Note: Descriptions are shown in the official language in which they were submitted.
3~2~4~3~
NOVEL ALDEHYDE-CONTAINING ~ETEROPOLYSACCHARDIES AND A
PROCESS FOR TH~IR . PREPARATIO~ . AND THE USE THEREOF
This invention relates to aldehyde-containing synthetic
heteropolysaccharides and a process for their preparation.
Polysaccharide compositions have been utilized in many diverse
industrial applications, for example, as thickeners, adhesives, sizing
.h~l 5 agents, e~c. Polysaccharides such as starch and cellulose, which have
been modified to contain aldehyde groups, have found use particularly in
the paper and text1le industries.
Both oxidative and non-oxidative methods have been employed to
introduce aldehyde groups onto polysaccharides. Oxidative methods
which have been used include treating with periodic acid, periodates,
alkali metal ferrates, or alkali metal bromites, as described, for
example, in U.S. Pat. Nos. 3,086,969 (issued April 23, 1963 to J.
Slager); 3,553,193 (issued Jan. 5, 1971 to D. LeRoy et al.); and
3,632,802 (issued Jan. 4, 1972 to J. BeMiller et al.). Non-oxidative
methods which have been used include the reaction of a polysaccharide
`~ with an aldehyde-containing reagent as described in U.S. Pat. Nos.
3,519,618 (issued July 7, 1970 to S. Parmerter) and 3,740,391 (issued
June 19, 1973 to L. Williams et al.).
Polygalactomannan gums (i.e. guar gum) and other natural galactose-
containiny polymers modified to possess aldehyde groups are useful ascrosslinking agents and have been employed in variou~ film-forming
applications as adhesives or binding agents in self-sustaining films.
Such aldehyde gum derivatives can be prepared by similar oxidative
and non-oxidative methods to those mentioned above or, as described in
-- 2 --
U.S. Pat. No. 3,297,604 (issued Jan. 10, 1967 to F. Germino), polygal-
actomannans and other natural polysaccharides containing galactose con-
figurations at the C4 position (i.e., talose) may be selectively
oxidized at the C6 position of the saccharide unit by the enzyme
galactose oxidase in order to yield aldehyde groups.
While commercially useful polysaccharide aldehydes have been
obtained by various oxidative and non-oxidative methods, there is a
continual demand to meet a broad industrial need for new polysaccharide
,, ",; ,~j
compositions with unique rheological properties which also possess the
aldehyde functionality.
There is therefore a need for aldehyde-containing heteropoly-
saccharides, the polysaccharides being capable of undergoing cross-
linking reactions alone or with other organic compounds. None of the
above references disclose or suggest the products herein.
The present invention provides a starch ether derivative having
the structure
R-O-CH2-CH2-0-Starch
~ wherein Starch-0 represents a starch mo1ecule and R represents a mono-
`¢~ saccharide with the oxygens 1inking the monosaccharide and the starch
being attached to the glycosidic carbon atom of the monosaccharide by
an acetal or ketal linkage and being attached to the starch by an ether
linkage. Typica1 monosaccharides includes hexoses such as glucose,
mannose, galactose, talose, gulose, allose, altrose, idose, fructose
and sorbose and pentoses such as xylose, arabinose, ribose, and lyxose.
The corn and wheat starch ether derivatives in aqueous solution after
gelatinization exhibit stable cook properties. Such cook stability
permits the derivatives herein to be utilized for example, in various
food and thickening applications.
The present invention also provides an aldehyde-containing starch
ether having the structure
R'~0-A-0-Starch, where A is -CH2CH2-or-OH2CH(OH)CH2- and R' is
1,
CH0
. O
H0
''~
represents a hexose containing a galactose configuration at the C4
position with the oxygens linking the monosaccharide and the starch
being attached to the glycosidic carbon atom of the hexose by an acetal
linkage and to the starch by an ether linkage.
The aldehyde-containing starch ether derivatives are prepared by
reacting a mixture of a) an aqueous dispersion of a starch ether having
the formula
H
, 20 R"-0-A-0-Starch, where R" is
' '. 7.,
; and b) a galactose oxidase enzyme in the presence of oxygen whereby
the C6 position of the monosaccharide is oxidized to form a carbonyl
group.
The present invention also prov~des an improved process for
preparing an artificial flavor comprising heatlng together in an
aqueous medium, a mixture comprlsing at least one amino acid and
. . .
-- 4 --
a saccharide, wherein at least a portion of the saccharide is
replaced with a starch aldehyde having the structure R'-O-A-O-Starch.
Glycosides may be prepared from mono- and polysaccharides which
contain a reducing carbon atom. This carbon atom, which is located in
the terminal saccharide ring, is capable of reacting with an alcohol to
form glycosidic products attached by an acetal or ketal linkage, de-
pending on the mono- or polysaccharide employed.
A. Halohydrin and Glycidyl Glycoside Reagents.
.i.~,i.,. ~
One class of glycosides applicablè for use as reagents in prepar-
ing the glycoside starch ethers useful herein include glycosides
having the formula:
R"-O-CH2-CH-CH2 or R"-~-CH2-CH-CH2
A A' O
wherein R" is as shown above and represents a monosaccharide containing
a galactose configuration at the C4 position and where the O lS
attached to the glycosidic carbon atom of the monosaccharide (i.e., the
C1 position), and A and Al are alternately a hydroxyl or a halogen
- ~ selected from the group consisting of chlorine or bromine.
; The halohydrin or glycidyl glycosides may be prepared according to
the methods described in U.S. Pat. No. 3,931,148 (issued Jan. 6, 1976 to
W. Langdon) which teaches that glycosides may be prepared by reacting
monosaccharides at temperatures of about 94 to 108C with 3-chloro-1,2-
propandiol in the presence of about 0.01 to 2.0 weight percent, based
on the reactants, of a strong acid catalyst.
The halohydrin or glycidyl glycosides are preferably prepared by
reacting the monosaccharide in an excess of 3-halo-1,2-propandiol in
the presence of a catlon exchange resin. By employing a cation ex-
~.2~
change resin, the glycosides may be prepared at moderate temperatures
without charring which is often caused by strong low molecular weight
acids at the higher temperatures mentioned above. The reaction is
conducted with stirring at a temperature of about 55-80C over a period
of about 3-20 hours. After the reaction is complete, the mixture is
filtered in order to remove the cation exchange resin. The excess
diol may then be removed by vacuum distillation or washing with organic
solvents in order to obtain the 3-halo-2-hydroxypropyl glycoside.
The halogenated propandiols which may be employed include 3-chloro-
1,2-propandiol and 3-bromo-1,2-propandiol. The use of the chloro deri-
vative is preferred due to its commercial a~ailability and cost. ~hile
a saccharide to diol ratio of as little as 1:1.4 has been employed, a
preferred ratio is at least 1:3 to 1:6, most preferably 1:5.
Any cation exchange resin may be used in the glycoside prepara-
tion. Suitable exchange resins include sulfonated-crosslinked poly-
styrene such as commercially available Amberlit~'IR-120 from Rohm and
Haas, Dowex 50 f~om Dow Chemical and Permutit Q from Permutit; sulfon-
ated phenolics such as Ouolite C-3 from Diamond Shamrock; and sulfon-
_ ated coals such as Zeo Karb ~ from Permutit. The preferred cation
exchange resin is Dowex 50. The amount of resin useful herein isabout 1 part resin to 2-8 parts by weight of saccharide, preferably 1
part resin to 4-5 parts saccharide.
The glycidyl glycosides useful herein may be prepared by reacting
a 3-halo-2-hydroxypropyl glycoside with an alkali metal hydroxide in
order to form the epoxide group. Typically, the glycoside is mixed
with an aqueous alkaline solution while cooling. The mixture is neu-
tralized with acid and then dissolYed in alcohol in order to precipi-
. tate the metal salts formed. After filtration, the glycidyl glycoside
* Trade Marks
. .
~-~9~
may be recovered by removing the alcohol and water by vacuum distil-
lation.
B. Haloethyl ~lycoside Reagents.
Another class of glycosides which are useful reagents in prepar-
ing the glycoside starch ethers herein have the formula:
R-0-CH2CH2x
wherein R-0 represents a monosaccharide where 0 is attached to the
glycosidic carbon atom of the monosaccharide and X is chlorine or bro-
.. ,.,~.~ . i.
mine. Any monosaccharide containing a reducing carbon atom may be re-
acted with a haloethanol in the presence of a strong acid catalyst or a
cationic exchange resin, by similar methods described above in order to
obtain the haloethyl glycoside. Typical monosaccharides include, for
example, glucose~ fructose, sorbose, mannose, galactose, talose,
xylose, and ribose.
The haloethyl glycosides specifically useful for preparing the
starch ethers which are oxidized by enzyme treatment have the formula:
R"-0-CH2CH2X
where R"-0 and X are as defined above.
In some instances, the haloethyl glycosides are preferably
employed in the preparation of the starch ethers useful herein because
impur~ties (i.e., 1,3-dichloro-2-propanol) present in the 3-halo-1,2-
propandiol, used to prepare the halohydrin glycosides, are very diffi-
cult to remove from the glycosides and as such will react with starch
as a crosslinker.
The halohydrin, glycidyl and haloethyl glycosides herein are cap-
able of reacting under etherification conditions with polysaccharides
including, for example, starches and starch conversion products derived
from any plant source; starch ethers and esters; cellulose and cellulose
~ x~
-- 7
derivatives and various plant gums and gum derivatives.
C. Hydroxypropyl and Ethyl Glycoside Starch Ether Derivative
Preparation.
The applicable starch bases which may be used in preparing the
glycoside starch ether derivatives herein may be derived from any plant
source including corn, potato, sweet potato, wheat, rice, sago, tapioca,
waxy maize, sorghum, high amylose corn, or the like. Also included are
~ the conversion products derived from any of the latter bases including,
- for example, dextrins prepared by the hydrolytic action of acid and/or
heat; oxidized starches prepared by treatment with oxidants such as
sodium hypochlorite; fluidity or thin-boiling starches prepared by en-
zyme conversion or mild acid hydrolysis, and derivatized starches such
as ethers and esters. The starch base may be a granular starch or a
gelatinized starch, i.e., non-granular starch.
Methods for preparing the modified starch bases useful herein are
well-known to those skllled in the art and discussed in the literature.
See, for example, R. L. Whistler, Methods in Carbohydrate Chemistry,
~ Vol. IY, 1964, pp. 279-3Il; R. L. Whistler et al., Starch-Chemistry and
- -: Technology, Vol. II, 1967, pp. 293-450; and R. Davidson and N. Sittig,
~ r`~. ~
Water Soluble Resins, 2nd Ed., 1968, Chapter 2.
~ The starch e~herification reactions herein may be represented by
; the ~ollowlng equations:
0~1-
25 I. R"-O-CH2CHCH2 -~ Starch OH ~ R"-O-CH2CHCH2-0-Starch
A A' OH
0~1-
II. R"-O-CH2CH2X ~ Starch-OH ~ R"-O-CH2CH2-0-Starch
4~
wherein Starch-OH represents a starch molecule and R", A, A', and X
are as defined abo~e.
It should be noted that use of a glycidyl glycoside herein will
result in the same starch reaction product (see Equation I) as will use
of the halohydrin glycoside. The etherification reaction proceeds only
under alkaline conditions after the halohydrin group is first converted
to the epoxide form.
Equation II represents the specific reaction of the preparation of
~1
m ~i the starch ethers useful in the preparation of the novel starch alde-
hydes herein. It is, however, only one embodiment of the reaction
which produces novel starch derivatives from haloethyl glycosides and
starch which may be represented by the equation:
R-O-CH2CHzX + Starch-OH R-O-CH2CH2-0-Starch
. . ,
wherein Starch-OH, R, and X are as previously defined. While not
wi-shing to be bound by theory, it is believed that the haloethyl group
reacts with the starch molecule through a neighboring group
- participation mechanism.
The practitioner will recognize that the starch molecule is a
polysaccharide composed of many anhydroglucose units, each having three
free hydroxyl groups (except the non-reducing end glucose units which
: ,.. i .
contain four free hydroxyl groups) which may react with the glycoside
reagent. Thus, the number of such displacements or the degree of sub-
stitutlon (D,S.) will vary with the particular starch, the ratio of,: '
`~r~ reagent to starch, and to some extent, the reaction conditions.
FurthermQre, since it is known that the relative reactivity of each of
the hydroxyl groups within the anhydroglucose unit is not equivalent,
it is probable that some will be more reactive with the reagent than
others.
..
. .
4,'3~
The monosaccharide portion of the glycoside reagents also contain
free hydroxyl groups. It should therefore be understood that during the
etherification reaction, there is a possibility that a glycoside reagent
may react with another reagent molecule. Such a reaction would yield
a saccharide-containing molecule which would still contain an unreacted
glycidyl or haloethyl group capable of reacting with starch and a sac-
charide unit which contains the galactose configuration at the C4
position. No crosslinking will result from this reaction since there
,. ,ii~ . j~.,
-~ is only one reactive site per molecule.
The starch reaction may be conducted by a number of techniques
:~ known in the art employing, for example, an aqueous reaction medium, an
organic solvent medium, or a dry heat reaction technique wherein a wet
starch cake is impregnated with the glycoside reagent then subjected to
dry heat.
In the preferred method, the reaction is carried out in an aqueous
` medium using either an aqueous slurry or an aqueous dispersion of ~he
starch base. The glycoside reagent may be added to the reaction mix-
ture as a solid or an aqueous solution. The preferred concentration of
the solution is 20-50% by weight, based on the weight of reagent. In
; 20 an alternative method, the glycoside reagent solution is brought to the
desired alkaline pH prlor to its addition to the starch base, this
being accomplished by the addition of sufficient alkali. In another
variatlon, dry starc~l may be added to an alkaline solution or ~he glyco-
' side reagent.
The amount of glycoside reagent to be employed in the reaction with
the starch herein will generally vary from about 0.1 to 100~ by weight,
based on the weight of dry starch, depending on such factors as the
starch based used, the glycoside reagent used, the degree of substitu-
3~ ~3~
- 10
tion desired in the end product, and, to some extent, the reaction
conditions used.
The starch reaction is carried out under alkallne conditions, at a
pH of 11-13, preferably 11.4-12.4. Alkali may be added to the starch
slurry or dispersion either prior to or after the addition of the gly-
coside reagent. The pH is conveniently controlled by the addition of
sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethyl-
ammon;um hydroxide, and the like. The preferred base is sodium
~ l
hydroxide.
When conducting the reaction with granular starches~ it may some-
times be desirable to carry out the reaction in the presence o~ salts,
e.g. sodium sulfate, in amounts of from about 10 to ~0~ by weight, bas-
ed on dry starch. The presence of sodium sulfate ac~s to suppress swel-
ling of the starch and gives a more filterable product. The sodium
sulfate is not used in the calcium hydroxide reactionsO
The reaction mixture is agitated under the desired reaction condi-
tions. The reaction time may vary from 0.5 to 20 hours~ depending on
such factors as the amount of the glycoside reagent employed, the temp-
erature, the pH, the scale of the reaction, and the degree oF substi-
- 20 tution desired. In general, the preferred range of reaction times is
from 6 to 16 hours.
The reactlon is carried out at a temperature o~ from 20-95C.,
preFerably 25-~5C. It will he recognized by the pract1tioner that
the use of temperatures above about 60C. with granular starches in
an aqueous medium will result in granule swelling and filtration dif-
ficulties or in gelatinization oF the starch. In instances where high-
er reaction temperatures are desired, an aqueous solution containing a
;water-miscible so1vent may be employed to prevent swelling.
~;~9~L4;~
After completion of the reaction, the pH of the reaction mixture
is adjusted to a value of from 3 to 7 with any co~lercial acid such as
hydrochloric acid, sulfuric acid, acetic acid, and the like. Such
acids may be conveniently added as a dilute aqueous solution.
Recovery of the derivatives may be readily accomplished, with the
particular method employed being dependent on the form of the starch
basé. Thus, a granular starch is recovered by filtration, optionally
washed with water to remove any residual salts, and dried. The granu-
lar starch products may also be drum-dried, spray-dried, or yelatiniz-
ed and isolated by alcohol precipitation or freeze drying to form non-
granular products (i.e. gelatinized). If the starch product is non-
granular, it may be purified by dialysis to remove residual salts and
isolated by alcohol precipitation, freeze drying, or spray drying.
D. Aldehyde-Containing Starch DeriYative Preparation.
The aldehyde-containing starch derivatives herein can be
prepared according to the invention by enzymatic oxidation of those
glycoside starch ethers described above and shown in Equations I and
II, wherein the glycoside substituent (R") is the monosaccharide contain-
ing a galactose configuration at the C4 position. Such monosaccharides,
are exemplified by galactose and talose:
HOH2C HOH2C
H~ HO~
~alactose talose
,j"~
.~
L4~
- 12 -
Oxidation at the C6 position of the glycoside substituent is
effected by incubating the starch ether derivative which has been
dispersed in an aqueous buffer solution in an amount determined by tne
solubility of the components, with the galactose oxidase. The reaction
is conducted in the presence of oxygen at a pH range from 4 to 9,
preferably 5 to 8, and at a temperature of about 10* to 60C with
ambient temperatures preferred. The oxidation is preferably conducted
in the presence of the enzyme catalase which facilitates the reduction
of hydrogen peroxide (a byproduct of the oxidation) to water and oxygen.
After the incubation, the enzyme is inactivated (i.e., by re-
moval of the oxygen source, heating, or lowering the pH). The starch
aldehydes may then be isolated by known procedures or remain in
solution.
Starch reacted with 2-haloethyl galactoglycoside and then oxidized
with galactose oxidase, for example, would yield a starch derivative
having randomly occurring aldehyde-containing galactose side chains
as depicted below:
Glu-Glu-Glu-Glu-
~
H OH
~ ~ where - Glu Glu - Glu - Glu - represents the starch chain.
:'~
. . .
.... ..
4~
The aldehyde functionality present on the starch derivatives herein
renders the products use~ul, for example, as paper strengthening addi-
tives. This aldehyde functionality also makes theM useful as co-reac-
tants in the Maillard reaction, the well-known browning and flavor-
producin~ reaction occurring in foods (see U.S. Pat. No. 3,716,380
issued Feb. 13, 1973 to P.J. van Pottelsberghe de la Potterle for a
description of this reaction, as well as U.S. Pat. Nos. 3,615,600 and
3,761,287 issued Oct. 26, 1971 and Sept. 25, 1973 to C. H. T. T.
Zevennar and K. Jaeggi, respectively, and Brit. Pat. No. 1,285,568
published Aug. 16, 1972 by J. L. Godman et al.).
The process for preparing artificial flavors using the Maillard
reaction typically involves reacting together, in the presence of
water, a saccharide, one or more amino acids, and optionally other
ingredients such as hydrogen sul~ide (see Brit. 1,285,568), succinic
acid and a hydroxycarboxylic acid ~see U.S. 3,615,600), a polyalcohol
(see U.S. 3,761,2~7), or a lower carboxylic acid or fatty acid (see
U.S. 3,716,380).
Suitable amino acids include glycine, alanine, proline, hydroxy-
7 proline, threonine, arginine, glu ~mic acid, aspartic acid, histidine,
lysine, leucine, isoleucine, serine, valine, and taurine. Smaller
, amounts of tyrosine, tryptophan, cystein, phenylalanine, and methionine
are not objectionable, depending upon the flavor desired. Di-, tri-,
or higher peptides, or proteins giving rise to the requisite amino
acids can also be used. Protein hydrolysates are convenient sources.
The saccharides conven~ionally used include monosaccharides or
di-, tri-, or polysaccharides which yield monosaccharides under the
Maillard reaction conditions. The above aldehyde-containing hetero-
4;~.
- 14 -
polysaccharides are used as a partial or total replacement for these
saccharides.
Factors which affect the nature and quality of the flavor produced
include the nature and relative amounts of saccharide, amino acid, and
other optional components, as well as the amount of water and
temperature and time of the reaction.
All parts and percentages in the following examples are given by
weight and all temperatures are in degrees Celsius unless otherwise
noted. The carbonyl content oF the starch aldehydes was determined
using the procedure described in "Quantitative Organic Analysis via
Functional Groups", 3rd Edition by Sidney Siggia (John Wiley & Sons,
Inc., New York, 1949), p. 73.
EXAMPLE 1
This example illustrates the preparation of the halohydrin and
haloethyl glycoside starting materials employed herein:
a. 3-Chloro-2-hydroxypropyl galactoglycoside
To a 0.5 liter round-bottom flask equipped with condenser, mech-
anical stirrer and means for heating, there was added 80 g. (0.44 mole)
of galactose, 237 9. (2.15 moles) of 3-chloro-1,2-propandiol, and 20 g.
.~,.
Dowex 50W-X8 cation exchange resin (1.9 meq/ml) in H~ form. The mix-
ture was heated to 60-63C and stirred at that temperature for 16 hours.
The reaction mixture was cooled and then filtered over a yauze cloth to
remove the resin. The reaction mixture was clear and light yellow in
color. Unreacted diol was removed by vacuum distillation at 80C at 2
mm Hg. The hygroscop~c solid product was slurried in acetone and fil ~r
ed three t~mes to remove residual impurities then dried in a vacuum
; dessicator.
, ~
4;3~
- 15 -
b. 2-Chloroethyl ga1actoglycoside
To an apparatus similar to that described in Part a, was added
80 g. of galactose, 217 g. (2.69 moles) 2-chloroethanol, and 20 g. Dowex
50W-X8. The mixture was heated to and stirred at 55C for 16 hours and
at 80C for an additional 4 hours. The cation exchange resin was re-
moved as above. The unreacted 2-chloroethanol was then removed by vacuum
distillation at 30-35C at 0.1 mm. Hg. then dried in a vacuum dessicator.
EXAMPLE 2
~,~, This example illustrates the preparation of an ethyl yalactoglyco-
side starch ether.
A total of 100 parts of corn starch and 10 parts 2-chloroethyl
galactoglycoside ~as is) were added to a solution of 3.0 parts sodium
hydroxide and 30 parts sodium sulfate in 150 parts water. The mixture
was agitated for 16 hours at 40-45C. The pH was then lowered to 5.5
by the addition of 9.3g aqueous hydrochloric acid. The starch
derivative (A) was recovered by filtration, washed three times with
~` distilled water and air dried.
Aqueous slurries containing 96 parts water and 8 parts oF the
derivatlzed starch product or its underivatized base were cooked for
i 20 comparison in a boiling water bath for 20 minutes. The gelatinized
cooks stood overnight at room temperature before examination. The corn
base cook produced a f~rm gel. The derivatized starch cook, on the
other hand, did not form a gel but was stabilized.
EXAMPLE 3
This example illustrates the preparation of an ethyl yalactogly-
coside ether of a cationic fluidity starch.
Corn starch which had been acid hydrolyzed to a final water
~; ` fluidity (WF) of 75 was first reacted with 2.7~ diethylaminoethyl
- 16 -
chloride hydrochloride as described in U.S. 2,876,217 (issued on March
3, 1959 to E. Paschall). Thereafter the cationic fluidity starch was
reacted with 30g 2-chloroethyl galactoglycoside as in Example 2. The
starch derivative (B) was also recovered by filtration, washed three
times with distilled water and air dried.
EXAMPLE 4
Hydroxypropyl galactoglycoside ethers of various starch bases were
prepared according to the procedure described in Example 2. The
`q reaction data may be found in Table I.
TABLE I
Hydroxypropyl
Galactoglycoside Reactants
Starch Ether Starch Starch% 3-chloro-2-hydroxy=
Base WFpropyl galactoglycoside
C waxy maize -* 10
D waxy maize85 20
E corn 74 20
F tapioca 80 20
*Starch base was not hydrolyzed.
Comparative Sample G was prepared by reacting 85 WF waxy maize with
20~ 3-chloro-1,2-propandiol.
EXAMPLE 5
This example illustrates the preparation of an aldehyde-containing
starch derivative by enzymatic oxidation of the ethyl galactoglycoside
starch ether of Example 3.
A total of 6.0 9. of derivative B was slurried in 90 ml. of pH 7
phosphate buffer solution (0.68 parts potassium phosphate, monobasic and
0.16 parts sodium hydroxide in 10~ parts distilled water) which contained
~r1
0.15 9. Dowicide A (a preservative obtained from Dow Chemical Corp.).
,. , ~ ,
4~34
The slurry was cooked for 20 minutes in a boiling water bath (BWB) to
gelatinize the starch then cooled to 35C at which time the Brookfield
viscosity of the 30% solids sample was measured (20 rpm, spindle #5) as
0.45 Pas. (450 cps.). A total of 1.7 mg. (225 units~ of galactose
oxidase and 30 mg (60,000 units) catalase were dissolved in 5 ml. of
additional buffer solution then added directly ~o the starch dispersion.
While under continuous oxyyen purge the rnixture was agitated at 37C
for four days after which time the reaction was stopped by the elimina-
.. ~
,,: ,!, tion of the oxygen purge. The 6.4g solids starch dispersion after oxida-
tion had increased in Brookfield viscosity (20 rpm, spindle #7) to over
200 Pas. (200,000 cps). The material had a carbonyl content of 0.54%.
EXAMPLE 6
Hydroxypropyl galactoglycoside starch ether derivative, C, was
similarly oxidized with galactose oxidase to yield a starch aldehyde
derivative.
A total of 14.0 9. of C and 0.25 g. Dowicide A was slurried in 286
ml. of the phosphate buffer solution and cooked as in Example 5. The
4.5g solids dispersion had an initial Brookfield viscosity (20 rpm,
spindle #5) of 3.8 Pas. (3,800 cps~). A total of 0.57 mg. (75 units)
galactose oxidase and 10 mg. (20,000 units) catalase were dissolved in
;,
21 ml. buffer solution. The enzyme solution was added to the starch
dispersion and then reaction was conducted For 24 hours under the
conditions descrlbed in Example 5. The 4.9% solids starch dispersion
after oxidation had increased in Brookfield viscosity (20 rpm, spindle
~5) to about 5,9 Pas. (5,900 cps.). The material had a carbonyl
content of 0 32X
In aqueous dispersion, this particular starch aldehyde product was
observed to be uniquely thixotropic, i.e., while stirring it appeared
- 18 -
thin, however, when stirring ceased, the product would reform a gel
structure.
EXAMPLE 7
Starch galactoglycosides D, E, and F and comparative starch sample
G were also oxidized with galatose oxidase as described in Example 5.
The reaction oonditions and results may be found in Table Il.
TABLE II
Starch galact_glycoside D E F G*
% Dispersion Solids 30 15 15 30
Initial Brookfield Viscosity** 0.38 0.175 0.225 0.200
in Pas. (cps.) (380) ~175) (225) (200)
~,
Enzyme Treatment:
Galactose oxidase 15 30 30 15
units/g. starch
Catalase 4,000 8,000 8,000 4,000
units/g. starch
Reaction Conditions:
Temperature (C) 37 37 37 37
Time 16 hr. 4 days 4 days 4 days
Results:
% Dispersion Solids 25.5 11.2 11.5 11.5
Final Brookfield Viscosity** >200 0.250 0.225 0.~00
in Pas. (cps.) (~200,000) (250) (225) (200)
% Carbonyl Content 0.67 0.25 0.30 0.00
* Comparat~ve.
** Measured at 20 rpm, Splndle ~5.
In a like manner, starch may be reacted with 2-chloroethyl
taloglycoside or 3-chloro-2-hydroxypropyl taloglycoside, as described
in Example 2, to yield an ethyl or hydroxypropyl taloglycoside starch
ether. These starch ether derivatives may be similarly treated with
~ ~,
- 19 -
galactose oxidase as described above to also provide starch aldehyde
derivatives.
EXAMPLE 8
This example illustrates the use of an ethyl galactoglycoside
starch ether in a pourable sauce formulation.
Corn starch was treated with 20% of 2-chloroethyl galactoglycoside
as described in Example 2. The ethyl galactoglycoside starch ether (H)
was added to a barbecue sauce formulation and compared with a similar
sauce which employed the underivatized corn starch base. The following
recipe was employed:
Ingredients Parts
Starch derivative 2.5
Sugar 3.0
Salt 0.3
Paprika 0.2
Chili Powder 0.2
Cinnamon 0.2
Ground Cloves 0.2
Tomato Puree 47.4
Minced Onion 5.3
Worcestershire Sauce 6.6
Water 26.2
Vinegar 7.9
~5 25 The sauces were heated to 85~C (185F), held for 15 minutes, and
` cooled overn~ght at room temperature prior to observation. The sauce
containing starch glycoside ~H) was smooth and pourable. This was in
contrast to the sauce prepared with ~e underivatized corn starch which
resulted in a lumpy, very heavy product~
.43~
- 20 -
EXAMPLE 9
This example describes the use of the starch aldehydes herein as
paper strength additives.
Corn starch which had been acid hydrolyzed to a final WF of 70 was
first reacted with 3.0q diethylaminoethyl chloride hydrochloride as in
Example 3. Thereafter the control cationic fluidity starch (J) was
reacted with 20~ 2-chloroethyl galactoglycoside as in Example 2.
A lO g. sample of the ethyl galactoglycoside was oxidized with 250 units
of starch ether galactose oxidase in the presence of 60,000 units of
catalase resulting in a starch aldehyde (K) having an aldehyde content
of 0.40~
Unbleached softwood Kraft was refined to a 550 Canadian Standard
Freeness. A total of 3.3~ alum was added to the furnish and the pH
was adjusted to 5.5. The starch derivatives were added to the furnish
and four g. handsheets were prepared on the Noble and ~ood Sheet Mold,
pressed, and dried at 149C (300F). The Z-directional strength of
the sheets was ~.easured using a Scott Bond apparatus. The dry
strength of the sheets was recorded in 0.0138 meter-kilograms
(foot-pounds) in thousandths. The addition level of the starch was
13.6 kg./907.2 kg. (30 lb.lton). Test results are given in Table III.
TABLE III
Starch Derivative Dry Strength
Blank 234
Control (J) 293
Starch Aldehyde (K) 323
* Trade Mark
- 21 -
The results show that the starch aldehyde gave improved dry
strength in comparison to the starch base control from which it was
prepared.
EXAMPLE 10
This example describes the preparation of an artificial flavor
using the s-tarch aldehyde herein as a replacement for the saccharide
used in the Maillard reaction.
A mixture of histidine tO.75 g.), tyrosine (0.63 g.), glutamic acid
. . i
~14.21 g.), glycine (0.14 g.), alanine (1.10 g.), and leucine (1.03 g.),
in water is adjusted to pH 6 ~NaOH). The starch aldehyde of Example 5
(3.6 g.), glucose (4.5 g.), and sodium sulfide nonahydrate (2.68 g.) are
added, the volume is made up to 76 ml. with water and the mixture is
heated with stirring under reflux in a 130DC bath for about 6 hours.
After cooling, corn flour (55.2 g.) rnay be added and the product
freeze-dried to yield a powdered flavor.
In surnmary, the present invention is seen to provide ethyl
glycoside starch ether derivatives. Moreover, starch aldehydes are
provided which are useful in conventional applications where starch
aldehydes prepared by other chemical oxidative and nonoxidative means
have been found useful, i.e., in paper and textile sizing. The starch
aldehydes are also useful as crosslinking agents. In rr~ny cases, when
sel~-crosslinked, the starches exhibit signiFicant viscosity increases
which rnake them useful as thickeners in various applications including
food systems.
