comprised of a highly-branched glucan having a-1,4 and
-1,6 linkages, denominated amylopectin, and a
substantially linear glucan, having almost exclusively
a-1,4 linkages, ~ denominated amylose. Methods of
determining~ the amounts of each are referenced in R.L.
Whistler et al.~, Starch: Chemistry and Technology, pp.
25-35 (Academic Press, Inc., New York, New York,
1984), the disclosure of which is incorporated by
reference. ~ As used herein, the term "amylose" includes
native amylose ~and~, unless otherwise expressly noted in
context, modified ~amylose. Examples of modified amylose
include acid-modif~ied amylose,~ enzyme-modified amylose
(e.g. a-amyiase, ~ amylase, isoamyiase, or pullulanase)
and chemically~ substituted amylose, provided the levels
of chemical substitution le. g . hydroxypropylation,
` 30 crosslinking, etc. ) are insufficient to prevent
precipitation and enzymatic hydrolysis of the amylose to
the desired degree. Starches having a substantial
proportion (i.e. at least 15% by weight) of amylose are
' ~
:~
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WO 93/1067~ PCr/US92/065X9
2 1 t ,~ 8-
preferred and examples of these include the common
non-mutant starches of cereals, tubers and legumes,
e . g . corn, wheat, rice, potato, tapioca, and pea .
Preferred for use herein are starches derived from corn
5 (Zea mays) such as common corn starch - and high
amylose corn starch, each of which are examples of
starches containing greater than 15% amylose. Examples
; of such starches from high amylose corn include
~ Hl-SET ~) C and HYLONTM (each about 5~O amylose by
; ~ 10 weight) and HY~ONTM Vll (about 70O amylose by
weight), all ava;lable from National Starch and Chemical
Corporation, Bridgewater, New Jersey.
In certain embodiments, the starch is
comprised of a ~ major amount of amylose. In such
15 ~ embodiments~, the~ ~starch employed is from a mutant
variety of native ~starch which contains a major amount of
amylose or is obtained by ~ractionation of amylose from a
starch variety containlng both~ amylose and amylopectin.
Methods for the fractionation ~of amylose~ and amylopectin
20 ~ from native~ starch ~are disclosed in~, for example, U.S.
Patent No. 3,067,067 (Etheridge).
If the~ starch chosen as a starting material is
not in~ pre-gelatinized ~or instant form, the starch must
be gelatinized ~or~pasted prlor to~ precipitation of the
25~ ~amylose. The~gelatinization or pasting;process disrupts,
at~ least in ~s~ubstantial part, the assoc~ative bonding of
the starch ~molecules~ in the starch granule. This permits
the amylose to associate ancl precipitate. This disruption
is accomplished~ by ~heating ~a slurry~ of the starch to a
30 sufficient temperature for a~ sufficient length of .time
depending upon the inherent resistance of the particular
starch to gelatinization and the amount of moisture
i ~ present in the~ slurry. The slurry will typically be
,
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WO 93/10675 PCI /US92/065X9
. .
g
comprised of a major amount of water (i.e. at least 50~
by weight) and a minor amount of the starch starting
; material (i.e. Iess than about 50~ by weight).
Preferably, the starch slurry will contain at least a~out
5 5% starch, typically between about 10% to about 25%
starch. The pH of the slurry will generally be
substantially neutral, i.e. from about 3.5 to about 9 and
more preferably from about 6 to 8, to minimize
hydrolysis of the; starch molecules. The time,
10 temperature, slurry solids and pH should be optimized to
gelatinize the starch, yet minimize hydrolysis of the
starch.
The appropriate temperature, pressure and
period of treatment needed to provide a starch paste is
preferably obtained by processing aqueous starch
slurries in equipment commonly known in the art as
steam injection~ ~heaters or jet cookers . I n such
equipment, ~superatmospheric steam is injected and mixed
with a wateri slurry~ of starch in a throat section of a
20~ ~ jet~. ~ Upon ~ contact;~ with the ~ injected steam, the starch
granules are~ ;~uniformly and thermally treated under
turbu!ent condition~s whereupon ~ ~the starch ~ranules are
gel~atinized and~ ` solubilized . ~Examples of steam injection
heaters wherein ~thé~ temperature, pressure and feed rate
25 ~ c an ~be regulated t o provide th~e desired starch pastes
are disclosed ~in~U.~S. Patent Nos. 3,197,337; 3,219,4B3;
~; ànd 3,133,B36. ~ More uniformly solubilized starch pastes
are obtained by use of the steam injection heater in
combination~with: a~ holding zone such as coiled tubing or
30 a pressurized~ ~ tank constructed to minimize liquid
channe~ing. Other pasting equipment, e . g . heat
exchangers,~ homogenizers, cookers, votators, sizeometer
cookers, kettle cookers, etc., may be employed provided
.
WO 93/1067~ PCI/US92/06589
~ 1 4 ~ - l o-
the pasting conditions can be adequately maintained.
The starch solution may also be treated to
remove impurities therefrom. Treatment with, for
example, activated carbon will remove residual proteins
5 and lipids that may contribute to off-flavors and/or
colors.
The gelatinized starch is then optionally
treated with a ~debranching enzyme, i . e . an enzyme
capable of hydrolyz;ng the 1, 6-glucosidic bond of
10 amylopectin without~ significant capability of hydrolyzing
the~ 1,4-glucosldic~ bond. Enzymes from a variety of
I ~ sources are capabl'e o f debranching amylopectin. U.S.
Patent No. 3~,370,840 (Sugimoto et al.) describes sources
of ~ debranching`~ enzymes, the disclosure of which is
15 incorporated ~ herein~ by reference. Examples of useful
enzymes include~puliulanases derived from bacteria of the
genus ~ Aerobacter~ ~ (e.g. E.C. 3.2.1.41 pullulan
6-glucanohydrolase)~ ~ ~ and ~ isoamylases derived f rom
bacteria ~of~t~he~ genus Pseudo~monas (e.g. E.C. 3.2.1,68
20~ ~ glycogen~ ~ ~ 6-glucanohydrolase). Particularly useful
enzymes include ~thermostable ~ enzymes, e . g . thermostable
pullulanases~ às~ disclosed in PCT Publ. ~No. WO 92/026~4,
published~February~20, 1992, the disclosure of which is
incorporated~ by~ re~ference, and which are obtained from
25 ;~; members of the~ ~'genus Pyrococcus. The debranching
enzyme may~'be~in~ solution~ during debranching or it may
be immobilized~ on~ a so!id support.
The~ debranching enzyme preparation should be
as specific~ as~ ~; possible for the hydrolysis of the
30 1 ,6-glucosidic ~ bond of amylopectin and amylose. Thus,
the enzyme~- preparation, if it contains a mixture of
enzymes, is ~ preferably essentially free of enzymes
capable of ~ ~hydrolyzing a-l ,4-glucosidic bonds.
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WO 93/1067~ PCl/US92/06589
2 ~
Minimizing hydrolysis of a-1,4-glucosidic bonds will help
to minimize the amounts of dextrose and soluble oligomers
produced during debranching. Because these soluble
saccharides are not believed to contribute to the
5 functionality of the debranched material, minimizing their
production will enhance the yield of functional material.
The debranching enzyme is allowed to act upon
the solubilized starch con~tain;ng amylopectin. The
` optimum concentration of enzyme and substrate in the
10 debranching medium~ will, in general, depend upon the
level of activity of the enzyme which, in turn, will vary
depending upon the ~ enzyme source, enzyme supplier and
:~ the concentration~ of the enzyme in commercial batches.
When the isoamylase E . C . 3 . 2 .1 . 68, derived f rom
15 Pseudomonas ~ ~amyloderamosa, ~ available from Sigma
'C~hemical Co., St. :Louis, Missouri, is employed, typical
condltions ~include~-the~ treatment~ of a starch solution at
5% ~to 30% ~by~ weight ;starch solids with about 50 units of
enzyme,~ per ~gram ~of ~starch, for a period of about 48
20~ hours to obtai;n substantially. compiete debranching.
The ~ optimum pH and temperature of the
; debranching~ mediu'm `will also depend upon the choice of
i enzyme~. The ~ debranching medium may, in~ addit;on to
the water ~ used ~ to~'~ soiubilize the starch;, contain buffers
25 t o ensure thàt~the~ pH~ will be maintàined at an optimum
level throughout~ the~ ~debranching. Examples of useful
bufters~ incl~ude~ acetates, citrates, ~and;'the salts of other
weak acids. With ~ the iisoamylase described above, the
pH is preferably maintained at; about 4.C) to 5.0 and the
:30~ temperature~ from: ~about 40C to about S()C. With the
thermostable ~ pu~llulanase described above, the pH is
preferabiy maintained ~between 5 and 7 and the optimum
temperature should be ~between 85C and 115C.
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WO g3/1067; PCl/US92~065~')
211 J~'~2
--12--
The debranching is allowed to proceed until
the desired degree of debranching has been obtained.
The precise degree of debranching needed to obtain the
desired particle gel of the debranched amylopectin starch
5 may vary dependlng upon the source of the starch and
the precise properties desired in the resulting gel.
Preferably, the degree of debranching is sufficient to
.
convert more than about 80% of the amyl~pectin in the
starch to short chain amylose and, more preferably, at
lO least about 90~Q of the amylopectin.
In preferred embodiments, essentially all of the
amylopectin is converted to short chain amylose. The
amount of short chain amylose can be measured by gel
permeation ch~romatography as set forth in U. S. Patent
No. 4,971,723, ~wherein short chain amylose is calculated
from the relative area of the peak obtained within the
molecular weight ~ ~ range of 500 to 20,000. Thus,
preferably less~ ;than 20% of the amylopectin that was
originally~ ~ present w;ll be pres~ent as molecular species
20~ havlng a molecular weight in excess of;20,000 gimol, and
most preferably,~ essentially no amylopectin having a
molecula~r we~ght~ n~ excess of ~20,000 g/mol will remain.
lt~s;hould be~;noted;~that if amylose~ Is ~present, at least a
portion; thereof~may be debranched ;to produce molecules
25 ~ ~ above the 20,000 g/mol cut-off and molecules below the
20,000 g/mol ~cut-off. To~ measure how much of the
material elutl~ng~ between 500 g/moi and 20,000 g/mol is
debranched amylopectin and how mucll is debranched
amylose, it may be necessary to fractionate the starting
30 ~ starch into ~its~amylose and amylopectin fractions and
;` then debranch and elute each f~action separately.)
~ ,
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WO 93/10675 PCr/US92/065X9
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-13-
The solution of gelatinized st~rch is then
allowed to form a precipitate. Generally, the solution
will be cooled from the temperature at which the starch
is pasted to reduce the solubility of the gelatinized
5 starch therein. The solution will typically be held at
elevated temperature (e.g. 65C to 90C) until
substantial equilibrium is achieved between the
~ ,
supernatant and the precipitate. The precipitate can be
isolated from the supernatant, e. g . by centrifugation,
10 prior to fragmentation, but isolation from the
supernatant is~not~necessary to form a useful product.
Heating (e~. g . to about 70C) of the particles
while in contact with the aqueous medium to dissolve at
least a portion of ;the mass of the particles and then
15 cooling of the suspension/solution can also be employed
in forming the ~ particle gel of this invention. This
heatlng to ~an elevated temperature and then reformation
;of the~ particles ~tends to make the particles resistant to
melting or'dissolving when an aqueous dispersion of the
20~ partlclés is~ exposed to heat~ in processing, ë. g . in a
pasteurization~ ~ ~ stép. In general, the higher the
tèmperature'~to ~whlch the particles in ~the liquid medium
are~ ~ heated ~ ~ta~nd~ thus the~ greater~;~ the amount of
p~recipitate~ that ~ is redissolved),~ ~the higher the
25 ~ ~ temperature~ ~at which the resulting aqueous dispersion of
the particles~will~be~stable. ~Repetition of the dissolving
and reformation~ may improve the temperatu~re stability of
the resulting a~queous dispersion.
It is~ ~also~ ~advantageous to heat the precipitate
30 to redissolve~ a su~bstantial portion of the low melting
polysaccharides~ ~and then treat the heated~ suspension of
precipitate ;~wit~ acid or enzyme to hydrolyze soluble
~ : ~
polysaccharides~ in~ the solution . ( It may also be
: '
WO 93/1067~ 2 1 ~ ~ t ~ ~ PCr/US92/06589
- 1 4 -
advantageous to filter the slurry while hot to remove
soluble polysaccharides or their hydrolysates. ) The
dissolving and reprecipitation steps alone improve the
stability of the aqueous dispersion by increasing the
S amount of the fragmented precipitate which remains as
insoluble fragments in an aqueous dispersion that is
exposed to heat. Further, a slow rate of heating and/or
cooling (e.g. from about 0.005C/min. to about
0~5C/min. ~for each) may be advantageous. However,
10 the remaining soluble fraction of the precipitate can
associate to form relatively large particles that are
present in ~the ~precipitate after fragmentation and that
can contribute a~ "chalky" or "gritty" texture to the
dispersion. T;reatment of the heated suspension/solution
15 of the precipitate w~th acid or enzyme to hydrolyze a
substantial portion~ of ;the soluble fraction can reduce or
eliminate such~ ~;large partic~les. Typical treatment
conditions will invol~ve mild hydrolysis; catalyzed by acid,
e.g. i n a ~ 'solutlon~ of ~ 0 1 N ~ HCI for one hour, or,
20~ preferably,~by~ enzyme, e.g. a-amylas~e~
; The~ prec~p~tated~ omylose~ s 'then treated with
:an ~a-amylase~enzyme,~ ~I.e. an'~endo-enzyme capable of
hydrolyzing ~the~ 4-glucosidic bond ~ of amylose and
amylopectin to: yield~products having- an a configuration.
25 ~ ~ The ~enzyme~ ~ ~is~ ~allowed ~ to act~; upon the precipitated
amylose and~ ~théreby hydrolyze ~ those regions in the
precipitate that~ are ~susceptible ~ to hydrolysis ~ The
optimum concentratlon of enzyme and substrate in the
hydrolysis medium~ will, in general, depend upon the
3 0 level of acti~vity~of~the enzyme~which, in turn, will vary
depending upon ~:the enzyme source, enzyme supplier and
the concentration~of the~ enzyme in commercial batches.
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W 0 93tlO67~ P ~ /US92/06589
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The a-amylase can be from a variety of
sources. Common sources of a-amylase are bacterial,
e.g. Bacillus subtilis, or fungal, e.g. Asper~illus
oryzae, or mammalian, e. 9 . human salivary, porcine
5 pancreatic, etc. The optimum pH and temperature of the
hydrolysis medium will also depend upon the choice of
enzyme. The hydrolysis medium may, in addition to the
water used i n the hydrolysis of the starch, contain
buffers to cnsure ~that the pH will be maintained at an
10 optimum level'- throughout the hydrolysis. Examples of
useful buffers i nclude acetates, citrates, phosphates,
and'~ the salts ~of~ other weak acids. With porcine
' pancreatic a-amylase, the pH is preferably maintained at
a'bout 6.0 to 8.0~:an~d~the temperature from about 20C to
15 about 30C.~
The hyd~rolysis is allowed to proceed until the
desired~ degree ~ of~-~hydroiysi 5~: has been obtained. The
u ~ precise~ degree~ of~ hydrolysis ~; needed to obtain the
desired; particle ~ gel o f the fragmented, a-amylase
1 20 ~ hydrolyzed amylose~ precipitate may vary depending upon
the sourcei ~of the starch and the precise properties
' desired~in ~'he~resujlti~ng gel. Typically, the degree of
hydroiysis~will be~sùch that fragmentation of the product
will ~yield~a~ gel~ that exhibits ~a trans;tion from a region
25~ ~ of ~ ~substantially~ ~constant dynamlc elastic modulus (G')
'versus ~ shear ~strain~ to a region of decreasing G' versus
shea~r strain~ said~' transit;on be;ng at a shear strain of
less than about~ 5Q m;llistrain, and preferably less than
about 10 mill;strain.~ The transition indicates fracture of
30 the part;cle~network~ with the~ particle gel and is typically
a sharp transit;on.~ The dynamic elast~ic modulus can be
measured with ~ a ~Bohlin model VOR Rheometer, from
Bohlin Rheolog;, l~nc., East Brunswick~, New Jersey.
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-16-
After the desired degree of hydrolysis is
obtained, the a-amylase enzyme in solution is
deactivated, e. g . by heating to denature the enzyme.
The hydrolysis medium may be concentrated by removal
5 of water therefrom, e.g. by evaporation, to facilitate
precip;tat;on .
The isolated a-amylase hydrolyzed amylose
precipitate is typically washed and then dried ~e. g . to a
, ~
low moisture ~content, typically 3-12%) after isolation to
10 allow for handling~ and storage prior to further
; processing. Examples of drying techniques include
spray drying, flash ~drying, tray drying, belt dry;ng,
and sonic drying. The dried precipitate may be
hygroscopic. ~ Thu~s, some rehydration during handling
~and storage may occur. Depending upon the precise
composition ~ ~of ~ the precipitote and the conditions
(including length~-of~time) of~ storage, steps to maintain
the moisture at~a ~ low content may be necessary (e.g.
moi~sture barrier packaging and~or control of humidity in
20~ the storage ~environment) . ~ if the moisture content is
allowed to~rise~too~ far~ ~e.g. greater than about 20%, or
possibly ~greater ~ than 15%), bulk handling problems
and/or~microbiological stability~problems~might arise.
The~;a-amylase ~ hydrolyzed amylose precipitate
;~ 25~ is ~subjected ~to~a~ physical fragmentation as by mechanical
disintegration,~ .e~ fragmented. The degree of
fragmentation ~ will be ~ sufficient to cause` the precipitate
to form a ~ particle ~ gel in an aqueous medium. The
mechanical; ~disintegration of the precipitate may be
carried out ~ n~ ~several ways, as by subjecting it to
attrition in~ a mill,~ or~ to a high speed shearing action, or
to the ac~tion ~of high pressures. Disintegration is
generally ca~rrled~out in~ ;the~ presence of a major amount
.
WO 93/1067~i PCI/US92/065X9
2 1 1 ~ r ~
--17--
by weight of a liquid medium, preferably water.
Although tap water is the preferred liquid medium for
the dispersion of fragmented starch precipitate, other
liquids are suitabie provided sufficient water is present
5 to hydrate the fragmented starch precipitate and, thus,
result in a dispersion having the characteristics of a
particle gel. Sugar solutions, polyols, of which ~Iycerol
is an examp:le, alcohols, particularly ethanol,
isopropanol, and the like, are good examples of suitable
10 liquids that can be in admixture with water in the liquid
medium. Typically, however, the starch precipitate will
be physically fragmented in potable water.
The mechanical disintegration is preferably
accomplished by subjecting an aqueous dispersion of the
15 precipitate to high shear, e.g. in a Waring blender or a
homc?genizer such as that disclosed in U . S . Patent No.
4,533,254 (Cook et al. ) and commercially available as a
MICROFLUIDIZERTM from Microfluidics Corporation,
Newton, Massachusetts, or a homogenizer such as the
20 RANNIETM high~ pressure laboratory homogenizer, Model
Mini-lab, type~ 8~.30 H, APV Rannie, Minneapolis,
Minnesota. Homogenizers useful in forming suspensions
or emulsions~ are~ described generally by H. Reuter,
"Homogenizatlon", ~EncYclopedia of Food Science, pp.
25 ~ 374-376, (M. S. Peterson and A. H. Johnson, eds., AVI
I ~ Publ. Co., Westport, Connecticut, 1978), L. H. Rees
and W. D. Pandoife, "Hcmogenizers", EncYclopedia of
Food ~Enqineering, pp. 467-472 (C. W. Hall et al. eds.,
AVI Publ. Co., Westport, Connecticut, 1986), and W. C.
30 Griffin, "Emulsions", EncYclopedia of Chemical
Technoloqy, Vol. 8, pp. 900-930 (Kirk-Othmer, eds.,
John Wiley ~ Sons, Inc., New York, New York, 3d ed.,
1979), the disclosures of which ~re incorporated herein
by reference.
WO 93/1067~ PCr/US92/065X9
2 ~ 2
The temperature of the starch precipitate
during the fragmentation step should be maintained below
the temperature at wh;ch a major portion of the
precipitate will dissolve in the aqueous medium. Thus,
it may be desirable to cool the precipitate during
disintegration. Alternatively, heat produced during
fragmentation may cause the precipitate to dissolve, but
cooling may cause the dissolved precipitate to
`reprecipitate and; form a useful product. Whatever
10 method is used, ~the ~disintegrat~on is carried out to such
an extent ;that~ the ~ resulting finely-divided product is
characterized by its`ability to form a particle gel in the
liquid medium in which it is attrited or in which it is
subsequent\y ~ dispersed .
15 ~ ; ~ The ~ ;~starch particles which make up the
particle gel can~ ~be analyzed in a variety of ways.
Rheologic-l ~ measurements can ~ be made to determine the
rheological~;characteristics of;~ the resulting dispersion.
Typlcaliy~,~ the~àqueo~us dis~persion of starch particles will
1 20~ ` ex~hibit a~ ~ transition in dynamic elastic modùlus ~G')
versus~shear~ st~rain~at less than about 50 millistrain, and
preferabiy ~ ies-s than ~ about lO milllstrain, said transition
beingi~from~ a~substantiaily~ constant G' versus shear
strain ~to ~a~ ~decreasing G' ~ ~versus~ shear stra;n. The
25~ transition~ indicates ~ fractu~re ~ of ~ ;the particle network
withi~n the~ particle~ gel and ~is typically a sharp
transition . ~
Ana!ysis of the starch particles formed after
dissolution~ shows~ that the starch has a measurable
3 0 crystall jnity. ~ The ~ crystalline ~ regions of particles
derived from fully debranched waxy ;maize starch
(essentially no ~amylose compone~nt) exhibit a diffraction
pattern characteristic of a starch material consisting
,~
: :: :
W O 93/1067~ PC~r/US92/065X~
2~5.~ ~
_19_
essentially of A-type starch crystals. The crystalline
regions of particles derived from substantially fully
debranched common corn starch (about 28% amylose)
exhibit a diffraction pattern characteristic of a starch
5 material consisting essentially of B-type starch crystals.
It should also be noted that mechanical
disintegration may be sufficient to produce an aqueous
dispersion having the desired particle gel
characteristics, but still leave a sufficient number of
10 particles of suffîcient size to exhibit a "particulate" or
"chalky" mouthfeel when ingested. Such chalkiness can
be reduced by the mild hydrolysis discussed above or by
reducing the particle size of the starch precipitate
before, during or after mechanical disintegration so that
15 substantially all (typically at least about 95~, preferably
at least 99%) of the precipitate will pass a U . S . #325
mesh sieve (i.~e. ;~substantially all particles are less than
45 microns). An example of a milling device suitable for
such size ~reduction is a TROSTTM Air Impact Mill from
20 Garlock, Inc., Newton, Pennsylvania.
The~ use of the fragmented, a-amylase
hydrolyzed amylose precipitate allows for the replacement
of a substantial portion (e.g. from 10% to 100~ by
weight) of t~he~ fat and/or oil in a food formulation. The
25 precise level ~ of replacement that is possible without
significantly ~ decreasing the organoleptic quality of the
food will generally vary with the type of food. For
~' example, in a French-style salad dressing, it is
generally possible to completely replace the oil component
30 that is normally ~ present. I n other types of foods, e . g .
frostings, icings, cream fillings, ice cream, margarine,
etc., a maJor amount of the fat and/or oil (e. 9. about
50% to about 80%) can be replaced with little effect on
WO 93/1067;~ PCI /US92/0658~
2 1. ~ 'J5 ~
-20-
the organoleptic desirability of the food. Examples of
typical foods in which fat and/or oii can be replaced
include frostings (e.g. icings, glazes, etc. ), creme
fillings, frozen desserts (e.g. ice milk, sherbets, etc. ),
5 dressings (e.g. pourable or spoonable salad and/or
sandwich dressings), meat products (e. g. sausages,
processed meats, etc. ), cheese products (e.g. cheese
sp reads, p roces sed cheese foods ), ma rga ri ne, f ru it
butters, other imitation dairy products, puddings (e.g.
10 mousse desserts), candy (e . 9 . chocolates, nougats,
etc. ), and sauces, toppings, syrups and so on.
Generally, it will be desirable to remove
sufficient fat from a gi~en food formulation to achieve a
reduction in calories of at least one-third per customary
15 serving or make a label claim of "cholesterol-free". (In
this regard, see, for example, the list of standard
serv;ng sizes for various foods published in Food
Labelling; Serving Sizes, 55 Fed. Reg. 29517 ~1990) (to
be codified at ~1 C. F. R. 101 .12), the disclosure of
20 which is incorporated herein by reference, and the
restrictions on labelling "cholesteroi-f ree" at Food
Labelling; Definitions of the Terms Cholesterol Free, Low
Cholesterol and~ Reduced Cholesterol, 55 Fed. Reg. 29456
(1990)). It shs:~uld also be ~noted that the fat removed
2 5 from a particular~ formulation may be replaced with an
equal amoun t by weight o~ an aqueous dispersion of
fragrnented starch precipitate, but that such equality
~, may not be necessary or desirable in all instances.
Further, it may~ be desirable to remove fat and add
30 another ingredient (e. g . a gum, polydextrose, a protein,
etc. ) along with the aqueous dispersion of starch
precipitate.
:
WO 93/1067~ PCI/US92/06589
2:1 1 5 1 ,1 ;
-21 -
While this invention is generally directed to
the replacement of fat and/or oil in a food formulation, it
is of course within the contemplation of this invention
that a fragmented, a-amylase hydrolyzed amylose
; 5 precipitate wiil be used in an entirely new formulation to
which it contributes fat-like organoleptic qualities but is
~; ~ not, in the~ strictest sense, replacing a pre-existing fat
or oil ingredient. Moreover, it is contemplated that the
` fragmented, a-amylase hydrolyzed amylose precipitate will
10 ~ have utility as a~ thickener, bodying agent, or the like
in foods that normally~ do not have a significant fat or oil
component. ~ ~
In general, the fragmented, a-amylase
hydrolyzed amylose~ precipitate is incorporated into the
15 ~ food ~as an aqueous~dispersion, typically comprised of a
major ~amount ~(i.e~ ~greater than 50~ by weight) of water
o r other liquid ~medium and ;~a; minor amount (i.e. Iess
than 50% by weight, typically 1Q% to 40%) of starch
precipitate ~solids. ~ Alternatively, the isolated precipitate
20 ~ ~can be~ ~mlxed~ ~with the ~ood along ~with water and then
- subjected~ to~ ;disintegration in those instances when the
other ~ogredlents~of~the~food~ are capable of withstanding
the condition of disintegratlon, e~.;g. a salad dressing or
u i mitation sour cream. ~ ~ ~
; 25; ~ ; It ~is:: contempl~ated that commercial production
and ~ ~ ~;use ~ may ~ involve hydrolysis, mechanical
disintegration, ~ and ~ dryin g (e.g. spray drying) of the
:: : :
, ~ ~ fragmented starch precipitate to produce an item of
commerce. ~ This item of commerce; will then be purchased
30 ~ ~by a~; food~ processor for use ~as an ingredient. To
incorporate the~ dried, fragmented, a-amylase hydrolyzed
amylose precipitate~ into a food p~roduct, it may be useful
and/or necessary to further mechanically disintegrate the
:
: :
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WO 93/1067~ PCr/US92/065X~
X ~ i 2
-22-
starch precipitate while dispersing it into the foodstuff
in which it will be employed. However, the techniques
employed for such mechanical disintegration should not
need to be nearly as vigorous as the ori`ginal mechanical
disintegration prior to drying.
As noted above, the terms "food" and
foodstuffs" are intended broadly, as relating to both
nutritional and/or functional food ingredients. It is
contemplated that one or more food ingredients may be
mixed with the~ ~ aqueous dispersion of fragmented,
a-amylase hydrolyzed amylose precipitate, or even dry
mixed with the~ a-amylase hydroiyzed amylose precipitate
prior to mechanical dis~ntegration.
Among ~ the food ingredients which may be
included in ~ the food formulations of this invention are
flavors, thickeners~ (e.g. starches ~ and hydrophilic
colloids) ,; nutrierrts ~ (e. g. carbohydrates, proteins,
I ipids,~ etc.~ antioxldants, antimicroblal ~agents, non-fat
milk so!ids,~egg~:solids,~acidulants, and~so~on.
20~ Hydrophllic ~ colloids can `include natural gum
material such~ ~as ~xanthan ~gum, gum tragacanth, locust
bean gum,~ ;guar~ ;gum,~ algin, alginates, gelatin, !rish
moss,~ pectin,~gum~àrabic, ~gum ghatti, gum karaya and
plant~ hemicelluloses, e.g. c orn ~ hull gum. ~ Synthetic
25~ ~ gums~ such ~ ~as ~ ~water-soluble salts of carboxymethyl
celluiose~ càn~; also~be used~. ;IStalches can al~o ~ be added
to the food.- ~;Examples of suitable~ starches include corn,
waxy maize, ~vheat, rice, potato, and tapioca starches.
Non-fat milk solids which can be used in the
30 compositlons of th~ls invention are ~the solids of skim milk
and include proteins, mineral matter and milk sugar.
Other proteins such ~as casei~n, sodlurn caseinate, c:alcium
~: : : : : :
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::~ : ~ :
:
: ::
WO 93/tO675 PCr/US92/065X9
" .
~ ~J~
-23-
caseinate, modified casein, sweet dairy whey, modified
whey, and whey protein concentrate can also be used
herein .
For many foods, it is accepted practice for the
user to add the required amount of eggs in the course
of preparation ~ and this practice may ~e followed just as
well herein. If desired, however, the inclusion of egg
solids, in particularj ~egg albumen~ and dried yolk, in the
food are allowable ~alternatives. Soy isolates may also be
used herein in place;of the egg albumen.
Dry; or liquid flavoring agents may be added to
the formulation~ These include cocoa, vanilla, chocolate,
~ , ~
coconut, peppermint, pineapple, cherry, nuts, spices,
salts, flavor;~enh~ancers, among others.
lS ~ Aci~ulants~ commonly added to foods include
lactic acid, citric acid, tartaric acid, malic acid, acetic
acid,~ phosphoric~acid, and hydrochloric~acid.
Generally, the other components of the various
types of food ~formu~lations wi~il be conventional, although
~precise amou`nts~ of individual components and the
presence of ~ some ~ of the conventional components may
m ~ well be unconventional in a given formulation. For
examp!e, the~ conventional~ other components for foods
such as~ frozen~desserts~ and ~dressings, are described in
25~ European Pàtent~ Publication ~ No. 0 340 035, published
November 2, ~ 1989~ (the ~ pe~t~nent disclosure of which is
incorporated herein b:y reference), and the components
and processing~ of table spreads is disclosed in U . S .
Patent No. 4~,869,919 (Lowery), the disclosure of which
i5: incorporated:~by~reference.
- ~ ~ A ~ particularly advantageous use of the
, ~ ~
fragmented starch ~precipitates described herein may be
the use thereof ~ to replace~ a portion of the shortening
, . . .
:: : :
WO 93/1067~ PCI/US92/06589
2 1 1 ~ ~ 4 ~ -24-
used in a layered pastry article . I n layered pastry
articles (Danish, croissants, etc. ), layers of a bread
dough are assembled with a "roll-in" placed between the
layers. The roll-in commonly contains a "shortening"
S (i.e. a fat and/or oil component) from an animal (e.g.
butter~ or vegetable (e. g . partially hydrogenated
soybean oil) source. The assembled article, optionally
containing a filling ~or topping, is then baked to form a
finished pastry. At least a portion of the shortening of
10 an otherwise conventional roll-in can be replaced with an
aqueous dispersion of fragmented, a-amylase hydrolyzed
amylose precipitate, ~ preferably in admixture with an
emulsifier (e.g.~ mono- and/or d;-glycerides), and used
t~o make a layered pastry.
5 ~ The following examples will illustrate the
invention and variations thereof within the scope and
spirit of the invention will be~ apparent therefrom. All
parts, percentages,~ ratios and the like are by weight
throughout this~ specification and the appended claims,
20 ~ unless ~otherwise noted in context.
25: :~ ~
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WO 93/10~7~ PCr/VS9~/065X9
-25-
EXAMP LES
E~CAMPLE 1
Into a 4-liter beaker was placed 118 grams of
potato amylose (A0512 Sigma Chemical Co., St. Louis,
Missouri) and 2242 grams deionized water to give a 5%
slurry. The slurry was heated to 98C in ~ water bath
to solubilize the amylose and this solution was placed in
; ~ ~ 10 a refrigerator overnight to promote precipitation/
crystaliization . ~ ~ The~ resulting slurry was centrifuged at
about 6000 x g using an IEC model 1~-22 centrifu~e and
the supernatant was discarded. The wet sediment was
,
resuspended in~ deionized water to about 2000 ml volume
15 and heated to 98C in a water bath to solubilize that
port~on of amylose susceptible to solubilization at that
temperature ~ then~ the mlxture was placed in a
refrigerator o vernight to promote precipitation/
crystallization. ~ The resulting slurry was again
20~ centrifuged~ as~ ~before ~ and the sup rnatant discarded.
The~ sediment was~resuspended in water, heated to 98C
in; ~a water~ ~bath ~ to solubilize some amylose, cooled to
promote precipitatlo`n/crysta~llizatlon and centrifuged one
n ~ last time. The~ resulting centrifuged we~ sediment
25 containing 8~.1%~dry substance was placed in a sample jar
: and stored in~a refrigerator.~ ~ ~
Int o a;~ 5-liter 3-neck~ round bottom flask
equipped witlh a stirrer and temperature controlled water
bath was placed 7~2 grams ~ of the wet freshly
30 ~ precipitated potato~ amylose above, ~ 2356 grams deionized
water and 64; grams of molar phosphase buffer at pH
6.9. The suspension was stirred and the pH maintained
; ~ at 6.9. To thissuspension was added 320 units
::: : ~ : : :
: :
,
9'~ }~ }~f "; ;~
WO 93/1067~ PCr/US~2/065X9
2 ~
-26-
(5 units/gram amylose) of porcine pancreatic ~-amylase
enzyme (A6255, Sigma Chemical Co., St. Louis,
Missouri). The mixture was allowed to react with
stirring at 25C for 24 hours then one half of the
5 mixture was added to 8: volumes of ethanol (formula 3A)
with stirring in a 4-liter beaker. The resulting aqueous
alcoholic mixture was centrifuged as above at about 6000
x g and the sedîment dried in a vacuum oven overnight
at 50C.
:: 10A 10~6 dry: solids slurry of the dried product
above was sheared ~ using a small Waring blender at
controlled cond~tions ~(120 volts, 60C, 8 1/2 minutes)
and left to stand 3 hours before the sample was sent for
analysis for yleld~ stress, 170 NMR wate~r immobilization,
15: molecular weight by: GPC~ and ,old-water solubles. The
: :results of these a~nalyses of the resulting creme are as
follows. An anal~ysls of ~ the molecular weight (by gel
permeation chromatography) showed ~ a weight average
(Mw): of ~SS,900, a :number average (Mn): of: 9,100 and a
20 ~ péak molecula r ~:~weight of 3 2,000. Thè water
immobîlizatîon ~by~ ~7O: NMR) ~exhibited by the creme was
., ; ~ . .
177~ sec ' and~the~yleld: stress was 531 pascals. The
: cold-water solubles: of: the~ powder~ were: 13% by weight.
It~ is~ specu~1ated: that~ further enzyme hydrolysis
25: :to:: give:~ a level-off DP~ of about 65 will result in even
greater o17 NMR ~water immobillzation values.
' ,
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WO 93/1067~ PCI/US92/06~8g
2 ~15 l /æ ~
-27- -:
EXAMPLE 2
SPOONABLE SALAD DRESSING :
5 A spoonable dressing can be prepared from the creme of
Example 1 as follows.
I n~redients %, wt .
Part A
:
Water ~ 22 . 00
ISOSWEET (~) 100 high fructose
corn syrup (Staley) 17.0n
Vinegar, white, 100 grain 10.00
SWEETOSE (~) 4300~ corn syrup (Staley) 5.00
$TAR-DRI ~ 35R~ corn syrup solids (Staley) 3.20
DELTA 7393 starch ~Staley) 2.85
~:
Salt ~: 1.80
Carboxymethyl cèllulose 7MF (Aqualon) ().20
: Mustard ~ powder (McCormick) 0.10
Titanium~ dioxide~ ~(Warner-Jenkinson) 0.0~
Garlic: powder: : - ~ : 0.05
Onion powder ~ 0. 05
Paprika ~ 0.0125
~ Calclum disodium: E:DTA 0.0075
: ~ : Pa rt B ~
Creme of Example 1 (10% dry solids~ 27.40
Soybean oil 8.00
Egg yolk, fresh: ~ 2.00
: : : Lemon juicei sin~le strength 0.25
Tota l100 . 00
. . .
WO 93/1067:. PCI /US92/065~9
~ } 1
-28-
P roced u re
~..
1. Place water, vinegar, ISOSWEET, and SWEETOSE
into a steam jacketed, swept surface cooker.
5 2. Thoroughly blend the dry ingredients of Part A,
then disperse them into the water/vinegar/syrup
mixture with agitation. Continue mixing while
heating with steam to 190F. Maintain this
temperature for 5 minutes (with mixing); then
immediately cool to 90F.
3. Transfer Part A to a Hobart bowl; add egg yolk,
creme, and lemon juice. Mix at low speed for 5
minutes with paddle.
4. Slowly add soybean oil and mix for another 5
minutes.
5. Process through a colloid mill at a 0.026" setting.
Pack off finished product.
20;
: 25
:
:.
~.:
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WO 93/1 067:. PCI /USg2/06s89
-29- 2 1 ~
EXAMPLE 3
BUTTERMILK DRESSING
- 5 A buttermilk dressing can be prepared from the creme of
Example 1 as follows.
In~redients ~, wt.
Buttermilk, liquid, 1% fat 30.00
: Water 23 . 94
Creme of Example 1 23.50
STAR-DRI (É~) 10 maltodextrin ~Staley) 8.00
Vinegar, white, 100~ grain 5.40
: S~asoning mix #962-2489 (Griffith Labs) 5.00
Buttermilk solids, Beatreme #983 (Beatrice) 1.00
Instant TENDER-JEL-(~) C starch (Staley) 1.00
Salt 0 75
Sugar ~ ~ 0.65
~; Carboxymethyl ceilulose, 7 MF (Aqualon) 0.40
Titanium dioxide (Wàrner-Jenkinson) 0.10
Potassium ~ sorbate ~ 0 . 08
;Sodium benzoate i 0.0725
Garlic powder 0.05
~Onion powder 0 05
Calcium disodium E:DTA 0.0075
Total 100.00
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WO 93tl067:. PCI /US92/0658
211S ~ 30-
P roced u re
1. Blend all dry ingredients together.
2. Place water and buttermilk into a Hobart mixing
bowl. Disperse the dry ingredient blend int~ this
water/buttermilk mixture; mix with a Hobart paddle
for 10 minutes at low speed.
3. Add the creme and mix for 10 minutes at medium
` ~ speed .
10 4. Add vinegar and mix for 1 minute.
5. Process through a col!oîd mill at a 0.02" setting.
Pack off finished product.
.
1 5
; :,
~: :
25~
: ::
.:
:
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WO g3/10675 ' PCI /US92/06589
,
EXAMPLE 4 ~ t~
FRENCH DRESSING
5 A French dressing can be prepared from the creme of
Example 1 as follow,s.
In-qredlents ~ %, wt.
~Creme of Example 1 35.00
I:SOSWEET (g) ~I~OO high fructose ~
corn syrup (Staley) ~ 25 . 00
' ~ Water 23.98
Vine~ar, white~ IOO~:~graln 10.00
,` I5~ Tomat~ paste, 24-26% solids ~ 3.50
Sa~t; ~ 1 . 50
Seasoning mix~ #912-0135 (Griffith Labsl 0.30
MIRA-THIK~ :468~ starch (Staley) 0.30
: Seasoning mix #F34037 (McCormick) 0.10
:;20~ ~Xanthan~:gum,~Kelt~rol~: TF (Kelco): 0.10
G:u:ar gum #8/22~ TIC ~Gums) ~ 0.05
E~ Mustard powder: :~ ~ : 0.05 ' "' ~
Potass i um~ sorbah~ 0 . 05 ' ~ '
::Titanium~ dioxide (~Wa~rner-Jenkinson) 0.04 :"
25~ `Paprika ~ 0.0225
Calcium disodium :EDTA : : 0.0075
Color, yellow ~FD~C #5/#6 ~ to suit
Total 100.00 ,",:
,, : :
,
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WO 93/1067~ P~/US92/(~6589
2 ~ 1 Ll 2
-32 -
P rocedu re
1. Place water and iSOSWEET into a Hobart bowl.
Blend all dry ingredients together and disperse into
the water and ISOSWEET mixture. Mix at low speed
and allow to hydrate for 5 minutes.
2. Add tomato paste, creme and vinegar. Mix for 5
mi n utes .
3. Process through a colloid mill at a û.02" setting.
Pack off finished product.
:
';',:
~:~: : 25
...
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WO 93/1067: PCl`/US92/06589
2 1 ~ c `~
-33 -
EXAMPLE 5
DIJON DRESS I NG
5 A Dijon vinaigrette dressing can be prepared from the
creme of Example 1 as fo!lows.
I n~redients ~, wt .
Water 38.90
: Creme of Example 1 25.00
Vinegar, white, 100 grain 14.00
Sugar 6. 50
:~ Dijon mustard (McCormick) 6.00
15: Lemc>n juice, single strength 6.00
S~lt : 2 . 35
Spice blænd #F3037~:~(McCormick) 1.00
Xanthan gum, Keltrol TF ( Kelco) 0.14
R~d be!l pepper, :dried (McCormick) 0.05 :
Potassium~ sorbate 0.04
Annatto extract~ (Warner-Jenkinson) 0.0125
~: ~ : ; Caicium disodium EDTA 0.0075 ~
Total100.0Q :.
: ~ ,';~,
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:
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WO 93/1067:- PCI/US92/065X9
21 ~t h~ 2
-34 -
.
Procedu re
1. Place water in Hobart bowl.
2. Blend together all dry ingredients except the spice
blend and red pepper. Disperse the dry ingredient
blend into the water and~ mix with a paddle at low
speed for S minutes.
. ~ :
3. Add the creme, mustard, vinegar and lemon juice.
Mix for 5 minutes at low speed.
10 4. Process through:~a~colloid mill at a 0;.02" setting.
5.~ Blend in spice blend~ and red pepper. Then pack
off product. ~
. :
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WO 93/10675 PCl /US92/06589
2~ i S.l ~ .
-35 -
EXAMPLE 6
SOVR CREAM
5 A sour cream can be prepared from the creme of Example
as fol lows .
.
In~redients %, wt.
.
Creme of Example 1 39.79
~: ~ Sour cream, 18-20% fat 29.83
Water 23 . 41
Non-fat dry milk, low heat (Land O'Lakes)5.97
Lactic acid, 8830 0 - 40
15~ :Xanthan~gum, Rhodigel (Rhone-Poulenc) 0.20
Salt : : 0 . 20
Sodium citrate, hydrous, ~:
fine granular (Pfizer) 0.20
Total 100.00
~ : ~
P ro~ed ~l re
1:.: Add lactic acid~:to wa:ter, thoroughly mix at Speed 1
25~ with; a Hobart ~ mixer equipped with ~ a ~ wire whip .
2:. Mix in sour cream~ and then all dry ingrediénts; mix
until the mi~xture is uniform .
: 3. Blend in the creme to form a semi-homogeneous
:
mixtu re .
30 ~ 4. Homogenize for smoothness.
5. Pack off and refrigerate until ready to use.
:: :
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WO 93/1067:~ PCl/US92/06~X9
-36 -
EXAMPLE 7
TABLE SPREAD
5 A table spread can be prepared from the dry precipitate
of Example 1 as follows.
I n~redients %, wt .
::. 10 Part A
` Water 25.00 :
Xanthan gum, Rhodigel (Rhone-Poulenc) o. 1n
:
Pa rt B
Water 32 . 7306
Dry precipitate of;:Example 1 12.90
STAR-DRI (~) ~ 15. maltodexrin (Staley) 7.00
Whey powder sweet, #~7231 :(Land O'Lakes)1.00
Salt :; ~ 0 90
: 20 Potassium sorbate 0.10 ::
Calcium~ disodium:~ EDTA 0.0075
Artiflcial color, egg shade #08038 0.0()04 -~
(Warner-Jenkinson)
Pa rt C ~ ; ~
STALE`~ 400-0300 partially hydrogenated ~:
corn oii (Staley) 19.83
Monoglycerides, :Dimodan LSK (Grinsted) 0.24
Leci.hin, M-C-Thin AF1/SB (Lucas Meyer) 0.15
~:: 30 Flavor #57.752iA (Firmenich) 0.03 -
: Antioxidant, Tenox 2 (Eastman) 0.01
B-Carotene, 30% in vegetable oil
(Hoffmann-LaRoche) 0.0015
Total 100.00
; ~
.
WO g3/1067~ P~/l 'S92/06SX9
37 2 ~ 3 ,~
Mixin~ Procedure
, .
1. Vse a high speed mixer to mix Part A ingredients
until xanthan gum is dissolved
- 5 2. Comb;ne Par t A and ~ Part B ingredients and mix at
slow speed until uniform. :-.
3. While mixing, heat Part; A and Part B mixture to
120-t30F.
4. Mix Part C i ngredients together and heat to
~ 120-130F.
5. Pour aqueous; pha~s~e (Parts A and B) into oil phase
(Part C) while~ stirring vigorously .
6. Homogenize the entire mixture at a pressure of :
8,000~ to 15,000;~ psi~ and an~ output temperature of
140-150F.`
7. ~ ~ Immediately cool to~ 50F while stirring.
8.:~ : ; Pack ~off and~refrigerate.;
20 `:
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EXAMPLE 8
ALPHA-AMYLASE HYDROLYSIS OF HEAT TREATED,
DEBRANCHED 55% Ah~YLOSE CORN STARCH
A 2% solids slurry of 559~ high amylose corn
starch ~HI-SET C) was prepared by mixing 452.3 grams
(400 grams dry basis) of Hl-SET C corn starch with
deionized water to give a total volume of 20 liters. The
10 suspension was heated in 2-liter batches up to 160C in
a pressure reactor then cooled to about 30C to 50C by
passing the hot solution through a cooled heat exchanger
tube. The pH of the solution was adjusted to
approximately ~ 4.5 'and the solution was placed in two
5 12-liter round bottom flasks equipped with agitation,
condensers, and ~heat controlled water baths. The
temperature was adjusted to 45C and 400 units per gram
dry basis starch of isoamylase enzyme (f rom Hayashibara
Co~. and~ containing~ 865,000 units/gram) was added to
2 0~ ~ each~ solution.~ The~ solutions were allowed to react 20
hours ~ then~ the~ Z%~ solids solutions/dispersions (the
debranched starch~ ~tends to precipitate with time) were
heated~ to 160C in~the pressure reactor as before to
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~ ~ ,comptétely dissolve t he precipitated starch and make it
25 ~ more readily ava~ilable for isoamylase enzyme attack. The
solutions were cooled, the pH again checked and found
to be~ approximate,ly 4 . 5, then 400 units per gram dry
basis starch of isoamylase enzyme was again added and
; ~ the reaction was~allowed to proceed 18 hours at 4SC for
3() a total reaction time of 38 hours.
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The 2~ solution/suspension after 38 hours of
isoamylase digestion was heated to approximately 95C to
inactivate enzyme then concentrated by rotary
evaporation over a 2-day period (stored in a refrigerator
5 overnight) to approxlmately 15~ solids. This slurry was
dried on stainless steel trays at 60C in a forced air
oven overnight and the dried material ground to pass
through a US #60 mesh sieve.
To 380 grams (350 grams dry basis) of the
10 above dried, screened material was added 1,720 grams of
deionized water to give ~a 20~ solids slurry. The slurry
was heat treated byi ;controlled heating in a tèmperature
controlled water bath from 50C up to 100C at the rate
of 0.05C per m;nute followed by controlled cooling from
100C down to 50C ~at the rate of ().OSC per minute.
The heat treated slurry ;~was poured onto a stainiess steel
tray~ and dried in ~a~forced air oven~ at 50C then ground
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to pass through a~ US. #6~ mesh sieve. This sample
served as ~a substrate~for a-amylase hydrolysis treatment
20~ to~improve the ease of ~creme formation on sheari`ng.
The above ~ starch substrate was enzyme
hydroiyzed at 20%~ solids ~(375~ grams total ~slurry wt. ) at
; 25C with 15 units/gram starch of porcine pancreatic
a-amylase (Sigma~ Chemical ~ ~ Company) . Sampîes of
25 ~ ~ reaction slurry were~withdrawn (125 grams each) after 8
hours~, 21 hours~ and 48 hours~ of hydrolysis and the pH
adjusted to 3.5 to Ina~ctivate ~enzyme. ~ The 8 hour and 21
hour samples were ;filtered on a Buchner funnel followed
by wash;ng with about 25U ml each with deionized water.
30 The sample hydrolyzed 48 hours would not filter (very,
very slow) and ~was centrifuged (7000 x g), the
supernatant discarded, then deionized ~.~ater added back
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to the original sample weight. After stirring to give a
homogenous mixture, this slurry was centrifuged as
above and the supernatant discarded. This procedure
was repeated a final time. All wet cakes or sediment
S (from filtration or from~centrifugation) were mixed with 8
volumes of ethanol (formula 3A) to denature any
remaining enzyme. They were then either filtered or
centrifuged one last time. The wet cakes and sediment
were dried in a 50C forced air oven and ground to pass
0 through a US #60 mesh sieve. The products were
welghed ~ and ~yields ~ were calculated for each . Yield
stress ~ values were~ o btained on 20~ solids cremes
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prepared by shearing at 120 volts, 60C for 8 1/2
minutes ~with a Waring~ blender~ equipped with a small
5~ jacketed j ar. ~ The~ ~ yield stress values were measured :`
using~ a ~ B~rookfield~ viscometer after the ~ cremes stood at
least; 3 hQurs at~ room temperature. The analytical
; r esults are reported~ ~below .
20~ a-Amylase
Hydrolysis ~ Prodùct ~Yield Stress,
Time,~ hr. ~ Yield, 96 db ~ Pascals
8 ~ 87 . 0 ~ 288
25~ 21 ~ 84.2 ~ 348 -~
48 ~ 80. 9 365
It was noted that the texture of the 8 hour
creme was the most gritty~ while the 48 hour sample was
30~ ~more~ creamy and~ ~;less~ gritty. ~ It ~ ~s~ speculated that
continued enzyme~ ~hydrolysis~ would continue to improve
texture (less ;gritty~) ~and Increase yie1d ~stress values.
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It was noted that the pH of the 48 hour
hydrolyzed sample declined to 5.7 ~from 6.9). It is
likely that this was caused by undesirable fermentation
to form organic acids. Such a large decline in pH likely
5 also causecl reduced enzyme hydrolysis activity compared
to what may have occurred if the pH had remained at
6 . 9 .
It is concluded that the enzyme hydrolysis
gave considerable improvement in the shearability of the
heat treated,~ debranched high amylose starch. In :
addition, it ~also ~resulted in improved smoothness of
textu re .
` ~ EXAMPLE 9 ~ '
DEBRANCHED;~'HIGH; AMYLOSE CORN STARCH
A 55% ~amylose corn starch (HI-SET C) is made
2~ up ~to 25%~ sol~ds~'~then~ jet ~cooked~ at ;160C wlth a
retention time o f n~10 minutes at 160C then cooled to
100C. ~The~: pH :~of~ the~ solution if ~ adjusted: to pH 6Ø
- Novo~ thermostablel'~ ~pullulanase enzyme as described in
WQ~ 92/02614 ~s~ added~ at 50; units per gram of starch and
25~ ~ the~:reaction ls ;allowed to proceed at 100C for 24 hours
at which~ time ~GPC~ana~iysis ~;will show that less than 10%
'~ ~ of ~ the remaining''amylose or amylopectin molecules are
above about 100,(100 molecular weight.
The~ ~debranched ~solution is treated with 3%
30 w/w (weight; ~by~ ~weight ~ basis)~ of decolorizing carbon
(based on starch~dry ~substance weight) at 90C. The
coiorless carbon~ treated ~solution is cooled to 5C for 16
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hours to bring about crystallization. The crystallized
mass is dried in a spray drier at 15% solids after dilution
with water.
The spray dried material is made up to 20~
S solids and heated from 50C to 100C at 0.û5C/minute
then cooled to 100C at 0.05C/minute. The heat treated
material is adjusted to pH 6.9 and treated at 20% solids
at 25C for 24 hours using approximately 50 units per
gram dry starch of porcine pancreatic -amylase enzyme.
The resulting slurry is adjusted to pH 3.5, with 10% HCI
heated to 60C and held at that pH and temperature
about 1 hours~ to inactivate enzyme then microfiltered at
60C to reduce the soluble saccharide content to less
tha~n 10% (measured at room temperature). The retentate
1S slurry is spray dried at about 15% solids to give a heat
stable, shearable starch based fat replacer having a
yield stress at 20~ solids greater than 400 pascals.
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