CA2115054A1 - Debranched amylopectin starch as a fat replacer - Google Patents

Abstract

A method of preparing reduced fat foods is provided which employs a debranched amylopectin starch. A debranched amylopectin starch is dissolved and then allowed to form an aqueous dispersion of particles that is useful in replacing fat in a variety of food formulations. The debranched amylopectin starch can be derived from a starch which contains amylopectin, e.g. common corn starch and waxy maize starch, by gelatinizing the starch followed by treatment with a debranching enzyme, e.g. isoamylase or pullulanase and precipitation of the debranched starch.

Description

` ~W093/03629 PCI`/US92/06645 r~J .L ~ t) ~}L

DEBRJWCHED ~MYLOPE~TIN STARCH AS A FAT REPl~CER

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CROSS-REFERENCE TO RELATED APP~ICATION
This app!ication is a continuation-in-part of U . S . application Serial No . 07/746,381, filed August 16, 1991, and U. S . application Serial No. 07/798,291, filed November 26, 1991i the:~ disclosure of each of which are incorporated herein by reference.

FIELD OF~ THE INVENTION
This~ i nvention relates to food formutations in which at least a portion of the fat and/or oil is replaced by a carbohydrate. ~ ~

BACKGROUND OF THE INYENTION
n~ U.S.~ Patent No. 4,510,166 (Lenchin et al.) discloses converted~starchès having a~ DE less than 5 and certa~in paste and ge! characteristics which are ussd as a 20~ fat~ and/or~oil repiacement in various foods~, including ice cream ~ and ~ mayonnaise,~ The ~converted starches are described ~ as dextrins~ acid-converted starches (fluidity starches)~, en~yme-converted~ starches~ and oxidized starches. It is~ a!so~ disclosed that if the converted 25~ starches~ ~are,~not~ ~rendered~;~cold-water soluble by the conversion, ~they~ are ~; pregelatinired ;prior to use or cooked~ during ~use. ~
A product; bulletin entitled "Paselli SA2; The Natural Alternative~ ~to ~ Fats and Oils" ~AVEBE b.a., 30~ Foxhol, Holland, Ref~ No. 05.12.~31.167 EF) discloses the u5e of a low-DE-hydrolysate (DE ~less than 3) made from potato starch as a replacement for fifty percent of the : :

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WO 93/03629 . PCI/US92~0664C- -~^;3~1.5~5l1 fat with an amount of the low-DE-potato starch hydrolysate plus water (starch hydrolysate at 28% dry solids) equal to the amount of fat replaced.
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 c~ream.
U.S.~ ~Patent ~ No. 4,971,723 (Chiu) discloses partially debranch~d' starch prepared by enzymatic hydrolysis of ~the ~a~ 6-D-glucosidic bonds of the starch, 15 ~ comprisi~ng amylopectin,; partially~ debranched amy!opectin and up to 80~ by weight, short chain amylose and that the partially debranch'ed~ ~starch i5 useful in a variety of ways depending ~upon~ the~ ~degree~ o~ debranching. It is disclosed ~that ~a~waxy;~ maize ~starch (or other waxy 20~; starch) can be partialiy~debranched (i.e. to 2596 to 70%
short ~ ~chai;n 'amylose~ to ~ ~yield~ ~ su*;cient short chain amylose to form a'thermally~revers;ble gel in an aqueous starch ~suspension~. '; ;l~t~is ~further~disclosed that the same degree of ~debranching~o~ ~waxy ~starches is preferred for 25~ lending a ~ fat-like,~ lubricatin 9 texture to an aqueous starch: dispersion~

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`. WO 93/0362g . PCr/USg2/06645 2 1150~-1 SUMMAPcY OF THE INVENTION
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In one aspect, this invention relates to a food formulation having a reduced level of fat and/or oil comprising a mixture of a foodstuff and a particle gel 5 comprising a minor amount of debranched amylopectin starch particles dispersed within a major amount of an aqueous liquid as a replacement for at least a substantial portion of the fat and/or oil of said food formulation.
In another aspect, this invention relates to a :~ 10 method of formulating a ~food containing a fat and/or oil ~ingredient comprising repiacing at lea,st a substantial portion of said fat and/or: oil ingredient with a particle geî comprising a minor amount of debranched amylopectin ~: starch~ particles dispersed within a major amount of an . .
15 ~ aqueous liquid. ;; :
By "debranched amylopectin starch particles"
is meant a starch material; comprised of amylopectin which has :been subjected to ~enzymatic debranching followed by dissolotion in an ~ aqueous liquid and then particle 20 ~, ~ formation; therein ~ to: form a particle gel. The :debranching and; dissol(Jtion: will be sufficient to produce particles which will :form an :aqueous dispersion having the characteristics~of a:~particle gel.
In another ~aspect ~this invention relates to a 25 ~ :imethod of mak-ng~ ~ a~ composition of matter useful in reptacing fat and/or: oil in a food formulation comprising ~:: dissolving a minor~ amount: of a debranch~ed amylopectin ` ~ ; starch in a major arnount of an aqueous liquid and then forming particles of said debranched amylopectin starch 30 ~ ::dispersed in said~ aqueous: liquid, said dissolving and :~ ~ forming being effective to form a particle gel of said ::: : : composition.

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WO 93/036~g PCI~/US92/066 In another aspect, this invention relates to an aqueous dispersion useful as a replaçement for fats and/or oils comprising a particle gel comprised of a major amount by weight of water and a minor amount by weight ~; 5 of debranched amylopectin starch particles dispersed therein .
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 ~ ;cou~rse; of consuming~ edible fare. The term "fats and/or oils"~ ~is inten~ded to broadly cover ~ ~edîble lipids in general, ~ specifically~ the ~fatty acid triglycerides commonly found in foods. The terms thus include solid fats, plasti~ ~ shortenings,~ fluid oils ~and ~fully or partially lS ~ ~hydrogenated oils), and the like. Common fatty acid triglycerides ~include cottonseed oil, soybean oil, corn oil, peanut oi!, ~ canola~ oil,~ sesame oil, palm ilr palm kernei oil, menhaden oil, whale oil, lard, and tallow.
The technology;~ot;~fats and/or oils is described generally 20~ bY~ `T~ H. Applewhite, ~ "Fats and Fatty Oils", EncycloPedia~ ` of ~Chemical Technoloqy, Vol. 9, pp.
795~ (Kirk-Othmer, ~eds~.~, John ~Wiley ~ Sons, Inc~, New~Yor~k,~ New~ York,~ 3d ed. j t980), the disclosure of which~ is incorporated by~reference.
25~ The~ use~of~the terms~"major" and "minor" in context together~in~ this specification is~meant to imply that the major~ component;~is present~ 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.;

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BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the dynamic elastic modulus ~G') in kilo pascals as a function of strain in millistrain fo~ debranched amylopectin starch precipitates at 15%
5 precipitate solids having different degrees of debranching. -DETAILED DESCRIPTION OF THE INVENTION
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The debranched amylopectin starch particles are made by the sequential steps of debranching, dissolution, and particle formation of a starch material containing amylopectin. Starch is generally comprised of a high!y-branched glucan having a-1,4 and a-1,6 15 linkages, denominated amylopectin, and a substantially linear glucan, having almost exclusively a~1,4 linkages, denominated arnylose. Methods of determining the amounts of each are referenced in R. L. Whistler et al., Starch: ChemistrY and Technoloqyt pp. 25-3S (Academic 2û~ Press, Inc., New ~York, New~ York, 1984), the disclosur~
; of which is incorporated by reference. Starches having ;a ~ major proportion ( i . e. at leas t 50~ ~ by weight) of amylopectin are preferred and examples o~ these include the ccmmon non-mutant starches of cereals, tubers and 25; ~ legumes, e.g. corn, wheat, ricej potato and tapioca, pea and mutant varieties comprised of a major proportion of amylopectin, e.g. waxy maize~ Common starches derived from corn ~(Zea mays) such as corn starch and waxy maize starch, each of which are examples of starches 30 containing less than 40% amylose, are useful herein.
However, starches containing a major amount of amylose ~e. g ~ 50% to 75g6 by weight) are also useful and may be - preferred depending upon the precise .

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properties desired in the final product. Examples of such starches from high amylose corn include Hl-SET (~ C and HYLONTM (each about 5596 amylose by weight) and HYLONTM Vl I (about 70% amylose by 5 weight), all available from National Starch and Chemical Corporation, Br;dgewater, New Jersey.
In certain embodiments, the starch consists essentially of amylopectin . I n such embodiments, the starch employed; is ~from a mutant variety of native 10 starch which ~ consists essentially of amylopectin or is amylopectin derived ~i ~from~ a native ~ starch variety containing both amylosé and amylopectin. Methods for the fractionation of amy!ose and amylopectin from native starclr are disclosed ~ in, for example, ~I. S . Patent No.

3,067,067 (Etheridgé).. ~ ~
m ~ If the starch chosen as a starting material is not ;n pre-gelatinized ~or instant form, the starch must be gelatinized ~ o r ~ pasted prior to debranching. The g elat;nization or pasting~ process disrupts, at least in 20~ ~ substantial part, the ~associative bonding of the starch molecules in the~ ~;starch granule. This permits the enzyme~ access ~ to~the ~molecule to more easily and uniformly debranch the amylopectin molecules. This d;sruption is accomplishei~ by heating a slurry of the Z5 ~ starch to a sufficient~;temperature for a sufficient length of time depending~ upon~ the inherent resistance of the particular starch~ to ~gelatinization and the amount of moisture present in ~the slurry. The slurry will typically `~ be comprised of a~ major~ amount of water (i.e. at least 30 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 about 5~ starch, typically between about 10~ to about 25%

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starch. The pH of the slurry will generally be substantially neutral, ;.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, 5 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 10 preferably obta;ned 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 aj~water slurry~ of starch in a throat section of a ~; 15 jet. Upon contact with the injected steam, the starch granules are uniformly and thermally treated under turbulent conditions~ ~whereupon the starch granules are ~ ~ .
gelatinized and solubiiized. Examples of steam injection .
heaters wherein the temperature, pressure and feed rate ~ can be regulated~to provide the desired starch pastes are disclosed ~in U~.S~. Patent Nos. 3,197,337; 3,219,483;
and 3,133,836. ~ More u~niformly solubilized starch pastes are obtained by`~ use of the steam injection heater in combination ~with a~ holding zone such as coiled tubing or a pressurized ~ tank ~constructed to minimize liquid channeling. ~ Other ~ pa~sting ;equipment, e. g . heat exchangers, homog~enizers, cookers, votators, sizeometer cookers, kettie cookers, etc., may be employed provided the pasting cond;tions ~can ~be adequately maintained.
The gelatinized starch is then treated with a debranching enzyme,~ ~ i.e. an enzyme capable of hydrolyzing the ~1,6-glucosidic bond of amylopectin without significant ~ ~capability of hydrolyzing the . .

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1,4-glucosidic bond. Enzymes from a variety of sources are capable of debranching amylopectin . U. S . Patent No. 3,370,840 (Sugimoto et al. ) describes sources of debranching enzymes, the disclosure of which is incorporated herein by reference. Examples of useful enzymes include pullulanases derived from bacteria of the genus Aerobacter ;(e.g. E.C. 3.2.1.41 pullulan 6-glucanohydrolase) and isoamylases derived from bacteria of the genus~ Pseudomonas ~e. g . E . C . 3 . 2 .1 . 68 glycogen 6-glucanohydrolase). Particularly useful enzymes include thermostable enzymes, e.g. thermostable pullulanases as disclosed~ in PCT Publ. No. WO 92/02614, published February 20, 1992, the disclosure of which is incorporated by reference, ~ and which are obtained from members of the genus~ ~Pyrococcus. The debranching enzyme ~may be in solution dùring debranching or it may be immobilized on a solid support.
, , The debranching enzyme~preparation should be as specific as ~ possible for the hydrolysis of the l,~-glucosidic bond~ of amylopectin and amylose. Thus, ~the enzyme preparation,; if it contains ~ a mixture of ~ enzymes,~; is~ preferably essentially free of enzymes i ~ `capable~ of hydro1yzing a-1,4-glucosidic bonds.
Minimizing hydrolysls of a- 1 i4-glucosidic bonds will help to~minimize~ the amounts of~ dextrose and soluble oligomers p~r~oduced during ~ debranching. ~ Because these soluble ~` ~ saccharides are ~ not ~ believed to contribute to the 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 containing amylopectin. The optimum concentrat~on of enzyme and substrate in the debranching medium will, i n general, depend upon the .
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level of activity of the enzyme which, in turn, will vary depending upon the enzyme source, enzyme supplier and the concentration of the enzyme i n commercial batches .
When the isoamylase E . C . 3 . 2 .1. 68, derived f rom 5 Pseudomonas amy!oderamosa, available f rom Sigma Chemical Co., St. Louis, Missouri, is employed, typical conditions includ ~ 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 10 ~ ;hours to obtain substantially complete debranching.
The~ optimum pH and tem~erature of the debranching medium ~will also depend upon the choice of enzyme. The debranching medium may, in addition to the water used to solubilize the starch, contain buffers 15` ~ to ~ensure that the;~`pH; wil! be maintained at an optimum , ~ ~
level throughout~ ~the debranching. Examples of useful buffers include acetates, ~citrates, and the salts of other weak .acids. With- the~ Isoamylase described above, the pH~ is~preferably;~maintained at about 4.0 to 5.0 and the ;température from~àbout~ 40C~ to about 50C:. With the thermostable ~ pul!ulànase ~described above, the pH is ;preferably ~mainta~ned;~between~5 and 7 and the optimum temperature should~be ~between 85C and 115C.
The~ debranching ~is allowed to proceed until the desired ;degrée;~of debranching has been obtained.
The ~precise ~degree of debrànching needed to obtain the desirediparticle~gel of~the~debranched amylopectin starch may vary depending upon the sourcé of the starch and the precise propert;es ~ desired in the resulting gel.
Preferably, the degree~of ~ debranching is sufficient to convert more than àbout; 80% of the amylopectin in the starch to short ~chain amylose and, more preferably, at least about 90% ol tbe amyiopectin.

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In preferred embodiments, essentially all (i.e.
~reater than 99% by weight) of the amylopectin is converted to short chain amylose. The amount of short chain amylose can be measured by gel permeation 5 chromatography 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 ~; ~ 10 originaily present will be present as molecular species having a ~molecu!ar weight in excess of 20,000 g/mol, and most~ preferably, essentially no amylopectin having a molecular weight in ~excess of 20,000 g/mol will remain.
(It should be noted~ that if amylose is present, at least a 15~ portion thereof may~be~debranched to produce molecules above the 20,000 g/mol cut-off and molecules below the 20,000 g/mol cut-off. ~ ~To measure how much of the mate~rial eluting ~ bètween ~ 500 g/mol and 20,000 g/mol is debranched~ amylopectin ~ ~ and how much is debranched 20 ~ amylose,~it~ may ~be~necessary to fract;onate the starting starch~ :into ~its ~amylose~ and amylopectin fractions and ;th~en debranch and~el~ute~each~fraction separately.) It has;~ been found, as described more fully below, that when~ waxy ~ maize starch was debranched, 25 ~ ~dissolved, ~and ~then~ allowed to form dispersed particles, a~ degréé of debranching of only about 57% resulted in an aqueous dispersion ~ ~that displayed the rheological characteristics of ~a polymer gel. However, when the . I
debranching waslallowed~to proceed to 69~6, 85%, or 100%, 30 an aqueous dispersion~ of the starch particles displayed rheolog;cal properties more characteristic of a particle gel, with the~ 85% ~and lOOg6 debranched samples exhibiting more particle gel~ character than the 69~ debranched samples .

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After the desired degree of debranching is obtained, debranching enzyme in solution is deactivated, e.g. by heating to denature the enzyme. If an immobilized enzyme is employed, the contact time of the 5 solubilized starch is adjusted so that the starch is ' removed from the enzyme when the desired degree of debranching is obtained. The debranching medium may be concentrated by remova! of water theref rom, e . g . by evaporat;on, to facilitate precipitation. The debranching 10 med;um may also be ' treated to remove impurities therefrom. Treatment ~ with, for example, activated carbon will remove residual proteins and lipids that may contribute to off-flavors and/or colors.
~ ~ ~ The solution ~of debranched starch is then ;~ ~ ' 15typically treated ~ to isolate the debranched amylopectin starch therefrom. Generally, the solution will be cooled, e . g . to ambient temperatu re, to reduce the solubility of the debranched ~ starch ~ therein and thereby cause the debranched amylopectin starch to form a precipitate.
20 ; ~The solution will~ ' typically be allowed to stand until substantial equilibrium Is achieved ~ between the ~supernatant and the~precipitate. The precipitate can be ;solated from the~ supernatant, ~ e.g. by centrifugation, but isolation from ~thé~ supernatant is not necessary to 25 form a~ useful product.~
The isolated debranched amylopectin starch ~: , precipitate is typically~washed and then dried (e.g. to a low~ moisture content, ty~pically 3-12%) after isolation to allow for handling ~ ~ and storage prior to further 30 ~ processing. Examples ~of drying techniques include spray drying, flash drying, tray drying, belt drying, and sonic dryin~g. The dried precipitate may be hygroscopic. Thus, some rehydration during handling - wog3/03629 2 ~ ~ ~ 'J ~ i PCI/US92/06645 and storage may occur. Depending upon the precise composition of the precipitate and the conditions (including length of time) of storage, steps to maintain the moisture at a low content may be necessary (e. g .
5 moisturé barrier packaging and/or control of humidity in the storage environment~. If the moisture content is allowed to rise too far (e. g . greater than about 20~Lo~ or possibly greater than 15%), bulk handling problems and/or microbiological stability problems might arise.
10The debranched amylopectin starch precipitate may also be otherwise chemically modified. Examples of such chemical modification include the product of reaction with bleaching agents (e. g ~ hydrogen peroxide, peracetic acid, ammonium persulfate, chlorine (e.g.
15 calcium and/or sodium hypochlorite or sodium chlorite), ~h and permanganate (e. g . potassium permanganate) );
esterifying agents~ ~ (e.g. acetic anhydride, adipic anhydride, octenyl succinic anhydrides, succinic anhydride, vinyl ~ acetate); including phosphorous 20 compounds (e~. g . monosodium orthophosphate, phosphorous oxyc~hloride, sodium tripolyphosphate, and sodium ~trimetaphosphatel; ~ and/or etherifying agents (e.g. acrolein~ epichlorohydrin, and/or propylene oxide), provided~ such ~ chemical modification will not 25 ~ prevent dissolution of the debranched starch and formatio~n~ ;of deb~ranched starch particles. Such chemical modifications~ wil!~ typically be accomplished after the `debranching step, but may be accomplished prior to the debranching or effected by using a modified starch as a ;~
30 starting material ~for the debranching step, provided such modification~ does not preclude debranching.
It~ is contemplated that commercial production and use may involve hydrolysis, and drying (e. 9. spray ':~

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WO 93/03629 PCr/US92/06645 drying~ of the starch precipitate to produce an item of commerce. This item of commerce will then be purchased by a food processor for use as an ingredient. To incorporate the dried, debranched amylopectin starch 5 precipitate into a food product, it will be necessary to dissolve the starch precipitate and cause it to reprec;pitate to form a gel either in situ in a foodstuff or as a separate gel which can be dispersed into the foodstuff in which it will be employed.
10The debranched amylopectin starch is used to form a~ particle gel~ by ~dissolution in an aqueous liquid followed by the~; formatio n of particles. Dissolution is generally accomplished by mixing the debranched amylopectin starch ~ with a ma~or amount by weight of an lSaqueous medium, ~preferably tap water, and holding the mixture at a témperature which will cause at least a maJor amount by~ ~weight~of the starch to dissolve (i.e. at least 5096 by weight). Although tap ~water is the ; preferred liquid~ ~ medium for the dissolution of the 20~debra~nched starch, other liquids are sllitable provided '7 suf~ficient water ~is~ ~present ~to hydrate the particles of starch~ ~which; form ~and~,~; thus, result in a dispersion - ~
;having~ ~the characteristic~s ~of a particle gel. Sugar ~;
solution~s,~ Polyo!s, ~ of w~hich~ glycerol is an example, 25 ~ alcohols, particularly~ ethanoi, isopropanol, and the like, are ~good ;examples~ of~ suitable liquids that can be in admixture with~;wate~r~ in~ the liquid~ medium.
The amount of water will be sufficient to dissolve at least ~a~ major portion by weight of the 30~ ~ debranched starch at~ an; elevated temperature ~e.g.
90C). The ratio o~f ~water to debranched amylopectin starch solids wil I typically range from about 19:1 to about 1:1, more; ~typically 9:1 to about 2:1. The ..
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: ., wo g3io3629 ~ i ;L ~ PCr/US92/06645 dissolution of the debranched amylopectin starch in the liquid medium will be facilitated by simple mixing of the debranched amylopectin starch and liquid medium. Heat can be applied to the mixture and/or the liquid medium S can be preheated, as desired, to cause the debranched starch to dissolve.
The debranched amylopectin starch is dissolved under conditions such that the molecular fragments of debranched starch wi~ associate to form particles.
10 These particles form a~ dispersod solid phase within the aqueous media. ~ The formation of - the particles can be considered precipitation of ~the debranched starch from solution, but the particles remain dispersed in the aqueous medium ~and~ do~ not settle out ~to an appreciable 5 ~ degree over~ any practical~ period. The dissolution and particle formation~ can be~ accomplished in a number of somewhat~ different way~s.; ~ ~ln ~ certain embodiments, the debranched ~ amylopect~n~ ~ starch is dissolved in the agueous medium in ~which~it will form a particle gel. The 2Q;~;- resulting;;solution~is then~cooled or allowed to cool, e.g.
to ~ ~ambient temperaturè, ~ ;to allow the debranched starch to~ associate to form~ dlspersed~ particles.
in ~ sther ~; embodiments, the debranched amylopectin starch~ will~ ~be dissolved in an aqueous 25 ~ medium which is~ removed ~ (e.~g~. ~ evaporated by spray drying)~ befo~e`-`the ~debranched amylopectin starch can associate to form~the~dispersed~ particles. The resulting dried debranched ~amylopectin starch can then be stored as a stable dry ~ powder prior to gel formation. Gel 30 formation is then ~accomplished by dissolution of the dry powder in a liquid medium fol!owed by association of the debranched starch to form dispersed particles.
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The debranched amylopectin starch particles which make up the particle gel can be analyzed in a variety of ways. Rheological measurements can be made to determine the rheological characteristics of the 5 resulting dispersion. Typically, the aqueous dispersion of debranched amylopectin starch particles will exhibit a transition in dynamic elastic modulus (G' ) versus shear ~; ~ strain at less than about 50 millistrain, and preferably less than about 10 millistrain, said transition being f rom 10 a substantially constant G' versus shear strain to a decreasing G' versus shear strain. The transition indicates f~racture ~of~ the particle network within the particle gel and is typically a sharp transition.
Analysis ;of the ;debranched amylopectin starch 15 particles formed ~after dissolution shows that the starch has a measurable `crysta!linity. The crystalline regions of particles derived ~from fully debranched waxy maize starch ~essentially~ no~ amylose~ component) exhibit a diffraction ~ ~pattern~ characte~ristic~ of a starch material 20 c onsisting essentially of ~ A-type starch crystals . The crystàlline regions~ of particles derived from substantially fully~debranched~common~corn starch (about 28% amylose) exbibit~ a diffraction~ pattern char-cteristic of a starch material consisting ~essentialty~ of B-type starch crystals.
25;~ Heating~ ~(e.g. ;to about 70C) of the particles while in conta:ct ~ with the~ aqueouj medium to dissoive at least a portion of ~the~ mass~ of the ~particles and then cooling of the suspension/solution can also be employed i n forming the partic!e gel of this invention. This 30 heating to an elevate:d~ temperature and then reformation of the particles tends~ to ~nake the particles resistant to , melting or dissolving when an aqueous dispersion of the particles is exposed to heat in processing, e. g . in a ~ ' WO 93/0362~ PCI`/US92/0664~ - . -J5 ~

pasteurization step. In general, the higher the temperature to which the particles in the liquid medium are heated (and thus the greater the amount of precipitate that is redissolved), the higher the 5 temperature at which the resulting aqueous dispersion of - the particles will be stable. Repetition of the dissolving and reformation may improve the temperature stability of the result;ng aqueous dispersion. Further, a slow rate of heating andtor cooling (e.g. from about 0.005C/min.
10 to about 0.5C/min.,~for each) may be advantageous.
The us~e of ~ the ~debranched amylopectin starch particles altows~ ~for ~the replacement of a substantial portion (e. g . from 10~ to 100~ by weight) of the fat and/or oil ;n a food formulation. The precise level of 15 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-styte salad ~dressing, it~ is generaliy possible to completely replace the; oil component that is normally - ~ -20~ ~present. In~ oth r types~ of foods, e.g. frostings, icings,~ cream fillings, ~;ce cream, margarine, etc., a major~amount~of the ~fat~and~or oil (e.g. about 50% to about ôO%) can ~be replaced with little effect on the organoleptic desirabii~ity~ of the food. Examples of typical 25 ~ foods ~i~n~ which~fat~ and/or oil can be replaced include frostings ~e~g.~ ic;ngs, glazes, etc. 3, creme fillings, frozen ~ desserts ~ ~ (e. g . ice milk, sherbets, etc. ~, dressings (e.g. pourable or spoonable saiad and/or sandwich dressings) ,~ meat products (e. g. sausages, 30 processed meats, etc. ), cheese products (e. g . cheese .
spreads, processed cheese foods), margarine, fruit butters, other imitat;on dairy products, puddings (e. g .

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rnousse desserts), candy (e. g . chocolates, nougats, etc.), and sauces, toppings, syrups and so on.
Generally, it will be desirabie to remove sufficient fat from a given food formulation to achieve a 5 reduction in calories of at least one-third per customary serving or make a label claim of "cholesterol-free". ~In this regard, see, for example, the list of standard servîng sizes for various foods published in Food Labelling; Serving Sizes, 55 Fed. Reg. 29517 (1990) (to be codified at 21 C. F. R. 101.12), the disclosure of which is incorporated herein by reference, and the restrictions on labelling "cholesterol-free" at Food Labelling; Definitions of the Terms Cholesterol Free, Low Chole~terol and Reduced Cholesterol, 55 Fed. Reg. 29456 ~; 15 (1990)). It should ~also be noted that the fat removed from a particular formulation may be replaced with an equal amount by weight of an aqlJeous dispersion of sta-rch precipitate, but that such equality may not be ~ :: : :
necessary or desirable in all instances. Further, it may 20 be desirable to remove fat and add another ingredient (e. g .; a gum, polydextrose, a protein, etc. ) along with the aqueous~dispersion~ of starch precipitate.
While this invention is generally directed to the replacement of fat and/or oil in a food formulation, it 25 is of course within the contemplation of this invention thàt a debranched ~ amylopectin starch will be used in ~n entirely new formulatioQ to which it contributes fat-like organoleptic qualities but is not, in the strictest sense, replacing a pre-existing fat or oil ingredient. Moreover, 30 it is contemplated that the debranched amylopectin starch will have utility as a thickener, bodying agent, or the like in foods that normally do not have a significant fat or oil component.

WO 93/03629 PCI/U!~i92/0664~
~ 1 1 J O à ~1 ~1&-ln general, the debranched amylopectin starch is incorporated into the food ~s an aqueous dispersion, typically comprised of a major amount (i . e. greater than SQ% by weight) of water or other liquid medium and a minor amount ti.e. Iess than 5040 by weight, typically 10 to 40~0) of debranched starch solids. Alternatively, the isolated debranched amylopectin starch can be mixed with the food along with water and then subjected to dissolution and particle formation in those instances when the other ingredients of the food are capable of withstanding the conditions of dissoiution, e. g . a salad . .
dressing or imitation sour cream.
The debranched amylopectin starch can -~; ~ generally be heated while in a food system to dissolve a :
substantiai portion of the particles. It appears that , upon cooling, the debranched starch will reform into particles and the ~ resulting food product displays acceptable organoleptic properties . I n some food systems, however, reformation of the particles may be 2t~ inhibited or ~modified by~ the prcsence of an ingredient that can interact with t he solubilized debranched starch.
undesirable resuits will occur, a foodstuff containing the debranched~ amylopectin starch particles should not be subjected to conditions (e. g . elevated temperature) which wiil cause the particles (i.e. a majority by weight thereof) to dissolve. Accordingly, if the food f~rmulation is to ~ be cooked or otherwise heat~d to temperatures sufficient to dissolve the particles, such heatin~ should be completed prior to the addition of the debranched amylopectin ~starch to the food. It should be noted, however, that in many foods that are cooked, e.g. cheesecake,~ the internal temperature and/or moisture availability may be insuf~icient to dissolve the starch particles.

WO 93/03629 PCI/US92/06645 ~ 1 1 5 ~ ~ 1 -d~-.
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 5 mixed with the aqueous dispersion of debranched amylopectin starch precipitate, or even dry mixed with the debranched amylopectin starch prior to particle gel formation. ~ ~
Among the ~ food ingredients in the food 10 formulations of this invention include flavors, thickeners (e.g. starches and ~hydrophilic colloids), nutrients (e.g.
carbohydrates, protelns, lipids, etc. ), antioxidants, antimicrobial agents, non-fat milk solids, egg solids, acidulants, and so on~
Hydrophilic c o!loids can include natural gum material such as xanthan~ gum, gum tragacanth, locust bean ~ gum, guar gum, ~ algin, alginates, gelatin, Irish mos~s, pectin, gum ~arabic, gum ghatti, gum karaya and plant hemicelluloses, ~ e. g. ~ corn ~ hull gum. Synthetic 20~ gums ~such as ~ ~water-soluble salts of carboxymethyl cellulose can also~be~used. Starches can also be added to the~food.~ Examples of suitab!e starches include corn, waxy maize, wheat~,l rice, ~potato, and tapioca starches Non-fat~;~milk solids which can be used in the 25` ~ compositions of thi~s~invention are the solids of skim milk and ~include protelns,~ mineral matter and milk sugar.
Other proteins~ such~ as casein, sodium caseinate, calcium caseinate, modified casein, sweet dairy whey, modified whey, and whey proteiri concentrate can also be used ~:
30 herein. ;~ ~
For many~ foods, -it is accepted practice for the user to add the requ~red ~ amount of eggs in the course of preparation and~this~ practice may be followed just as ' .
: ' : ~

:

WO 93/03629 P~/US92/~)664~, well herein. If desired, howe~er, the inclusion of egg solids, in particular, 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, sa!ts, ~lavor enhancers, among others.
Acidulants 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 formulations will be conventional, although precise amounts of `individual components and the i5 presence of some of the conventional components may well be unconventional in a given formulation For example, the conventional other components for foods such as frozen desserts and dressings, are described in European Patent Publication No. 0 340 035, published November 2, 1989 (the pertinent disclosure of which is incorporated herein by reference), and the components and processing o f table spreads is disclosed in U . S
Patent No. 4,869,919 (Lowery), the disclosure of which is incorporated by reference.
A particularly advantageous use of the ; ~ ~ debranched starch ~ precipitates described herein may be the use thereof to replace a portion of the shortening 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 com~nonly contains a "shortening"
(i.e. a fat and~or oil comps~nent) from an animal (e.g.
butter) or vegetable (e.g. partially hydrogenated WO g3/03629 PCI`/US92/06645 ~ 1 :1 5 . ~

soybean oil) source. The assembled article, optionally containing a filling or toppin~1, is then baked to form a finished pastry. At least a portion of the shortening of an otherw;se conventional roll-in can be replaced with an aqueous dispersion of debranched amylopectin starch precipitate, preferably in adm;xture with an emulsifier (e.g. mono- and/or di-glycerides), and used to make a layered pastry.
The following examples will illustrate the :: ~
10 invention and variat;ons 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, unless~ otherwise noted in ~context.
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: ' WO 93/03629 2 1 1 J ~ ~ ~ PCI/US92/0664 -2~-EXAMPLES

E)CAMPLE 1 '~' A totally debranched~ waxy maize starch precipitate was prepared and fragmented as follows.
Into a 3-liter stainless steel beaker was placed 2000 grams of aqueous slurry containing 5~ dry solids waxy corn; starch. The ~pH~ was adjusted to 4.5 using 0.5 N
HCI ;and~ the~ beaker ~was placed ~ in a 95C water bath. ''~
The~ slurry was stirred ~and allowed to gelatinize and heat at 93-95C for 20-30 minutes. The major portion of the ,~
resulting waxy starch ~paste ~ (~1150 grams paste) was 15~ ;' placed into a pressure~ reactor and heated to 160C with stirring. After ~ stirring at 160C for 30 minutes the waxy starch solution~was~ cooled to ~45C and transferred -to a ~ 2-liter 3-neck~ round ~ bottom flask equipped with stirrer,~ thermomete~r~a~nd a~temperature controlled water 20~ bath.~ To the flask~at~;45C ~and pH ~4.5 was added 50 ';units~i~soamylase~enzyme~(Sigma~Chemical Co., St. Louis,-Missou~ri~ per gram~,~dry~ ~basis~ of starch. The enzyme reaction~ was allowed~ to~proceed with stirring at 45C for 48 hours. At the~`end ~ of ~ ~this ~ period, the solution was 25 ~ - ~heated~ ~ to ~ boi~ling~ (approximately; ~100,C) to inactivate enzyme then,cooledland :evaporated to Z0% solids using a rotary evaporator.
; i The resulting solution was allowed to set in a refrigerator to ;~precipitate/crystallize. The resulting ~-slurry was centrifuged~at about~ 10,000 g-force RCF in a Sorvall Centrifuge~ (GSA; rotor) ~ for 20 minutes. The ,' supernatant was ~ decanted.~ The sediment was resuspended in ~water ~ to the original 20% solids , ~ ' concentration volume,~ heated to boiling then cooled and : ~ : . ` ,`
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~ - ~.` WO 93/03629 PCI~/US92/06645 .. 21.,,~

again allowed to precipitate/crystallize on standing in a refrigerator. The resulting slurry was centrifuged as before and the sediment dried at 50C on a stainless ~1 tray in a forced air oven. The yield of product was s calculated to be 81.396 on a dry basis.
Three addition~l samples were prepared in a similar manner with minor variations in treatment.
Portions of all four samples were combined and heated to boiling to solubilize almost all material present in the 20%
solids preparation. ~ ~ The ~ hot solution was filtered through~ Whatman No.~ 1 fiiter paper on a Buchner funnel and the clear ~ filtrate was placed in a refrigerator overnight to precipitateicrystallize. The resulting mass was filtered usin g Whatman No. 1 filter paper on a Buchner funnel and;~ the precipitated mass was washed with additional water. The resulting wet cake was dried on a stainless steel tray overnight in a forced air oven at 50C. The dried~ product was ground to pass through a US #60 mesh sieve and~bottled.
Into a 250 ml 3-nec k round bottom flask was placed 65.0 grams ~of~ the dried product above (57.5 grams~dry~ basis)~and~106.7 grams of acidic aqueous solution~ containing ~ 3;.87 grams of 100% HCI
(approximately 1 N;~ HCI solution). The mixture was heated to 60C in a~water bath and stirred at 60C for 24 hours. The mixture was adjusted to pH 4. 5 with 4g~
NaOH and then ~centrifuged. The supernatant was ~;
discarded and the sediment resuspended in the same volume of water and centrifuged again. The wet cake .
was dried in a forced alr oven.
A 20.0% sollds creme of the above product was prepared by simply~ blending at full speed in a Waring blender at 60C for approximately 8 minutes with the temperature controlled.

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WO 93/03629 PCI`/US92/0664S
21.:~5~

-2Lt-Into a 3-liter, 3-neck round bottom flask equipped with stirrer, thermometer and temperature 5 regulated water bath was placed 2200 grams o~ S~6 solids gelatinized waxy maize starch paste, previously heated to 96C for 30 minutes~, heated to 160C for 30 minutes, then cooled to room temperature. To the waxy maize paste at pH 6.6 was added 11,000 units (100 units/gram 10 dry starch) of Novo Nortek Promozyme Pullulanase Enzyme. ~The mixture was stirred and ;maintained at 60C for 24 hours. Samples were taken at 6 hour, 18 hour, and 24 hour reaction periods, heated to about 90C for about 10 minutes to inactivate enzyme, then 15 freeze dried and analyzed by gel permeation chromatography (GPC) ~molecular weight.
After 24 ~hours, the reaction mixture was heated to about 90G~ to inactivate enzyme and the hot solution filtered~ th~rough ~Whatman #2 filter paper in a 20`~Buchn~er funnel. ~The~sturry was concentrated via rotary evaporator to 20~Q jsolids, then placed into a refrigerator at 4C o vernight. ~
The resulting precipitated mixture was centrifuged and ~ thé ~ supernatant discarded. The 25 ~ ~sediment was resuspended i n an equal volume of water, heated to about ~90C ~ and ~ allowed to precipitate in a ` refrigerator at 4C overnight. The precipitated mixture was centrifuged and the supernatant was discarded. The sediment was dried~ on stainiess steel trays at 35C
30 overnight. The dried product was ground to pass through a US ~ #60 ~ mesh sieve. Gel permeation chromatography (GPC) analytical results are reported below.
.
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WO 93/03629 PCI`/US92/06645 2 1 1; ;!j ) 1 Per Cent Less Reaction Peak Molecular Than 20,000 Time (hr) M Mn MW/MnWei.qhts Molecular Weight : 6 15,400 1,18612.975,224;2556;335 87.5 . 5 18 7,900 1,074 7.364,412;2637;335 94.3 24 6,747 1,014 6.762,000;2772;345 95.2 :

~: If a ~ finding of '80% saccharides having less than 20,000 ~molecular weight is considered as substantialiy completely ~debranched, then it can be seen that complete; debranching was achieved using pullulanase enzyme.
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A series~ of ~ debranched starch products were prepared from~waxy maize starch :under conditions similar to those employed~i~n~Examples 1 or 2, with isoamylase or ~:
pul~luianase, respectively.: Variations in conditions ~:
employed and results~:are shown in Table 1.

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W0 93/03629 ~ PCI/US92/06646.

-2~

E)CAMPLE

% Conversion 57 69 85 96 100 Debranching enzyme P P I P
( P - pullulanase) ( I - isoamylase) 10g6 Cold water solubles, ~: ~ powder 99 . 2 29 . 6 30. 637 . 7 24. 7 Yield stress, Too Too pascals gelled geOied 1110 17 428 Cold-~water solubles, 15 creme (gel~ 13.8 11.5 DSC: Onset C 43 47 - 47 57 enthalpy 9.5 29.3 - 21.3 20.6 : Water immobiiization ~:
(sec 1 by 1 7O NMR) 20~ 353 - 115 20:Ratio of 1,4 1,6 :;
linkages (by NMR) 31J1 120/1 - *
~:Concentration of -: .
:starch (during ::-hydrolysis~ 20 20 20 5 5 : 25 Units of ~nzyme : ::
:(perg s~arch) 3.79 7.5 ?200 tO0 100 :;
:: :
Number of precipitations 0 2 2 2 2 Centrifugation ~ No No No Yes No :~

* No a-1,6 linkages detected :

~` ~ W0 93~03624 PCI /US92/0664~
,a~l -2~-EXAMPLES ~-12 .

The gel samples were prepared using the debranched starches of Examples 3-7 by one of two 5 procedu~es. Examples 8 and 9 started with the dry powders from Examples 3 and 4, respectively. To prepare a creme, 15% solids suspensions were prepared then heated to about 90~C and held at 90~C with stirring ~or one minute wherein almost all the solid material appears to dissolve. In Examples 10, 11, and 12, where .

iimited sample was available, 25% creme samples were prepared ~s in Example 1 from the dry powder of Examples 5, 6, and 7, -respectively. The cremes were dilutecl to 15% solids by adding deionized water, then 15 heated with stirring to 90C~ and held at 9û~C for one minute. As with the powdered starting materials of ~; Examples 8 and 9, most of the solids in the samples appeared to dissolve on this treatment. All of the hot ~ . .
15% solids solutions were allowed to coo1 to room 20 temperature then~ stored in a refrigerator prior to being analyzed with a Bohlin Rheometer.
Dynamic strain ~ sweep evaluations were performed using a model VOR Bohlin Rheometer, from ~; Bohlin Rheologi, Inc., East Brunswick, New Jersey, on 25 the gels prepared above. The strain sYveep experiments were conducted with the creme products at 1 Hz frequency using a concentric cylinder geometry. During the test, strain was increased by changing oscillation amplitude and the dynamic elastic modulus (G') was 30 measured as a function of strain.
The G' values correspond to the strength of the network structure in the creme. The creme displays linear viscoelasticity at very low strains., i.e G' is WO 93~03629 PCI~/US92/0664~i 2 ~ .3 a : ~

independent of strain. Its behavior becomes non-linear (G' decreases as strain increases) at a certain critical strain where the material structure becomes more r'deformable". A short or brittle material will display a S transition from linear to non-linear viscoelasticity at a lower strain. If the transition occurs at a higher strain, this indicates a long ~and cohesive texture.
In ~Figure ~1, it can ~ be seen that the 57%
debranched gel showed only a slight break in its 10 network structure~ at somewhat less than 100 millistrain.
This sample a~ppeared to behave like a polymer gel where we ~ would expect a ~long and cohesive texture. By contrast, however, the 15Qo solids gels from debranched waxy maize starch~ ~;with 69% ~ debranching or greater 15 displayed structural ~breakdown at less than about 50 millistrain. l~he products ~ containing 85% and 100g6 ; debranched material; exhibited a transition at less than about ~ 10 ~ millistrain. ~ ~ These products thus showed particle~ gel rheology ~much ~ like that of CRISCOTM
20 ~ hydrogenated vegetable~ shortening ( Procter ~ Gamble ; Co., Cincinnati, Ohio). The ~ results of Example 11 prepared from the~powder~of Exampie 6) appeared to be anomalous ,~ and thus~ are ~not~ included here .
, ~
In general,~ particle gel compositions deform at 25~; iow strain values ~an~d ~usually do so with large changes in~ G' values. By contrast, polymer network gels usually deform at high ~ st~rain ~ values and typically display relatively low changés in G' values. -3S) : ~:

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' . ,' . WO ~3/11362g PCr/USg2106645 : ~

~ .1 . L ;,. O , A particle gel of debranched amylopectin starch can be prepared from the debranched starch of 5 Example 7 as follows. A sample of 25 parts by weight of the dry debranched starch of Example 7 is mixed with 75 parts by weight of tap water and heated with stirring to 90C and held at 90C for several minutes. The hot solution is then allowed to cool to room temperature and ~: : 10 then stored at about 5C overnight.
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' WO g310~629 PCI'/US92/06645 - `

E>CAMPLE 14 -. .
SPOONABLE SALAD DRESSING

A spoonable dressing can be prepared from the creme of Example 13 as follows.
.
I nqredients %, wt . :

: 10 Part A
Water . 22 . 00 ~.
ISOSWEET (É~) 100 high fructose ~:
corn syrup (Staiey) 17.00 ~:
~ Vinegar, white, 100 grain 10.00 ~ ~
;~ ~ 15 SWEETOSE(É~) 4300 corn syrup (Staley) 5.00 ~;
STAR-DRI ~) 35R corn syrup solids (Staley)3.20 ELTA 7393 starch (Staley) 2.85 Salt ~ 0 Carboxymethyl cellulose 7MF (Aqualon) 0.Z0 :;:
:Mustard ~ powder (McCormick) 0.10 :~ :
Titanium diox~de~:(Warner-Jenkinson) 0.0~ ~
Garlic powder 0.()5 -~:
Onion powder ~ Q.05 ~ ~:
Paprika ~ : 0.012S i::
25~ Calcium~disodium: EDTA 0.0075 Pa rt B
Creme of Example: 13 (10~ dry solids) 27.40 Soybean oil : 8. 00 Egg yolk, f~esh ~ 2.00 Lemon juice, single strength 0.25 Total 100.00 .,.

:

W0 93/03~29 2 1 1 ~ -j l PCI~/US92/06645 Procedu re t. 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 ~; 15 ~ minutes . -; 5. Process through a colloid mill at a 0.026" setting. -~
Pack off finished product.

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WO 93J0362g PCI`/US92/06645 2 1 1 ~

-3~- :
, ' ' BU I I ERMILK DRESSING

5 A buttermilk dressing can be prepared from the creme of ' Example 13 as follows. ,:'~
: In~redients : . %, wt. ;' '~
~ . :
Buttermilk, liquid, 1% ~at; 30.00 Water ~ , 23.94 Creme of,Example 13 ~ :: 23.50 STAR-DRI (É~) 10 maltodextrin (Staley) 8.Q0 Vinegar, :white, 100 grain :~ 5.40 Seasoning~mix #962-2489~(Griffith Labs) 5.00 Buttermilk solids, :Beatreme #983 (Beatrice) 1.00 nstant TENDER-JEL(~) C starch (5taley) 1.00 Salt . ~ : , 0. 75 Sugar ;~ 0. 65 :20~: Ca~rboxymethyl: cel!ulose,' 7 MF (Aqualonl 0.4~
Titanium~ dioxide (Warner-Jenkinson) 0.10 Potassium: sorbate ~ 0. 08 Sodium~ benzoate~ : 0. 0725 G~a rl ic powder :: : o . os 25; ~ Onion~ powder ; ~ 0~05 :Calcium~disodium ~E)T~ 0.0075 Total ;: : 30 ,:
. . .

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; WO 93/03629 PCI`/US92/0~645 2,, ~; 'J~

-3~-P rocedu re -:
1. Blend all dry ingredients together.
2. Place water and buttermilk into a Hobart mixing bowl. Disperse the dry ingredient blend into this water/buttermilk mixture; mix with a Hobart paddle for 10 minutes at low speed.
3. A~dd the creme and~ mix for 10 minutes at medium speed.
4.~ ~Add vinegar and mix for 1 minute.
5. ~Pro~ess~ th~rough~a ~colloid mill at a 0.02" setting.
Pack off finished product.
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, W~ 93/036~9 PCI`/US92/0664' 'v`~ .

FRENCH DRESSJNG
',, 5 A French dressing can be prepared from the creme of Example 13 as follows.

In~redients : ~, wt.
.

Creme of Example 13 ~ 35 00 : ISOSWE~T(~) 10()~high fructose .
corn syrup ( Staley) 25 . 00 Water 23 . 98 Vinegar, white~, 10û grain 10.00 5~ ~ Tomato~paste, 24-26% solids 3.50 Salt :: 1.50 Seasoning mix #912-0135 (Griffith Labs) 0.30 ;- MlRA-THIK~) 468 starch (Staley) O.30 Seasoning mix #F34037 lMcCormick) 0.10 20 ~ ~Xanthan :~um, Keltro! TF ~Kelco) 0.10 Guar gum~ #8/22 (TlC;:Gums):~ 0.05 Mustard powder ~ : : 0.05 :` Potas~sium sorbate ~ o.05 T jtanium dioxide :lWarner-Jenkinson) 0.04 25~ ; Paprika ~ 0.0225 Calcium disodium::EDTA: 0.0075 Color, yellow FD~C~ #5/#6 to suit Tota 1 100 . 00 ~:

30~
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,~
' ~' WO 93/03629 PCI`/US92/06645 ~ 1 1 O ' ) ' ~' Procedure -t. Place water and ISOSWEET into a Hobart bowl.
Blend all dry ingredients together and disperse into ~-the water and !SOSWEET mixture. Mix at low speed and allow to hydrate for 5 minutes.
2. Add tomato paste, creme and vinegar. Mix for 5 minutes .
3. Process through a colloid mill at a 0.02" setting.
Pack off finished product.

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WO 93~03629 PCI/US92/06~4~

O j ~ ' E)(AMPLE 1 7 DIJON DRESSING

5 A Dijon vinaigrette dressing can be prepared from the creme of Example 13 as follows.
: -~
I n~redients %, wt .

Water 38.90 -Creme of Example 13 ~5.00 Vinegar, white~ 100 grain 14.00 Sugar 6. 50 Dijon mustard (McCormick) 6 . 00 ::15 Lemon juice, single strength 6.00 Salt ~ 2.35 Sp~ice blend #F30378 ~McCormick3 1.00 Xanthan :~um, Keitrol~ TF~ tKelco) 0.14 Red beil pepper, ~dried ~McCormick) 0.05 :~: : 20 ~ Potassium sorbate ~ ~ 0.04 An~natto ;extract (Warner-Jenkinson3 0.0125 Calcium: disodiurn EDTA 0.0075 Total100.00 : ~: :: :.

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WO 93~03629 PCI/USg2/06645 2~ Q

Procedu re t. Place water in Hobart bowl.
2. Blend together all dry ingredients except the spice blend and red pepper. Disperse the dry ingredient b~end into the water and mix with a pacldle at low speed for 5 minutes.
3. Add the cremej mustard, vinegar and lemon juice.
Mix for 5 minutes at low speed.
10 4. Process through a colloid mcll at a 0.02" setting.
5. Blend in spice blend and red pepper. Then pack off product.

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WO 93/~3629 PCI`/US9~/06645 SOUR CREAM

5 An imit~tion sour cream can be prepared from the creme of Example 13 as follows.

In~redients % wt.
.
Creme of Example 13 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, 88go 0.40 Xanthan gum,: Rhodigel (Rhone-Poulenc) ().20 Salt 0. 20 ~ .
: Sodium citrate, hydrous, fine granular (P~izer) 0.20 :
Total 100.00 20:

Procedure 1. Add lactic acid to water, thoroughly mix at Speed 1 2 5~ with a Hobart mixe~r ~equipped with a wire whip.
2. Mix in sour cream and then: all dry ingredients; mix until the mixture is uniform.
:
3. Blend in th~ creme to form a semi-homogeneous rnixture.
: ~ ~ 30: 4. Homogenize for smoothness. -~
- ~ 5. Pack off and refrigerate until ready to use.

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WO 9~/03629 PCl~/US92/06~45 ~ ~ l S 9 j`1 .

DEB~ANCHED HIGH AMYLQSE STARCH
:
A 55~ amylose corn starch (Hl-SET C) is made up to 2596 solids ` then jet cooked at 160C with a retention time of 10 minutes at 160C then cooled to ~100C. The pH of the solution is adjusted to pH 6.0~
~; ~ Novo thermostable pullulanase~ enzyme as described in WO
92/02614 is added at~50 onits~ per gram of starch and the reaction is~allowed to,proceed at 100C for 24 hours, at which time GPC anaiysis will show that !ess than 10% of the remaining amylose and amylopectin molecules are above ,about 100,000 ~molecular weight.
I 5 ~ ~ The debra~nched solution is treated with 3%
w/w (weight by weight basis) of decolorizing carbon (based on stareh dry substance weight~ at 90C. The colorless carbon treated solution is cooled to 5C for 16 hours to bring about c~rystallization. The crystallized 20~ mass ~is dried ~ in a spray~ drier at 15% solids after dilution with ~ water .
The~ ~spray~ dried material is made up to 20 solids ~ and heated~ from ~ ~5()C to l00C at 0. 05C/minute then~ cooled to 100C at~0.05C/minute. The heat treated 2S material is treated~ at 20% solids~ at 80C for 24 hours in 0~.~2 N~ HCI then cooied~to~ room temperature. The acidic slurry is adjusted ~ to ~ pH 4. 5 with 10% NaOH and microfiltered to redu~ce the soluble saccharide content to ' less than 10%~ (measured at room temperature). The ~retentate slurry is spray dried at about 15~ solids to give a heat stable, ~starch based fat replacer.
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WO 93/03629 PCI/US92/0664~
2il3~

-4C - .

A gel is prepared from the dried product above by slurrying the fat replacer powder at 15% solids then heat;ng to 90C and holding at 90C with stirring one minute wherein almost all the material dissolves.
5 The solution is then cooled to about 4C then stored at 4C for abou t ~10 hours or longer during which time a gel is formed. The gel may then be utilized in various food formulations as a fat replacing composition.

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Claims (29)

What is claimed is:

1. A foodstuff having a reduced level of fat and/or oil comprising a mixture of a foodstuff and a particle gel comprising a minor amount of debranched amylopectin starch particles dispersed within a major amount of an aqueous liquid as a replacement for at least a substantial portion of the fat and/or oil of said foodstuff.

2. A foodstuff of Claim 1 wherein said particle gel exhibits a transition in dynamic elastic modulus versus shear strain from substantially constant dynamic elastic modulus to decreasing dynamic elastic modulus, said transition being exhibited at a shear strain of less than about 50 millistrain.

3. A foodstuff of Claim 1 wherein said debranched amylopectin starch is derived from starch from a variety of Zea mays.

4. A foodstuff of Claim 1 wherein said debranched amylopectin starch is derived from a starch consisting essentially of amylopectin.

5. A foodstuff of Claim 1 wherein said debranched amylopectin starch is derived from waxy maize starch.

6. A foodstuff of Claim 1 wherein said debranched amylopectin starch is composed of more than about 80% by weight short chain amylose.

7. A foodstuff of Claim 1 wherein said debranched amylopectin starch is essentially free of amylopectin having a molecular weight in excess of 20,000 g/mol.

8. A method of formulating a foodstuff containing a fat and/or oil ingredient comprising replacing at least a substantial portion of said fat and/or oil ingredient with a particle gel comprising a minor amount of debranched amylopectin starch particles dispersed within a major amount of an aqueous liquid.

9. A method of Claim 8 wherein said particle gel exhibits a transition in dynamic elastic modulus versus shear strain from substantially constant dynamic elastic modulus to decreasing dynamic elastic modulus, said transition being exhibited at a shear strain of less than about 50 millistrain.

10. A method of Claim 8 wherein said debranched amylopectin starch is derived from starch from a variety of Zea mays.

11. A method of Claim 8 wherein said debranched amylopectin starch is derived from a starch consisting essentially of amylopectin.

12. A method of Claim 8 wherein said debranched amylopectin starch is derived from waxy maize starch.

13. A method of Claim 8 wherein said debranched amylopectin starch is composed of more than about 80% by weight short chain amylose.

14. A method of Claim 8 wherein said debranched amylopectin starch is essentially free of amylopectin having a molecular weight in excess of 20,000 g/mol.

15. A method of making a composition of matter useful in replacing fat and/or oil in a food formulation comprising dissolving a minor amount of debranched amylopectin starch in a major amount of an aqueous liquid and then forming particles of said debranched amylopectin starch, said dissolving and forming being effective to form a particle gel of said composition.

16. A method of Claim 15 wherein said particle gel exhibits a transition in dynamic elastic modulus versus shear strain from substantially constant dynamic elastic modulus to decreasing dynamic elastic modulus, said transition being exhibited at a shear strain of less than about 50 millistrain.

17. A method of Claim 15 wherein said debranched amylopectin starch is derived from starch from a variety of Zea mays.

18. A method of Claim 15 wherein said debranched amylopectin starch is derived from a starch consisting essentially of amylopectin.

19. A method of Claim 15 wherein said debranched amylopectin starch is derived from waxy maize starch.

20. A method of Claim 15 wherein said debranched amylopectin starch is composed of more than about 80% by weight short chain amylose.

21. A method of Claim 15 wherein said debranched amylopectin starch is essentially free of amylopectin having a molecular weight in excess of 20,000 g/mol.

22. An aqueous dispersion useful as a replacement for fats and or oils comprising a particle gel comprised of a major amount by weight of an aqueous liquid and a minor amount by weight of debranched amylopectin starch particles dispersed therein.

23. An aqueous dispersion of Claim 22 wherein said particle gel exhibits a transition in dynamic elastic modulus versus shear strain from substantially constant dynamic elastic modulus to decreasing dynamic elastic modulus, said transition being exhibited at a shear strain of less than about 50 millistrain.

24. An aqueous dispersion of Claim 22 wherein said debranched amylopectin starch is derived from starch from a variety of Zea mays.

25. An aqueous dispersion of Claim 22 wherein said debranched amylopectin starch is derived from a starch consisting essentially of amylopectin.

26. An aqueous dispersion of Claim 22 wherein said debranched amylopectin starch is derived from waxy maize starch.

27. An aqueous dispersion of Claim 22 wherein said debranched amylopectin starch is composed of more than about 80% by weight short chain amylose.

28. An aqueous dispersion of Claim 22 wherein said debranched amylopectin starch is essentially free of amylopectin having a molecular weight in excess of 20,000 g/mol.

29. A method of making a composition of matter useful in replacing fat and/or oil in a food formulation comprising:
(a) gelatinizing a starch having an amylose content of less than about 40% by weight;
(b) debranching the amylopectin in said gelatinized starch in a debranched medium to convert more than about 80% by weight of the amylopectin to short chain amylose and form a debranched amylopectin starch in said medium;
(c) isolating said debranched amylopectin starch from said medium and drying said debranched amylopectin starch to a microbiologically stable moisture content;
(d) dissolving a minor amount of said dried debranched amylopectin starch in a major amount of an aqueous liquid and then forming particles of said debranched amylopectin starch said dissolving and forming being effective to form a particle gel of said composition.