Patent Description:
Tapioca starch can provide a number of desirable properties to various foods. It is commonly used as a thickener in puddings, yogurts, fruit fillings, and other foods in which a soft-textured gel is desired. However, tapioca starches, because they contain ~<NUM>% amylose, gel fairly quickly after cooking and cooling. This means that tapioca-thickened products often need to be processed hot and not allowed to cool until they are in containers. This can add significant cost and undesirably reduce process flexibility.

There remains a need in the art for starches, especially high-amylose starches, that can remain in an ungelled state for significantly longer than conventional tapioca starches.

<CIT> relates to a process for the preparation of an inhibited starch. <CIT> relates to starch-containing pre-cooked wet food products. <CIT> relates to a cold-water-swelling granular starch. <CIT> relates to foods containing thermally-inhibited starches. <CIT> relates to the production of inhibited non-pregelatinized granular starches which are useful as ingredients in food compositions.

One aspect of the disclosure is a delayed-gelling, inhibited tapioca starch having.

Another aspect of the disclosure is a process comprising.

to provide a cold-water swelling, delayed-gelling starch.

Another aspect of the disclosure is a method for making a food product, comprising cooking a starch as described herein in the presence of water, providing the cooked starch in combination with one or more other food ingredients, and allowing the starch to form a gel.

Another aspect of the disclosure is a dry mix including a starch as described herein, in admixture with one or more additional dry food ingredients.

In certain embodiments, the delayed-gelling, inhibited starches as otherwise described herein have an amylose content in the range of <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, <NUM>-<NUM>%, or <NUM>-<NUM>%. For example, in certain particular embodiments, the delayed-gelling, inhibited starches as otherwise described herein have an amylose content in the range of <NUM>-<NUM>%, or <NUM>-<NUM>%.

In some embodiments, the delayed-gelling, inhibited starch as otherwise disclosed herein has a sedimentation volume in the range of <NUM>-<NUM>/g. In still other embodiments, the delayed-gelling, inhibited starch as otherwise disclosed herein has a sedimentation volume in the range of <NUM>-<NUM>/g. In various additional embodiments, the delayed-gelling, inhibited starch as otherwise disclosed herein has a sedimentation volume in the range of <NUM>-<NUM>/g, or <NUM>-<NUM>/g, or <NUM>-<NUM>/g, or <NUM>-<NUM>/g, or <NUM>-<NUM>/g, or <NUM>-<NUM>/g. The person of ordinary skill in the art will appreciate that the sedimentation volume is a measure of the degree of inhibition of the starch, and will select a desired range of sedimentation volumes for a particular end use for the delayed-gelling, inhibited starches described herein.

As used herein, sedimentation volume is the volume that <NUM> cooked starch occupies in <NUM> (i.e. total, including the starch) of salted buffer solution (<NUM>% sodium chloride in pH <NUM> phosphate buffer). This value is also known in the art as "swelling volume. " Sedimentation volumes as described herein are determined by first cooking the starch at <NUM>% solids in the salted buffer by suspending a container containing the slurry in a <NUM> water bath and stirring with a glass rod or metal spatula for <NUM> minutes, then covering the container and allowing the paste to remain at <NUM> for an additional <NUM> minutes. The container is removed from the bath and allowed to cool on the laboratory bench. The resulting paste is brought back to the initial weight by addition of water (i.e., to replace any evaporated water) and mixed well. <NUM> of the paste (which contains <NUM> starch) is weighted into a <NUM> graduated cylinder containing <NUM> pH buffer containing <NUM>% NaCl, and the total weight of the mixture in the cylinder is brought to <NUM> using the buffer. The cylinder is allowed to sit undisturbed for <NUM> hours. The volume occupied by the starch sediment (i.e., as read in the cylinder) is the sedimentation volume for <NUM> of starch, i.e., in units of mL/g.

In some embodiments, the delayed-gelling, inhibited starch as otherwise disclosed herein has a % solubles value in the range of <NUM>-<NUM>%. In other embodiments, the delayed-gelling, inhibited starch as otherwise disclosed herein has a % solubles value in the range of <NUM>-<NUM>%. In various additional embodiments, the delayed-gelling, inhibited starch as otherwise described herein has a % solubles value in the range of <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, or <NUM>-<NUM>%, <NUM>-<NUM>%, or <NUM>-<NUM>%.

In the sedimentation volume test described above, the supernatant above the granular sediment contains soluble starch, i.e., the portion of the starch that is not retained by the inhibited granules of the sediment. The amount of soluble starch can be quantified by withdrawing a portion of the supernatant, and quantitatively hydrolyzing the starch to dextrose using acid or enzyme, then measuring the concentration of dextrose, e.g., using an instrumental analyzer such as a glucose analyzer available from YSI Incorporated. The concentration of dextrose in the supernatant can be converted algebraically to the % soluble value of the starch.

The present inventors have determined that particular combinations of sedimentation volumes and % soluble values provide especially desirable performance. The delayed-gelling, inhibited starches as otherwise described herein, the point corresponding to (sedimentation volume, % solubles) in a plot of % solubles vs. sedimentation volume falls within the polygon defined by the points (<NUM>/g, <NUM>%), (<NUM>/g, <NUM>%), (<NUM>/g, <NUM>%) and (<NUM>/g, <NUM> %).

In certain particular embodiments of the delayed-gelling, inhibited starches as otherwise described herein, the sedimentation volume is in the range of <NUM>-<NUM>/g, and the % solubles value is in the range of <NUM>-<NUM>% (e.g., <NUM>-<NUM>%, <NUM>-<NUM>%, <NUM>-<NUM>%, <NUM>-<NUM>%, or <NUM>-<NUM>%).

As described above, the inhibited starches described herein have delayed-gelling characteristics. The delayed-gelling, inhibited starches as otherwise described herein have a gel time of at least <NUM> hours after being cooked in pH <NUM> phosphate buffer containing <NUM>% NaCl at <NUM>% starch solids for <NUM> minutes at <NUM>, then being allowed to sit undisturbed at <NUM>. In certain such embodiments, the delayed-gelling, inhibited starch has a gel time of at least <NUM> hours, or at least <NUM> hours.

While the delayed-gelling, inhibited starches described herein have delayed gel times, in certain desirable embodiments they do form a gel. The delayed-gelling, inhibited starches as otherwise described herein have a gel time of no more than <NUM> hours after being cooked in pH <NUM> phosphate buffer containing <NUM>% NaCl at <NUM>% starch solids for <NUM> minutes at <NUM>, then being allowed to sit undisturbed at <NUM>. For example, in certain such embodiments, the delayed-gelling, inhibited starches as otherwise described herein have a gel time of no more than <NUM> hours, no more than <NUM> hours, or no more than <NUM> hours after being cooked in pH <NUM> phosphate buffer containing <NUM>% NaCl at <NUM>% starch solids for <NUM> minutes at <NUM>, then being allowed to sit undisturbed at <NUM>.

The gel time is the time at which the material becomes a gel, as defined by the time when the storage modulus (G') becomes the same as the loss modulus (G"), i.e., when the value of tan(δ) becomes <NUM>. Moduli can be measured by oscillatory rheometry at <NUM> as is conventional in the art.

The delayed-gelling, inhibited starches described herein can be made with relatively little color. For example, certain embodiments of the delayed-gelling, inhibited starches as otherwise described herein have a Yellowness Index of no more than <NUM>, for example, in the range of <NUM>-<NUM> or <NUM>-<NUM>. In certain desirable embodiments, the Yellowness Index is less than <NUM> (e.g., <NUM>-<NUM> or <NUM>-<NUM>). Yellowness Index is determined via ASTM E313.

Notably, the delayed-gelling, inhibited starches described herein can be made without many of the conventional chemical modifiers used in making conventional modified and/or inhibited starches. Accordingly, in certain desirable embodiments, the delayed-gelling, inhibited starches described herein can be marked as so-called "clean-label" starches. For example, a delayed-gelling, inhibited starch as otherwise described herein is not hydroxypropylated. A delayed-gelling, inhibited starch as otherwise described herein is not acetylated. A delayed-gelling, inhibited starch as otherwise described herein is not acetylated. A delayed-gelling, inhibited starch as otherwise described herein is not carboxymethylated. A delayed-gelling, inhibited starch as otherwise described herein is not hydroxyethylated. A delayed-gelling, inhibited starch as otherwise described herein is not phosphated. A delayed-gelling, inhibited starch as otherwise described herein is not succinated (e.g., not octenylsuccinated). The starch is not cationic or zwitterionic.

Similarly, the delayed-gelling, inhibited starches described herein can be made without use of the cross-linkers typically used in the inhibition of starch. A delayed-gelling, inhibited starch as otherwise described herein is not crosslinked with phosphate (e.g., using phosphorus oxychloride or metaphosphate). A delayed-gelling, inhibited starch as otherwise described herein is not crosslinked with adipate. A delayed-gelling, inhibited starch as otherwise described herein is not crosslinked with epichlorohydrin. A delayed-gelling, inhibited starch as otherwise described herein is not crosslinked with acrolein.

And the delayed-gelling, inhibited starches of the disclosure can be made without using other harsh chemical treatments common in the art. A delayed-gelling, inhibited starch as otherwise described herein is not bleached or oxidized with peroxide or hypochlorite.

In certain embodiments (but, as described below, not in all embodiments), the delayed-gelling, inhibited starches as otherwise described herein are made by pH-adjustment of starch to neutral or basic pH using a medium that is more than <NUM>% water (e.g., more than <NUM>% water or even more than <NUM>% water), drying of the starch and heat treatment of the dried starch.

The delayed-gelling, inhibited starches of the disclosure can be made without dextrinization, and as such do not contain substantial amounts of the repolymerized branched chains typical of dextrins. A delayed-gelling, inhibited starch as otherwise described herein substantially lacks <NUM>,<NUM>- and <NUM>,<NUM>- branching. Such branching can be determined using nuclear magnetic resonance techniques familiar to the person of ordinary skill in the art.

The delayed-gelling starches of the present disclosure can have a variety of viscosities as measured by a Rapid Visco Analyzer. For example, in certain embodiments a delayed-gelling, inhibited starch as otherwise described herein can have a viscosity as measured by RVA is in the range of <NUM>-<NUM> cP. In certain such embodiments, the viscosity as measured by RVA is in the range of <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, <NUM>-<NUM> cP, or <NUM>-<NUM> cP, <NUM>-<NUM> cP, or <NUM>-<NUM> cP. The viscosity is measured by RVA at <NUM>% solids in a pH <NUM> phosphate buffer containing <NUM>% NaCl at a stir rate of <NUM> rpm. The initial temperature of the analysis is <NUM>; the temperature is ramped linearly up to <NUM> over <NUM> minutes, then held at <NUM> for <NUM> minutes, then ramped linearly down to <NUM> over <NUM> minutes, then held at <NUM> for <NUM> minutes, after which time the viscosity is measured. Notably, when a pasting peak is displayed at times of about <NUM>-<NUM> minutes, the final viscosity measured is higher than the pasting peak viscosity. When the pasting peak is absent, the viscosity during the <NUM> hold is flat, or increases.

As noted above, the delayed-gelling, inhibited starches of the disclosure are not pregelatinized.

In certain embodiments, the delayed-gelling, inhibited starches of one aspect of the disclosure remain substantially granular upon cooking. As used herein, granularity is determined by cooking the starch at <NUM>% solids in the salted buffer by suspending a container containing the slurry in a <NUM> water bath and stirring with a glass rod or metal spatula for <NUM> minutes, then covering the container and allowing the paste to remain at <NUM> for an additional <NUM> minutes, then allowing the paste to cool to room temperature. Following such cooking, swollen but intact granules can be observed microscopically. The person of ordinary skill in the art would understand that minor deviations from granularity are allowed. For example, in certain embodiments of the delayed-gelling, inhibited starches as otherwise described herein, no more than <NUM>% of the starch granules become non-intact upon cooking (i.e. as described above with respect to granularity). In certain such embodiments, no more than <NUM>% or even no more than <NUM>% of the starch granules become non-intact upon cooking (i.e., as described above with respect to granularity). The person of ordinary skill in the art can determine whether starch granules remain intact by viewing them under a microscope (e.g., with staining), as is conventional in the art.

The delayed-gelling, inhibited starches according to certain embodiments of the disclosure are shear stable, and thus can be suitable for a wide variety of process conditions.

Certain desirable embodiments of the delayed-gelling, inhibited starches as described herein are substantially digestible. For example, in certain embodiments of the delayed-gelling, inhibited starches as otherwise described herein, the amount of fiber is less than <NUM>% as determined by AOAC <NUM>. In certain such embodiments, the amount of fiber is less than <NUM>% or even less than <NUM>%.

As noted above, the delayed-gelling starches of the first aspect of the disclosure are inhibited. As used herein, "inhibited" means that the starches are inhibited from gelatinization (i.e., similar to conventional cross-linked starches). Inhibited starches may vary with respect to their degree of inhibition, as characterized by their observed viscosity and other characteristics under the RVA analysis cooking conditions described herein. A starch that is substantially completely inhibited will resist gelatinization. A starch that is highly inhibited will swell to a limited extent and show a continuing rise in viscosity, but will not attain a peak viscosity. A starch that is moderately inhibited will exhibit a lower peak viscosity and a lower percentage breakdown in viscosity compared to the same starch that is not inhibited. A starch that is lightly inhibited will show a slight increase in peak viscosity, and a lower percentage breakdown in viscosity compared to control (uninhibited) starch.

The delayed-gelling, inhibited starches of the disclosure may be made using a variety of methodologies. A variety of starch feedstocks can be used (e.g., a native starch such as a tapioca starch, a dent corn starch, a wheat starch or a rice starch). The starch feedstock can be pre-treated, for example, to reduce the amount of lipid and/or protein present in the starch, as is conventional in the art.

In certain embodiments, the starches are made using the methods described in <CIT>, which is hereby incorporated herein by reference in its entirety. Thus, a method for making the starches described herein can include.

The alcoholic medium generally comprises at least one alcohol, particularly a C1-C4 monoalcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol and the like. One or more other substances may also be present in the alcoholic medium, such as a non-alcoholic organic solvent (particularly those that are miscible with the alcohol) and/or water. However, in one embodiment of the method the alcoholic medium does not contain any solvent other than alcohol and, optionally, water. Aqueous alcohols, for example, may be used to advantage. The alcoholic medium may comprise, for instance, <NUM>% to <NUM>% by weight alcohol (e.g., ethanol) and from <NUM>% to <NUM>% by weight water. In one embodiment, the alcoholic medium contains from <NUM>% to <NUM>% by weight alcohol (e.g., ethanol) and from <NUM>% to <NUM>% by weight water, the total amount of alcohol and water equaling <NUM>%. In another embodiment, the alcoholic medium contains <NUM>% to <NUM>% by weight alcohol (e.g., ethanol) and from <NUM>% to <NUM>% by weight water, the total amount of alcohol and water equaling <NUM>%. In other embodiments, not more than <NUM>% or not more than <NUM>% by weight water is present in the alcoholic medium. The quantity of alcoholic medium relative to starch is not considered to be critical, but typically for the sake of convenience and ease of processing sufficient alcoholic medium is present to provide a stirrable and/or pumpable slurry. For example, the weight ratio of starch: alcoholic medium may be from about <NUM> : <NUM> to about <NUM> : <NUM>.

In certain methods, at least some amount of treatment agent (base and/or salt) is present when the starch feedstock is heated in the alcoholic medium. However, it is advantageous that large amounts of treatment agent (relative to starch) need not be used in order to achieve effective inhibition of the starch, in contrast to previously known starch modification processes. This simplifies the subsequent processing of the inhibited starch and lowers potential production costs. Typically, at least <NUM>% by weight of treatment agent (based on the dry weight of starch used) is employed, although in other embodiments at least <NUM>%, at least <NUM>%, at least <NUM>%, at least <NUM>% or at least <NUM>% by weight of treatment agent is present. For economic reasons, generally no more than <NUM>% or <NUM>% by weight of treatment agent is present.

Typically, the mixture of starch, alcoholic medium and treatment agent is in the form of a slurry. In certain embodiments, it may be desirable to adjust the pH of the slurry to a particular value. It can be difficult to measure the pH of such a slurry due to the presence of the alcohol. In an embodiment where it is desired to make the slurry basic by adding a base, a suitable amount of base can be determined as if the slurry is a slurry of starch in deionized water alone and then scaled up to the actual amount while keeping the same ratio of base and starch.

The slurry may, for example, be neutral (pH <NUM> to <NUM>) or basic (pH greater than <NUM>). In one embodiment, the pH of the slurry is at least <NUM>. In another embodiment, the pH of the slurry is at least <NUM>. The slurry pH in another embodiment is not more than <NUM>. In other embodiments, the pH of the slurry is <NUM>-<NUM>, <NUM>-<NUM> or <NUM>-<NUM>. In still other embodiments, the pH of the slurry is <NUM>-<NUM> or <NUM>-<NUM>.

The alcohol-treatment agent treatment of the starch may be effected by first placing the starch in the alcoholic medium and then adding treatment agent (e.g., base and/or salt). Alternatively, the treatment agent may be first combined with the alcoholic medium and then contacted with the starch. The treatment agent may be formed in situ, such as by separately adding a base and an acid which react to form the salt which functions as the treatment agent.

Suitable bases for use in the process include, but are not limited to, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide, calcium hydroxide and sodium hydroxide, alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and calcium carbonate, alkali metal and ammonium salts of phosphorus-containing acids such as tetrasodium pyrophosphate, ammonium orthophosphate, disodium orthophosphate, and trisodium phosphate, and any other bases approved for use under the applicable regulatory laws. Strong bases as well as weak bases may be utilized.

Suitable salts for use in these methods include water-soluble substances which ionize in aqueous solution to provide a substantially neutral solution (i.e., a solution having a pH of from <NUM> to <NUM>). Alkali metal-containing salts are particularly useful, as are salts of organic carboxylic acids (e.g., a sodium or potassium salt) such as acetic acid, adipic acid, itaconic acid, malonic acid, lactic acid, tartaric acid, citric acid, oxalic acid, fumaric acid, aconitic acid, succinic acid, oxalosuccinic acid, glutaric acid, ketoglutaric acid, malic acid, fatty acids and combinations thereof.

Mixtures of different treatment agents may be used. For example, the starch may be heated in the alcoholic medium in the presence of both at least one base and at least one salt.

The starch, alcoholic medium and treatment agent are heated for a time and at a temperature effective to inhibit the starch to the desired extent. Generally speaking, temperatures in excess of room temperature (i.e., <NUM> or greater) will be necessary. At the same time, extremely high temperatures should be avoided. The heating temperature can be, for example, <NUM> to <NUM>. Typically, temperatures of from <NUM> to <NUM>, <NUM> to <NUM>, or from <NUM> to <NUM>, or from <NUM> to <NUM> will be sufficient. The heating time generally is at least <NUM> minutes but no more than <NUM> hours and typically <NUM> minutes to <NUM> hours. In general, a desired level of starch inhibition may be achieved more rapidly if the heating temperature is increased.

The specific conditions of time of treatment, temperature of treatment, and proportions of the components of the mixture of starch, alcoholic medium and treatment agent are generally selected such that the starch is not gelatinized to a significant extent. That is, the starch remains non-pregelatinized as described above.

When the temperature selected for the heating step exceeds the boiling point of one or more components of the alcoholic medium, it will be advantageous to carry out the heating step in a vessel or other apparatus capable of being pressurized. The treatment may be conducted within a confined zone in order to maintain the alcoholic medium in a liquid state. Additional positive pressure could be employed, but is generally not necessary. The starch may be slurried in the alcoholic medium together with the treatment agent under conditions of elevated temperature and pressure and treated for a time sufficient to change the starch's viscosity characteristics. Such treatment may be conducted in a stirred tank reactor on a batch basis or in a tubular reactor on a continuous basis, although other suitable processing techniques will be apparent to those skilled in the art. In another embodiment, the starch may be in the form of a bed within a tubular reactor and a mixture of the alcoholic medium and treatment agent passed through such bed (optionally, on a continuous basis), with the bed being maintained at the desired temperature to effect inhibition of the starch.

In embodiments in which a base has been utilized as a treatment agent, the mixture of starch, alcoholic medium and base may be combined with one or more acids, once the heating step is completed, for the purpose of neutralizing the base. Suitable acids for use in such neutralization step include, but are not limited to, phosphorus-containing acids such as phosphoric acid, carboxylic acids such as acetic acid, adipic acid, itaconic acid, malonic acid, lactic acid, tartaric acid, oxalic acid, fumaric acid, aconitic acid, succinic acid, oxalosuccinic acid, glutaric acid, ketoglutaric acid, malic acid, citric acid, fatty acids and combinations thereof, as well as other types of acids such as uric acid. If the inhibited starch is intended for use as a food ingredient, the acid generally should be selected to be one that is permitted for such use under applicable regulations. Typically, sufficient acid is added to lower the pH of the mixture to about neutral to slightly acidic, e.g., a pH of from about <NUM> to about <NUM> or from about <NUM> to about <NUM>.

The neutralization with acid may be carried out at any suitable temperature. In one embodiment, the slurry of starch, base and alcoholic medium is cooled from the heating temperature used to approximately room temperature (e.g., about <NUM> to about <NUM>) prior to being combined with the acid to be used for neutralization. The neutralized mixture may thereafter be further processed as described below to separate the inhibited starch from the alcoholic medium. In another embodiment, however, neutralization of the base is followed by further heating of the starch slurry. Such further heating has been found to be capable of modifying the rheological properties of the inhibited starch obtained, as compared to the viscosity characteristics of an analogously prepared starch that has not been subjected to heating after neutralization of the base.

Generally speaking, such further heating step is advantageously carried out at temperatures in excess of room temperature (i.e., <NUM> or greater). At the same time, extremely high temperatures should be avoided. The heating temperature can be, for example, <NUM> to <NUM>. Typically, temperatures of from <NUM> to <NUM>, <NUM> to <NUM>, or from <NUM> to <NUM>, or from <NUM> to <NUM> will be sufficient. The heating time generally is at least <NUM> minutes but no more than <NUM> hours and typically <NUM> minutes to <NUM> hours.

The mixture of starch and alcoholic medium may be processed so as to separate the starch from the alcoholic medium. Conventional methods for recovering particulate solids from liquids such as filtration, decantation, sedimentation or centrifugation may be adapted for such purpose. The separated starch may optionally be washed with additional alcoholic medium and/or alcohol and/or water to remove any undesired soluble impurities. In one embodiment, neutralization of residual base is accomplished by washing the recovered starch with an acidified liquid medium. Drying of the separated starch will provide an inhibited non-pregelatinized granular starch in accordance with the disclosure. For example, drying may be performed at a moderately elevated temperature (e.g., <NUM> to <NUM>) in a suitable apparatus such as an oven or a fluidized bed reactor or drier or mixer. Vacuum and/or a gas purge (e.g., a nitrogen sweep) may be applied to facilitate removal of volatile substances (e.g., water, alcohol) from the starch. The resulting dried inhibited non-pregelatinized granular starch may be crushed, ground, milled, screened, sieved or subjected to any other such technique to attain a particular desired particle size. In one embodiment, the inhibited starch is in the form of a free-flowing, granular material.

In one embodiment, however, the starch is subjected to a desolventization step at a significantly higher temperature (e.g., greater than <NUM> or greater than <NUM> or greater than <NUM>). Excessively high temperatures should be avoided, however, since degradation or discoloration of the starch may result. Such a step not only reduces the amount of residual solvent (alcohol) in the product but also provides the additional unexpected benefit of enhancing the degree of inhibition exhibited by the starch. Desolventization temperatures can, for example, be about <NUM> to about <NUM>. Typical temperatures are <NUM> to <NUM> or <NUM> to <NUM>. The desolventization may be carried out in the presence or in the absence of steam. Steam treatment has been found to be advantageous in that it helps to minimize the extent of starch discoloration which may otherwise occur at such an elevated temperature. In one embodiment, steam is passed through a bed or cake of the inhibited starch. The starch desolventization methods of <CIT>, incorporated herein by reference in its entirety for all purposes, may be adapted for use. Following steam treatment, the inhibited starch may be dried to reduce the residual moisture content (e.g., by heating in an oven at a temperature of from about <NUM> to about <NUM> or in a fluidized bed reactor).

In one embodiment, the treated starch, which has been recovered from the alcoholic medium, is first brought to a total volatiles content of not more than about <NUM>% by weight or not more than about <NUM>% by weight. This can be accomplished, for example, by first air or oven drying the recovered starch at moderate temperature (e.g., <NUM> to <NUM>) to the desired initial volatiles content. Live steam is then passed through the dried starch, the system being maintained at a temperature above the condensation point of the steam. A fluid bed apparatus may be used to perform such a steam desolventization step.

In general, it will be desirable to carry out desolventization under conditions effective to result in a residual alcohol content in the inhibited starch of less than <NUM> weight % or less than <NUM> weight % or less than <NUM> weight %.

Following desolventization, the inhibited starch may be washed with water and then re-dried to further improve color and/or flavor and/or reduce the moisture content.

Of course, the person of ordinary skill in the art can use other methodologies to arrive at the starches described herein. The starch feedstock can, for example, be subjected to a pH adjustment and heated. The pH adjustment can be performed by contacting a pH-adjusting agent with the starch; examples of pH-adjusting agents include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, lactic acid, malic acid, citric acid, fumaric acid, succinic acid, glutaric acid, malonic acid, tartaric acid and carbonic acid, as well as their alkali metal salts (e.g., potassium and/or sodium salts). The pH-adjusting agent can be contacted with the starch feedstock in any convenient fashion, e.g., as a slurry in liquid (e.g., water, alcohol (e.g., as described above, including ethanol or isopropanol), including aqueous alcohol such as aqueous ethanol, or another solvent); in dry form; in damp form (e.g., in a mist in a solvent (such as water, aqueous ethanol, or another solvent); or in the form of a damp dough of the starch (e.g., with water, aqueous ethanol, or another solvent). And when an alkali metal salt of an acid is to be used, it can be formed in situ, e.g., by adding the acid and an alkali metal hydroxide or carbonate in separate steps.

The pH adjustment can be performed to yield a variety of pH values. For example, in certain embodiments, and as described in <CIT>, the pH adjustment can be performed to yield a pH in the range of <NUM>-<NUM>. In other, alternative embodiments, the pH adjustment can be performed to yield a pH in the range of <NUM>-<NUM>, e.g., in the range of <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or about <NUM>, or about <NUM>, or about <NUM>, or about <NUM>, or about <NUM>, or about <NUM>, or about <NUM>, or about <NUM>, or about <NUM>. When the pH adjustment is performed in a slurry, the pH of the slurry is the relevant pH. When the pH adjustment is performed in a substantially non-liquid form (e.g., a dough, or in damp solid), the pH of the solid material at <NUM>% in water is the relevant pH. The amount of the pH-adjusting agent relative to the starch can vary, for example, from <NUM>-<NUM> wt% on a dry solids basis, e.g., <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, <NUM>-<NUM> wt% or <NUM>-<NUM> wt%. Desirably, the pH adjusting agent is mixed thoroughly with the starch feedstock. This will require different process conditions depending on the form in which the pH adjustment is performed. If the pH adjustment is performed in a slurry, simply stirring the slurry for a few minutes may be sufficient. If the pH adjustment is performed in a drier form (e.g., in a damp solid or a dough), more substantial contacting procedures may be desirable. For example, if a solution of the pH-adjusting agent is sprayed onto dry starch feedstock, it can be desirable to mix for about <NUM> minutes then store for at least a few hours.

After the pH-adjusting agent is contacted with the starch, the starch can be heated (i.e. while still in contact with pH-adjusting agent). The starch can be, for example, heated at a temperature in the range of <NUM>-<NUM>, e.g., <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>. The starch can be heated for up to, for example, <NUM> hours. The starch can be heated in a variety of forms. For example, the starch can be heated in alcohol or nonaqueous solvent slurry (e.g., under pressure if the boiling point of the solvent not sufficiently above the heating temperature); as a dough of starch, water, and non-water solvent to suppress granular swelling (e.g., as disclosed in <CIT>), or in a dry state (solvent can be removed using conventional techniques such as filtration, centrifugation and/or heat-drying, e.g. as described above with respect <CIT>). The starch can be dried as a result of the heating process; a separate drying step is not necessary.

As the person of ordinary skill in the art will appreciate, the starch feedstock may be purified, e.g., by conventional methods, to reduce undesirable flavors, odors, or colors, e.g., that are native to the starch or are otherwise present. For example, methods such as washing (e.g., alkali washing), steam stripping, ion exchange processes, dialysis, filtration, bleaching such as by chlorites, enzyme modification (e.g., to remove proteins), and/or centrifugation can be used to reduce impurities. The person of ordinary skill in the art will appreciate that such purification operations may be performed at a variety of appropriate points in the process.

Another aspect of the disclosure is a cold water swelling, delayed-gelling starch made by a process comprising providing a non-pregelatinized starch as described herein, and subjecting it to any of the processes described (specifically or generically) in <CIT>. For example, the process can include subjecting a non-pregelatinized starch of the disclosure, slurried in aqueous C2-C3 alkanol, to conditions of high temperature (e.g., <NUM>-<NUM> (<NUM>-<NUM> °F)) and pressure (e.g., at or above autogenic pressure, e.g., <NUM> mPa-<NUM> MPa (<NUM>-<NUM> psig). Such treatment can be performed, for example, <NUM>-<NUM> minutes.

In either instance, the first step in carrying out the process is the preparation of a slurry comprised of about <NUM> to about <NUM> parts by weight dry substance basis (dsb) of an ungelatinized corn starch in a liquid medium comprised of about <NUM> to about <NUM> parts by weight of an alcohol selected from ethanol, denatured ethanol, propanol and isopropanol and about <NUM> to about <NUM> parts by weight of water, provided that the liquid medium for the slurry contains about <NUM> to about <NUM>% by weight of water inclusive of the water in the starch (i.e., the weight ratio of alcohol to water is about <NUM>:<NUM> to <NUM>:<NUM>). Preferably the slurry is comprised of about <NUM> to about <NUM>% by weight of starch (dsb) and about <NUM> to about <NUM>% water.

Flavor and toxicity problems, which may be associated with the use of propanol and/or isopropanol in the processing of food acceptable starch products, are avoided when ethanol is used as the alcohol component of the process slurry. It is noted, however, that from a functional point of view, that is, in terms of producing a granular starch product exhibiting cold-water solubility and gelling characteristics, isopropanol performs as well as ethanol and denatured ethanol.

The aforedescribed slurry of an ungelatinized corn starch in an aqueous alcohol medium is heated to a temperature of about <NUM> to about <NUM> (about <NUM>° to about <NUM>° F). under autogenic pressure for about <NUM> to about <NUM> minutes. The heating process can be conducted as a batch process in a sealed vessel or as a continuous or semi-continuous process by passing the slurry through a heated confined zone at a rate calculated to give a residence time for the slurry in the heated zone of about <NUM> to about <NUM> minutes. Preferably the starch slurry is heated to a temperature of about <NUM> to about <NUM> (about <NUM> °F to about <NUM>° F). for a period of about <NUM> to about <NUM> minutes to convert the ungelatinized corn starch to the present cold-water-swelling starch having high cold-water solubility. In a most preferred embodiment of the present process, the ungelatinized corn starch slurry contains about <NUM> to about <NUM>% by weight of starch (dsb) and the liquid medium for the slurry contains about <NUM> to about <NUM>% by weight of water (i.e., the weight ratio of alcohol to water is about <NUM>:<NUM> to <NUM>:<NUM>); conversion of the ungelatinized corn starch to the present cold-water-swelling/soluble starch is accomplished by heating the slurry to a temperature of about <NUM> to about <NUM> (about <NUM>° to about <NUM>° F). for a period of about <NUM> to about <NUM> minutes.

After the heating step, the slurry is preferably cooled to below about <NUM>° F. , and the product cold-water-swelling granular starch is separated from the liquid medium component of the slurry by filtration or centrifugation. Following the recovery of the starch product from the reaction slurry, the starch is typically washed with <NUM> or more volumes of the alcohol used in the process, and dried and/or desolventized by conventional methods. For example, the starch can be dried in an oven to a certain volatiles level and then contacted with a hot humid gas, preferably moist air or steam, while the starch is maintained at a temperature from about <NUM> to about <NUM> (about <NUM>° to about <NUM>° F). for a time sufficient to reduce the alcohol content of the starch to a food acceptable level.

The cold water swelling, delayed-gelling starch so prepared can have, for example, an amylose content in the range of <NUM>-<NUM>% (or any other amylose content as described above); a % solubles in the range of <NUM>-<NUM>% (or any other % solubles as described above); and a gel time of at least <NUM> hours after being cooked in pH <NUM> phosphate buffer containing <NUM>% NaCl at <NUM>% starch solids for <NUM> minutes at <NUM>, then being allowed to sit undisturbed at <NUM> (or any other gel time as described above).

Another aspect of the disclosure is a cold water swelling, delayed-gelling starch, having.

In various embodiments, the cold water swelling, delayed-gelling starches of the disclosure can have the properties described above with respect to the delayed-gelling, inhibited starches (e.g., identity of starch; % solubles; gel times; Yellowness Index; chemical treatments and modifications; dextrinization and branching; viscosity; digestibility).

Another aspect of the disclosure is a method for making a food product. The method includes cooking a starch as described herein the presence of water; and providing the cooked starch in combination with one or more other food ingredients. For example, a starch as described herein can be combined with one or more other food ingredients that include water, and cooking the combination of the starch and the food ingredients. In particular embodiments, the method includes pasteurization, retorting, kettle or batch cooking, or ultra-high temperature processing. Advantageously, when the food product is cooked, it can take a longer time to gel, and thus allow for longer times to hold cooked product, to convey cooked product (e.g., by pumping), and to fill cooked product into containers before the product sets to gel.

Accordingly, yet another aspect of the disclosure is a food product including a starch as described herein, e.g., in a cooked, gelled form.

The food product can be, for example, a tomato-based product, a gravy, a sauce, a soup, a pudding, a salad dressing, a yogurt, a sour cream, a cheese, or a fruit filling or topping. A variety of cooking methods can be used, for example, pasteurization, retorting, kettle cooking, batch cooking and ultra-high temperature processing. The cooking is desirably sufficient to substantially convert the starch to a gel form. Advantageously, the starches described herein can take a longer time to gel, and thus allow for longer times to hold cooked product, to convey cooked product (e.g., by pumping), and to fill cooked product into containers before the product sets to gel. Notably, the starches described herein can be used as replacement for gelatin in gelled foods.

With respect to yogurt and other cultured dairy products, advantageously, the starches described herein can gel slowly enough that the product can be cultured, pumped into a container, and only then allowed to gel. Accordingly, a method for making a cultured dairy product (e.g., yogurt, sour cream, crème fraiche) can include providing a dairy mixture comprising a dairy feed and a starch as described herein; culturing the dairy mixture to provide a cultured dairy product (e.g., for at least <NUM> hours, at least <NUM> hours, or at least <NUM> hours); transferring the cultured dairy product to a container in an ungelled state; and allowing the cultured dairy product to gel in the container.

In other embodiments, the food product is a baked good, e.g., a bread, a pastry, a pie crust, a donut, a cake, a biscuit, a cookie, a cracker, or a muffin. In such embodiments, the cooking can include baking. In some embodiments, the use of the starches described herein in a baked good (i.e., in the dough or batter thereof) can help reduce staling. In other embodiments, the starch can be included in, e.g., a filling inside the baked good.

The starches described herein can be used in a wide variety of other foods. For example, in certain embodiments of the starches and methods of the disclosure, the starch is used in a food selected from baked foods, breakfast cereal, anhydrous coatings (e.g., ice cream compound coating, chocolate), dairy products, confections, jams and jellies, beverages, fillings, extruded and sheeted snacks, gelatin desserts, snack bars, cheese and cheese sauces, edible and water-soluble films, soups, syrups, sauces, dressings, creamers, icings, frostings, glazes, tortillas, meat and fish, dried fruit, infant and toddler food, and batters and breadings. The starches described herein can also be used in various medical foods. The starches described herein can also be used in pet foods.

A variety of other food products can advantageously be made using the starches of the present disclosure. For example, food products in which the starches of the present disclosure are useful include thermally- processed foods, acid foods, dry mixes, refrigerated foods, frozen foods, extruded foods, oven-prepared foods, stove top-cooked foods, microwaveable foods, full-fat or fat- reduced foods, and foods having a low water activity. Food products in which the starches of the present disclosure are particularly useful are foods requiring a thermal processing step such as pasteurization, retorting, or ultra-high temperature (UHT) processing. The starches of the present disclosure are particularly useful in food applications where stability is required through all processing temperatures including cooling, freezing and heating.

Based on processed food formulations, the practitioner may readily select the amount and type of the starches of the present disclosure required to provide the necessary thickness and gelling viscosity in the finished food product, as well as the desired texture. Typically, the starch is used in an amount of <NUM>-<NUM>%, e.g., <NUM>-<NUM>%, by weight, of the food product.

Among the food products which may be improved by the use of the starches of the present disclosure are high acid foods (pH <<NUM>) such as fruit-based pie fillings, baby foods, and the like; acid foods (pH <NUM>-<NUM>) such as tomato-based products; low acid foods (pH ><NUM>) such as gravies, sauces, and soups; stove top- cooked foods such as sauces, gravies, and puddings; instant foods such as puddings; pourable and spoonable salad dressings; refrigerated foods such as dairy or imitation dairy products (e.g., yogurt, sour cream, and cheese); frozen foods such as frozen desserts and dinners; microwaveable foods such as frozen dinners; liquid products such as diet products and hospital foods; dry mixes for preparing baked goods, gravies, sauces, puddings, baby foods, hot cereals, and the like; and dry mixes for predusting foods prior to batter cooking and frying. The starches of the present disclosure are also useful in preparing food ingredients such as encapsulated flavors and clouds.

In other embodiments, the food product is a confection.

The starches of the present disclosure may also be used in various non-food end use applications where chemically modified (crosslinked) inhibited starches have conventionally been utilized, such as cosmetic and personal care products, paper, packaging, pharmaceutical formulations, adhesives, and the like.

Another aspect of the disclosure is a dry mix comprising a starch as described herein, in admixture with one or more food ingredients. When the dry mix is cooked (i.e. in the presence of water), it can take a longer time to gel, and thus allow for longer times to hold cooked product, to convey cooked product (e.g., by pumping), and to fill cooked product into containers before the product sets to gel. The dry mix can be, for example, a dry mix for a baked good, e.g., a bread, a pastry, a pie crust, a donut, a cake, a biscuit, a cookie, a cracker, or a muffin.

A delayed-gelling, inhibited tapioca starch according to the disclosure (sedimentation volume <NUM>/g, <NUM>% solubles) was cooked as described above with respect to the RVA analysis and stained with iodine (tincture, <NUM>%). A photomicrograph of the resulting cooked starch paste is shown in <FIG>. As the person of ordinary skill in the art will appreciate, the individual starch granules evident in <FIG> are consistent with inhibition of the starch.

RVA cooking curves of various tapioca starches are provided in <FIG>. The ramped-up and -down temperature program refers to the right-hand temperature scale, while the RVA curves refer to the left-hand viscosity scale. The traces are, top-to-bottom on the right side of the graph, for starches of sedimentation volumes of <NUM>, <NUM>, <NUM>, <NUM> and <NUM>/g. The viscosity is measured by RVA at <NUM>% solids in a pH <NUM> phosphate buffer containing <NUM>% NaCl at a stir rate of <NUM> rpm. The initial temperature of the analysis is <NUM>; the temperature is ramped linearly up to <NUM> over <NUM> minutes, then held at <NUM> for <NUM> minutes, then ramped linearly down to <NUM> over <NUM> minutes, then held at <NUM> for <NUM> minutes, as shown on the graph of <FIG>. The viscosity was measured throughout the heating and cooling cycle, and is plotted on the graph of <FIG>.

Sedimentation volumes and % solubles for a variety of tapioca starches of the disclosure were measured; a plot of sedimentation volume is provided as <FIG>. The starches of the disclosure are identified as "slow gelling" starches, while conventional crosslinked tapioca starches (Comparative A and Comparative C, below) are identified as "conventional crosslinked" starches. Notably, the % solubles value for the starches decrease with decreasing sedimentation volume, as shown in the plot of <FIG>.

To evaluate textural attributes, various starches of the disclosure and commercial tapioca starches were cooked at <NUM>% solids in <NUM>% NaCl aqueous solution. They were evaluated by panelists both on the day of cook, and the next day following overnight refrigeration. The sample set included seven delayed-gelling inhibited tapioca starches of the present disclosure, of a variety of sedimentation volumes. These samples are described in Table <NUM>. The six commercially available tapioca starches included unmodified tapioca, two chemically cross-linked tapioca starches, and a tapioca starch cross-linked and viscosity-stabilized by the addition of hydroxypropyl substitution, as described in Table <NUM>.

Table <NUM> gives properties of the reduced-gel rate starches. The range in sedimentation volumes of highest interest for food applications is typically considered to be <NUM>-<NUM>/g. Product color is included.

Comparative A is a phosphate crosslinked tapioca starch made by slurrying tapioca starch in water at <NUM> under alkaline conditions; adding <NUM>% POCl<NUM> and allowing to react for <NUM> minutes, then neutralizing the slurry, and filtering, washing and drying the resulting crosslinked starch.

Comparative B is a hydroxypropyl-modified, phosphate crosslinked tapioca starch made by slurrying tapioca starch in water at <NUM> under alkaline conditions, adding propylene oxide and allowing to react to <NUM>% hydroxypropyl substitution, then adding <NUM>% POCl3 and allowing to react for <NUM>, then neutralizing the slurry, and filtering, washing and drying the resulting crosslinked starch.

Comparative C is a phosphate crosslinked tapioca starch made by slurrying tapioca starch in water at <NUM> under alkaline conditions; adding <NUM>% POCl<NUM> and allow to react for <NUM> minutes, then neutralizing the slurry, and filtering, washing and drying the resulting crosslinked starch.

Six novice panelists were divided into two groups. Each group evaluated the fresh starch pastes in the afternoon on the day of cook. The panel also evaluated the starch paste the next day. For the fresh cooked starch paste, the panelists evaluated.

For the day-old starch paste (mostly gelled), the panelists evaluated.

Each attribute was rated on a <NUM> point line scale. References with different ratings were provided to each group. The references for each attributes are:.

A typical property of tapioca food starches is that they form soft gels. This is desirable for such applications as yogurt, dairy desserts, and fruit fillings. Some of the starches for these applications are conventionally cross-linked (inhibited) to give process tolerance, but not otherwise modified. For applications where gel formation is not desirable, and to improve freeze-thaw or storage stability, tapioca starches are conventionally further modified by the addition of side groups, such as hydroxypropyl. The bulky side groups prevent the starch molecules from associating to form gel networks. Unmodified tapioca, because it is not crosslinked, has no shear stability. The granules rupture upon cooking, giving the paste a stringy texture that is typically considered undesirable. Because tapioca is about <NUM>% amylopectin, the paste is slow to set back. (It is believed that most of the extra-granular starch in cross-linked tapioca pastes is amylose, which is responsible for the gel formation.

<FIG> is a bar graph showing firmness and opacity ratings on the day of cook, with firmness on the left of each pair, and opacity on the right of each pair. The comparative tapiocas, with the exception of the hydroxypropyl-stabilized Comparative B, have firmness ratings of <NUM>-<NUM>. Comparative B's rating is <NUM>. For these, opacity trends with firmness. It is reasonable to expect that the structure responsible for firm texture also scatters light. The starches of the present disclosure, on the other hand, have opacity values similar to the firmer commercial samples, but with firmness ratings closer to the hydroxypropyl -stabilized starch, ranging in score from <NUM> to <NUM>.

<FIG> is a bar graph showing the paste thickness (left) and stringiness (right) ratings on the same day as cooking. The commercial, cross-linked, non-stabilized starches have very thick textures with little stringiness. Comparative D and Comparative B have thin textures and considerable stringiness. The samples of the present disclosure are similar to Comparative D and Comparative B in paste thickness and stringiness on the day of cook.

For the comparative tapiocas, thickness and stringiness appear to be inversely related. The starches with highest thickness have little stringiness; the starches with lowest thickness have the highest stringiness. For the starches of the present disclosure, thickness and stringiness trend together. The starches with highest thickness have the highest stringiness, and vice versa. Thickness and stringiness trend with level of inhibition - samples <NUM>, <NUM>, and <NUM> are the most inhibited of the set, with SVs of <NUM> and <NUM>, and have the lowest thickness and stringiness scores.

Following overnight refrigeration the commercial starches changed little, whereas the experimental starches changed dramatically. <FIG> is a bar graph showing the firmness ratings of certain starches the day following refrigeration. (The samples had been warmed to room temperature before evaluating. ) The firmness values in this chart can be compared to those of <FIG>. The firmness ratings of the crosslinked commercial starches remained between <NUM> and <NUM> while the hydroxypropyl-stabilized Comparative B remained at <NUM>. (Comparative D dropped from <NUM> to <NUM>. ) The starches of the present disclosure, however, increased from <NUM>-<NUM> up to <NUM>-<NUM>, and became the firmest samples in the set.

Similar trends were seen with other textural attributes that reflect gel formation. The surfaces of the pastes of the starches of the present disclosure were more reflective on the day of cook than the cross-linked commercial samples, whereas the cross-linked commercial samples were deemed to have a grainier texture than the experimental on the day of cook. Following overnight refrigeration, graininess had increased dramatically and surpassed the commercial samples, and the reflectiveness of the paste surfaces had decreased.

Principal component analysis (PCA) and factor loaded variance analysis were performed on the data. Analyzing a data set with PCA is meant to reduce confounds of common terms and eliminate redundancies and non-essential attributes in defining product in a product space. It looks for underlying structure in the data, and allows samples to be compared in terms of their principal components.

Table <NUM> shows the PCA data for the products on the day of cook. The first three components account for <NUM>% of product variance (cumulative). Principal component (PC) <NUM> accounts for <NUM>% of product variance. PC <NUM> and PC <NUM> account for <NUM>% and <NUM>% of product variance, respectively.

Table <NUM> shows the attributes loading for each PC on the day of cook. A high absolute number means the attribute is loaded heavily on that PC. As seen in Table <NUM>, PC1 is driven by firmness, thickness, jiggle elasticity, shininess, stringiness and opacity. PC2 is driven by graininess and, to a much lesser degree, syneresis.

The data indicate that all the starches of the present disclosure are less firm, less thick, less jiggly, and less opaque than all of the non-stabilized commercial tapiocas. Samples <NUM>, <NUM>, <NUM>, and <NUM> seem behave similarly to the hydroxypropyl-stabilized Comparative B on the day of cook. Samples <NUM> and <NUM> - the middle inhibition starches of the disclosure, seemed to behave similarly to each other.

Table <NUM> shows the PCA data for the products on the day after cook. The first three components account for <NUM>% of product variance (cumulative). Principal component (PC) <NUM> accounts for <NUM>% of product variance. PC <NUM> and PC <NUM> account for <NUM>% and <NUM>% of product variance, respectively.

Table <NUM> shows the attributes loading for each PC on the day after cook. PC1 on the day after cook is driven by firmness, shininess, press elasticity, jiggle elasticity, and opacity. PC2 is driven by syneresis.

A series of experimental food products were made using various starches, including the Comparative A and C starches above and four starches of the disclosure (<NUM>, <NUM>, <NUM> and <NUM>, having sedimentation volumes of <NUM>, <NUM>, <NUM> and <NUM>/g, respectively.

Samples <NUM> and <NUM> (sedimentation volumes <NUM> and <NUM>/g, respectively) were tested in a yogurt model system along with Comparative A. Yogurt compositional formula and batch formula are given in Tables <NUM> and <NUM>, respectively.

Starch integrity in the yogurts was qualitatively evaluated by microscopy after staining with iodine and tipping with soap to help dissipate protein from the field of view.

Brookfield viscosity with a Helipath attachment and appropriate T-bar spindle was measured <NUM> hours after production. Data was collected in triplicate.

Firmness/gel strength was measured immediately after removing from the refrigerator using a TAXT. Plus texture analyzer with the TA-<NUM><NUM>-mm puncture probe. The test was conducted in compression using a pre-test speed of <NUM>/sec, test speed of <NUM>/sec and post-test speed of <NUM>/s after a trigger force of 5gf. Analysis was conducted <NUM> times per sample over <NUM> samples (total of <NUM> measurement points).

The viscosity of all yogurts made was similar and within normal batch to batch variation, though the yogurt was made with Sample <NUM> was the highest, as shown in Table <NUM>, below. Instrumental texture analysis of the yogurt samples was also similar. The closeness of the viscosity and texture values suggests that the casein network formation is the primary contributor to viscosity in this application.

<FIG> is a set of microscope images of the test yogurts obtained at 200x magnification. Microscopically, the Sample <NUM> and Comparative A yogurts contained intact starch granules after processing, although the Sample <NUM> yogurt was still slight underswollen. Sample <NUM> yogurt was partially fragmented.

Starches <NUM> and <NUM> (sedimentation volumes <NUM> and <NUM>/g, respectively) were tested in the pudding model system along with Comparative C. The test formulation is provided in Table <NUM>.

Starch integrity in the puddings was qualitatively evaluated by microscopy after staining with iodine and tipping with soap to help dissipate protein from the field of view.

Brookfield viscosity with Helipath attachment and appropriate T-bar spindle was measured <NUM> hours after production. Samples were tested immediately after removing from the refrigerator. Since the samples had settled within those <NUM> hours, the samples were stirred prior to viscosity and rheology measurements. Analysis was conducted on triplicate samples. Viscoelastic properties of the puddings were measured using a DH-<NUM> advanced rheometer with a <NUM> cross-hatched parallel plate and Peltier bottom plate over a strain sweep from <NUM> to <NUM>% at a frequency of <NUM> and temperature of <NUM> C. Analysis was conducted in duplicate.

<FIG> is a set of viscoelasticity measurements of the puddings. In the kettle-cooked pudding, Sample <NUM> (sedimentation volume <NUM>/g) provided similar viscosity as Comparative C, while Sample <NUM> (sedimentation volume <NUM>/g) (Table <NUM>). The viscoelastic properties of the Sample <NUM> and Comparative C puddings were also quite similar in terms of the storage modulus G' and tan δ, whereas the Sample <NUM> pudding had much higher loss modulus G" due to its more liquid like nature and low viscosities.

<FIG> is a set of microscope images of the test puddings obtained at 200x magnification. All of the starches appeared under-swollen when viewed under the microscope. In particular, Comparative C appeared the most under-swollen, though also provided high viscosity. The starch in all puddings settled or precipitated within <NUM> hours of production.

In general, Sample <NUM> (sedimentation volume <NUM>/g) performed similarly to the Comparative C reference.

Samples <NUM> and <NUM> (sedimentation volumes <NUM> and <NUM>/g, respectively) were tested in the ultra-high temperature (UHT) vanilla pudding model system along with Comparative A. The test formulation is given in Table <NUM>.

Starch integrity in the desserts was qualitatively evaluated by microscopy after staining with iodine and tipping with soap to help dissipate protein from the field of view.

Brookfield viscosity with Helipath attachment and appropriate T-bar spindle was measured <NUM> hours after production. Samples were tested immediately after removing from the refrigerator. Analysis was conducted on triplicate samples.

Firmness was measured immediately after removing from the refrigerator using a TAXT. Plus texture analyzer with the TA-<NUM><NUM>-mm puncture probe. The test was conducted in compression using a pre-test speed of <NUM>/sec, test speed of <NUM>/sec and post-test speed of <NUM>/s after a trigger force of 5gf. Analysis was conducted <NUM> times per sample over <NUM> samples (total of <NUM> measurement points).

Table <NUM> provides analytical characterization of the test desserts. In the UHT dairy dessert, Comparative A provided the highest viscosity. Sample <NUM> (sedimentation volume <NUM>/g) and Sample <NUM> (sedimentation volume <NUM>/g) provided very similar viscosities lower than Comparative A.

<FIG> is a set of microscope images of the test desserts obtained at 200x magnification. Starch granules were underswollen for Comparative A and Sample <NUM>, while the granules were optimally swollen for Sample <NUM>. Sample <NUM>, while underswollen, provides the most similar performance to Comparative A.

Starches <NUM> and <NUM> (sedimentation volumes <NUM> and <NUM>/g, respectively) were tested in the bakery fruit filling model system along with Comparative A and Comparative C. The test formulation is given in Table <NUM>.

Starch integrity in the fillings was qualitatively evaluated by microscopy after staining with iodine.

Color and translucency was measured using a Hunter ColorFlex colorimeter. A <NUM> black ring is inserted into the sample cup and the cup is then filled with sample. A white ceramic disk is then pushed down through the sample until it rests on top of the black disk. This will give a constant light path and white background. The cup with sample is then placed on the instrument port for measurement of L*, a*, b* attributes (after standardization with the white and black tiles). Samples were tested in triplicate.

Table <NUM> provides analytical characterization of the test fillings. In the fruit filling, both Comparative A and Comparative C provided high viscosity even though these starches have vastly different sedimentation volumes. Sample <NUM> provided similar high viscosity while Sample <NUM> was somewhat lower.

<FIG> is a set of microscope images of the test fillings obtained at 200x magnification. Sample <NUM> provided the optimal swelling when viewed microscopically while all other starches were underswollen. All test fillings were stored in the refrigerator and subsequently gelled and syneresed within <NUM> hours of refrigerated storage.

The color of the fruit fillings was also assessed as translucency and lack of color contribution is often an advantage of tapioca starches, particularly for this type of application. ΔE<NUM> is an instrumental measure of the relative degree of color difference from a chosen standard, and when the Comparative C fruit filling is chosen as that standard all of the test fruit fillings provide similar color, as shown in Table <NUM>. As a rule of thumb, ΔE<NUM> <<NUM> is not considered different in color visually.

The particulars shown herein are by way of example and for purposes of illustrative discussion of various aspects and embodiments of the materials and methods of the present disclosure, and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects thereof. In this regard, no attempt is made to show details of the starches and methods described herein in more detail than is necessary for the fundamental understanding thereof, the description taken with the drawings and/or examples making apparent to those skilled in the art how various forms thereof may be embodied in practice. Thus, before the disclosed materials and methods are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparati, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

The terms "a," "an," "the" and similar referents used in the context of describing the materials and methods disclosed herein (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. Ranges can be expressed herein as from one particular value, and/or to another particular value.

All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended merely to better illuminate the materials and methods of the disclosure and does not pose a limitation on the scope of the materials and methods otherwise disclosed. No language in the specification should be construed as indicating any non-claimed element as being essential to the practice of the invention.

Unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to". Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words "herein," "above," and "below" and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term "comprise" or "comprises" means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase "consisting of" excludes any element, step, ingredient or component not specified. The transition phrase "consisting essentially of" limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about. " Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained in the materials and methods of the disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Groupings of alternative elements or embodiments of the materials and methods disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified.

Some embodiments of the methods and materials are described herein. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The present inventors expect skilled artisans to employ such variations as appropriate, and the intend for the materials and methods of the disclosure to be practiced otherwise than specifically described herein. Accordingly, this disclosure contemplates all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.

Furthermore, numerous references have been made to patents and printed publications throughout this specification.

Claim 1:
A delayed-gelling, inhibited tapioca starch having
an amylose content in the range of <NUM>-<NUM>%;
a sedimentation volume; and
a % solubles value;
wherein a point corresponding to (sedimentation volume, % solubles value) in a plot of % solubles value vs. sedimentation volume falls within the polygon defined by the set of points (<NUM>/g, <NUM>%), (<NUM>/g, <NUM>%), (<NUM>/g, <NUM>%) and (<NUM>/g, <NUM>%), when the sedimentation volume is measured as disclosed in the description and the % solubles value is measured as disclosed in the description;
wherein the starch is not pregelatinized, is not hydroxypropylated, is not acetylated, is not carboxymethylated, is not hydroxyethylated, is not phosphated, is not succinated, is not cationic or zwitterionic, is not crosslinked with phosphate, is not crosslinked with adipate, is not crosslinked with epichlorohydrin, is not crosslinked with acrolein, is not bleached or oxidized with peroxide or hypochlorite, is not dextrinized, does not contain substantial amounts of the repolymerized branched chains typical of dextrins, and substantially lacks <NUM>,<NUM>- and <NUM>,<NUM>- branching; and
wherein the starch has a gel time of at least <NUM> hours and no more than <NUM> hours after being cooked in pH <NUM> phosphate buffer containing <NUM>% NaCl at <NUM>% starch solids for <NUM> minutes at <NUM>, then being allowed to sit undisturbed at <NUM>.