WO2022212356A1

WO2022212356A1 - Pregelatinized inhibited hollow starch products and methods of making and using them

Info

Publication number: WO2022212356A1
Application number: PCT/US2022/022318
Authority: WO
Inventors: Zheng YOU; Saravanan Suppiah SINGARAM
Original assignee: Tate & Lyle Solutions Usa Llc
Priority date: 2021-03-31
Filing date: 2022-03-29
Publication date: 2022-10-06
Also published as: GB2606585A; GB202107981D0; GB2606585B

Abstract

The present disclosure relates to pregelatinized inhibited starches having a novel hollow particle structure. One aspect of the disclosure is a pregelatinized inhibited particulate starch product in the form of a plurality of particles of starch, wherein at least 50% of the particles are substantially hollow, the pregelatinized inhibited particulate starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g. Starch products of the disclosure can be made by spray-drying a gelatinized starch dispersion in the presence of a blowing agent, and inhibiting the starch, e.g., using a crosslinking agent or heat treatment in the presence of an acid or a base.

Description

PREGELATINIZED INHIBITED HOLLOW STARCH PRODUCTS AND METHODS OF

MAKING AND USING THEM

Cross-Reference to Related Applications [0001] This application claims the benefit of priority of U.S. Provisional Patent Application no. 63/168860, filed March 31, 2021 , which is hereby incorporated herein by reference in its entirety.

Background of the Disclosure

Field of the Disclosure

[0002] The present disclosure relates generally to starch products. More particularly, the present disclosure relates to pregelatinized inhibited hollow starch products, and to methods relating to them, including methods for making and using them.

Technical Background

[0003] Starch products are often added to food and beverage products in order to adjust texture and thickness. An active area of research is the development of starches that provide high viscosity solutions with relatively low mass loading. Such super-thickening starches are applicable in a wide range of food, beverage, and non-food applications where particular rheological properties are desired with a low amount of added starch product.

[0004] One strategy towards achieving this combination is the development of highly- porous, inhibited starches. Highly-porous starches are theorized to provide high viscosity at low mass loadings, and also may possess enhanced absorption or adsorption properties, due to their high void volume. But a common problem among porous starches is their low stability to heat treatment. When starch is cooked in water, the individual granules hydrate and swell, and reach a peak viscosity, which desirably can provide thickness and texture to food products. With additional cooking and/or agitation, however, the starch granules can come apart, causing a loss of viscosity. In many contexts, it is desirable for a starch to resist degranularization upon cooking. Such starches are known as inhibited starches, and are useful in a wide variety of food products. But methods to produce highly-porous, starches are not well established.

[0005] There exists an ongoing need for inhibited starches which can effectively contribute to texture and thickness of food and beverage products even after cooking or other processing.

Summary of the Disclosure

[0006] One aspect of the disclosure is a pregelatinized inhibited particulate starch product in the form of a plurality of particles of starch, wherein at least 50% of the particles are substantially hollow, the pregelatinized inhibited particulate starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

[0007] Another aspect of the disclosure is a method for making a pregelatinized inhibited particulate starch product, the method comprising: providing an aqueous dispersion of a gelatinized starch, the starch dispersion including a blowing agent; spray-drying the aqueous dispersion under conditions to activate the blowing agent to provide a spray-dried particulate; and heating the spray-dried particulate to inhibit the starch, to provide a starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

[0008] Another aspect of the disclosure is a method for making a food product comprising providing a pregelatinized inhibited particulate starch product as described herein, and including the pregelatinized inhibited particulate starch product in the food product.

[0009] Other aspects of the disclosure will be evident from the detailed description provided herein.

Brief Description of the Drawings

[0010] FIG. 1 is a schematic cross-sectional view of a bubble-shaped starch particle according to the disclosure.

[0011] FIG. 2 is a schematic cross-sectional view of a bowl-shaped starch particle according to the disclosure.

[0012] FIGS. 3 and 4 are SEM images of a starch product of Example 2.

[0013] FIGS. 5 and 6 are optical microscopy images of fractions of a starch product according to Example 2.

[0014] FIGS. 7 and 8 are SEM images of starch products of Example 3.

[0015] FIGS. 9 and 10 are optical microscopy images of fractions of a starch product according to Example 3.

[0016] FIG. 11 is a plot of rheology data for starch products according to Examples 3 and 4.

[0017] FIGS. 12 and 13 are SEM images of starch products of Example 3.

[0018] FIGS. 14 and 16 are optical microscopy images of fractions of a starch product according to Example 3. [0019] FIGS. 16 and 17 are SEM images of the uncooked acid-thinned starch used as a feed in Example 5.

[0020] FIGS. 18 and 19 are SEM images of a starch product according to Example 5.

[0021] FIGS. 20-22 are optical microscopy images of starch products according to Example 5.

[0022] FIGS. 23-28 are SEM images of a starch product according to Example 6.

[0023] FIGS. 29-30 are optical microscopy images of starch products according to

Example 6.

[0024] FIGS. 31-34 are plots of rheology data for starch products according to Example 6

Detailed Description

[0025] The present inventors have unexpectedly determined that “hollow” pregelatinized starch particles can be made by spray-drying cooked starch in the presence of a blowing agent. Notably, inhibition of the starch (e.g., via crosslinking) in conjunction with the spray drying can help to preserve the shape of the particles, even upon hydration. Without wishing to be bound by theory, it is believed by the present inventors that the hollow shape of the particles can result in the starch having an increased thickening power per unit mass. Based on the disclosure herein, the person of ordinary skill in the art can perform the spray-drying and inhibition operations to provide a starch having a desired hollow particulate shape while being sufficiently inhibited to substantially maintain that hollow shape upon hydration.

[0026] Accordingly, one aspect of the disclosure is a pregelatinized inhibited particulate starch product in the form of a plurality of particles of starch. Notably, at least 50% of the particles are substantially hollow. The pregelatinized inhibited particulate starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

[0027] Spray-drying in the presence of a blowing agent can provide starch products in which a substantial fraction of the starch particles are substantially hollow. That is, in certain embodiments, a substantially hollow starch has a morphology characteristic of a particle blown by a blowing agent.

[0028] It can be desirable to provide a relatively high proportion of substantially hollow particles in the starch products described herein. For example, in certain embodiments as otherwise described herein, at least 60% of the particles are substantially hollow, e.g., at least 70% of the particles or substantially hollow. In certain embodiments as otherwise described herein, at least 80%, e.g., at least 85% or at least 90% of the particles are substantially hollow. In general, it is desirable to have as high a fraction as practical of the starch particles in substantially hollow form. But the person of ordinary skill in the art will appreciate that real world conditions may leave some minor fraction of the starch particles (e.g., in various embodiments as otherwise described herein, up to 30%, up to 20%, up to 10%, or up to 5%) not in substantially hollow form. While such particles may not have the same thickening power as substantially hollow particles, when they are present in minor amounts the overall product will enjoy the benefits of substantially hollow particles.

[0029] The person of ordinary skill in the art will appreciate from the present disclosure that a substantially hollow particle has an outer shell that defines an inner void. The outer shell may substantially enclose the inner void, e.g., in the case of a “bubble”-like shape, or may only partially enclose the inner void, e.g., in the case of a “bowl”-like shape. These are distinguished from porous particles, or solid particles (e.g., in the form of discs, flakes or globular shapes).

[0030] In certain embodiments of a pregelatinized inhibited particulate starch product as otherwise described herein, at least 50% of the particles have an inner void that forms at least 20% of a volume of the particle. Microscopy can be used to make this determination. The overall volume of a particle is defined by taking the outer envelope of the particle (i.e., by fitting the smallest possible surface across any concavities of the particle), and comparing the volume of the inner void with the volume of the outer envelope. An example is shown in schematic cross-sectional view in FIG. 1. Particle 100 is shown in cross-sectional schematic view with an outer shell 120 defining an inner void 130. Here, the particle is in a bubble-like shape. The volume of the overall particle is determined by closing off the openings 135 of the bubble with surfaces 140 (i.e., not real surfaces, merely used to model the overall particle volume) and determining the volume of the enclosed area. In this example, the volume of the inner void is well over 50% of the volume of the particle. Another example is depicted in the schematic cross-sectional view of FIG. 2. Particle 200 has an outer shell 220 defining an inner void 230. Here, the particle is in a bowl-like shape. The volume of the overall particle is determined by closing off the bowl with surface 240 (i.e., not a real surface, merely used to model the overall particle volume) and determining the volume of the enclosed area. In this example, the volume of the inner void is well over 50% of the volume of the particle.

[0031] In certain embodiments as otherwise described herein, at least 60%, e.g., at least 70%, of the particles of the starch product have an inner void that forms at least 20% of a volume of the particle. In certain embodiments as otherwise described herein, at least 80%, e.g., at least 85% or at least 90%, of the particles of the starch product have an inner void that forms at least 20% of a volume of the particle. In various embodiments as described herein, at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles have an inner void that forms in the range of 20-90%, or 20-80%, or 20- 70%, or 20-60% of the volume of the particle.

[0032] The volumes of the inner voids can be varied based, e.g., on spray drying conditions. For example, in certain embodiments as otherwise described herein, at least 50% of the particles have an inner void that forms at least 30% of a volume of the particle. For example, in certain embodiments as otherwise described herein, at least 80%, e.g., at least 85% or at least 90%, of the particles of the starch product have an inner void that forms at least 30% of a volume of the particle. In various embodiments as described herein, at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles have an inner void that forms in the range of 30-90%, or 30-80%, or 30-70%, or 30- 60% of the volume of the particle.

[0033] And in certain embodiments as otherwise described herein, at least 50% of the particles have an inner void that forms at least 40% of a volume of the particle. For example, in certain embodiments as otherwise described herein, at least 80%, e.g., at least 85% or at least 90%, of the particles of the starch product have an inner void that forms at least 40% of a volume of the particle. In various embodiments as described herein, at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles have an inner void that forms in the range of 40-90%, or 40-80%, or 40-70% of the volume of the particle.

[0034] Of course, the degree of hollowness of the particles can be measured in different manners. For example, in certain embodiments as otherwise described herein, at least 50% of the particles have an outer shell defining an inner void, the inner void having a depth of at least 1 micron and an opening formed in outer shell, the opening having an area of at least 1 square micron. This is depicted in the schematic cross-sectional view of FIG. 2. Particle 200 has an outer shell 220 defining an inner void 230. Here, the particle is in a bowl-like shape. The opening of the particle 235 has an area that is at least 1 square micron, and the inner void has a depth 145 that is at least 1 micron. In certain embodiments as otherwise described herein, at least 60% (e.g., at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 1 micron and an opening formed in outer shell, the opening having an area of at least 1 square micron. In certain embodiments as otherwise described herein, at least 80% (e.g., at least 85% or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 1 micron and an opening formed in outer shell, the opening having an area of at least 1 square micron. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the depth of the inner void is in the range of 1-50 microns, e.g., 1-40 microns, or 1- 30 microns or 1-20 microns. In certain embodiments as otherwise described herein, in at least 50% (e g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the area of the opening is in the range of 1-2000 square microns, e.g., in the range of 1-1500 square microns, or 1-1000 square microns, or 1-750 square microns, or 1-500 square microns, or 1-250 square microns.

[0035] The depths of the inner voids and the opening areas of the particles can be varied based, e.g., on spray drying conditions. For example, in certain embodiments as otherwise described herein, at least 50% of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns and an opening formed in outer shell, the opening having an area of at least 2 square microns. In certain embodiments as otherwise described herein, at least 60% (e.g., at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns and an opening formed in outer shell, the opening having an area of at least 2 square microns. In certain embodiments as otherwise described herein, at least 80% (e.g., at least 85% or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns and an opening formed in outer shell, the opening having an area of at least 2 square microns. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the depth of the inner void is in the range of 2-50 microns, e.g., 2-40 microns, or 2-30 microns or 2-20 microns. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the area of the opening is in the range of 2-2000 square microns, e.g., in the range of 2-1500 square microns, or 2-1000 square microns, or 2-750 square microns, or 2-500 square microns, or 2-250 square microns.

[0036] In certain embodiments as otherwise described herein, at least 50% of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns and an opening formed in outer shell, the opening having an area of at least 4 square microns. In certain embodiments as otherwise described herein, at least 60% (e.g., at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns and an opening formed in outer shell, the opening having an area of at least 4 square microns. In certain embodiments as otherwise described herein, at least 80% (e.g., at least 85% or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns and an opening formed in outer shell, the opening having an area of at least 4 square microns. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the depth of the inner void is in the range of 2-50 microns, e.g., 2-40 microns, or 2-30 microns or 2-20 microns. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the area of the opening is in the range of 4-2000 square microns, e.g., in the range of 4-1500 square microns, or 4-1000 square microns, or 4-750 square microns, or 4-500 square microns, or 4- 250 square microns.

[0037] In certain embodiments as otherwise described herein, at least 50% of the particles have an outer shell defining an inner void, the inner void having a depth of at least 4 microns and an opening formed in outer shell, the opening having an area of at least 16 square microns. In certain embodiments as otherwise described herein, at least 60% (e.g., at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 4 microns and an opening formed in outer shell, the opening having an area of at least 16 square microns. In certain embodiments as otherwise described herein, at least 80% (e.g., at least 85% or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 4 microns and an opening formed in outer shell, the opening having an area of at least 16 square microns. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the depth of the inner void is in the range of 4-50 microns, e.g., 4-40 microns, or 4-30 microns or 4-20 microns. In certain embodiments as otherwise described herein, in at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles, the area of the opening is in the range of 16-2000 square microns, e.g., in the range of 16-1500 square microns, or 16-1000 square microns, or 16-750 square microns, or 16-500 square microns, or 16-250 square microns.

[0038] But the person of ordinary skill in the art will appreciate that “substantially hollow” particles according to the disclosure are not so limited. Rather, a “substantially hollow” particle is any particle that has a relatively large internal void that is at least partially bounded by an outer shell.

[0039] The substantially hollow particles of the disclosure can take a variety of shapes. For example, in certain embodiments as otherwise described herein, at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles are rounded in shape, e.g., substantially spherical, substantially fractionally spherical, substantially spheroidal (e.g., oblate or prolate), substantially fractionally spheroidal, substantially ellipsoidal, or substantially fractionally ellipsoidal. “Fractional” shapes are those that are more bowl-like in nature, where the shell follows a fraction of the shape but not the complete shape.

[0040] In certain embodiments as otherwise described herein, substantially hollow particles generally have a low aspect ratio. For example, in certain such embodiments, at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles have a maximum aspect ratio of 3, e.g., 2.5, 2, or 1.5.

[0041] Substantially hollow particles can provide a starch product with a relatively low bulk density. Accordingly, in certain embodiments of the disclosure, a starch product as otherwise described herein has a bulk density in the range of 0.03 to 0.4 g/mL, e.g., 0.05 to 0.4 g/mL, or 0.1 to 0.4 g/mL, or 0.15 to 0.4 g/mL, or 0.03 to 0.35 g/mL, or 0.05 to 0.35 g/mL, or 0.1 to 0.35 g/mL, or 0.15 to 0.35 g/mL, or 0.03 to 0.3 g/mL, or 0.05 to 0.3 g/mL, or 0.1 to 0.3 g/mL, or 0.15 to 0.3 g/mL.

[0042] Notably, the starch products of the disclosure are inhibited. As the person of ordinary skill in the art will appreciate, inhibition can help to provide process tolerance. Process-tolerant starches resist breaking down into fragments and resist dissolution when processed. Thus, the inhibited starches described herein can resist degranularization upon cooking. This may be advantageous for a granular starch designed to increase viscosity, as the properties of the starch granules will not be lost upon cooking. Moreover, inhibition helps to lock in the shape of the substantially hollow particles, to make them resistant to collapse when hydrated, such that they occupy a relatively high specific volume when used in a food or beverage application. Inhibited starches may vary with respect to their degree-of- inhibition, as characterized by their sedimentation volume as described below.

[0043] Inhibited starches may vary with respect to their degree-of-inhibition, as characterized by their sedimentation volume. The person of ordinary skill in the art can, based on the present disclosure, tune inhibition chemistries and conditions to provide for a variety of sedimentation volumes. As described herein, starches of the disclosure have a solubles-corrected sedimentation volume in the range of 15-80 mL/g. As used herein, sedimentation volume is the volume occupied by one gram of cooked starch (dry basis) in 100 grams (i.e. total, including the starch) of salted buffer solution. This value is also known in the art as “swelling volume.” As used herein, the “salted buffer solution” refers to a solution prepared according to the following steps: a) Using a top loader balance, weigh out 20 grams of sodium chloride into a 2 liter volumetric flask containing a stir bar; b) To this add RVA pH 6.5 buffer (purchased from Ricca Chemical Company) so that the flask is at least half full; c) Stir to mix until sodium chloride is dissolved; d) Add additional RVA pH 6.5 buffer to a final volume of 2 liters;

[0044] Sedimentation volumes as described herein are determined by dispersing the starch (2.5 g) in RVA buffer with 1 % NaCI to a total weight of 50 g. 20 g of the resulting paste is transferred to a graduated cylinder with the same buffer, and the total weight of the starch slurry in the cylinder was adjusted to 100 g. The cylinder is inverted a few times to mix, then sealed and allowed to stand at room temperature for 24 hours. The volume occupied by the starch sediment (i.e. , as read in the cylinder, excluding any starch remaining in particulate suspension in the supernatant) is the sedimentation volume for 1 g of starch, i.e., in units of mUg. The degree of solubles can by collecting the supernatant from the experiment described above (including any fine particulate remaining in suspension in the supernatant), evaporating it to dryness, and weighing the residue. A solubles-corrected sedimentation volume is the sedimentation volume divided by the percentage of starch that is in the sediment, i.e., not in the supernatant. Accordingly, solubles-corrected sedimentation volume is (sedimentation volume) / (1 - grams supernatant residue). Thus, a material having a sedimentation volume of 20 ml_/g and 0.100 g of supernatant residue (i.e., 10% solubles) would have a solubles-corrected sedimentation volume of 22.22 ml_/g.

[0045] In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described herein has a solubles-corrected sedimentation volume in the range of 20-80 mL/g, e.g., 30-80 mL/g, or 40-80 mL/g or 50-80 mL/g. In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described herein has a solubles-corrected sedimentation volume in the range of 15-70 ml_/g, e.g., 20-70 ml_/g, or 30-70 mL/g, or 40-70 ml_/g or 50-70 mL/g. In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described herein has a solubles-corrected sedimentation volume in the range of 15-60 ml_/g, e.g., 20-60 mL/g, or 30-60 mL/g, or 40-60 mL/g. In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described herein has a solubles-corrected sedimentation volume in the range of 15-50 mL/g, e.g., 20-50 mL/g, or 30-50 mL/g. In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described herein has a solubles-corrected sedimentation volume in the range of 15-40 ml_/g, e.g., 20-40 mL/g.

[0046] As described in detail below, the pregelatinized inhibited particulate starch products described herein can be inhibited by a variety of chemistries. For example, in certain embodiments as otherwise described herein, the pregelatinized inhibited particulate starch product is a chemically-modified inhibited starch (for example, inhibited via crosslinking, e.g., with acrolein, phosphate, adipate or epichlorohydrin). In other embodiments, the pregelatinized inhibited starch product is inhibited by heat treatment, e.g., in the presence of an acid or a base (e.g., in the presence of an alcohol) as described below.

[0047] A wide variety of starch sources can be used in the pregelatinized inhibited particulate starch products described herein. For example, in certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described is a maize starch (e.g., waxy or non-waxy). In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described is a tapioca starch (e.g., waxy or non-waxy). In certain embodiments, a pregelatinized inhibited particulate starch product as otherwise described is a wheat starch, a rice starch, a potato starch, potato starch, an oat starch, a barley starch or a sago starch.

[0048] The pregelatinized inhibited particulate starch product can in certain embodiments be an acid-thinned starch. Acid-thinned starches can have a relatively lower viscosity than native starches, and as such can be more amenable to the blowing processes described herein.

[0049] Notably, the starch products described herein can be made without many of the conventional chemical modifiers used in the making of conventional modified and/or inhibited starches. Accordingly, in certain embodiments, the starches as otherwise described herein can be marked or labeled as so-called “clean-label” starches. For example, in certain embodiments as otherwise described herein, the starch product is not hydroxypropylated. In certain embodiments, the starch product is not acetylated. In certain embodiments, the starch product is not carboxymethylated. In certain embodiments, the starch product is not hydroxyethylated. In certain embodiments, the starch product is not phosphated. In certain embodiments, the starch product is not succinated (e.g., not octenylsuccinated). In certain embodiments, the starch product is not cationic or zwitterionic. In certain embodiments, the starch product has substantially no fatty acid residues. In certain embodiments, the starch product is not crosslinked with phosphate. In certain embodiments, the starch product is not crosslinked with adipate. In certain embodiments, the starch product is not crosslinked with epichlorohydrin. In certain embodiments, the starch product is not crosslinked with acrolein. In certain embodiments, the starch product is not bleached or oxidized with peroxide or hypochlorite.

[0050] The starch products of the present disclosure can have a variety of viscosities as measured by a Rapid Visco Analyzer (RVA). For example, in certain embodiments a starch product as otherwise described herein can have a viscosity as measured by RVA is in the range of 50-1000 cP at 5% solids. In certain such embodiments, the viscosity as measured by RVA at 5% solids is in the range of 50-850 cP, or 50-700 cP, or 50-500 cP, or 50-400 cP, or 50-300 cP, or 50-200 cP, or 100-1000 cP, or 100-850 cP, or 100-700 cP, or 100-500 cP, or 100-400 cP, or 100-300 cP, or 200-1000 cP, or 200-850 cP, or 200-700 cP, or 200-500 cP, or 400-1000 cP, or 400-850 cP, or 400-700 cP, or 600-1000 cP, or 600-850 cP.

[0051] To measure rheological properties, cooked starch at 5% ds is diluted with RVA buffer with 1% NaCI to obtain samples at particular ds levels (e.g., 4% ds, or 2.5% ds). The viscosity is measured using a stress control (DHR-3) rheometer from TA instruments, equipped with a lower Peltier plate and an upper parallel plate (40 mm diameter) with drawdown road and adaptor. All measurements are carried out at 25 °C using the following procedure:

• Amplitude sweep at 100 Rad/s from 0.1% to 100%;

• Frequency sweep from 100 Rad/s to 0.1 Rad/s; and

• Flow curves at shear rates of 0.01 s^~1 to 100 s^~1 _.

[0052] The viscosity is measured by RVA at 5% solids in a pH 6.5 phosphate buffer at 1% NaCI at a stir rate of 160 rpm. The initial temperature of the analysis is 50 °C; the temperature is ramped linearly up to 90 °C over 3 minutes, then held at 95 °C for 20 minutes, then ramped linearly down to 50 °C over 3 minutes, then held at 50 °C for 9 minutes, after which time the viscosity is measured. Notably, when a pasting peak is displayed at times of about 2-5 minutes, the final viscosity measured is higher than the pasting peak viscosity. When the pasting peak is absent, the viscosity during the 95 °C hold is flat, or increases.

[0053] The starch products described herein can be made with relatively little color. For example, certain embodiments of the starch products as otherwise described herein are relatively low in color, i.e. , have a Yellowness Index of no more than 10, for example, in the range of 3-10 or 5-10. In certain desirable embodiments, the starch products described herein are especially low in color, i.e., the Yellowness Index is less than 8 (e.g., 3-8 or 5-8). Yellowness Index is determined via ASTM E313.

[0054] In some embodiments as described herein, a starch product has a relatively low degree of solubles, i.e., determined as described above. For example, in certain embodiments as otherwise described herein, a starch product has no more than 20% solubles, e.g., no more than 15% solubles, or no more than 12% solubles, or no more than 10% solubles. Of course, in other embodiments, starch products can include relatively more solubles. The identity of the starch, the degree of any acid thinning and the degree of inhibition can affect the degree of solubles of the starch products described herein.

[0055] While individual particle sizes can be small when the starch products as described herein are dispersed in an aqueous system, it can be desirable for a dry starch product to have a larger particle size. Accordingly, in certain embodiments as otherwise described herein particles of the pregelatinized inhibited particulate starch product are agglomerated into multi-particle agglomerates.

[0056] As noted above, the starch products described herein can be made by spray drying in the presence of a blowing agent. Accordingly, another embodiment of the disclosure provides a method for making a pregelatinized inhibited particulate starch product, the method including providing an aqueous dispersion of a gelatinized starch, the starch dispersion including a blowing agent; spray-drying the aqueous dispersion under conditions to activate the blowing agent to provide a spray-dried particulate; and heating the spray-dried particulate to inhibit the starch.

[0057] Such methods can be used to provide starch products, e.g., having any combination of the characteristics described above with respect to the starch products described above.

[0058] Without intending to be bound by theory, the inventors surmise that the gelatinized starch is sufficiently plastic to be blown out into substantially hollow particles by the action of the blowing agent during the spray-drying. The heat of the spray-drying itself and/or a subsequent heat treatment can inhibit the starch. Advantageously, the inhibition of the starch (i.e., via crosslinking) can stabilize the substantially hollow particle shape, allowing the particles to have a high specific volume, even when dispersed in aqueous media. Examples of particular production techniques are described below.

[0059] The dispersion of gelatinized starch can be provided by cooking a starch feed (e.g., a granular starch feed) in aqueous dispersion. The starch can be any desired starch, e.g., as described above, and can in some embodiments be acid-thinned. Acid-thinning of starch can desirably help increase plasticity during the blowing stage, so that the starch particles can more conveniently be blown out into a desired substantially hollow shape. The starch feed is desirably not substantially inhibited, as inhibition can interfere with the plasticity necessary for blowing out the starch into substantially hollow particles. The person of ordinary skill in the art can select a solids content that provides desired spray-drying performance, in view of a desired degree of blowing, the plasticity of the starch (in turn based on starch molecular weight), and a desired inhibition process. In certain embodiments, the starch is provided at a solids content in the dispersion in the range of 3-25 wt%. The dispersion of the gelatinized starch can be provided to the spray-drying operation while warm, although in some cases it will be desirable to spray dry a starch that is closer to ambient temperature in order to prevent substantial premature reaction of blowing agent and/or inhibition agent.

[0060] A variety of blowing agents can be adapted for use based on the present disclosure. For example, in certain embodiments, the blowing agent is a compound that reacts to evolve a gas, e.g., upon heating during the spray drying. For example, in certain embodiments, the blowing agent is a bicarbonate, such as ammonium bicarbonate or sodium bicarbonate. In other embodiments, the blowing agent is a material that evaporates to evolve a gas, e.g., upon heating during the spray drying. For example, in certain embodiments, the blowing agent is carbon dioxide. Of course, the person of ordinary skill in the art can adapt other blowing agents for use based on the description herein. It can be desirable in some cases to include the blowing agent in the gelatinized starch dispersion only shortly before spray drying.

[0061] In certain embodiments as otherwise described herein, an inhibition agent can be included in the aqueous dispersion of the gelatinized starch, such that the heating during the spray-drying and/or a subsequent heating inhibits the starch. It may be desirable to add the inhibition agent to the aqueous dispersion of gelatinized starch just before the spray drying operation, to avoid substantial reaction before the spray drying.

[0062] As described above, the inhibition can be performed in a number of manners. In certain embodiments, the inhibition agent is a crosslinking agent, i.e. , an agent that itself forms a crosslink bridge between starch chains. A variety of crosslinking agents can be used, e.g., STMP, POCI3, adipate (e.g., acetic/adipic acid anhydride), epichlorohydrin, or acrolein. In certain embodiments as otherwise described herein, the inhibition agent is an acid that causes the inhibition of the starch during the heating of the spray-dried particulate. In other embodiments as otherwise described herein, the inhibition agent is a base that causes the inhibition of the starch during the heating of the spray-dried particulate.

[0063] As noted above, a variety of inhibition processes can be used to inhibit the starches as described herein, be it before the hydrolysis or after the hydrolysis. For example, in certain embodiments as otherwise described herein, conventional chemical modification can be used to inhibit the starch by reaction with a crosslinking agent. Crosslinking agents suitable for this purpose include acrolein, phosphate (e.g., using STMP or POCI3), adipate (e.g., using acetic/adipic mixed anhydride) and epichlorohydrin. An example of a crosslinking process is using POCI3 as crosslinking agent to provide a phosphate-crosslinked starch. The heating of the starch during the spray drying can be used to effect the crosslinking reaction, optionally with additional heat treatment after the nominal drying process is complete. The person of ordinary skill in the art can adapt conventional chemical modification processes for inhibiting the starches described herein.

[0064] In other embodiments, the starch is inhibited using a heat treatment, for example, by adjusting the pH of the starch to neutral or greater then spray-drying and heat-treating the starch as described herein. Such thermal processes for inhibition are familiar to the person of ordinary skill in the art. The spray drying conditions can provide the necessary heat, optionally with additional heating after the nominal drying process is complete. Suitable bases for use in such processes when used at substantially basic pH of the dispersion (e.g., 8-9.5) 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, calcium carbonate and potassium carbonate, and alkali metal and alkaline earth metal bicarbonates such as sodium bicarbonate, and potassium bicarbonate. Ammonium analogs of such bases are also suitable. Suitable salts for use in these methods include water-soluble substances that ionize in aqueous solution to provide a substantially neutral solution (i.e., a solution having a pH of from 6 to 8). Alkali metal-containing salts are particularly useful, as are salts of organic acids (e.g., a sodium or potassium salt) such as 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.

[0065] In other embodiments, the starch is inhibited using a heat treatment, for example, by adjusting the pH of the starch to acidic pH with an acid then spray-drying and heat- treating the starch as described herein. Such thermal processes for inhibition are familiar to the person of ordinary skill in the art. The spray drying conditions can provide the necessary heat, optionally with additional heating after the nominal drying process is complete. The pH of the dispersion can be, e.g., in the range of 2-6, e.g., in the range of 2-5, or 2-4, or 2-3, or 3-6, or 3-5, or 3-4, or 4-6, or 4-5, or 5-6. A variety of acids can be used, both organic and in organic. Examples of acids that may be suitable for use in the processes of the present disclosure include sulfuric acid, phosphoric acid, hydrochloric acid, itaconic acid, aconitic acid, malonic acid, lactic acid, tartaric acid, oxalic acid, fumaric acid, aconitic acid, succinic acid, acetic acid, oxalosuccinic acid, glutaric acid, ketoglutaric acid, malic acid, citric acid, fatty acids and carbonic acid.

[0066] In some embodiments, a separate acid or base need not be added; the acid or base can be the blowing agent or a degradation product thereof. For example, when a bicarbonate is used as a blowing agent, it can make the material sufficiently basic to cause inhibition upon heating. [0067] The heat treatment can be performed at a variety of temperatures and for a variety of times. For example, in certain embodiments as otherwise described herein, the heat treatment is performed at a temperature in the range of 100-200 °C, e g., 120-200 °C, or 120-180 °C, or 120-160 °C, or 120-140 °C, or 140-200 °C, or 140-180 °C, or 140-160 °C, or 160-200 °C, or 160-180 °C, or 180-200 °C. In certain embodiments, the heat treatment is performed for a time in the range of 20 seconds to 20 hours, e.g., in the range of 10 minutes to 2 hours. In certain embodiments, the heat treatment is performed as part of the spray drying operation; i.e. , the heat involved in the spray drying is sufficient to inhibit the starch. But in other embodiments, a separate heat treatment can be performed on the spray-dried starch.

[0068] In certain embodiments as otherwise described herein, the starch product is not crosslinked by acrolein, phosphate, adipate or epichlorohydrin, e.g., the starch product is inhibited via a heat treatment in the presence of an acid or a base.

[0069] While, as described above, it can in certain embodiments be preferable for the starches of the disclosure to not be chemically modified, in certain other embodiments chemical modification of the starches can be useful to further modify starch properties. Suh starches can be chemically modified, for example, by ethereal substitution (e.g., ethyl, hydroxypropyl) or ester substitution (e.g., acetate, octenyl succinic anhydride).

[0070] As the person of ordinary skill in the art will appreciate, the starch 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.

[0071] Optical microscopy can be used to access how intact the starch granules after dispersion in water. Often, the starch granules are stained with an iodine solution to improve visibility. Typically, the dispersed starch is visualized under bright field with or without polarized light. To prepare the starch, a 5% starch paste in RVA buffer with 1% NaCI at pH 6.5 is diluted with an equal volume of the same buffer, and then mixed with a further volume of 0.02N iodine solution. A drop of this mixture is added to a standard microscope slide and covered with a cover slip. The magnification is often 200X, but can take a range of values as required. [0072] More detailed images of granular starches can be acquired with a scanning electron microscope. Backscattered imaging mode and low vacuum (40 Pa) are most typically used. A typical procedure is as follows: a small amount of sample powder is put on the surface of a double sided adhesive pad mounted on a specimen stub. A dust remover (e.g., Super Friendly AIR’IT™, FisherBrand) is used to blow away excess powder particles. The electron microscopy images are collected at 500X and 1500X magnification, although a range of magnification values can be used as required.

[0073] Another aspect of the disclosure is a pregelatinized inhibited particulate starch made as described above. In certain embodiments of the pregelatinized inhibited particulate starch made as described above, at least 50% of the particles are substantially hollow. Such pregelatinized inhibited particulate starches can otherwise be as described above.

[0074] Another aspect of the disclosure is a method for preparing a food product, including dispersing a starch product as described herein in a food product. The dispersion can be performed at a variety of temperatures. Notably, as the starch is pregelatinized, the dispersion need not be performed at high temperatures. Accordingly, in certain embodiments, the starch product is dispersed in the food product at a temperature of no more than 95 °C, e.g., no more than 90 °C, no more than 70 °C, or even no more than 50 °C. In certain embodiments of the methods as otherwise described herein, the starch product is dispersed in the food product at a temperature in the range of 15-95 °C, e.g., 15- 90 °C, 15-70 °C, 15-50 °C, 15-30 °C, 20-95 °C, 20-90 °C, 20-70 °C, or 20-50 °C. Of course, the starch product can be dispersed in food at a different temperature, e.g., a higher temperature than those described here. For example, in some cases starch products can be used in high-sugar foods in which cooking temperatures are very high. The starch products can help to provide hydration in the presence of the sugar, which would otherwise prevent non-starch product in the food from cooking.

[0075] The dispersion of the starch product can be performed such that the starch granules remain substantially undisintegrated in the food product. For example, in certain embodiments of the methods as otherwise described herein, at least 50% (e.g., at least 75%, or even at least 90%) of the starch granules swell but do not substantially disintegrate when dispersed in the food product.

[0076] Another aspect of the disclosure is a food product that includes a starch as described herein dispersed therein. Desirably, the starch granules of the starch product are substantially undisintegrated in the food product. For example, in certain embodiments of the methods as otherwise described herein, at least 50% (e.g., at least 75%, or even at least 90%) of the starch granules are swollen but not substantially disintegrated in the food product.

[0077] The starch products of the disclosure can be used in a variety of food products. For example, in certain embodiments of the methods and food products as otherwise described herein, the food product is a liquid. In certain embodiments of the methods and food products as otherwise described herein, the food product is a soup, a gravy, a sauce (e.g., a mayonnaise, a white sauce or a cheese sauce), a dressing (e.g., a salad dressing, e.g., pourable or spoonable), a filling or topping (e.g., a fruit filling or topping), or a dairy product (e.g., a yogurt, a sour cream or a quark). The starch products of the disclosure can be useful in egg-free food products, e.g., to provide properties otherwise provided by eggs; accordingly, in certain embodiments of the methods and food products as otherwise described herein, the food product is egg-free. For example, the starch products of the present disclosure can be used in various embodiments in salad-dressings, mayonnaises, and various other oil/water emulsions such as cheese sauces, as well as in high-sugar fillings such as pie fillings.

[0078] In various additional embodiments, the food product can be, for example, a tomato-based product, a soup, a pudding, a custard, a cheese product, a cream filling or topping, a syrup (e.g., a lite syrup), a beverage (e.g., a dairy-based beverage), a glaze, a condiment, a confectionary, a pasta, a frozen food, a cereal.

[0079] A variety of cooking methods can be used, for example, pasteurization, retorting, kettle cooking, batch cooking and ultra-high temperature processing.

[0080] The starches described herein can also be used to modify the properties of solid foods, e.g., baked goods, for example, acting as an anti-stalant to provide a softer product that retains a fresher texture after storage. Accordingly, 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.

[0081] 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, high-temperature short-time treatment, 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.

[0082] 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 0.1-35%, e.g., 0.5-6.0%, by weight, of the food product.

[0083] Among the food products which may be improved by the use of the starches of the present disclosure are high acid foods (pH <3.7) such as fruit-based pie fillings, baby foods, and the like; acid foods (pH 3.7-4.5) such as tomato-based products; low acid foods (pH >4.5) 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.

[0084] In other embodiments, the food product is a confection.

[0085] 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.

[0086] The starches described herein can allow for a variety of novel products and processes. For example, one embodiment of the disclosure is a method of making a dressing. The method includes combining water, acid (e.g., vinegar or lemon juice), a starch as described herein and egg yolks to provide a homogeneous mixture. To that homogenous mixture, oil is added and emulsified to provide the sauce. In another embodiment, a method for making a dressing includes combining water, acid (e.g., vinegar or lemon juice) and egg yolks to form a homogeneous mixture. To that homogeneous mixture, a slurry of a starch of the disclosure in oil is added an emulsified to provide the sauce. As the person of ordinary skill in the art, flavorings, seasonings, salt and sweeteners can be added as desired at any point in the process.

[0087] 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.

[0088] 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.

[0089] Based on processed food formulations, the person of ordinary skill in the art may readily select the amount and type of the starches of the present disclosure required to provide the necessary texture and viscosity in the finished food product. Typically, the starch is used in an amount of 0.1-35%, e.g., 0.1-10%, 0.1-5%, 1-20%, 1-10%, or 2-6%, by weight, of a finished food product. The starches described herein can also be used in preblends and dry mixes, e.g., in amounts in the range of 0.1-95%, e.g., 0.1-80%, 0.1-50%, 0.1-30%, 0.1- 15%, 0.1-10%, 0.1-5%, 1-95%, 1-80%, 1-50%, 1-30%, 1-15%, 1-10%, 5-95%, 5-80%, 5- 50%, 5-30%, 20-95%, 20-80%, or 20-50%.

[0090] Further description is provided with respect to the Examples, below.

Example 1 - General synthetic technique for a preoelatinized inhibited hollow starch using a crosslinkinq agent

[0091] As described above, a number of different chemical crosslinking agents can be used in the preparation of pregelatinized inhibited hollow starches according to the disclosure. A general procedure for using STMP as a crosslinking agent is provided below; the person of ordinary skill in the art can adapt this procedure for use of different crosslinking agents.

[0092] A native starch is dispersed at 4% dry solids in deionized water to provide a dispersion having a total mass of 1000 g in a 2 L stainless steel beaker. The pH is adjusted to in the range of 8 and 11.5 using sodium hydroxide, and the sample is heated at 95 C with stirring for 10 minutes, followed by heating without stirring for 20 minutes. The resulting cooked dispersion is allowed to cool to room temperature, and is brought back to 1000 g mass with deionized water. Ammonium bicarbonate (15.1 g) and sodium trimetaphosphate (0.2-0.8 g, to arrive at 0.5-2 wt% on starch dry weight) are added to the starch dispersion immediately before spray drying. A LabPlant™ SD-06 spray dryer is used to spray dry the starch dispersion. Example settings are: fan, 50; inlet temperature, 200 C; pump speed, 5 mL/min. The pump is primed and the nozzle cleaned with an initial flow of deionized water, then the feed tube is switched to the beaker containing the starch dispersion. The spray- dried starch is collected into a 150 mL aluminum weighing pan, and heated at 85 °C overnight. The oven temperature was raised to 150 °C and the heat treatment continued for 2 hours to provide a pregelatinized, inhibited hollow starch product as described herein.

Example 2 - Spray-drying of waxy corn starch in the presence of ammonium bicarbonate without additional inhibiting agent

[0093] A native waxy corn starch was dispersed at 3% dry solids in deionized water to provide a dispersion having a total mass of 1000 g in a 2 L stainless steel beaker. The sample was heated at 95 °C with stirring for 30 minutes. The resulting cooked dispersion was allowed to cool to room temperature, and is brought back was 1000 g mass with deionized water. Ammonium bicarbonate (11.3 g) was added to the starch dispersion immediately before spray drying. A LabPlant™ SD-06 spray dryer was used to spray dry the starch dispersion; settings were: fan, 50; inlet temperature, 180 °C; pump speed, 5 mL/min. The pump was primed and the nozzle cleaned with an initial flow of deionized water, then the feed tube was switched to the beaker containing the starch dispersion. The spray-dried starch was collected into a 150 mL aluminum weighing pan, and heated at 85 °C overnight. The oven temperature is raised to 150 °C and the heat treatment continued for 8 hours.

[0094] SEM images of the spray-dried starch before the additional heat treatment were collected using a JSM-6010LA Analytical Scanning Electron Microscope (JOEL, Tokyo, Japan). The starch powder was adhered on the specimen holder using a double sided tape. Excessive powder was removed by blowing with a can of condensed gas. Low vacuum was used for sample visualization. The specimen was studied under magnification of 500X and 1000X. The sample was focused at the initial location then moved away quickly to a different spot to take images. This practice was to avoid surface damage of the starch granule by the electron beam. Images at 500x and 1000x are respectively shown in FIGS. 3 and 4. The particles formed aggregates, and the size of these particles varies from ~ 5 pm to ~ 20 pm estimated based on the scale bar shown in the images. The particles appear much fuller and more spherical, compared to those obtained in the absence of the blowing agent.

[0095] The sedimentation volume was determined as generally described above, modified as described below: 0.87 g of the sample after subsequent heat treatment was weighed into ajar, and propylene glycol was added to a total weight of 1.74 g to help predisperse the starch to avoid clumping. The sample was mixed with a glass rod, but there was not enough propylene glycol present to make a good paste. 20 g buffer was added, and the mixture was stirred with a glass rod for about 10 min to provide a lumpy suspension, then left overnight. The sample was then transferred to a tared graduated cylinder. The jar was rinsed with buffer multiple times, and all the liquid was recovered and transferred to the graduated cylinder to ensure complete transfer of the starch. Additional buffer was added to total weight of 100 g. The graduated cylinder was covered with parafilm and inverted a few times to mix the starch suspension; The graduated cylinder was placed on the bench and the swelling volume was recorded after 24 h. The suspension exhibited three phases in the graduated cylinder; a clear upper layer, a slightly cloudy middle layer, and a bottom layer of sedimented starch. The bottom phase occupied 25 ml_ and the bottom plus middle layer occupied 75 ml. in total. The sedimentation volume is determined based on the starch weight and the volume in the bottom phase to be about 28.7 mL/g.

[0096] Samples were taken from the middle and bottom layers for microscopic study. Samples were visualized under an Olympus BX51 microscope with a PAXcam 2+ camera and PAX it! Software under the bright field without polarized light. Approximately 6 drops sample were mixed with two drops of 0.02 N iodine solution. A drop of this mixture was added to a standard microscope slide and covered with a cover slip. The magnification is 200X for all the images collected. Images are shown in FIGS. 5 (bottom phase) and 6 (middle layer). The bottom layer contained larger starch particles, and the middle layer contained tiny particles. The large particles in the bottom phase are clumping and the individual particles appeared flat instead of round particles as observed under the SEM before hydration.

[0097] A portion of the spray-dried product (before heat treatment) was added to a graduated cylinder, and the cylinder was tapped gently on the table to pack the starch. 1.22 g of starch occupied a volume of 21 ml_, resulting in a bulk density of about 0.058 g/mL, which is significantly lower than the 0.238 g/mL value of a corresponding spray dried product made without blowing agent.

[0098] Accordingly, a starch dispersion at 3% solids in deionized water was spray-dried with ammonium bicarbonate as blowing agent. SEM demonstrated that most of the particles were in the range of 5-20 pm in size, and they appeared full, round and clustered. A thermal treatment was performed on the spray-dried product, which was sufficient to inhibit the starch particles and prevented them from disintegrating in water or buffer, even though no additional inhibiting agent was present. Compared to a corresponding produced without the blowing agent, this product has bigger particle size, lower bulk density. However, some collapse of particle shape was observed in the buffer.

Example 3 - Spray-drying of waxy corn starch in the presence of ammonium bicarbonate with acid inhibition

[0099] A native waxy corn starch was dispersed at 4% dry solids in pH 5.0 buffer to provide a dispersion having a total mass of 1000 g in a 2 L stainless steel beaker. The sample was heated at 95 °C with stirring for 30 minutes. The resulting cooked dispersion was allowed to cool to room temperature, and was brought back to 1000 g mass with deionized water. 15.1 g ammonium bicarbonate was added and the material was spray- dried as described above in Example 2. A portion of the spray-dried material was subjected to heat treatment - 85 °C overnight and 150 °C for five hours.

[0100] SEM images were collected as described above for the material before and after the additional heat treatment (FIGS. 7 and 8, respectively).

[0101] To determine sedimentation volume, 2.5 g (dry solid weight) of the heat-treated product was dispersed in RVA buffer with 1 % NaCI to a total weight of 50 g. 20 g of the resulting starch paste was transferred into a graduated cylinder with the same buffer, and the total weight of the starch slurry in the cylinder was adjusted to 100 g. The graduated cylinder was inverted a few times with parafilm covered to mix the slurry. The sedimentation volume was read after 24h. The sedimentation volume was determined to be 30 mL/g. The sedimented layer and the supernatant layer were analyzed by optical microscopy as described above in Example 2; FIG. 9 provides a 200x image of the supernatant layer and FIG. 10 provides a 200x image of the sedimented layer. Notably, the particles remained intact and swollen after being dispersed in buffer. The soluble amylopectin was low. The bulk density of the heat-treated material was determined as described above to be 0.050 g/mL.

[0102] A portion of the heat-treated material was dispersed in the RVA buffer with 1% NaCI at 5% solids. The sample quickly formed a paste. A reference starch was cooked in the same buffer at 5% solids. The cooking conditions were 95 °C, for 6 min with stirring and 20 min static). These samples were evaluated for viscosity on a rheometer from TA Instruments, equipped with a lower Peltier plate and an upper parallel plate (40 mm diameter). All the tests were carried out using the following procedure at 25 °C: Amplitude sweep test at 100 Rad/s from 0.1% to 100%; Frequency sweep from 100 Rad/s to 0.1 Rad/s; Flow curves at shear rates 0.01 to 100 s ¹. Viscosity data are shown in FIG. 11; the top trace is the reference starch and the middle trace is the experimental starch. [0103] Thus, hollow particles were obtained by spray drying cooked native maize starch from an acidic buffer in the presence of ammonium bicarbonate, followed by additional heat treatment. The spray dried product was low in bulk density (~ 0.05 g/mL) and particle sizes are in the range of 5-20 pm based on SEM images. The residual acid of the buffer in conjunction with the heat treatment was sufficient to inhibit the material such that particles remained intact and swollen after being dispersed in buffer, with a low soluble amylopectin background.

Example 4 - Spray-drying of dent corn starch in the presence of ammonium bicarbonate with acid inhibition

[0104] A native dent corn starch was treated in the same manner as described above in Example 3. SEM images were collected as described above for the material before and after the additional heat treatment (FIGS. 12 and 13, respectively). Sedimentation volume was determined as described above to be 24 mL/g. The sedimented layer and the supernatant layer were analyzed by optical microscopy as described above in Example 2; FIG. 14 provides a 200x image of the supernatant layer and FIG. 15 provides a 200x image of the sedimented layer. Notably, the particles remained intact and swollen after being dispersed in buffer. The bulk density of the heat-treated material was determined as described above to be 0.054 g/mL. Viscosity data are shown in FIG. 11; the bottom trace corresponds to this material.

[0105] Thus, hollow particles were obtained by spray drying cooked native maize starch from an acidic buffer in the presence of ammonium bicarbonate, followed by additional heat treatment. The spray dried product was low in bulk density (~ 0.05 g/mL) and particle sizes are in the range of 5-20 pm based on SEM images. The residual acid of the buffer in conjunction with the heat treatment was sufficient to inhibit the material such that particles remained intact and swollen after being dispersed in buffer.

Example 5 - Spray-drying of acid-thinned starch in the presence of ammonium bicarbonate and acid inhibiting agent

[0106] An acid-thinned corn starch (alkali fluidity 80 mL, as measured by European method A1550) was dispersed at 20% dry solids in pH 5.0 buffer to provide a dispersion having a total mass of 1000 g. The sample was heated at 95 °C with stirring for 10 minutes and without stirring for 20 minutes. The resulting cooked dispersion was allowed to cool to 80 °F, and was brought back was 500 g mass with deionized water. Ammonium bicarbonate (11 g) was added to the starch dispersion immediately before spray drying. A LabPlant™ spray dryer was used to spray dry the starch dispersion; settings were: fan, 40; inlet temperature, 230 °C; pump speed, 5 mL/min, reduced to 4 mL/min during the run. The feed suspension was maintained at The pump was primed and the nozzle cleaned with an initial flow of deionized water, then the feed tube was switched to the beaker containing the starch dispersion. The spray-dried starch was collected into a 150 mL aluminum weighing pan, and heated at 85 °C overnight. The oven temperature was raised to 150 °C and the heat treatment continued for 1, 3 and 5 hours for different portions of material.

[0107] SEM images were obtained as described above of the uncooked acid-thinned starch (FIG. 16, 500x; FIG. 17, 1000x) and of the spray-dried material before additional heat treatment (FIG. 18, 500x; FIG. 19, 1000x). The spray-dried material was expanded in size into globular particles.

[0108] The spray-dried samples after heat treatment were dispersed in the salted RVA buffer and the particle morphology was studied under the optical microscope with iodine staining. Images are shown in FIGS. 20-22 (1 h, 3h, 5h, respectively). The particles swell less in the 5 hour sample, consistent with its higher inhibition level. There was also visible dent starch dispersed in the spray-dried particles; dent starch is also observed in the feed acid- thinned starch, believed to be the result of damage to the starch during acid thinning.

[0109] Sedimentation volumes were determined. 2.5 g (dry solid weight) of heat-treated product (at 1, 3 and 5 hours) was dispersed in RVA buffer with 1% NaCI to a total weight of 50 g. 20 g of the starch paste was transferred into a graduated cylinder with the same buffer, and the total weight of the starch slurry in the cylinder was adjusted to 100 g. The graduated cylinder was inverted a few times with parafilm covered to mix the slurry. The sedimentation volume was read after 24 h. The supernatant from each cylinder was collected and the % solubles were determined. The measured sedimentation volumes were all about 25 ml_/g, but the solubles content decreased with heat treatment time (1 h, 39.9%;

3 h, 20.2%; 5 h, 14.0%), which is consistent with the prediction that longer heat treatment time increases inhibition level. The adjusted sedimentation volumes were 42, 31 and 29 mL/g respectively.

[0110] The viscosities of the heat-treated products as well as of a reference starch were measured at various degrees of solids (DS) in the RVA buffer plus 1% NaCI using a stress control (DHR-3) rheometer from TA Instruments, equipped with a lower Peltier plate and an upper parallel plate (40 mm diameter). In order to make the upper parallel plate geometry compatible with the DHR-3 rheometer, a drawdown rod and an adaptor were used. All the tests were carried out using the following procedure at 25 °C: Amplitude sweep test at 100 Rad/s from 0.1% to 100%; Frequency sweep from 100 Rad/s to 0.1 Rad/s; Flow curves at shear rates 0.01 to 100 s ¹. Data (in mPa-s) are presented in the Table below:

[0111] Thus, hollow particles were prepared by spray-drying acid-thinned starch with a blowing agent, with heating in the presence of residual acid providing inhibition. The solubles-corrected swelling volume and the degree of solubles were correlated.

Example 6 - Sprav-drvinq of waxy corn starch in the presence of ammonium bicarbonate with sodium trimetaphosphate (STMP) inhibition

[0112] A native waxy corn starch was dispersed at 3% dry solids or 4% dry solids in deionized water to provide a dispersion having a total mass of 750 g in 1 L stainless steel beakers. pH was adjusted to 11.5. The samples were heated at 95 °C with stirring for 10 minutes, followed by 30 minutes without stirring. The resulting cooked dispersions were allowed to cool to room temperature, and were brought back to 750 g mass with deionized water. 11.6 g ammonium bicarbonate (35% dry solids basis) was added to each sample, followed by 0.45 g STMP (1.5% w/w dry starch basis) to a 4% starch dispersion, 0.225 g STMP (0.75% w/w) to a 4% starch dispersion, and 0.1125 g STMP (0.5% w/w) to a 3% starch dispersion. A Buchi B-290 Mini Spray Dryer was used to spray dry the starch dispersion; settings were as follows: aspirator at 95%; pump at 5-6% (1.5 mL/min to 1.8 mL/min); pulse cleaning at 1/s; inlet temperature, 173 °C to 180 °C; and outlet temperature between 110 °C to 120 °C. The pump was primed and the nozzle cleaned with an initial flow of deionized water, then the feed tube was switched to the beaker containing the starch dispersion. The spray-dried starch was collected into a 150 mL aluminum weighing pan, and heated in an oven at 130 °C for 2 hours. After removal from the oven, the spray-dried material was allowed to cool.

[0113] SEM images were collected as described above for the 4% starch, 1.5% STMP material and for the 4% starch, 0.75% STMP material (FIGS. 23-25 and 26-28, respectively). [0114] To determine sedimentation volume, 4.0 g (dry solid weight) of the heat-treated product was dispersed in RVA buffer with 1% NaCI to a total weight of 100 g. 25 g of the resulting starch paste was transferred into a graduated cylinder with the same buffer, and the total weight of the starch slurry in the cylinder was adjusted to 100 g. The graduated cylinder was inverted a few times with parafilm covered to mix the slurry. The sedimentation volume was read after 24h. The sedimentation volume for the 4% (ds) starch, 1.5% STMP composition was determined to be 16 mL/g. The SV for the 4% (ds) starch with 0.75%

STMP was measured to be 18 mL/g, and the SV for the 3% (ds) starch with 0.5% STMP was measured to be 24 mL/g.

[0115] Samples were visualized under an Olympus BX51 microscope with a PAXcam 2+ camera and PAX it! Software under the bright field without polarized light. One volume of the 4% (ds), no heat treatment starch paste or 4% (ds) cooked starch paste in RVA buffer with 1% NaCI at pH 6.5 was diluted with an equal volume of the same buffer, and then mixed with a further volume of 0.02N iodine solution. A drop of this mixture is added to a standard microscope slide and covered with a cover slip. A magnification of 200X was used for all images collected. Images are shown in FIGS. 29-30. FIG. 29 provides an image of the 4% (ds), no heat treatment starch. FIG. 30 provides an image of 4% (ds), cooked, blown starch, showing larger particles and some apparent aggregation or co-location. The individual particles appeared generally flat rather than round as observed under the SEM before hydration.

[0116] Heat-treated, spray-dried material was dispersed in the RVA buffer with 1% NaCI in amounts to yield 1%, 2.5%, 5% mixtures of the 3% starch, 0.5% STMP material and a 7.5% mixture of the 4% starch, 1.5% STMP material. The rheological behavior of these samples was evaluated on a rheometer from TA Instruments. Higher concentration samples (7.5%) were tested with a parallel plate setup, with a lower Peltier plate and an upper parallel plate (40 mm diameter). A concentric cylinder or “cup-and-bob” system was used for samples of lower concentration (1%, 2.5% and 5%). All the tests were carried out using the following procedure at 25 °C: Amplitude sweep test at 1 Rad/s from 0.01% to 100%; Frequency sweep from 100 Rad/s to 0.1 Rad/s; Flow curves at shear rates 0.01 to 100 s-1.

[0117] Dynamic modulus behavior of the 7.5% mixture of the 4% starch, 1.5% STMP material is shown in FIG. 31. A linear viscoelastic region was detected in 0.01-2% strain range, and a strain of 0.1% was selected to run frequency sweep tests. Dynamic oscillatory data are shown in FIG. 32, where a slight increase in storage modulus (G’) and a sharp increase in loss modulus (G”) were seen with increasing frequency. The values of G’ were higher than those of G” at all frequencies, and no crossover of G’ and G” was observed. Thus, the 7.5% sample behaves as a weak physical gel with predominantly elastic gel-like behavior. Flow curves at shear rates from 1.0 to 100 s-1 for the 1%, 2.5% and 5% mixtures of the 4% starch, 1.5% STMP material (FIG. 33) and the 3% starch, 0.5% STMP material are shown in FIG. 33 and FIG. 34, respectively. In both cases, viscosity was seen to increase with increasing starch concentration, and the samples prepared at 1% exhibited Newtonian fluid behavior while, at higher concentrations, non-Newtonian behavior was observed.

[0118] Viscosity was measured as described above, and viscosity results are included in the product characterization Table below:

[0119] Thus, disc-like and hollow particles were obtained by spray drying cooked native waxy corn starch in a basic buffer in the presence of ammonium bicarbonate and STMP, followed by additional heat treatment. The spray dried product had particle sizes in the range of 5-20 pm based on SEM images.

[0120] Additional aspects and embodiments are provided by the enumerated embodiments below, which can be combined in any combination and in any number that is not logically or technically inconsistent.

Embodiment 1. A pregelatinized inhibited particulate starch product in the form of a plurality of particles of starch, wherein at least 50% of the particles are substantially hollow, the pregelatinized inhibited particulate starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

Embodiment 2. The pregelatinized inhibited particulate starch product according to embodiment 1 , wherein at least 60% of the particles are substantially hollow, e.g., at least 70% of the particles or substantially hollow. Embodiment 3. The pregelatinized inhibited particulate starch product according to embodiment 1 , wherein at least 80%, e.g., at least 85% or at least 90% of the particles are substantially hollow.

Embodiment 4. The pregelatinized inhibited particulate starch product according to any of embodiments 1-3, wherein at least 50% (e.g., at least 60% or at least 70%) of the particles have an inner void having a volume that is at least 20% of a volume of the particle.

Embodiment 5. The pregelatinized inhibited particulate starch product according to any of embodiments 1-3, wherein at least 80% (e.g., at least 85% or at least 90%) of the particles have an inner void having a volume that is at least 20% of a volume of the particle.

Embodiment 6. The pregelatinized inhibited particulate starch product according to embodiment 4 or embodiment 5, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an inner void having a volume that is in the range of 20-90% (e.g., 20-80%, or 20-70%, or 20-60%) of the volume of the particle

Embodiment 7. The pregelatinized inhibited particulate starch product according to any of embodiments 1-3, wherein at least 50% (e.g., at least 60% or at least 70%) of the particles have an inner void having a volume that is at least 30% of a volume of the particle.

Embodiment 8. The pregelatinized inhibited particulate starch product according to any of embodiments 1-3, wherein at least 80% (e.g., at least 85% or at least 90%) of the particles have an inner void having a volume that is at least 30% of a volume of the particle.

Embodiment 9. The pregelatinized inhibited particulate starch product according to embodiment 7 or embodiment 8, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an inner void having a volume that is in the range of 30-90% (e.g., 30-80%, or 30-70%, or 30-60%) of the volume of the particle

Embodiment 10. The pregelatinized inhibited particulate starch product according to any of embodiments 1-3, wherein at least 50% (e.g., at least 60% or at least 70%) of the particles have an inner void having a volume that is at least 40% of a volume of the particle. Embodiment 11. The pregelatinized inhibited particulate starch product according to any of embodiments 1-3, wherein at least 80% (e.g., at least 85% or at least 90%) of the particles have an inner void having a volume that is at least 40% of a volume of the particle.

Embodiment 12. The pregelatinized inhibited particulate starch product according to embodiment 10 or embodiment 11, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an inner void having a volume that is in the range of 40-90% (e.g., 40-80%, or 40-70%) of the volume of the particle.

Embodiment 13. The pregelatinized inhibited particulate granular starch according to any of embodiments 1-12, wherein at least 50% (e.g., at least 60%, or at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 1 micron, and an opening having an area of at least 1 square micron.

Embodiment 14. The pregelatinized inhibited particulate granular starch according to any of embodiments 1-12, wherein at least 80% (e.g., at least 85%, or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least

1 micron, and an opening having an area of at least 1 square micron.

Embodiment 15. The pregelatinized inhibited particulate starch product according to embodiment 13 or embodiment 14, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an inner void having a depth in the range of 1-50 microns, e.g., 1-40 microns, or 1-30 microns or 1-20 microns.

Embodiment 16. The pregelatinized inhibited particulate starch product according to any of embodiments 13-15, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an opening having an area in the range of 1-2000 square microns, e.g., in the range of 1-1500 square microns, or 1-1000 square microns, or 1-750 square microns, or 1-500 square microns, or 1-250 square microns.

Embodiment 17. The pregelatinized inhibited particulate granular starch according to any of embodiments 1-12, wherein at least 50% (e.g., at least 60%, or at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least

2 microns, and an opening having an area of at least 4 square microns. Embodiment 18. The pregelatinized inhibited particulate granular starch according to any of embodiments 1-12, wherein at least 80% (e.g., at least 85%, or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 2 microns, and an opening having an area of at least 4 square microns.

Embodiment 19. The pregelatinized inhibited particulate starch product according to embodiment 17 or embodiment 18, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an inner void having a depth in the range of 2-50 microns, e.g., 2-40 microns, or 2-30 microns or 2-20 microns.

Embodiment 20. The pregelatinized inhibited particulate starch product according to any of embodiments 17-19, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an opening having an area in the range of 4-2000 square microns, e.g., in the range of 4-1500 square microns, or 4-1000 square microns, or 4-750 square microns, or 4-500 square microns, or 4-250 square microns.

Embodiment 21. The pregelatinized inhibited particulate granular starch according to any of embodiments 1-12, wherein at least 50% (e.g., at least 60%, or at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 4 microns, and an opening having an area of at least 16 square microns.

Embodiment 22. The pregelatinized inhibited particulate granular starch according to any of embodiments 1-12, wherein at least 80% (e.g., at least 85%, or at least 90%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 4 microns, and an opening having an area of at least 16 square microns.

Embodiment 23. The pregelatinized inhibited particulate starch product according to embodiment 21 or embodiment 22, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an inner void having a depth in the range of 4-50 microns, e.g., 4-40 microns, or 4-30 microns or 4-20 microns.

Embodiment 24. The pregelatinized inhibited particulate starch product according to any of embodiments 21-23, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an opening having an area in the range of 16-2000 square microns, e.g., in the range of 16-1500 square microns, or 16-1000 square microns, or 16-750 square microns, or 16-500 square microns, or 16-250 square microns.

Embodiment 25. The pregelatinized inhibited particulate starch according to any of embodiments 1-24 wherein at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles are rounded in shape, e.g., substantially spherical, substantially fractionally spherical, substantially spheroidal (e.g., oblate or prolate), substantially fractionally spheroidal, substantially ellipsoidal, or substantially partially ellipsoidal.

Embodiment 26. The pregelatinized inhibited particulate starch according to any of embodiments 1-25, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80% at least 85% or at least 90%) of the particles have a maximum aspect ratio of 3, e.g., 2.5, 2, or 1.5.

Embodiment 27. The pregelatinized inhibited particulate starch product according to any of embodiments 1-26, having a solubles-corrected sedimentation volume in the range of 20-80 mL/g, e.g., 30-80 mL/g, or 40-80 mL/g or 50-80 mL/g.

Embodiment 28. The pregelatinized inhibited particulate starch product according to any of embodiments 1-26, having a solubles-corrected sedimentation volume in the range of 15-70 mL/g, e.g., 20-70 mL/g, or 30-70 mL/g, or 40-70 mL/g or 50-70 mL/g.

Embodiment 29. The pregelatinized inhibited particulate starch product according to any of embodiments 1-26, having a solubles-corrected sedimentation volume in the range of 15-60 mL/g, e.g., 20-60 mL/g, or 30-60 mL/g, or 40-60 mL/g.

Embodiment 30. The pregelatinized inhibited particulate starch product according to any of embodiments 1-26, having a solubles-corrected sedimentation volume in the range of 15-50 mL/g, e.g., 20-50 mL/g, or 30-50 mL/g.

Embodiment 31. The pregelatinized inhibited particulate starch product according to any of embodiments 1-26, having a solubles-corrected sedimentation volume in the range of 15-40 mL/g, e.g., 20-40 mL/g.

Embodiment 32. The inhibited particulate starch product of any of embodiments 1 -31 , wherein the inhibited particulate starch product is a chemically-modified inhibited starch (for example, inhibited via crosslinking, e.g., with acrolein, phosphate, adipate or epichlorohydrin).

Embodiment 33. The pregelatinized inhibited particulate starch product of any of embodiments 1-31, wherein the inhibited particulate starch product is inhibited by heat- treatment.

Embodiment 34. The pregelatinized inhibited particulate starch product of embodiment 33, wherein the inhibited particulate starch product is inhibited by heat-treatment in the presence of an acid.

Embodiment 35. The pregelatinized inhibited particulate starch product of embodiment 33, wherein the inhibited particulate starch product is inhibited by heat-treatment in the presence of a base.

Embodiment 36. The pregelatinized inhibited particulate starch product of any of embodiments 1-35, wherein the starch is an acid-thinned starch.

Embodiment 37. The pregelatinized inhibited particulate starch product of any of embodiments 1-36, wherein the pregelatinized inhibited particulate starch product is a maize starch.

Embodiment 38. The pregelatinized inhibited particulate starch product of any of embodiments 1-36, wherein the pregelatinized inhibited particulate starch product is a tapioca starch.

Embodiment 39. The pregelatinized inhibited particulate starch product of any of embodiments 1-36, wherein the pregelatinized inhibited particulate starch product is a wheat starch, a rice starch, a potato starch, potato starch, an oat starch, a barley starch or a sago starch.

Embodiment 40. The pregelatinized inhibited particulate starch product of any of embodiments 1-39, wherein the pregelatinized inhibited particulate starch product wherein the inhibited particulate starch product is not hydroxypropylated. Embodiment 41. The pregelatinized inhibited particulate starch product of any of embodiments 1-40, wherein the pregelatinized inhibited particulate starch product is not acetylated.

Embodiment 42. The pregelatinized inhibited particulate starch product of any of embodiments 1-41, wherein the pregelatinized inhibited particulate starch product has substantially no fatty acid residues.

Embodiment 43. The pregelatinized inhibited particulate starch product of any of embodiments 1-42, wherein the pregelatinized inhibited particulate starch product is not carboxy methyl ated .

Embodiment 44. The pregelatinized inhibited particulate starch product of any of embodiments 1-43, wherein the pregelatinized inhibited particulate starch product is not hydroxyethylated.

Embodiment 45. The pregelatinized inhibited particulate starch product of any of embodiments 1-44, wherein the pregelatinized inhibited particulate starch product is not phosphated.

Embodiment 46. The pregelatinized inhibited particulate starch product of any of embodiments 1-45, wherein the pregelatinized inhibited particulate starch product is not succinated (e.g., not octenylsuccinated).

Embodiment 47. The pregelatinized inhibited particulate starch product of any of embodiments 1-46, wherein the pregelatinized inhibited particulate starch product is not cationic or zwitterionic.

Embodiment 48. The pregelatinized inhibited particulate starch product of any of embodiments 1-47, wherein the pregelatinized inhibited particulate starch product is not crosslinked with phosphate.

Embodiment 49. The pregelatinized inhibited particulate starch product of any of embodiments 1-47, wherein the pregelatinized inhibited particulate starch product is crosslinked with phosphate. Embodiment 50. The pregelatinized inhibited particulate starch product of any of embodiments 1-49, wherein the pregelatinized inhibited particulate starch product is not crosslinked with adipate.

Embodiment 51. The pregelatinized inhibited particulate starch product of any of embodiments 1-50, wherein the pregelatinized inhibited particulate starch product is not crosslinked with epichlorohydrin.

Embodiment 52. The pregelatinized inhibited particulate starch product of any of embodiments 1-51, wherein the pregelatinized inhibited particulate starch product is not crosslinked with acrolein.

Embodiment 53. The pregelatinized inhibited particulate starch product of any of embodiments 1-52, wherein the pregelatinized inhibited particulate starch product is not bleached or oxidized with peroxide or hypochlorite.

Embodiment 54. The pregelatinized inhibited particulate starch product of any of embodiments 1-53, wherein the pregelatinized inhibited particulate starch product has a viscosity at 5% solids in the range of 50-1000 cP in an RVA test.

Embodiment 55. The pregelatinized inhibited particulate starch product of any of embodiments 1-53, wherein the pregelatinized inhibited particulate starch product has a viscosity in the range of 50-850 cP, or 50-700 cP, or 50-500 cP, or 50-400 cP, or 50-300 cP, or 50-200 cP, or 100-1000 cP, or 100-850 cP, or 100-700 cP, or 100-500 cP, or 100-400 cP, or 100-300 cP, or 200-1000 cP, or 200-850 cP, or 200-700 cP, or 200-500 cP, or 400-1000 cP, or 400-850 cP, or 400-700 cP, or 600-1000 cP, or 600-850 cP in an RVA test at 5% solids.

Embodiment 56. The pregelatinized inhibited particulate starch product of any of embodiments 1-55, wherein the pregelatinized inhibited particulate starch has a relatively low color, i.e., a Yellowness Index of no more than 10.

Embodiment 57. The pregelatinized inhibited particulate starch product of any of embodiments 1-55, wherein the pregelatinized inhibited particulate starch has a relatively low color, i.e., a Yellowness Index of 3-10 or 5-10. Embodiment 58. The pregelatinized inhibited particulate starch product of any of embodiments 1-55, wherein the pregelatinized inhibited particulate starch has an especially low color, i.e., a Yellowness Index of no more than 8.

Embodiment 59. The pregelatinized inhibited particulate starch product of any of embodiments 1-58, wherein the pregelatinized inhibited particulate starch has no more than 20% solubles.

Embodiment 60. The pregelatinized inhibited particulate starch product of any of embodiments 1-58, wherein the pregelatinized inhibited particulate starch has no more than 15% solubles, or no more than 12% solubles, or no more than 10% solubles.

Embodiment 61. The pregelatinized inhibited particulate starch product of any of embodiments 1-60, wherein particles of the pregelatinized inhibited particulate starch product are agglomerated into multi-particle agglomerates.

Embodiment 62. The pregelatinized inhibited particulate starch product of any of embodiments 1-61, having a bulk density in the range of 0.03 to 0.4 g/mL, e.g., 0.05 to 0.4 g/mL, or 0.1 to 0.4 g/mL, or 0.15 to 0.4 g/mL, or 0.03 to 0.35 g/mL, or 0.05 to 0.35 g/mL, or 0.1 to 0.35 g/mL, or 0.15 to 0.35 g/mL, or 0.03 to 0.3 g/mL, or 0.05 to 0.3 g/mL, or 0.1 to 0.3 g/mL, or 0.15 to 0.3 g/mL.

Embodiment 63. A method for making a pregelatinized inhibited particulate starch product, the method comprising providing an aqueous dispersion of a gelatinized starch, the starch dispersion including a blowing agent; spray-drying the aqueous dispersion under conditions to activate the blowing agent to provide a spray-dried particulate; and heating the spray-dried particulate to inhibit the starch, to provide a starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

Embodiment 64. The method according to embodiment 63, wherein the blowing agent is a compound that reacts to evolve a gas, e.g., upon heating during the spray-drying.

Embodiment 65. The method according to embodiment 63, wherein the blowing agent is a bicarbonate, e.g., ammonium bicarbonate, sodium bicarbonate. Embodiment 66. The method according to embodiment 63, wherein the blowing agent is a material that evaporates upon the spray drying.

Embodiment 67. The method according to embodiment 63, wherein the blowing agent is carbon dioxide.

Embodiment 68. The method according to any of embodiments 63-67, wherein the starch dispersion includes a crosslinking agent, e.g., STMP or adipate, and wherein the heating of the spray-dried particulate crosslinks the starch with the crosslinking agent.

Embodiment 69. The method according to any of embodiments 63-67, wherein the starch dispersion includes an acid, the acid causing the inhibition of the starch during the heating of the spray-dried particulate.

Embodiment 70. The method according to any of embodiments 63-67, wherein the starch dispersion includes a base, the base causing the inhibition of the starch during the heating of the spray-dried particulate.

Embodiment 71. The method according to embodiment 69 or embodiment 70, wherein the acid or base is the blowing agent or a degradation product thereof.

Embodiment 72. The method of any of embodiments 63-71 , wherein the heat treatment is performed at a temperature in the range of 100-200 °C, e.g., 120-200 °C, or 120-180 °C, or 120-160 °C, or 120-140 °C, or 140-200 °C, or 140-180 °C, or 140-160 °C, or 160-200 °C, or 160-180 °C, or 180-200 °C.

Embodiment 73. The method of any of embodiments 63-71 , wherein the heat treatment is performed for a time in the range of 20 seconds to 20 hours, e.g., in the range of 10 minutes to 2 hours.

Embodiment 74. The method of any of embodiments 63-73, wherein the heat treatment is performed as part of the spray drying.

Embodiment 75. The method according to any of embodiments 63-74, wherein in the starch product at least 50% of the particles are substantially hollow. Embodiment 76. The method according to any of embodiments 63-75, wherein the starch product is as further described according to any of embodiments 2-62.

Embodiment 77. A pregelatinized inhibited particulate starch product prepared by a process according to any of embodiments 63-76.

Embodiment 78. The pregelatinized inhibited particulate starch product of embodiment 77, wherein in the starch product at least 50% of the particles are substantially hollow.

Embodiment 79. The pregelatinized inhibited particulate starch product of embodiment 77 or embodiment 78, as further described in any of embodiments 2-62.

Embodiment 80. A method for making a food product comprising providing a pregelatinized inhibited particulate starch product of any of embodiments 1-62, 77 and 78 and including the pregelatinized inhibited particulate starch product in the food product.

Embodiment 81. The method of embodiment 80, wherein the including the pregelatinized inhibited particulate starch product in the food product includes cooking the pregelatinized inhibited particulate starch product in the food product.

Embodiment 82. The method of embodiment 80, wherein the including the pregelatinized inhibited particulate starch product in the food product includes dispersing the pregelatinized inhibited particulate starch product in the food product without cooking.

Embodiment 83. A food product comprising the pregelatinized inhibited particulate starch product according to any of embodiments 1-62, 77 and 78.

Embodiment 84. The method or food product according to any of embodiments 80-83, wherein the food product is a gravy, a sauce, a soup, or a stew.

Embodiment 85. The method or food product according to any of embodiments 80-83, wherein the food product is a dressing.

Embodiment 86. The method or food product according to any of embodiments 80-83, wherein the food product is a dairy product, e.g. a yogurt. Embodiment 87. The method or food product of any of embodiments 80-83, wherein the food product is a tomato-based product, a gravy, a sauce such as a white sauce or a cheese sauce, a soup, a pudding, a salad dressing (e.g., pourable or spoonable), a yogurt, a sour cream, a pudding, a custard, a cheese product, a fruit filling or topping, a cream filling or topping, a syrup (e g., a lite syrup), a beverage (e g., a dairy-based beverage), a glaze, a condiment, a confectionary, a pasta, a frozen food, a cereal, or a soup.

Embodiment 88. The method or food product of any of embodiments 80-83, wherein 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.

Embodiment 89. The method or food product of any of embodiments 80-83, wherein the food product is selected from 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.

Embodiment 90. The method or food product of any of embodiments 80-83, wherein the food product is selected from high acid foods (pH <3.7) such as fruit-based pie fillings, baby foods, and the like; acid foods (pH 3.7-4.5) such as tomato-based products; low acid foods (pH >4.5) 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.

Embodiment 91. The method or food product of any of embodiments 80-83, wherein the food product is 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.

Embodiment 92. The method or food product of any of embodiments 80-83, wherein the food product is a medical food. Embodiment 93. The method or food product of any of embodiments 80-83, wherein the food product is a pet food.

Embodiment 94. A dry mix comprising an inhibited porous starch product of any of embodiments 1-62, 77 and 78, in admixture with one or more additional dry food ingredients.

Embodiment 95. The dry mix of embodiment 94, wherein the dry mix is a dry mix for preparing a product selected from baked goods, gravies, sauces, puddings, baby foods, hot cereals; or is a dry mix for predusting foods prior to batter cooking and frying.

Claims

What is claimed is:

1. A pregelatinized inhibited particulate starch product in the form of a plurality of particles of starch, wherein at least 50% of the particles are substantially hollow, the pregelatinized inhibited particulate starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

2. The pregelatinized inhibited particulate starch product according to claim 1, wherein at least 80%, e.g., at least 85% or at least 90% of the particles are substantially hollow.

3. The pregelatinized inhibited particulate starch product according to any of claims 1-2, wherein at least 50% (e.g., at least 60% or at least 70%) of the particles have an inner void having a volume that is at least 30% of a volume of the particle.

4. The pregelatinized inhibited particulate granular starch according to any of claims 1- 3, wherein at least 50% (e.g., at least 60%, or at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 1 micron, and an opening having an area of at least 1 square micron.

5. The pregelatinized inhibited particulate starch product according to claim 4, wherein at least 50% (e.g., at least 60%, at least 70%, at least 80%, at least 85% or at least 90%) of the particles have an opening having an area in the range of 1-2000 square microns, e.g., in the range of 1-1500 square microns, or 1-1000 square microns, or 1-750 square microns, or 1-500 square microns, or 1-250 square microns.

6. The pregelatinized inhibited particulate granular starch according to any of claims 1- 5, wherein at least 50% (e.g., at least 60%, or at least 70%) of the particles have an outer shell defining an inner void, the inner void having a depth of at least 4 microns, and an opening having an area of at least 16 square microns.

7. The pregelatinized inhibited particulate starch product according to any of claims 1-6, having a solubles-corrected sedimentation volume in the range of 20-80 ml_/g, e.g., 30-80 mL/g, or 40-80 ml_/g or 50-80 mL/g.

8. The pregelatinized inhibited particulate starch product according to any of claims 1-7, having a solubles-corrected sedimentation volume in the range of 15-40 ml_/g, e.g., 20-40 mL/g.

9. The inhibited particulate starch product of any of claims 1-8, wherein the inhibited particulate starch product is a chemically-modified inhibited starch (for example, inhibited via crosslinking, e.g., with acrolein, phosphate, adipate or epichlorohydrin).

10. The pregelatinized inhibited particulate starch product of any of claims 1-8, wherein the inhibited particulate starch product is inhibited by heat-treatment.

11. The pregelatinized inhibited particulate starch product of claim 10, wherein the inhibited particulate starch product is inhibited by heat-treatment in the presence of an acid.

12. The pregelatinized inhibited particulate starch product of any of claims 1-11, wherein the pregelatinized inhibited particulate starch product is a maize starch or a tapioca starch.

13. The pregelatinized inhibited particulate starch product of any of claims 1-12, wherein the pregelatinized inhibited particulate starch product wherein the inhibited particulate starch product is not hydroxypropylated, is not acetylated, has substantially no fatty acid residues, is not carboxymethylated, is not hydroxyethylated, is not phosphate, is not succinated (e.g., not octenylsuccinated), is not cationic or zwitterionic, is not crosslinked with phosphate, is not crosslinked with adipate, is not crosslinked with epichlorohydrin, and is not crosslinked with acrolein.

14. The pregelatinized inhibited particulate starch product of any of claims 1-13, wherein the pregelatinized inhibited particulate starch product has a viscosity at 5% solids in the range of 50-1000 cP in an RVA test.

15. The pregelatinized inhibited particulate starch product of any of claims 1-14, wherein the pregelatinized inhibited particulate starch has no more than 20% solubles.

16. The pregelatinized inhibited particulate starch product of any of claims 1-15, having a bulk density in the range of 0.03 to 0.4 g/mL, e.g., 0.05 to 0.4 g/mL, or 0.1 to 0.4 g/mL, or 0.15 to 0.4 g/mL, or 0.03 to 0.35 g/mL, or 0.05 to 0.35 g/mL, or 0.1 to 0.35 g/mL, or 0.15 to 0.35 g/mL, or 0.03 to 0.3 g/mL, or 0.05 to 0.3 g/mL, or 0.1 to 0.3 g/mL, or 0.15 to 0.3 g/mL.

17. A method for making a pregelatinized inhibited particulate starch product, the method comprising providing an aqueous dispersion of a gelatinized starch, the starch dispersion including a blowing agent; spray-drying the aqueous dispersion under conditions to activate the blowing agent to provide a spray-dried particulate; and heating the spray-dried particulate to inhibit the starch, to provide a starch product having a solubles-corrected sedimentation volume in the range of 15-80 mL/g.

18. The method according to claim 17, wherein the blowing agent is a compound that reacts to evolve a gas, e.g., upon heating during the spray-drying.

19. The method according to claim 17, wherein the blowing agent is a material that evaporates upon the spray drying.

20. The method according to any of claims 17-19, wherein the starch dispersion includes a crosslinking agent, e.g., STMP or adipate, and wherein the heating of the spray-dried particulate crosslinks the starch with the crosslinking agent.

21. The method according to any of claims 17-19, wherein the starch dispersion includes an acid, the acid causing the inhibition of the starch during the heating of the spray-dried particulate.

22. The method of any of claims 17-21, wherein the heat treatment is performed at a temperature in the range of 100-200 °C, e.g., 120-200 °C, or 120-180 °C, or 120-160 °C, or 120-140 °C, or 140-200 °C, or 140-180 °C, or 140-160 °C, or 160-200 °C, or 160-180 °C, or 180-200 °C.

23. A pregelatinized inhibited particulate starch product prepared by a process according to any of claims 17-22.

24. A method for making a food product comprising providing a pregelatinized inhibited particulate starch product of any of claims 1-16 and 23 and including the pregelatinized inhibited particulate starch product in the food product.

25. A food product comprising the pregelatinized inhibited particulate starch product according to any of claims 1-16 and 23.

26. The method or food product according to claim 24 or claim 25, wherein the food product comprises one or more of a gravy, a sauce, a soup, or a stew; a dressing; a dairy product, e.g. a yogurt; a tomato-based product, a gravy, a sauce such as a white sauce or a cheese sauce, a soup, a pudding, a salad dressing (e.g., pourable or spoonable), a yogurt, a sour cream, a pudding, a custard, a cheese product, a fruit filling or topping, a cream filling or topping, a syrup (e.g., a lite syrup), a beverage (e.g., a dairy-based beverage), a glaze, a condiment, a confectionary, a pasta, a frozen food, a cereal, or a soup; a bread, a pastry, a pie crust, a donut, a cake, a biscuit, a cookie, a cracker, or a muffin; or a food product selected from 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. a food product selected from high acid foods (pH <3.7) such as fruit-based pie fillings, baby foods, and the like; acid foods (pH 3.7-4.5) such as tomato-based products; low acid foods (pH >4.5) 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; a food product 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. a medical food; and/or a pet food.