U.S. patent application number 10/826218 was filed with the patent office on 2005-10-20 for encapsulation of oxygen sensitive agents.
Invention is credited to Makarious, Afaf G., Trubiano, Paolo C..
Application Number | 20050233002 10/826218 |
Document ID | / |
Family ID | 34935094 |
Filed Date | 2005-10-20 |
United States Patent
Application |
20050233002 |
Kind Code |
A1 |
Trubiano, Paolo C. ; et
al. |
October 20, 2005 |
Encapsulation of oxygen sensitive agents
Abstract
The present invention relates to the use of a mixture of
modified starch and protein for encapsulating oxygen sensitive
agents, wherein the modified starch is a starch derivative
containing a hydrophobic group or both a hydrophobic and a
hydrophilic group which has been further enzymatically hydrolyzed
by an exo-enzyme. The encapsulated materials have a high level of
active agent and retention and provide excellent oxidation
resistance. Further, the encapsulated materials are useful in a
variety of products, including food products.
Inventors: |
Trubiano, Paolo C.;
(Somerville, NJ) ; Makarious, Afaf G.; (East
Brunswick, NJ) |
Correspondence
Address: |
Karen G. Kaiser
NATIONAL STARCH AND CHEMICAL COMPANY
10 Finderne Avenue
Bridgewater
NJ
08807-0500
US
|
Family ID: |
34935094 |
Appl. No.: |
10/826218 |
Filed: |
April 15, 2004 |
Current U.S.
Class: |
424/490 ;
435/101 |
Current CPC
Class: |
B01J 13/02 20130101 |
Class at
Publication: |
424/490 ;
435/101 |
International
Class: |
A61K 009/48; C12P
019/04; A61K 009/16; A61K 009/50 |
Claims
1. A composition comprising an active agent encapsulated in a
mixture comprising at least one modified starch and at least one
protein, the modified starch comprising a starch derivative
containing a hydrophobic group or both a hydrophobic and a
hydrophilic group which has been degraded by an exo-enzyme and the
protein selection from the group consisting of caseins and soy
proteins.
2. The composition of claim 1, wherein the starch is derivatized
with a reagent selected from the group consisting of
octenyisuccinic anhydride and dodecenylsuccinic anhydride.
3. The composition of claim 1, wherein the starch is degraded by an
enzyme selected from the group consisting of .beta.-amylase,
glucoamylase, maltogenase, pullulanase, exo-alpha-1,4glucosidase,
exo-1,4-alpha-D-glucan maltotetrahydrolase, and exo-1,4-alpha-D
glucan maltohexahydrolase.
4. The composition of claim 1, wherein the starch is derivatized
with octenylsuccinic anhydride-and is degraded by glucoamylase.
5. The composition of claim 1, wherein the protein is sodium
caseinate.
6. The composition of claim 4, wherein the protein is sodium
caseinate.
7. The composition of claim 1, wherein the protein is soy
protein.
8. The composition of claim 4, wherein the protein is soy
protein.
9. The composition of claim 1, wherein the active agent is an
oxygen sensitive agent.
10. The composition of claim 1, 5, 6, 7 or 8 wherein the active
agent is selected from the group consisting of unsaturated fatty
acids, citrus oils, vitamins, tocopherols, tocotrienols,
beta-carotene, marine oils, and omega-3 fatty acids.
11. The composition of claim 1, 5, 6, 7 or 8 wherein the active
agent is selected from the group consisting of marine oils and
omega-3 fatty acids.
12. The composition of claim 11, wherein the starch has a dextrose
equivalence of from about 20 to about 80.
13. The composition of claim 11, wherein the starch has a viscosity
of less than about 30 seconds as measured by the funnel method.
14. The composition of claim 11, wherein the ratio of starch to
protein is in an amount of from about 30:70 to 90:10.
15. The composition of claim 11, wherein the ratio of starch to
protein is in an amount of from about 40:60 to 80:20.
16. The composition of claim 15, wherein the active agent is
present in an amount of from about 5 to 70% (wt/wt) based upon the
weight of the starch, protein and active agent.
17. The composition of claim 15, wherein the active agent is
present in an amount of from about 15 to 60% (wt/wt) based upon the
weight of the starch, protein and active agent.
18. A method of making the composition of claim 1, 5, 6, 7 or 8
comprising a) mixing a protein and a modified starch in an aqueous
medium at a temperature below that of the Maillard reaction to form
an encapsulating mixture, b) adding an active agent to the
encapsulating mixture to form a active agent/encapsulating mixture,
and c) homogenizing the active agent/encapsulating mixture to form
an emulsion.
19. The method of claim 15, further comprising drying the
emulsion.
20. A product comprising the composition of claims 1, 5, 6, 7 or 8
wherein the product is selected from the group consisting of food
products, pharmaceutical products, personal care products, hair
care products, paper products, animal care products, and household
products.
21. The product of claim 20, wherein the product is selected from
the group consisting of cereal, powdered drink mix, instant coffee,
instant tea, powdered sauce mix, powdered gravy mix, instant soup,
powdered dressing, intermediate moisture foods and bakery product.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to the use of a mixture of
modified starch and either casein and/or soy protein for
encapsulating oxygen sensitive agents, wherein the modified starch
is a starch derivative containing a hydrophobic group or both a
hydrophobic and a hydrophilic group which has been further
enzymatically hydrolyzed by an exo-enzyme. The present invention
also relates to the resultant encapsulated material and its use in
a variety of products.
SUMMARY OF THE INVENTION
[0002] The present invention relates to the use of a mixture of
modified starch and casein and/or soy protein (hereinafter protein)
for encapsulating oxygen sensitive agents, wherein the modified
starch is a starch derivative containing a hydrophobic group or
both a hydrophobic and a hydrophilic group which has been further
enzymatically hydrolyzed by an exo-enzyme. The encapsulated
materials have a high level of active agent and retention while
providing excellent oxidation resistance. Further, the encapsulated
materials are useful in a variety of products, including food
products.
[0003] As used herein, the term exo-enzyme is intended to mean an
enzyme capable of cleaving the 1,4-linkages of the starch molecule
from the non-reducing ends to produce mono- and/or di-saccharides.
The enzyme may also be capable of cleaving the 1,6-linkages, but
this is an optional capability.
[0004] As used herein, oxygen sensitive agent is intended to mean
one which is susceptible to oxygen.
[0005] As used herein, dextrose equivalent (DE) is defined as the
reducing power of the hydrolyzate. Each starch molecule has one
reducing end: therefore DE is inversely related to molecular
weight. The DE of anhydrous D-glucose is defined as 100 and the DE
of unhydrolyzed starch is virtually zero.
[0006] As used herein, water fluidity (WF) is intended to mean a
starch measurement using a Thomas Rotational Shear-type Viscometer
(commercially available from Arthur A. Thomas CO., Philadelphia,
Pa.), standardized at 30.degree. C. with a standard oil having a
viscosity of 24.73 cps, which oil requires 23.12.+-.0.05 sec for
100 revolutions. Accurate and reproducible measurements of water
fluidity are obtained by determining the time which elapses for 100
revolutions at different solids levels depending on the starch's
degree of conversion: as conversion increases, the viscosity
decreases.
[0007] As used herein, funnel viscosity is intended to mean
viscosity as measured using the following procedure. The starch
dispersion to be tested is adjusted to between 19% and 25% (w/w)
measured by refractometer. The temperature of the dispersion is
controlled at 22.degree. C. A total of 100 ml of the starch
dispersion is measured into a graduated cylinder. It is then poured
into a calibrated funnel while using a finger to close the orifice.
A small amount is allowed to flow into the graduate to remove any
trapped air and the balance is poured back into the funnel. The
graduated cylinder is then inverted over the funnel so that the
contents draw (flow) into the funnel while the sample is running.
Using a timer, the time required for the 100 ml sample to flow
through the apex of the funnel is recorded. The glass portion of
the funnel is a standard 58.degree., thick-wall, resistance glass
funnel whose top diameter is about 9 to about 10 cm with the inside
diameter of the stem being about 0.381 cm. The glass stem of the
funnel is cut to an approximate length of 2.86 cm from the apex,
carefully fire-polished, and refitted with a long stainless steel
tip with is about 5.08 cm long with an outside diameter of about
0.9525 cm. The interior diameter of the steel tip is about 0.5952
cm at the upper end where is attached to the glass stem and about
0.4445 cm at the outflow end with the restriction in the width
occurring at about 2.54 cm from the ends. The steel tip is attached
to the glass funnel by means of a Teflon tube. The funnel is
calibrated so as to allow 100 ml of water to go through in six
seconds using the above procedure.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The present invention relates to the use of a mixture of
modified starch and protein for encapsulating oxygen sensitive
agents, wherein the modified starch is a starch derivative
containing a hydrophobic group or both a hydrophobic and a
hydrophilic group which has been further enzymatically hydrolyzed
by an exo-enzyme. The encapsulated materials have a high level of
active agent and retention and provide excellent oxidation
resistance. Such encapsulating agents can be processed at high
solids during the encapsulation process. Further, the encapsulated
materials are useful in a variety of products, including food
products.
[0009] All starches and flours (hereinafter starch) are suitable
for use herein and may be derived from any native source. A native
starch, as used herein, is one as it is found in nature, including
those developed by plant breeding, and bioengineered starches.
Typical sources for the starches are cereals, tubers, roots,
legumes and fruits. The native source can be corn, pea, potato,
sweet potato, banana, barley, wheat, rice, sago, amaranth, tapioca,
arrowroot, canna, sorghum, and waxy or high amylose varieties
thereof. As used herein, the term "waxy" is intended to include a
starch containing at least about 95% by weight amylopectin and the
term "high amylose" is intended to include a starch containing at
least about 45% by weight amylose. In one embodiment, the starch
base is selected from the group consisting of corn, waxy maize,
tapioca, potato, and rice starch.
[0010] Also included as useful base starch materials are the
conversion products derived from any of the above starches
including fluidity or thin-boiling starches prepared by oxidation,
.alpha.-amylase conversion, mild acid hydrolysis or heat
dextrinization, and derivatized starch such as ethers and
esters.
[0011] In one embodiment, the base is a pregelatinized starch.
Pregelatinization and techniques for achieving pregelatinization
are known in the art and disclosed for example in U.S. Pat. Nos.
4,465,702, 5,037,929, 5,131,953, and 5,149,799. Also see, Chapter
XXII-- "Production and Use of Pregelatinized Starch", Starch:
Chemistry and Technology, Vol. III--Industrial Aspects, R. L.
Whistler and E. F. Paschall, Editors, Academic Press, New York
1967. The term pregelatinized is intended to mean swollen starch
particles, which have lost their birefringence and/or Maltese
crosses in polarized light. Such pregelatinized starches
derivatives are substantially soluble in cold water without
cooking. In this context "soluble" does not necessarily mean the
formation of a true molecular solution, but may also mean a
colloidal dispersion. In one embodiment, the starch is completely
pregelatinized.
[0012] In one embodiment, the starch base or pregelatinized starch
base is a fluidity starch converted by mild acid degradation or
heat dextrinization methods that are well known in the art. For
example, see Rutenberg, "Starch and Its Modifications," Handbook of
Water-Soluble Gums and Resins, Davidson, Editor, McGraw-Hill, Inc.,
New York, N.Y., 1980, pp. 22-36. A combination of one or more of
these conversion techniques may be used. The conversion is
typically carried out before treatment with a hydrophobic or a
hydrophobic/hydrophilic reagent and before the enzyme treatment. If
desired, the starch base may be converted by treatment with an
a-amylase enzyme to produce a fluidity starch in the manner
disclosed in U.S. Pat. No. 4,035,235. Such conversion is not
typically used if a high viscosity system is desired.
[0013] The starch may be derivatized by treatment with any reagent
or combination of reagents which contributes encapsulating
properties to the starch. The reagent must contain a hydrophobic
moiety and may contain a hydrophilic moiety. The hydrophobic moiety
may be an alkyl or an alkenyl group which contains at least five
carbon atoms or an aralkyl or aralkenyl group which contains at
least six carbon atoms, and in one embodiment up to about
twenty-four carbon atoms. The hydrophilic moiety may be contributed
by the reagent or the starch's own hydroxyl groups may serve as the
hydrophilic moiety and the reagent may contribute only the
hydrophobic moiety.
[0014] Any process for derivatizing starch which yields the desired
blend of hydrophobic or hydrophobic and hydrophilic functions on
the starch molecule and thereby yields stable encapsulation
properties may be used to prepare the modified starch of the
present invention. Suitable derivatives and methods for producing
them are known in the art and disclosed in U.S. Pat. No. 4,626,288
which is incorporated herein by reference. In one embodiment, the
starch is derivatized by reaction with an alkenyl cyclic
dicarboxylic acid anhydride by the method disclosed in U.S. Pat.
Nos. 2,613,206 and 2,661,349, incorporated herein by reference. In
another embodiment, the starch is derivatized by reaction with
octenylsuccinic anhydride or with dodecenylsuccinic anhydride.
[0015] Where a low viscosity is desirable, one embodiment uses an
octenyl succinic half ester derivative of an amylopectin containing
starch, which has been converted to a water fluidity (WF) of up to
about 60. In another embodiment, such converted OSA starch is a
waxy corn starch. Water fluidity is an empirical test of viscosity
measured on a scale of 0-90 wherein fluidity is the reciprocal of
viscosity. In yet another embodiment, the converted starch is
treated with at from about 0.1% to about 3.0% for food products and
at least about 0.1% for other products, of the octenyl succinic
anhydride. In the alternative, a hydroxypropyl octenyl succinic
derivative may be used.
[0016] After derivatizing the starch, it is further enzymatically
hydrolyzed by at least one exo-enzyme capable of cleaving the
1,4-linkages of the starch molecule from the non-reducing ends,
while maintaining substantially high molecular weight portions of
the starch base. The enzymes useful in the present invention thus
include, but are not limited to, .beta.-amylase, glucoamylase,
maltogenase, pullulanase, exo-alpha-1,4-glucosidase,
exo-1,4-alpha-D-glucan maltotetrahydrolase, and exo-1,4-alpha-D
glucan maltohexahydrolase. In one embodiment, the enzyme is chosen
from the group consisting of .beta.-amylase and glucoamylase. In
another embodiment, the enzyme is not capable of substantially
cleaving the 1,6-linkages of the starch molecule.
[0017] The enzymatic hydrolysis of the starch base is carried out
using techniques known in the art. The amount of enzyme used is
dependent upon the enzyme source and activity, base material used,
and the amount of hydrolysis desired. In one embodiment, the enzyme
is used in an amount of from about 0.01 to about 1.0%, in a second
embodiment from about 0.01 to 0.3%, by weight of the starch.
[0018] The optimum parameters for enzyme activity will vary
depending upon the enzyme used. The rate of enzyme degradation
depends upon factors known in the art, including the enzyme
concentration, substrate concentration, pH, temperature, the
presence or absence of inhibitors, and the degree and type of
modification. These parameters may be adjusted to optimize the
digestion rate of the starch base.
[0019] The starch may be pregelatinized before hydrolysis, and may
need to be pregelatinized if using an enzyme that cannot hydrolyze
granular starch to the degree desired. The gelatinization process
unfolds the starch molecules from the granular structure, thereby
permitting the enzyme to more easily and uniformly degrade the
starch molecules.
[0020] Generally the enzyme treatment is carried out in an aqueous
or buffered slurry at a starch solids level of about 10 to about
40%, depending upon the base starch being treated. A solids level
of from about 15 to 35% is useful in one embodiment, from about 18
to 25% useful in another embodiment, of the instant invention. In
the alternative, the process may utilize an enzyme immobilized on a
solid support.
[0021] Typically, enzyme digestion is carried out at the highest
solids content feasible without reducing reaction rates in order to
facilitate any desired subsequent drying of the starch composition.
Reaction rates may be reduced by high solids content as agitation
becomes difficult or ineffective and the starch dispersion becomes
more difficult to handle.
[0022] The pH and temperature of the slurry should be adjusted to
provide effective enzyme hydrolysis. These parameters are dependent
upon the enzyme to be used and are known in the art. In one
embodiment a temperature of about 22 to about 65.degree. C. is
used; in another from about 50 to about 62.degree. C. In one
embodiment, the pH is adjusted to about 3.5 to about 7.5; in
another from about 4.0 to about 6.0, using techniques known in the
art.
[0023] The enzyme reaction is continued until the desired end point
(i.e., sufficient degradation to provide the desired functionality
for the particular application) has been reached. In one
embodiment, the enzyme reaction is continued until a dextrose
equivalent of at least about 20 and up to about 80 is reached; in
another until a dextrose equivalent of from about 30 to about 50
has been reached. The end point may be determined by a change in
viscosity, by reducing sugar content (such as measured by dextrose
equivalents), or by any other method known in the art for measuring
the level of enzyme degradation of the starch molecule. In general,
the enzyme reaction will take from about 0.1 to about 24 hours and
in one embodiment will take from about 0.5 to about 4 hours. The
time of the reaction is dependent upon the type of starch used, the
amount of enzyme used, and the reaction parameters of solids
percent, pH, and temperature.
[0024] The enzyme degradation is then terminated by any technique
known in the art such as acid or base deactivation, heat
deactivation, ion exchange, and solvent extraction. For example,
acid deactivation may be accomplished by adjusting the pH to lower
than 2.0 for at least 30 minutes or heat deactivation may be
accomplished by raising the temperature to about 85 to about
95.degree. C. and maintaining it at that temperature for at least
about 10 minutes to fully deactivate the enzyme. Heat deactivation
is not suitable if a granular product is desired as the heat
necessary to deactivate the enzyme will generally also gelatinize
the starch.
[0025] The resultant solution is typically adjusted to the desired
pH according to its intended end use. In general, the pH is
adjusted to from about 5.0 to about 7.5, and in one embodiment from
about 6.0 to about 7.0, using techniques known in the art.
[0026] The resulting starch is characterized by a relatively low
viscosity, moderately high dextrose equivalent, neutral taste, and
by its unique functionality as an encapsulating agent.
[0027] The viscosity of the resultant starch should be less than
about 30 seconds and in one embodiment is from about 8 to about 25
seconds, each as measured by the funnel method. In another
embodiment, the viscosity of the starch is from about 8 to about 15
seconds as measured by the funnel method. Viscosity is an important
parameter in contributing to efficient encapsulation.
[0028] The resultant starch should have a dextrose equivalent of at
least about 20 and up to about 80. In one embodiment, the dextrose
equivalence is from about 30 to about 50.
[0029] The resultant starch should have a percent sugars of at
least about 20% and up to about 80%. In one embodiment, the percent
sugars, is from about 30 to about 40% glucose and in another from
about 30 to about 35% glucose.
[0030] The encapsulating material also contains protein, by which
is meant casein and/or soy protein. Casein is intended to include
salts thereof. Soy protein is intended to include soy protein
concentrate and soy protein isolate. In one embodiment, sodium
caseinate is used. In another embodiment, soy protein isolate is
used. The ratio of starch to protein is in an amount of from about
30:70 to 90:10. In another embodiment, the ratio of starch to
protein is in an amount of from about 40:60 to 80:20.
[0031] The protein may be added to the starch dispersion/solution
and used as a liquid. In another embodiment, the starch/protein
dispersion/solution may be concentrated prior to usage. In yet
another embodiment, the starch/protein dispersion/solution may be
dried using any method known in the art and stored until use. In an
alternate method, the dry protein is added to the dried starch. In
one embodiment, drying of the individual components or the
starch/protein mixture is conducted by a method selected from the
group consisting of drum drying, spray drying or freeze drying.
[0032] Except for the drying step, the protein/starch mixture may
be prepared at temperatures below those at which a Maillard
reaction occurs. In one embodiment, the mixture is prepared at room
temperature (about 22.degree. C.). In another embodiment, at a
temperature below 55.degree. C., in yet another below 40.degree. C.
and in still yet another below 30.degree. C.
[0033] The starch/protein encapsulating agent may be used to
encapsulate any active agent and in one embodiment is used to
encapsulate an oxygen sensitive agent. Oxygen sensitive agents are
intended to include, without limitation, unsaturated fatty acids
such as gamma-linolenic acids, citrus oils such as orange oils,
vitamins such as Vitamin A, Vitamin E, Vitamin C, and Vitamin D,
tocopherols, tocotrienols, phytosterols, Vitamin K, beta-carotene,
marine oils, and omega-3 fatty acids. In a further embodiment, the
starch/protein encapsulating agent is used to encapsulate marine
oil or omega-3 fatty acids, including concentrated omega-3 fatty
acids.
[0034] The active agent may be any substance which will not react
with the starch/protein system, including but not limited to oils,
fats, flavors, colors, fragrances, vitamins, and pharmaceuticals.
In particular, the starch/protein of the present invention is
useful for emulsifying or encapsulating oil-based active agents.
These oils may be volatile or non-volatile and are generally
characterized by being water immiscible but dispersible
(emulsifiable) in water in the presence of an encapsulating
agent.
[0035] The active agents may be encapsulated using the
starch/protein encapsulating agents of the present invention and
techniques known in the art. In one embodiment, the starch/protein
encapsulating agent may be dispersed in water, the active agent may
be added and emulsified, and the emulsion may then be dried to form
the encapsulated material. Drying may be accomplished by any
appropriate method known in the art, including but not limited to
spray drying, extrusion, spray chilling, and fluid bed coating. In
one embodiment, the active agent is homogenized (emulsified) in a
solution/dispersion of the starch/protein mixture and then spray
dried. Emulsification and drying conditions may be controlled by
one skilled in the art to yield encapsulated material with the
desired attributes. For example, if volatile or heat labile active
agents are used, relatively low temperatures will be used to reduce
loss and/or inactivation of the active agent. One skilled in the
art may also vary the average particle size of the emulsion to
obtain the desired results. In one embodiment, the particle size of
the emulsion is about one micron.
[0036] The resultant encapsulated materials are in the form of a
dry, free-flowing powder. These materials have the advantage of
achieving and maintaining consistently high active agent levels,
and/or excellent oxidation resistance.
[0037] The encapsulated material prepared with the present
encapsulating agents consistently achieves and maintain a
relatively high level of the active agent. The active agent may be
present in an amount of from about 5 to 70% (wt/wt) based upon the
encapsulated material (starch/protein plus active agent). In
another embodiment, the active agent is present in an amount of
from about 15 to 60% (wt/wt).
[0038] A high level of active agent is desirable to reduce the cost
of producing the final product as encapsulating agents are often
expensive. Further, some encapsulating agents may contribute
adverse or undesirable properties to the final system and it is
thus desirable to reduce the amount of encapsulating agent
used.
[0039] It is important not only to achieve a high level of active
agent, but also to maintain it so as to enable a longer shelf life.
The present encapsulating agents also retain the oil so as to
provide a low surface oil. This is particularly true when
glucoamylase is used to enzymatically hydrolyze the starch. The
surface oil may be measured by methods known in the art such as by
washing the encapsulated powder with a suitable solvent. Reduction
of surface oil is important as increased surface oil indicates that
the load of the active agent is not being maintained and
inefficiency of encapsulation. Thus, reduction of surface oil
results in a longer shelf life.
[0040] The present encapsulating agents also provide a relatively
high level of oxidation resistance, thereby prolonging storage
stability of the encapsulated material and shelf life of the final
product. Oxidation resistance may be measured by methods known in
the art. Oxidation resistance is important not only for flavor
considerations of the oil, but also to maintain the activity of
various materials. To further increase oxidation resistance, an
anti-oxidant and/or reducing agent may be added to the oil.
[0041] The encapsulated material is stable when stored as a powder
and releases the active agent upon exposure to moisture. The
resultant encapsulated material may be used at any level desired,
the amount being dependent upon the amount of active agent to be
incorporated and the product in which it is to be used. In one
embodiment in which the encapsulated materials are used in a food
product, the encapsulated material is used in an amount of from
about 0.01 to about 10% by weight of the food product and in
another embodiment up to about 5% (wt/wt).
[0042] The resultant encapsulated material may be used in various
food products including, but not limited to, cereals; powdered
drink mixes; instant coffees and teas; powdered sauce and gravy
mixes; instant soups; powdered dressings; bakery products including
breads and bread products; intermediate moisture foods including
shelf stable nutrition bars; flavors; fragrances; colorants; and
other dry food products. Upon preparation of powdered and instant
products, the moisture triggers the release mechanism, providing
the active agent to the consumer.
[0043] The resultant encapsulated material may also be used in a
variety of pharmaceuticals including vitamins; personal care
products including antiperspirants, deodorants, soaps, fragrances,
and cosmetics; hair care products, such as hair sprays, mousses,
shampoos, cream rinses, and gels; paper products such as diapers,
sanitary napkins, paper towels, tissues, toilet tissues; animal
care products such as kitty litter; and household products such as
carpet cleaners, and air fresheners.
EXAMPLES
[0044] The following examples are presented to further illustrate
and explain the present invention and should not be taken as
limiting in any regard. All percents are on a weight/weight basis
unless otherwise stated. Room temperature was approximately
22.degree. C.
[0045] The following analytical tests were used to measure various
parameters in the examples.
[0046] Determination of Dextrose Equivalents (DE)
[0047] The dextrose equivalent of starch may be determined by using
the Reducing Sugars test described in Food Chemicals Codex, 4th
ed., Jul. 1, 1996. Section 5, General Tests and Assays, Appendix X:
Carbohydrates (Starches, Sugars, and Related Substances) or
Standard Analytical Method #E-26 for Dextrose Equivalent from the
Corn Refiners Association.
[0048] Oxidation Resistance Analysis
[0049] p-Anisidine Value (AOCS Official Method Cd 18-90, 1997),
peroxide value (AOCS Official Method Cd 8-53, 1997), fatty acids
profile (AOAC 996.06, 2000, modified) were tested to establish
compliance with the current quality standards for EPA and DHA.
[0050] Oil Retention (Loading) Analysis
[0051] To determine the oil retention of the encapsulated material,
15 grams of the spray dried, encapsulated oil and 150 ml distilled
water are mixed to reconstitute the emulsion. The emulsion is
heated to reflux and held for four hours. The mixture is then
cooled and the separated oil is removed and weighed. 1 % Retention
= volume of oil extracted .times. specific gravity of oil
Theoretical oil weight .times. 100
Example 1
Preparation of the Derivatized Starch
[0052] (a) Using OSA
[0053] 500 grams of waxy maize starch were slurried in 750 ml
water. The pH was adjusted to 7.5 using 3% sodium hydroxide. 15
grams of octenylsuccinic anhydride (OSA) were added in one-third
increments every thirty minutes while maintaining the pH at 7.5
using 3% sodium hydroxide with constant agitation. The starch was
then filtered out and washed with 750 ml water. The starch was then
reslurried in 500 ml water and the pH adjusted to 5.5 with 3:1
hydrochloric acid. The starch was then filtered, washed with 750 ml
water, and air dried to produce an OSA starch.
[0054] (b) Using DDSA
[0055] Example 1(a) was repeated using dodecenylsuccinic anhydride
(DDSA) in place of OSA.
Example 2
Preparation of the Modified Starch
[0056] a. Using glucoamylase
[0057] 100 grams of the OSA starch of Example 1 were slurried in
300 ml water and the pH adjusted to 5.5 using dilute hydrochloric
acid. The slurry was gelatinized by jet cooking in a C1-339 jet
cooker, commercially available from National Starch and Chemical
Company, at 300.degree. F. (149.degree. C.), at a chamber pressure
of 55 psi (379.2 kPa), and a slurry rate of 6 ml/min with the steam
valve open at 75% capacity.
[0058] The temperature of the starch solution was then decreased to
55.degree. C. 0.05% glucoamylase (AMG 200 L, commercially available
from Novo Nordisk) based on the weight of the starch was added and
the reaction was allowed to proceed at 55.degree. C. with constant
mixing for approximately 2.5 hours until a dextrose equivalent of
36 and a viscosity of 17 sec at 25% solids and 22.degree. C. using
the funnel method. The enzyme was then deactivated by heating the
dispersion to 90.degree. C. and maintaining the elevated
temperature for 30 minutes. The dispersion was then cooled to room
temperature and spray dried using an inlet temperature of
200.degree. C., an outlet temperature of 100.degree. C. and a feed
rate of 65 ml/min.
[0059] b. Using .beta.-amylase
[0060] 100 grams of the OSA starch of Example 1 were slurried in
300 ml water and the pH adjusted to 5.5 using dilute hydrochloric
acid. The slurry was gelatinized by jet cooking in a C1-339 jet
cooker, commercially available from National Starch and Chemical
Company, at 300.degree. F. (149.degree. C.), at a chamber pressure
of 55 psi (379.2 kPa), and a slurry rate of 6 ml/min with the steam
valve open at 75% capacity.
[0061] The temperature of the starch solution was then decreased to
55.degree. C. 0.2% .beta.-amylase (Spezyme BBA 1500, commercially
available from Genencor) based on the weight of the starch was
added and the reaction was allowed to proceed at 55.degree. C. with
constant mixing for approximately 4 hours until a dextrose
equivalent of 36 and a viscosity of 17 sec at 25% solids and
22.degree. C. using the funnel method. The enzyme was then
deactivated by heating the dispersion to 90.degree. C. and
maintaining the elevated temperature for 30 minutes. The dispersion
was then cooled to room temperature and spray dried using an inlet
temperature of 200.degree. C., an outlet temperature of 100.degree.
C. and a feed rate of 65 ml/min.
[0062] c. Using a Combination of .beta.-Amylase and Pullulanase
[0063] 100 grams of the OSA starch of Example 1 were slurried in
300 ml water and the pH adjusted to 5.25 using dilute hydrochloric
acid. The slurry was gelatinized by jet cooking in a C1-339 jet
cooker, commercially available from National Starch and Chemical
Company, at 290.degree. F. (143.3.degree. C.), at a chamber
pressure of 40 psi (275.8 kPa), and a slurry rate of 3.5 ml/min
with the steam valve open at 75% capacity.
[0064] The temperature of the starch solution was then decreased to
58.degree. C. 5.0% of pullulanase (Promozyme, commercially
available from Novo) by weight of starch was added and allowed to
react for approximately 18 hours with constant mixing. Then 0.1%
.beta.-amylase (Spezyme BBA 1500, commercially available from
Genencor) based on the weight of the starch was added and the
reaction was allowed to proceed at 58.degree. C. with constant
mixing for approximately 2.5 hours until a dextrose equivalent of
32 and a viscosity of 14 sec at 25% solids and 22.degree. C. using
the funnel method. The enzymes were then deactivated by heating the
dispersion to 95.degree. C. and maintaining the elevated
temperature for 30 minutes. The dispersion was then cooled to room
temperature and spray dried using an inlet temperature of
200.degree. C., an outlet temperature of 100.degree. C. and a feed
rate of 65 ml/min.
Example 3
Preparation of the Encapsulating Agent
[0065] a) 300 g of sodium caseinate were dispersed in 2450 ml of
distilled water at room temperature, using mechanical agitation at
moderate speed. 300 g of modified starch of Example 2b were then
added to the solution, and the mixture was agitated under moderate
condition until smooth.
[0066] b) 200 g of soy protein isolate were dispersed in 2233 ml of
distilled water at room temperature, using mechanical agitation at
moderate speed, until no lumps were present. 200 g of modified
starch of Example 2b were then added to the solution, and the
mixture was agitated under moderate condition until smooth.
[0067] c) 300 g of soy protein isolate were dispersed in 3750 ml of
distilled water at room temperature, using mechanical agitation at
moderate speed, until no lumps were present. 300 g of modified
starch of Example 2b were then added to the solution, and the
mixture was agitated under moderate condition until smooth.
Example 4
Encapsulation of Fish Oil, Omega-3 Fatty Acid
[0068] a) 200 g of fish oil were added to the matrix prepared in
example 3a. The mixture was prehomogenized using a Barinco
laboratory homogenizer. The solution was agitated at moderate speed
for 2 minutes. This pre-emulsion was then homogenized using an APV
homogenizer to reach a particle size of approximately 1 micron. The
emulsion was spray-dried using a Niro Utility Spray Drier # 3-068
with a centrifugal atomizer installed. The inlet temperature was
approximately 130.degree. C. and the outlet temperature
approximately 80.degree. C. The flow rate was kept at about 50
ml/min.
[0069] b) 200 g of fish oil were added to the matrix prepared as in
example 3b. The same homogenization and spray drying procedure
described in example 4a was followed.
[0070] c) 600 g of fish oil and 2000 ppm of a natural antioxidant
(mixed tocopherols) were added to the matrix prepared as in example
3c. The same homogenization and spray drying procedure described in
example 4a was followed.
Example 5
Comparative Examples
[0071] To compare the process with existing art, Sample 4a was
produced at elevated temperature, (60.degree. C.). This sample had
a higher degree of oxidation and lower sensory quality compared to
the present low temperature treatment.
Example 6
Preparation of A Bread Product
[0072]
1 a) White Pan Bread Ingredient Weight (g) Flour - Patent 600.00
Sugar 48.00 Shortening 30.00 Salt 12.00 Dough conditioner 6.00
Yeast (instant) 9.00 Calcium propionate 1.80 Water 378.00
Encapsulated fish oil (example 4a) 16.0 Total 1084.80
[0073] The ingredients were mixed in a Hobart mixer with dough hook
at speed 1 for 2 minutes. The speed was then increased to speed 2
for until dough was developed (about 12 minutes). The dough was
allowed to rest for five minutes. 510 grams of the dough were made
into a round loaf and allowed to rest for an additional five
minutes. The dough was placed in a pan and proofed at 37.8.degree.
C. (100.degree. F.) and 80% relative humidity for 60 minutes. The
bread was baked for 22 minutes at 215.6.degree. C. (420.degree.
F.).
[0074] b) Example 6a was repeated using the encapsulated fish oil
of Example 4b.
[0075] c) Example 6a was repeated using the encapsulated fish oil
of Example 4c.
[0076] A panel of 8-10 trained panelists evaluated Examples 6a, 6b
and 6c breads. The sensory test was performed on white bread
containing 100 mg of EPA/DHA per a 50 g serving. All breads showed
a better sensory profile when compared with breads produced using
commercially available fish powders.
Example 7
Preparation of an Energy bar
[0077]
2 Ingredient % Formula Concentrated soy protein 7.8 Protein drink
powder-soy 7.6 Protein drink powder-whey 7.6 Corn Starch (HI-MAIZE
.RTM. 260 8.4 starch) Non fat dry milk (NFDM) 8.7 Peanut flour 4.0
Modified potato starch 2.8 Encapsulated fish oil (example 2.1 4c)
HFCS 19.6 Honey 10.09 Raisin Paste 7.2 Soy Oil 2.8 Glycerin 1.2
Oats-Quick oats 6.2 Soy Nuts 3.7 TOTAL 100
[0078] The protein blends, HI-MAIZE.RTM. 260 starch, NFDM, peanut
flour and potato starch were mixed at low speed for approximately 5
minutes until well blended. Mixing was continued while the liquid
ingredients (HFCS, honey, raisin paste, soybean oil and glycerin)
were added. The mixing was continued until uniform. The soy nuts
were chopped using a coffee grinder. The oats and soy nuts were
added and mixed at low speed until uniformly blended. The mixture
was formed into desired size by extruding or pressing and enrobed
in chocolate.
[0079] Sensory tests on the bar were positive and showed good
acceptability of the product.
* * * * *