Octenyl succinylated waxy tapioca starch, emulsions containing same and methods for producing same

Abstract

The present disclosure relates generally to starch products. More specifically, the present disclosure relates to octenyl succinylate modified uninhibited waxy tapioca starches, emulsions containing them, foods containing such emulsions, and methods of making such compositions. In one aspect, the present disclosure provides uninhibited waxy tapioca starches having an amylopectin content in the range of 90-100% and a degree of octenyl succinylation of at least 1.0% by weight on a dry solids basis. The starch can be provided in a pre-gelatinized form. Other aspects of the present disclosure include emulsions stabilized by such starches, as well as foods, beverages, personal care compositions, nutraceutical compositions, and pharmaceutical compositions containing them.

Description

[Technical field]

[0001] The present disclosure relates generally to starch products. More specifically, the present disclosure relates to octenyl succinylate modified uninhibited waxy tapioca starch, emulsions containing them, food products containing such emulsions, and methods of making such compositions. [Background technology]

[0002] Commercially available high molecular weight heated starch emulsifiers, such as those used in salad dressings, tend to gel upon retrogradation when used in various food systems. Such gel formation is undesirable as it can cause changes in the sensory properties of the food, loss of emulsion stability, and generally shorten the shelf life of the food. These gels are particularly problematic in formulations that require refrigerated storage.

[0003] One traditional method of providing a starch emulsifier is to modify corn starch with octenyl succinic anhydride, which adds octenyl succinate groups to the starch. This provides some protection against retrogradation, but still makes the starch susceptible to gel formation under refrigerated conditions. This is also true when waxy corn starch is used. Waxy corn starch does not contain amylose, which degenerates quickly to form a hard gel, but amylopectin can slowly recombine to form a gel. This is a common problem with emulsions based on octenyl succinylated waxy corn starch.

[0004] There remains a need for low temperature stable emulsifying starch products.

[0005] Summary of the Invention One aspect of the present invention is Amylopectin content ranging from 90 to 100%, and having a degree of octenylsuccinylation of at least 1.0% by weight based on dry solids; Where: Starch is not inhibited, The starch is waxy tapioca starch that is pregelatinized.

[0006] Another aspect of the present invention is a method for producing a Amylopectin content ranging from 90 to 100%, and having a degree of octenylsuccinylation of at least 1.0% by weight based on dry solids; Where: The starch is uninhibited waxy tapioca starch.

[0007] Another aspect of the present disclosure is an emulsion comprising a hydrophobic phase emulsified with an aqueous phase and stabilized by gelatinized starch that is a gelatinization product of waxy tapioca starch, the waxy tapioca starch having an amylopectin content in the range of 90-100% and a degree of octenylsuccinylation in the range of at least 1.0% by weight on a dry solids basis, the starch being uninhibited.

[0008] Another aspect of the present disclosure is a method of making an emulsion, comprising mixing a hydrophobic phase, an aqueous phase, and waxy tapioca starch as described herein under conditions sufficient to form an emulsion (e.g., under shear).

[0009] Another aspect of the present disclosure is a food, beverage, personal care composition, nutraceutical composition, or pharmaceutical composition comprising the emulsion described herein.

[0010] Other aspects of the present disclosure will become apparent in light of the present disclosure. [Brief description of the drawings]

[0011] [Figure 1] 1 is a micrograph of waxy tapioca starch and waxy corn starch. [Diagram 2] 1 is an RVA curve comparing a thinned waxy tapioca starch of the present disclosure with a comparative waxy corn starch and a comparative non-waxy tapioca starch. [Diagram 3]1 is an RVA curve comparing a waxy tapioca starch of the present disclosure with a comparative waxy corn starch and a comparative non-waxy tapioca starch. [Figure 4] 1 is a plot of droplet size distribution of emulsions made with waxy tapioca starch of the present disclosure and a comparative waxy corn starch. [Diagram 5] 1 is a photograph of emulsions made with waxy tapioca starch of the present disclosure and comparative waxy corn starch after refrigerated storage. [Figure 6] 1 is a light microscope image of a non-gelatinized waxy tapioca starch of the present invention, a pregelatinized waxy tapioca starch of the present invention, a comparative non-gelatinized waxy corn starch, and a comparative pregelatinized waxy corn starch. [Figure 7] 1 is a photograph of a waxy tapioca starch of the present disclosure and a comparative waxy corn starch before and after a freeze-thaw process. [Figure 8] 1 is a micrograph of an emulsion made without emulsifying starch, an emulsion containing waxy tapioca starch of the present disclosure, and a comparative emulsion containing waxy corn starch. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] As previously mentioned, emulsions based on uninhibited octenyl succinylated waxy corn starch as an emulsifier exhibit poor refrigeration stability over time due to retrogradation of the amylopectin and formation of a set gel. This is particularly problematic in refrigerated food and beverage products such as salad dressings. The present inventors have found that uninhibited octenyl succinylated waxy tapioca starch is as effective as an emulsifier as uninhibited waxy corn starch, but is unexpectedly much more cold stable.

[0013] Thus, one aspect of the invention is a waxy tapioca starch having an amylopectin content in the range of 90-100% and a degree of octenylsuccinylation of at least 1.0% by weight on a dry solids basis, which starch is uninhibited and which starch is pregelatinized. As described herein, such a product can be used to form emulsions without cooking.

[0014] In this aspect of the disclosure, the waxy tapioca starch is pregelatinized. As will be appreciated by those skilled in the art, pregelatinization is essentially a pre-cooking treatment of starch that disrupts the semi-crystalline structure of native starch particles, thereby eliminating the need for subsequent high temperature treatment to impart viscosity to foods. As used herein, a "pregelatinized" starch is one in which 25% or less of its granules are birefringent, i.e., exhibit a so-called "Maltese cross" of high absorbance through the granule when viewed under a polarized microscope. For example, in certain embodiments, 10% or less, 5% or less, or 2% or less of the granules of the pregelatinized starch exhibit birefringence. As will be appreciated by those skilled in the art, there are numerous methods of cooking starch to pregelatinize it, including, for example, jet cooking, drum drying, and spray cooking (optionally in combination with agglomeration). Waxy tapioca starch can be pregelatinized after octenyl succinylation, or pregelatinized waxy tapioca starch can be used as a feed for octenyl succinylation.

[0015] Another aspect of the present disclosure is waxy tapioca starch having an amylopectin content in the range of 90-100% and a degree of octenyl succinylation of at least 1.0% by weight on a dry solids basis, wherein the starch is not inhibited. Such starches may, in some embodiments, be non-gelatinized. As described herein, such non-gelatinized starch products may be used in making emulsions in a process in which the starch is heated and gelatinized.

[0016] The starch of the present disclosure is waxy tapioca starch. Those skilled in the art will appreciate that various native starches vary in the relative amounts of the two major components of starch polysaccharides: amylose (a linear, α-1,4 linked polyglucoside) and amylopectin (a branched α-1,4 linked polyglucoside with α-1,6 linked branch points). So-called "waxy" starches (as that term is used herein) contain at least 90% amylopectin (i.e., the total amount of amylose and amylopectin) by weight. In various embodiments, waxy tapioca starches described elsewhere herein have an amylopectin content ranging from 95-100% by weight. In various embodiments, waxy tapioca starches described elsewhere herein have an amylopectin content of at least 99% by weight, or at least 99.9% by weight. Due to its high amylopectin content, waxy starch has different properties than non-waxy starch, such as being more viscous and able to form a paste that stays cohesive for longer.

[0017] Those skilled in the art can distinguish between waxy tapioca starch and starches of different plant sources, for example, by microscopic examination and comparison with standards. Those skilled in the art can, for example, observe the starch material under a microscope, optionally stain with iodide, and use the size and shape of the observed granules to determine the type of starch. For example, photomicrographs of waxy corn starch and waxy tapioca starch are shown in FIG. 1. As shown in the figure, the granules of waxy corn starch are generally polygonal in shape, while the granules of waxy tapioca starch are more rounded in shape. Staining can be used to distinguish waxy tapioca starch from non-waxy tapioca starch, with waxy material appearing brown when stained with iodine and non-waxy material appearing blue. As those skilled in the art can appreciate, different types of starch from different sources can have different textures and rheological properties and therefore may be desirable to use in different food applications.

[0018] The inventors have noticed a difference in branch length distribution between octenyl succinylated waxy tapioca starch and octenyl succinylated waxy corn starch. As one skilled in the art will appreciate, amylopectin has a comb-like structure, with short branches connected to a long backbone. The inventors have noted that the distribution of the lengths of these branches can have a significant effect on performance. Without being bound by theory, the inventors hypothesize that this difference in branch length distribution may contribute to the improved refrigerated storage stability observed in the waxy tapioca starch of the present disclosure. In various embodiments, the waxy tapioca starch described elsewhere herein has a branch length ratio (DP6-12) / (DP13-24) of at least 0.470, such as at least 0.475, where DP6-12 is a distribution of short chain branches having chain lengths from 6 to 12 and DP13-24 is a distribution of short chain branches having chain lengths from 13 to 24.

[0019] To measure the branch length distribution, samples are debranched with isoamylase (i.e., cleaving the 1,6-α glucosyl bonds that connect the branches to the 1,4-α linked backbone) and then the debranched samples are analyzed by chromatography. Waxy tapioca starch samples (20 mg on a dry basis) are mixed with 10 mL of acetate buffer (0.01 M, pH 4) and then heated in a boiling water bath for 1 h. After cooling to 50 °C, the gelatinized starch is branched by adding 20 μL of isoamylase (Megazyme, Wicklow, Ireland). Starch branching is continued overnight (≥12 h) and then the sample is heated in a boiling water bath for 30 min to inactivate the enzyme. After cooling to room temperature, 1–1.5 mL of sample is passed through a 45 μm filter and injected into an AS-DV autosampler (Dionex ICS-3000, Dionex, Sunnyvale, CA) of an HPAEC equipped with a pulsed amperometric detector and a CarboPac® PA1 analytical column. The sample is eluted with a gradient program of 40% eluent B at 0 min, 50% at 2 min, 60% at 10 min, and 80% at 40 min. Here, eluent A is 100 mM aqueous sodium hydroxide, and eluent B is 150 mM aqueous sodium hydroxide containing 500 mM sodium acetate. During the measurement, the flow rate and separation temperature are maintained at 1 mL / min and 25 °C, respectively. Peaks are integrated according to a baseline automatically created by Chromeleon® version 6.8 (Thermo Fisher Scientific, Waltham, MA). The relative area% of each detectable DP (area of ​​each peak in the chromatogram expressed as a percentage of the total area of ​​all peaks) is calculated by Chromeleon®. DP2, DP3, and DP6 are confirmed with a composite standard of maltose, maltotriose, and maltohexaose at 50 ppm. "DP" stands for degree of polymerization, and "DPX" indicates a chain of dextrose residues of length X. The HPLC peak areas are combined as follows: DP1-5, DP6-12, DP13-24, DP25-36, and DP37+, each of which is quantified as a percentage of the total peak area.

[0020] In various embodiments, the waxy tapioca starches described elsewhere herein have a branched chain length ratio (DP6-12) / (DP13-24) of at least 0.480, such as at least 0.485. In various embodiments, the waxy tapioca starches described elsewhere herein have a branched chain length ratio (DP6-12) / (DP13-24) of at least 0.490, such as at least 0.495. In various embodiments, the waxy tapioca starches described elsewhere herein have a branched chain length ratio (DP6-12) / (DP13-24) of at least 0.500, such as at least 0.485. For example, in various embodiments, the amylopectin fraction of waxy tapioca starch has a branch length ratio (DP6-12) / (DP13-24) of 0.470 to 0.540, e.g., 0.475 to 0.540, or 0.480 to 0.540, or 0.485 to 0.540, 0.490 to 0.540, or 0.495 to 0.540, or 0.470 to 0.530, or or 0.475 to 0.530, or 0.480 to 0.530, or 0.485 to 0.530, or 0.490 to 0.530, or 0.495 to 0.530, or 0.470 to 0.520, or 0.475 to 0.520, or 0.480 to 0.520, or 0.485 to 0.520, 0.490 to 0.520, or 0.495 to 0.520.

[0021] As described above, the waxy tapioca starch of the present disclosure is octenyl succinylated, and has a degree of octenyl succinylation of at least 1.0% by weight on a dry solids basis. In various embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenyl succinylation of at least 1.2% by weight, such as at least 1.3% by weight. In various embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenyl succinylation of at least 1.4% by weight, such as at least 1.5% by weight. In various embodiments, the waxy tapioca starch has a degree of octenyl succinylation of at least 1.6% by weight, such as at least 1.8% by weight. In various embodiments, the waxy tapioca starch has a degree of octenyl succinylation of at least 2.0% by weight, such as at least 2.2% by weight. For example, in some embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenylsuccinylation in the range of 1.0-5.0% by weight, e.g., 1.2-5.0% by weight, or 1.3-5.0% by weight, or 1.4-5.0% by weight, or 1.5-5.0% by weight, or 1.6-5.0% by weight, or 1.8-5.0% by weight, or 2.0-5.0% by weight, or 2.2-5.0% by weight. In some embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenyl succinylation in the range of 1.0-4.0% by weight, e.g., 1.2-4.0% by weight, or 1.3-4.0% by weight, or 1.4-4.0% by weight, or 1.5-4.0% by weight, or 1.6-4.0% by weight, or 1.8-4.0% by weight, or 2.0-4.0% by weight, or 2.2-4.0% by weight. In some embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenylsuccinylation in the range of 1.0-3.0% by weight, e.g., 1.2-3.0% by weight, or 1.3-3.0% by weight, or 1.4-3.0% by weight, or 1.5-3.0% by weight, or 1.6-3.0% by weight, or 1.8-3.0% by weight, or 2.0-3.0% by weight, or 2.2-3.0% by weight.In some embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenylsuccinylation in the range of 1.0-2.8% by weight, e.g., 1.2-2.8% by weight, or 1.3-2.8% by weight, or 1.4-2.8% by weight, or 1.5-2.8% by weight, or 1.6-2.8% by weight, or 1.8-2.8% by weight, or 2.0-2.8% by weight, or 2.2-2.8% by weight. In some embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenyl succinylation in the range of 1.0-2.5% by weight, e.g., 1.2-2.5% by weight, or 1.3-2.5% by weight, or 1.4-2.5% by weight, or 1.5-2.5% by weight, or 1.6-2.5% by weight, or 1.8-2.5% by weight, or 2.0-2.5% by weight. In some embodiments, the waxy tapioca starch described elsewhere herein has a degree of octenyl succinylation in the range of 1.0-2.2% by weight, e.g., 1.2-2.2% by weight, or 1.3-2.2% by weight, or 1.4-2.2% by weight, or 1.5-2.2% by weight, or 1.6-2.2% by weight, or 1.8-2.2% by weight. In some embodiments, the waxy tapioca starch described elsewhere herein has an octenylsuccinylation degree of 3.0% by weight or less, e.g., 2.8% by weight or less, or 2.5% by weight or less, or 2.2% by weight or less. The octenylsuccinylation degree is quantified as the weight percent of bound octenylsuccinylic acid residues and can be determined as a percentage of the total weight of the waxy tapioca starch on a dry solids basis as follows: Weigh 0.35 g of starch sample into a tared 25.0 mL volumetric flask. Add 5 mL of deionized water and 2 mL of 1N NaOH and incubate the sample at 80° C. for 1 hour. The sample is then cooled slightly and 2.0 mL of 1N HCl is added. Add 5 mL of acetonitrile to precipitate the starch, then fill the volumetric flask with mobile phase (55:45 volumetric ratio of water:acetonitrile) and shake well to mix. Transfer the sample solution into a centrifuge tube and centrifuge at 5500-5900 rpm for 10-12 min or until the solution is clear, then filter through a 0.45 µm filter into an HPLC vial.HPLC is used to measure the concentration of octenyl succinylates in samples, which can be related to the amount of octenyl succinylates bound to starch. Those skilled in the art will select appropriate chromatographic conditions, but in the examples described herein, a Waters 2695Separations Module equipped with a Waters 2487Dual λ absorbance detector and a Phenomenex Gemini C18 4.60x150mm column is used at a flow rate of 1mL / min and a detection wavelength of 203nm. In some embodiments described herein, the degree of octenyl succinylation is quantified according to the Food and Agriculture Committee / World Health Organization Joint Expert Committee on Food Additives (FOA JECFA) monograph, page 73.

[0022] A person skilled in the art can use any desired octenyl succinylation method. In one example of such a procedure, waxy tapioca starch, whether gelatinized or not, is slurried in water with stirring. A person skilled in the art will select a solids loading that provides the desired stirrability of the slurry. A solids content of 30-40% is a typical value, but it can be more or less. The pH of the starch slurry is adjusted to a range of 8.0-9.0. Octenyl succinic anhydride is slowly added and the pH is maintained at a slightly basic pH, e.g., 7.6-9.0, by adding an aqueous solution of a base, such as sodium hydroxide, sodium carbonate, sodium bicarbonate, etc. The starch slurry is mixed for 15-120 minutes to complete the reaction. The reaction efficiency is typically 60-85%, i.e., 60-85% of the octenyl succinic anhydride reacts with the starch and binds to the final product. One skilled in the art can determine the appropriate amount of octenylsuccinic anhydride reagent to add, along with other parameters, to achieve the desired degree of octenylsuccination. Once addition is complete, an acid such as hydrochloric acid or sulfuric acid (e.g., 1-12N) is added to lower the pH, e.g., to 4.5-7.0. The slurry is dewatered by standard procedures such as centrifugation or filtration, washed with water to remove salts, and then dried by common procedures such as air drying, oven drying, tray drying, flash drying, or belt drying. If desired, the resulting starch can be pregelatinized as described above; however, this is not required, since non-gelatinized starch can be used as a starch emulsifier feedstock in the production of emulsions as well.

[0023] The waxy tapioca starch of the present invention can be provided in a wide range of viscosities in aqueous suspension, and as one skilled in the art will appreciate, the desired viscosity of the waxy tapioca starch of the present invention will depend on its desired end use. For example, in some end uses, such as salad dressings and sauces, it is also desirable for the starch emulsifier to increase viscosity. In such cases, a waxy tapioca starch with a high viscosity can be used. In other end uses, such as beverages, it is desirable for the starch emulsifier to provide emulsification but contribute little to viscosity. In any use case, it may be advantageous for the aqueous phase containing the starch to have a similar viscosity to the hydrophobic phase to form an emulsion, as described herein. A similar viscosity results in better emulsification. For example, in some embodiments, the aqueous phase contains the waxy tapioca starch as a viscosity within at least 50% of the hydrophobic phase, or within at least 25% of the hydrophobic phase, or within at least 10% of the hydrophobic phase, or within at least 5% of the hydrophobic phase, or within at least 2% of the hydrophobic phase. The viscosity of each of these phases can be measured with a viscometer.

[0024] If the viscosity of the waxy tapioca starch of the present disclosure is higher than desired for a given application, it can be thinned to the desired viscosity, for example, using any of a variety of methods. For example, in various embodiments, the waxy tapioca starch is acid thinned, enzymatically thinned, and / or shear thinned. In various embodiments, acid thinning is used. In one example of an acid thinning method, the waxy tapioca starch is dispersed in water, for example, at 25-45% solids by weight. The pH of the resulting slurry is adjusted to less than 2.0 with a mineral acid, such as hydrochloric acid or sulfuric acid, and acid-catalyzed hydrolysis is allowed to proceed for a time sufficient to thin the starch to an appropriate degree. Viscosity can be monitored by measuring samples with a Rapid Visco Analyzer. Once the starch has reached the desired viscosity, an aqueous solution of base (such as sodium hydroxide, sodium carbonate, sodium bicarbonate, etc.) is added to adjust the pH to 7.6 or higher. The thinned starch can be collected by filtration and washed. Of course, other acid thinning processes can be used. Shear thinning and enzymatic thinning processes are also suitable, although in some embodiments, enzymatic thinning is not used.

[0025] A typical measure of the contribution to viscosity of a starch product is water fluidity. This is an experimental test of viscosity measured on a scale of 0 to 90, with fluidity being inversely proportional to viscosity. Water fluidity as used herein is measured as an alkaline water fluidity value as follows: 50 g of a 40 wt% dry solids dispersion of starch in deionized water is mixed with 70 mL of 2N NaOH for 3 minutes. The reference time for the water fluidity funnel is determined by measuring the time it takes for 100 mL of deionized water to pass through the funnel. The volume of the starch sample that passes through the funnel in the given time is measured. That volume (in mL) is the water fluidity. This measurement is normalized to water, and a variety of water fluidity funnels can be used. The measurements described in the examples were obtained using a water fluidity funnel with a cone tapered from a 100 mm opening to an internal diameter of 8.7 mm over 77 mm and a neck tapered from 8.7 mm to 7.0 mm over 44 mm. Quantification of water fluidity for purposes of this disclosure is determined in this manner. In various embodiments described elsewhere herein, the waxy tapioca starch of the present disclosure has a water fluidity of up to 70 mL. For example, in various embodiments, the waxy tapioca starch has a water fluidity of up to 60 mL, or up to 50 mL. In various embodiments, the waxy tapioca starch has a water fluidity in the range of 10-70 mL, e.g., 10-60 mL, or 10-50 mL, or 20-70 mL, or 20-60 mL, or 20-50 mL, or 30-70 mL, or 30-60 mL, or 30-50 mL.

[0026] As discussed above, the desired viscosity of the waxy tapioca starch of the present disclosure depends on its end use. Similarly, the desired water fluidity of the waxy tapioca starch of the present disclosure depends on its end use. For example, in end uses where it is desired to also provide a starch emulsifier with increased viscosity, such as salad dressings and sauces, the waxy tapioca starch of the present disclosure may have a water fluidity of up to 70 mL, e.g., up to 60 mL, or up to 50 mL. In various embodiments, the water fluidity of the waxy tapioca starch ranges from 10-70 mL, e.g., 10-60 mL, or 10-50 mL, or 20-70 mL, or 20-60 mL, or 20-50 mL, or 30-70 mL, or 30-60 mL, or 30-50 mL.

[0027] Alternatively, where it is desired that the starch emulsifier provide emulsification but do not substantially contribute to viscosity, starches having even higher water fluidities can be provided. For example, in some embodiments described herein, the waxy tapioca starches of the present disclosure have a water fluidity of at least 60 mL, e.g., at least 70 mL, or at least 75 mL, or at least 80 mL, or at least 85 mL, or at least 90 mL. In various embodiments, the water fluidity of the waxy tapioca starch ranges from 60 to 95 mL, e.g., from 60 to 90 mL, or from 60 to 85 mL, or from 60 to 80 mL, or from 65 to 95 mL, or from 65 to 90 mL, or from 65 to 85 mL, or from 65 to 80 mL, or from 70 to 95 mL, or from 70 to 90 mL, or from 70 to 85 mL, or from 70 to 80 mL, or from 80 to 95 mL, or from 80 to 90 mL, or from 90 to 95 mL. One skilled in the art can provide starches with the desired degree of thinning (or no thinning at all) to meet these or other water fluidity values.

[0028] In another method of measuring the viscosity of starch, the viscosity is measured by RVA at 5% solids in pH 6.5 phosphate buffer containing 1% NaCl at a stirring speed of 160 rpm. The initial temperature of the analysis is 50°C. The temperature is increased linearly to 95°C over 3 minutes, then held at 95°C for 20 minutes, then decreased linearly to 50°C over 3 minutes, then held at 50°C for 9 minutes, after which the viscosity is measured. In particular, if a pasting peak appears at about 2-5 minutes, the measured final viscosity will be higher than the pasting peak viscosity. In the absence of a pasting peak, the viscosity is plateau or increases during the 95°C hold. The starch products of the present disclosure can have a range of viscosities as measured by a rapid velocity viscometer (RVA). For example, in certain embodiments, the starch products described elsewhere herein can have a viscosity as measured by RVA of 5-2000 cP at 5% solids. In certain such embodiments, the viscosity as measured by RVA at 5% solids is in the range of 300-2000 cP, or 300-1800 cP, or 300-1600 cP, or 500-2000 cP, or 500-1800 cP, or 500-1600 cP, or 500-1400 cP, or 500-1200 cP, or 800-2000 cP, or 800-1800 cP, or 800-1600 cP, or 800-1400 cP, or 800-1200 cP. In certain such embodiments, the viscosity as measured by RVA at 5% solids ranges from 5-800 cP, or 5-600 cP, or 5-400 cP, or 5-200 cP, or 100-1000 cP, or 100-800 cP, or 100-600 cP, or 100-400 cP, or 300-1000 cP, or 300-800 cP, or 300-600 cP, or 500-1000 cP, or 500-800 cP. In certain embodiments, the starch products described elsewhere herein may have a viscosity as measured by RVA in the range of 100-1000 cP at 20% solids.For example, in various embodiments, the viscosity as measured by RVA at 20% solids ranges from 100-800 cP, or 100-600 cP, or 100-400 cP, or 100-200 cP, or 300-1000 cP, or 300-800 cP, or 300-600 cP, or 300-400 cP, or 500-1000 cP, or 500-800 cP, or 500-600 cP. In certain embodiments, the starch products described elsewhere herein may have a viscosity as measured by RVA in the range of 100-1200 cP at 45% solids. For example, in various embodiments, the viscosity as measured by RVA ranges from 100-1000 cP, or 100-800 cP, or 100-600 cP, or 300-1200 cP, or 300-1000 cP, or 300-800 cP, or 300-600 cP, or 500-1200 cP, or 500-1000 cP, or 500-800 cP, or 500-600 cP at 45% solids. Again, one of skill in the art can provide a starch with the desired degree of thinning (or no thinning at all) to meet the desired RVA viscosity value.

[0029] In particular, the disclosed starches are uninhibited. As one of ordinary skill in the art will appreciate, an inhibited starch is a starch that has been treated chemically or otherwise to resist granular disintegration upon heating. While inhibited starches are desirable in many situations, the starches of the present disclosure are uninhibited. As used herein, the term "inhibited starch" refers to a starch that exhibits "process resistance." As used herein, the term "process resistance" means that the starch particles swell in water when cooked, but substantially maintain their natural state during processing. Process-resistant starches do not break down into fragments or dissolve during processing. Inhibited starches may vary in terms of the degree of inhibition, characterized by microscopic examination and the amount of swelling observed. The degree of inhibition can be assessed by cooking the starch in water (typically 95°C for 30 minutes with hand stirring for the first 6 minutes) and then observing the cooking process under a microscope. Uninhibited starches are less likely to form granules or debris as they are readily soluble in water during cooking. Under a microscope, inhibited starches appear as swollen, intact particles, highly inhibited starches appear as small, dark particles, and slightly inhibited starches appear as large, light particles. Alternatively, the degree of inhibition can be assessed by measuring the sedimentation volume. As used herein, sedimentation volume is the volume occupied by 1 gram of cooked starch (dry basis) in 100 grams of salt buffer (i.e., total including starch). This value is also known in the industry as "swelling capacity." As used herein, "salt buffer" refers to a solution prepared according to the following procedure: Using a top-loader balance, weigh out 20 grams of sodium chloride into a 2-liter volumetric flask containing a stir bar. To this is added RVA pH 6.5 buffer (a phosphate buffer purchased from Ricca Chemical Co.) so that the flask is at least half full. Stir until the sodium chloride dissolves. Add RVA pH 6.5 buffer to bring the final volume to 2 liters.

[0030] The settling volume described here is measured by first cooking the starch at 5% solids in the salt buffer by suspending the container with the slurry in a 95°C water bath and stirring with a glass rod or metal spatula for 6 minutes, then covering the container and holding the paste at 95°C for an additional 20 minutes. The container is removed from the bath and cooled on the bench. The resulting paste is returned to its original weight by adding water (i.e., replacing the water that has evaporated) and mixed well. 20.0 g of paste (containing 1.0 g of starch) is weighed into a 100 mL graduated cylinder containing salt buffer and the total weight of the mixture in the cylinder is brought to 100 g using the buffer. The cylinder is left undisturbed for 24 hours. The volume occupied by the starch precipitate (i.e., the volume read in the cylinder) is the settling volume for 1 g of starch, i.e., in mL / g.

[0031] Because the waxy tapioca starches of the present disclosure are not inhibited, they do not have a substantial sedimentation capacity indicative of an inhibited starch. In many desirable embodiments of the present disclosure, particularly in the case of thinned starches, no boundary is observed between the precipitated starch and the supernatant liquid. The dispersed starch may appear transparent or translucent, but substantially no precipitate is observed. Of course, in some embodiments, there may be a small amount of solids at the bottom of the cylinder in the sedimentation capacity measurement, which represents non-dispersible material in the sample, but which corresponds to a measurement of less than 1 mL / g, e.g., less than 0.8 mL / g or less than 0.5 mL / g. In other words, in various embodiments, the waxy tapioca starches of the present disclosure do not have a measured sedimentation capacity in the range of 1-70 mL / g.

[0032] Tapioca based on the non-inhibited waxy starches described herein can be produced with relatively low color. For example, certain embodiments of the non-inhibited waxy starches based on tapioca described elsewhere herein are relatively light in color, i.e., have a Yellowness Index of 10 or less, such as in the range of 3-10 or 5-10. In certain desirable embodiments, the starches described herein are particularly light in color, i.e., have a Yellowness Index of less than 8, such as 3-8 or 5-8. The Yellowness Index is determined by ASTM E313.

[0033] As previously mentioned, the starches of the present disclosure are octenyl succinylated. However, the waxy tapioca starches described herein can be produced without other modifications. Thus, in various embodiments, the waxy tapioca starches described elsewhere herein are not hydroxypropylated. In various embodiments, the waxy tapioca starches described elsewhere herein are not acetylated. In various embodiments, the waxy tapioca starches described elsewhere herein are not carboxymethylated. In various embodiments, the waxy tapioca starches described elsewhere herein are not hydroxyethylated. In various embodiments, the waxy tapioca starches described elsewhere herein are not phosphorylated. In various embodiments, the waxy tapioca starches described elsewhere herein are not cationic or zwitterionic.

[0034] Also, because the waxy tapioca starches described herein are not inhibited, they can be made without the use of cross-linking agents typically used to inhibit starches. For example, in various embodiments, the waxy tapioca starches described elsewhere herein are not cross-linked with phosphoric acid (e.g., using phosphorous oxychloride or metaphosphoric acid). In various embodiments, the waxy tapioca starches described elsewhere herein are not cross-linked with adipate. In various embodiments, the waxy tapioca starches described elsewhere herein are not cross-linked with epichlorohydrin. In various embodiments, the waxy tapioca starches described elsewhere herein are not cross-linked with acrolein.

[0035] The waxy tapioca starches of the present disclosure are useful, for example, as emulsifiers. For example, the pregelatinized starches of the present disclosure can be used to make emulsions without cooking, while the non-gelatinized starches can be used to make emulsions in a process that includes cooking.

[0036] Thus, another aspect of the present disclosure is an emulsion comprising an emulsified phase, which is a hydrophobic phase emulsified within an aqueous phase, and stabilized by gelatinized starch, which is a gelatinization product of waxy tapioca starch, the waxy tapioca starch having an amylopectin content in the range of 90-100% and a degree of octenyl succinylation in an amount of at least 1.0% by weight on a dry solids basis, and the starch is uninhibited. The hydrophobic phase can be, for example, an oil or fat phase. The waxy tapioca starch can be as described in any embodiment herein, or any combination thereof. In particular, as discussed above, the waxy tapioca starch of the present disclosure may be provided in an emulsion having a viscosity and water fluidity suitable for the end use application.

[0037] In particular, the starches described herein are not inhibited, such that when gelatinized and placed in an aqueous system, the starch particles substantially disintegrate. Thus, the emulsions of the present disclosure are not so-called "Pickering emulsions," in which small particulate matter stabilizes the emulsion.

[0038] Those skilled in the art can adapt conventional emulsification techniques for use in producing the emulsions described herein.For example, another aspect of the present disclosure is a method for producing the emulsions described herein.One such method includes mixing a hydrophobic phase, an aqueous phase, and waxy tapioca starch, or any combination thereof, as described in any embodiment herein, under conditions sufficient to form an emulsion.

[0039] These methods often involve mixing under shear, for example in colloid mills, microfluidizers, homogenizers (e.g., Gaulin, APV), etc. In some cases, such treatment to form an emulsion further thins the starch.

[0040] In various embodiments, the processing to form the emulsion results in the starch being gelatinized. Thus, in such embodiments, non-gelatinized waxy tapioca starch can be used as an ingredient. The waxy tapioca starch can also be gelatinized in a separate step prior to emulsification. And, of course, as described herein, the waxy tapioca starch can be provided as an ingredient in pregelatinized form, so that further gelatinization is not required in making the emulsion.

[0041] The amount of starch used in the emulsions described herein can vary, but generally can be small. In various embodiments described elsewhere herein, the waxy tapioca starch is present in an amount of at least 1%, e.g., at least 2%, at least 5%, or at least 10% by weight of the hydrophobic phase. In various embodiments, the amount of waxy tapioca starch in the emulsion ranges from 1 to 200%, e.g., 2 to 200%, or 5 to 200%, or 10 to 200%, or 1 to 100%, or 2 to 100%, or 5 to 100%, or 10 to 100%, or 1 to 50%, or 2 to 50%, or 5 to 50%, or 10 to 50%, or 1 to 25%, or 2 to 25%, or 5 to 25%, or 10 to 25% by weight of the hydrophobic phase. Those skilled in the art will determine the desired rate of starch use based on the disclosure herein. The amount of "hydrophobic phase" in an emulsion can be determined by reference to the ingredients used to make the emulsion. The contribution of a material that is substantially partitioned between the aqueous phase and the hydrophobic phase to the amount of hydrophobic phase can be calculated in terms of a partition coefficient.

[0042] Emulsions can be made with a variety of droplet sizes, depending, for example, on the nature and relative amounts of the starch and emulsifying phase, and the conditions used for emulsification. For example, in various embodiments described elsewhere herein, the emulsions have an average emulsion droplet size (i.e., of the emulsifying phase) in the range of 0.2 to 100 microns, e.g., 0.2 to 75 microns, or 0.2 to 50 microns, or 0.2 to 25 microns, or 0.2 to 15 microns, or 0.2 to 5 microns, or 0.5 to 100 microns, or 0.5 to 50 microns, or 0.5 to 25 microns, or 0.5 to 15 microns, or 0.5 to 5 microns.

[0043] Emulsions can be made with various amounts of aqueous and hydrophobic phases. For example, in various embodiments, the aqueous phase is present in the emulsion in an amount ranging from at least 30% by weight, e.g., at least 35% by weight, or at least 40% by weight, or at least 45% by weight, or at least 50% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight. In various embodiments, the hydrophobic phase is present in an amount ranging from 0.5 to 70% by weight, e.g., from 0.5 to 50% by weight, or from 0.5 to 35% by weight, or from 0.5 to 15% by weight. As with the hydrophobic phase, the amount of "aqueous phase" in an emulsion can be determined with reference to the ingredients used to make the emulsion. The contribution of a material that is substantially distributed between the aqueous phase and the hydrophobic phase to the amount of the aqueous phase can be calculated in terms of a partition coefficient.

[0044] The emulsions described herein can be used in a variety of products. The inventors have found that the starches described herein can provide good stabilization of emulsions without undesirable effects on flavor. The starches can provide the desired resistance to processing variables such as heat, shear, and extreme pH, particularly over time under such conditions, and can provide rheological and textural stability over the desired shelf life. In various embodiments described herein, the waxy tapioca starches of the present disclosure do not retrograde over the desired shelf life. Thus, in various embodiments, the waxy tapioca starches of the present disclosure do not gel over the desired shelf life of the product, and in certain embodiments, the waxy tapioca starches do not gel under refrigerated conditions (e.g., about 4° C.) over the shelf life of the product.

[0045] For example, in various embodiments, the emulsions described elsewhere herein are in the form of a food or beverage product that may or may not require refrigeration. In various embodiments, the food or beverage product is a gravy, a sauce (e.g., mayonnaise, white sauce, or cheese sauce), a soup, or a stew. In various embodiments, the food or beverage product is a dressing, such as a salad dressing (e.g., pourable or spoonable). In various embodiments, the food or beverage product is a dairy product, such as yogurt, sour cream, ice cream, or ice milk. In various embodiments, the food or beverage product is a dairy substitute, such as a non-dairy creamer, a plant-based milk (such as oat milk, soy milk, or nut milk), or a food or beverage based thereon (e.g., an ice cream analog based on such milk), or a margarine. In various embodiments, the food or beverage product is a cream filling or custard. In various embodiments, the food or beverage product is a confectionery, such as chocolate. In various embodiments, the food or beverage product is a mousse, a smoothie, or a shake. However, those skilled in the art will appreciate that the emulsions described herein can be advantageously incorporated into a variety of other food and beverage products.

[0046] The emulsions can also be used in personal care products. Many personal care products in the form of lotions or creams contain an emulsifying system. Examples include shaving creams, skin lotions, hair conditioners, hair care products such as mousses and gels, sunscreens, facial masks, bath oils, body washes, etc. Other products such as dietary supplements or pharmaceutical compositions (e.g., those containing oily active substances dispersed in an aqueous carrier, such as ointments or liniments, such as so-called "fat emulsions" or "lipid emulsions" used in intravenous nutritional supplementation) can also be provided using the emulsions of the present disclosure. In particular, the starch of the present invention can provide excellent emulsifying capabilities and excellent stability to refrigeration, while being plant-derived and biodegradable.

[0047] As will be appreciated by those skilled in the art, some food and beverage products can be in the form of both emulsions and foams. For example, desserts such as ice cream and mousse often contain both emulsified fat and air bubbles. Such products are considered emulsions for the purposes of this disclosure.

[0048] The embodiment will now be described in more detail. Example 1 - Acid thinned octenylsuccinylated waxy tapioca starch Acid-thinned octenylsuccinylated waxy tapioca starch was prepared by acid-thinning waxy tapioca starch followed by treatment with octenylsuccinic anhydride as described herein. The resulting starch had a water fluidity of 45-50 mL and an octenylsuccinylated content of about 2% by weight. Comparative starches were prepared under essentially identical conditions but using waxy corn starch and non-waxy tapioca starch as the starch source.

[0049] RVA viscosity measurements were performed. The measured sample was 37 wt% dry solids in RVA buffer and the run profile was 20 min run, 160 rpm, initial 35°C, 6 min hold at 95°C, 6 min hold at 35°C. Figure 2 shows a plot comparing acid thinned waxy tapioca starch (OS-WxT) with acid thinned non-waxy tapioca starch (OS-NT) and acid thinned waxy corn starch (OS-WxC). Under these conditions, the final viscosity of acid thinned waxy tapioca starch and acid thinned waxy corn starch is approximately 1000 cP, while the final viscosity of acid thinned non-waxy tapioca starch is over 17000 cP.

[0050] Example 2 - Octenylsuccinylated waxy tapioca starch Octenylsuccinylated waxy tapioca starch was prepared by treating waxy tapioca starch with octenylsuccinic anhydride as described herein. The resulting starch had a water fluidity of 0 mL (i.e., the starch did not pass through the funnel over the time scale of the experiment) and an octenylsuccinylate content of about 2 wt.%. Comparative starches were prepared under essentially identical conditions, but using waxy corn starch and non-waxy tapioca starch as the starch source.

[0051] RVA viscosity measurements were performed. The measured samples were 2.75 wt% dry solids in RVA buffer with a run profile of 20 min run, 160 rpm, initial 50°C, 20 min hold 95°C, 9 min hold 50°C. A plot comparing unthinned waxy tapioca starch with unthinned non-waxy tapioca starch and unthinned waxy corn starch is shown in Figure 3. The final viscosities of the samples based on waxy tapioca starch, waxy corn starch, and non-waxy tapioca starch are 277 cP, 277 cP, and 133 cP, respectively.

[0052] Example 3 - Branch length distribution The branch chain length distributions of the starches of Examples 1 and 2 (OS-WxT), and of substantially identically processed non-waxy tapioca starch (OS-NT) and waxy corn starch (OS-WxC), were determined as described above, and the results are shown in the table below.

[0053] Chain length distribution (relative area%) of acid-thinned OS starch [Table 1]

[0054] Chain length distribution (relative area%) of unthinned OS starch [Table 2]

[0055] Example 4 - Emulsion The flavor oil encapsulation system was used to evaluate the emulsifying properties of the octenylsuccinylated acid thinned waxy tapioca starch of Example 1 and a substantially identically processed octenylsuccinylated acid thinned waxy corn starch, particularly their performance with respect to refrigerated storage.

[0056] The system contained 10 wt% orange oil, 10 wt% octenylsuccinylated acid thinned starch under test, and 80 wt% water. The ingredients were mixed and homogenized using a combination of high speed homogenization (11000 rpm for 3 min) using an IKAT25 high speed homogenizer (IKA, NC, USA) and microfluidization (7000 psi, 3 passes) using an M-110T Microfluidizer Processor (Newton, MA, USA).

[0057] The emulsions were analyzed for oil droplet size distribution and storage stability under refrigerated conditions. The particle size distribution of the freshly prepared emulsions was measured using a laser diffraction particle size analyzer Universal Liquid Module (LS 13 320, Beckman Coulter Life Sciences, Indianapolis, IN, USA).

[0058] As shown in Figure 4, the emulsion made with the waxy tapioca starch of Example 1 had a higher amount of oil droplets less than 1 μm in diameter than the emulsion made with the similar waxy corn starch, suggesting some improvement in the emulsifying properties of the waxy tapioca starch.

[0059] More importantly, the emulsions made with the waxy tapioca starch of Example 1 demonstrate improved storage stability under refrigerated conditions. The emulsions were refrigerated for 18 days at 4° C. As shown in the inverted sample tubes in FIG. 5, the emulsion stabilized with the waxy tapioca starch of Example 1 remained emulsified and fluid after refrigerated storage, whereas the emulsion based on waxy corn starch formed a gel and was not fluid after refrigerated storage.

[0060] Example 5 - Pregelatinized Octenylsuccinylated Waxy Tapioca Starch Pregelatinized octenylsuccinylated waxy tapioca starch was prepared by dispersing octenylsuccinylated waxy tapioca starch as described herein in deionized water at 20% (w / w). The starch slurry was heated to 90° C. for 30 minutes and pregelatinized using a spray dryer (Buchi Mini Spray Dyer (B-290)) with the following parameters: [Table 3]

[0061] The comparative starch was prepared under essentially identical conditions, but using octenyl succinylated waxy corn starch as the starch source. The products were collected and examined under an optical microscope, the results of which are shown in Figure 6. As shown in Figure 6, both pregelatinized starches lost birefringence, confirming that pregelatinization was successful.

[0062] Example 6 - Freeze / Thaw Stability of Pregelatinized Octenylsuccinylated Waxy Tapioca Starch The pregelatinized octenylsuccinylated waxy tapioca starch prepared in Example 5 was dispersed in deionized water at 7% solids by stirring at room temperature. The dispersion was dispensed into 125 mL glass bottles as 75 g samples. The samples were then subjected to a freeze / thaw process. The freeze / thaw process included the following steps: A. Freeze the samples in a freezer (e.g., at about -18°C) for at least 16 hours. B. Thaw the samples at room temperature for at least 6 hours. For comparison, the pregelatinized octenyl succinylated waxy corn starch of Example 5 was also subjected to the freeze / thaw treatment as described above. The results of the treatment for both starches are shown in FIG. 7. As can be seen from the photograph in FIG. 7, the pregelatinized octenyl succinylated waxy tapioca starch maintains its transparency after the freeze / thaw treatment, whereas the pregelatinized octenyl succinylated waxy corn starch dispersion turns white with starch aggregates settling to the bottom of the bottle. The aggregates indicate retrogradation of the pregelatinized octenyl succinylated waxy corn starch. Thus, the pregelatinized octenyl succinylated waxy tapioca starch provides better freeze / thaw stability than the pregelatinized octenyl succinylated waxy corn starch. The freeze / thaw stability indicates the superior refrigeration properties of the pregelatinized octenyl succinylated waxy tapioca starch.

[0063] Example 7 - Emulsion with pregelatinized octenyl succinylated waxy tapioca starch To prepare the emulsions using pregelatinized octenyl succinylated waxy tapioca starch as described in Example 5, the starch was dispersed in water by stirring at room temperature for 2 hours to prepare a starch emulsifier. Another starch thickener was dispersed in water and heated to 95°C for 30 minutes. The starch emulsifier and starch thickener dispersion were mixed with vinegar and oil. The mixture was then homogenized in a bench top mixer (Silverson mixer) at 3000 rpm for 10 minutes. A comparative emulsion was prepared without the starch emulsifier but using pregelatinized octenyl succinylated waxy corn starch under substantially identical conditions as described in Example 5. The complete emulsion formulation is as follows: [Table 4]

[0064] The emulsions were characterized by microscopy (200x magnification) to evaluate the size distribution of the oil droplets. The microscopic images are shown in Figure 8. As shown in Figure 8, when pregelatinized octenyl succinylated waxy tapioca starch was used, the emulsion contained uniformly dispersed oil droplets encapsulated by the starch. On the other hand, non-emulsified oil was observed in the emulsion without starch emulsifier. This confirmed the emulsification efficiency of pregelatinized octenyl succinylated waxy tapioca starch. Additionally, the Brookfield viscosity of the emulsions was measured immediately after preparation and after 3 weeks of storage at 4°C. The Brookfield viscosity was measured using the following parameters: 20 rpm, 20 seconds, spindle #27, 25°C. The emulsion containing pregelatinized octenyl succinylated waxy tapioca starch increased in viscosity by 21% after storage, whereas the emulsion containing pregelatinized octenyl succinylated waxy corn starch increased in viscosity by 32% after storage. Thus, pregelatinized octenyl succinylated waxy tapioca starch was shown to have improved refrigerated storage properties over pregelatinized octenyl succinylated waxy corn starch.

[0065] Further aspects of the present disclosure are provided by the embodiments listed below, which can be combined in any number and in any combination that is not technically or logically inconsistent. Embodiment 1. A waxy tapioca starch comprising: Amylopectin content ranging from 90 to 100%, and having a degree of octenylsuccinylation of at least 1.0% by weight based on dry solids; Where: Starch is not inhibited, The starch is pregelatinized. Embodiment 2. A waxy tapioca starch comprising: an amylopectin content ranging from 90 to 100% by weight, and having a degree of octenylsuccinylation of at least 1.0% by weight based on dry solids; Where: Starch is not inhibited. Embodiment 3. The waxy tapioca starch according to embodiment 1 or embodiment 2, having an amylopectin content in the range of 95-100%. Embodiment 4. The waxy tapioca starch of embodiment 1 or embodiment 2 having an amylopectin content of at least 99%. Embodiment 5. The waxy tapioca starch of embodiment 1 or embodiment 2 having an amylopectin content of at least 99.9%. Embodiment 6. The waxy tapioca starch according to any one of embodiments 1-5, wherein the amylopectin fraction of the waxy tapioca starch has a branch chain length ratio (DP6-12) / (DP13-24) of at least 0.470, such as at least 0.475, where DP6-12 is a distribution of short chain branches with chain lengths from 6 to 12 and DP13-24 is a distribution of short chain branches with chain lengths from 13 to 24. Embodiment 7. The waxy tapioca starch according to any one of embodiments 1-5, wherein the amylopectin fraction of the waxy tapioca starch has a branch length ratio (DP6-12) / (DP13-24) of at least 0.480, such as at least 0.485, where DP6-12 is a distribution of short chain branches with chain lengths between 6 and 12 and DP13-24 is a distribution of short chain branches with chain lengths between 13 and 24. Embodiment 8. The waxy tapioca starch according to any one of embodiments 1-5, wherein the amylopectin fraction of the waxy tapioca starch has a branching chain length ratio (DP6-12) / (DP13-24) of at least 0.490, such as at least 0.495, where DP6-12 is a distribution of short chain branches with chain lengths from 6 to 12 and DP13-24 is a distribution of short chain branches with chain lengths from 13 to 24. Embodiment 9. The waxy tapioca starch according to any one of embodiments 1 to 5, wherein the amylopectin fraction of the waxy tapioca starch is 0.470 to 0.540, for example 0.475 to 0.540, or 0.480 to 0.540, or 0.485 to 0.540, 0.490 to 0.540, or 0.495 to 0.540, or 0.470 to 0.530, or 0.475 to 0.530, or 0.480 to 0.530, or 0.485 to 0.530, 0.490 to and a branch chain length ratio (DP6-12) / (DP13-24) of 0.530, or 0.495-0.530, or 0.470-0.520, or 0.475-0.520, or 0.480-0.520, or 0.485-0.520, 0.490-0.520, or 0.495-0.520, where DP6-12 is a distribution of short length branches having chain lengths from 6 to 12 and DP13-24 is a distribution of short length branches having chain lengths from 13 to 24. Embodiment 10. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation of at least 1.2% by weight, such as at least 1.3% by weight. Embodiment 11. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation of at least 1.4% by weight, such as at least 1.5% by weight. Embodiment 12. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation of at least 1.6% by weight, such as at least 1.8% by weight. Embodiment 13. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation of at least 2.0% by weight, such as at least 2.2% by weight. Embodiment 14. The waxy tapioca starch according to any one of embodiments 1-9, wherein the starch has a degree of octenylsuccinylation in the range of 1.0-5.0% by weight, such as 1.2-5.0% by weight, 1.3-5.0% by weight, 1.4-5.0% by weight, 1.5-5.0% by weight, 1.6-5.0% by weight, 1.8-5.0% by weight, 2.0-5.0% by weight, 2.2-5.0% by weight. Embodiment 15. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation in the range of 1.0 to 4.0% by weight, such as 1.2 to 4.0% by weight, or 1.3 to 4.0% by weight, or 1.4 to 4.0% by weight, or 1.5 to 4.0% by weight, or 1.6 to 4.0% by weight, or 1.8 to 4.0% by weight, or 2.0 to 4.0% by weight, or 2.2 to 4.0% by weight. Embodiment 16. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation in the range of 1.0 to 3.0% by weight, such as 1.2 to 3.0% by weight, or 1.3 to 3.0% by weight, or 1.4 to 3.0% by weight, or 1.5 to 3.0% by weight, or 1.6 to 3.0% by weight, or 1.8 to 3.0% by weight, or 2.0 to 3.0% by weight, or 2.2 to 3.0% by weight. Embodiment 17. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation in the range of 1.0 to 2.8% by weight, such as 1.2 to 2.8% by weight, or 1.3 to 2.8% by weight, or 1.4 to 2.8% by weight, or 1.5 to 2.8% by weight, or 1.6 to 2.8% by weight, or 1.8 to 2.8% by weight, or 2.0 to 2.8% by weight, or 2.2 to 2.8% by weight. Embodiment 18. The waxy tapioca starch according to any one of embodiments 1-9, wherein the starch has a degree of octenylsuccinylation in the range of 1.0-2.5% by weight, such as 1.2-2.5% by weight, or 1.3-2.5% by weight, or 1.4-2.5% by weight, or 1.5-2.5% by weight, or 1.6-2.5% by weight, or 1.8-2.5% by weight, or 2.0-2.5% by weight. Embodiment 19. The waxy tapioca starch according to any one of embodiments 1 to 9, wherein the starch has a degree of octenylsuccinylation in the range of 1.0 to 2.2% by weight, such as 1.2 to 2.2% by weight, or 1.3 to 2.2% by weight, or 1.4 to 2.2% by weight, or 1.5 to 2.2% by weight, or 1.6 to 2.2% by weight, or 1.8 to 2.2% by weight. Embodiment 20. The waxy tapioca starch according to any one of embodiments 1-9, wherein the starch has a degree of octenylsuccinylation of 2.8% by weight or less, such as 2.5% by weight or less, or 2.2% by weight or less. Embodiment 21. The waxy tapioca starch of any one of embodiments 1-20, wherein the starch is not thinned. Embodiment 22. The waxy tapioca starch of any one of embodiments 1-20, wherein the starch is thinned. Embodiment 23. The waxy tapioca starch of embodiment 22, wherein the starch has been subjected to acid thinning, enzymatic thinning, and / or shear thinning. Embodiment 24. The waxy tapioca starch of embodiment 22, wherein the starch has undergone acid thinning. Embodiment 25. The waxy tapioca starch of embodiment 24, wherein the starch has not been subjected to enzymatic thinning. Embodiment 26. The waxy tapioca starch according to any one of embodiments 1-25, wherein the water fluidity is up to 70 mL, such as up to 60 mL, or up to 50 mL. Embodiment 27. The waxy tapioca starch according to any one of embodiments 1-25, wherein the water fluidity is in the range of 10-70 mL, such as 10-60 mL, or 10-50 mL, or 20-70 mL, or 20-60 mL, or 20-50 mL, or 30-70 mL, or 30-60 mL, or 30-50 mL. Embodiment 28. The waxy tapioca starch according to any one of embodiments 1-25, wherein the water fluidity is at least 60 mL, such as at least 70 mL, or at least 80 mL, or at least 90 mL. Embodiment 29. The waxy tapioca starch according to any one of embodiments 1-25, wherein the water fluidity is in the range of 60-95 mL, such as 60-90 mL, or 60-80 mL, or 70-95 mL, or 70-90 mL, or 70-80 mL, or 80-95 mL, or 80-90 mL, or 90-95 mL. Embodiment 30. The waxy tapioca starch according to any one of embodiments 1-29, having a viscosity in the range of 5-2000 cP in the RVA test at 5% solids. Embodiment 31. The waxy tapioca starch according to any one of embodiments 1-29, having a viscosity in the range of 300-2000 cP, or 300-1800 cP, or 300-1600 cP, or 500-2000 cP, or 500-1800 cP, or 500-1600 cP, or 500-1400 cP, or 500-1200 cP, or 800-2000 cP, or 800-1800 cP, or 800-1600 cP, or 800-1400 cP, or 800-1200 cP in an RVA test at 5% solids. Embodiment 32. The waxy tapioca starch according to any one of embodiments 1-29 has a viscosity in the range of 5-800 cP, or 5-600 cP, or 5-400 cP, or 5-200 cP, or 100-1000 cP, or 100-800 cP, or 100-600 cP, or 100-400 cP, or 300-1000 cP, or 300-800 cP, or 300-600 cP, or 500-1000 cP, or 500-800 cP in the RVA test at 5% solids. Embodiment 33. The waxy tapioca starch of any one of embodiments 1-29, having a viscosity in the range of 100-1000 cP at 20% solids. Embodiment 34. The waxy tapioca starch of any one of embodiments 1-29, having a viscosity in the range of 100-1200 cP at 45% solids. Embodiment 35. The waxy tapioca starch of any one of embodiments 1-34 does not have a measured sedimentation volume in the range of 1-70 mL / g. Embodiment 36. The waxy tapioca starch of any one of embodiments 1-35, wherein the waxy tapioca starch is not hydroxypropylated. Embodiment 37. The waxy tapioca starch of any one of embodiments 1-36, wherein the waxy tapioca starch is not acetylated. Embodiment 38. The waxy tapioca starch of any one of embodiments 1-37, wherein the waxy tapioca starch is not carboxymethylated. Embodiment 39. The waxy tapioca starch of any one of embodiments 1-38, wherein the waxy tapioca starch is not hydroxyethylated. Embodiment 40. The waxy tapioca starch of any one of embodiments 1-39, wherein the waxy tapioca starch is not phosphorylated. Embodiment 41. The waxy tapioca starch of any one of embodiments 1-40, wherein the waxy tapioca starch is neither cationic nor zwitterionic. Embodiment 42. An octenylsuccinylated waxy tapioca starch comprising: providing the waxy tapioca slurry at a basic pH; adding octenyl succinic anhydride to the slurry; maintaining a basic pH of the slurry; and It is produced by a process which includes the step of mixing the slurry for a period of time sufficient to obtain an octenylsuccinylated waxy tapioca starch. Embodiment 43. A method for producing an octenylsuccinylated waxy tapioca starch, comprising the steps of: providing the waxy tapioca slurry at a basic pH; adding octenyl succinic anhydride to the slurry; maintaining a basic pH of the slurry; and mixing the slurry for a period of time sufficient to obtain an octenylsuccinylated waxy tapioca starch. Embodiment 44. The waxy tapioca starch of any one of embodiments 1 to 41 produced by the method of embodiment 43. Embodiment 45. An emulsion comprising an emulsified phase, which is a hydrophobic phase emulsified with an aqueous phase, and stabilized by gelatinized starch, which is the gelatinization product of waxy tapioca starch, Amylopectin content in the range of 90-100%, and having a degree of octenylsuccinylation in an amount of at least 1.0% by weight based on dry solids; Where: Starch is not inhibited. Embodiment 46. An emulsion according to embodiment 45, wherein the gelatinized starch has the properties described for the pregelatinized starch according to any one of embodiments 1 to 42. Embodiment 47. A method for producing an emulsion (e.g., an emulsion as described in embodiment 45 or embodiment 46), comprising mixing a hydrophobic phase, an aqueous phase, and a waxy tapioca starch as described in any one of embodiments 1-42 under conditions sufficient to form an emulsion (e.g., under shear). Embodiment 48. The method of embodiment 47, further comprising gelatinizing the waxy tapioca starch. Embodiment 49. The emulsion or method of any one of embodiments 45-48, wherein the waxy tapioca starch is present in the emulsion in an amount ranging from at least 1% by weight of the hydrophobic phase, such as at least 2% by weight, at least 5% by weight, or at least 10% by weight. Embodiment 50. The emulsion or method of any one of embodiments 45-48, wherein the amount of waxy tapioca starch in the emulsion is in the range of 1 to 200% by weight of the hydrophobic phase, such as 2 to 200% by weight, or 5 to 200% by weight, or 10 to 200% by weight, or 1 to 100% by weight, or 2 to 100% by weight, or 5 to 100% by weight, or 10 to 100% by weight, or 1 to 50% by weight, or 2 to 50% by weight, or 5 to 50% by weight, or 10 to 50% by weight, or 1 to 25% by weight, or 2 to 25% by weight, or 5 to 25% by weight, or 10 to 25% by weight. Embodiment 51. The emulsion or method of any one of embodiments 45-50, wherein the average emulsion droplet size of the emulsion (i.e. of the emulsified phase) is in the range of 0.2 to 100 microns, e.g., 0.2 to 75 microns, or 0.2 to 50 microns, or 0.2 to 25 microns, or 0.2 to 15 microns, or 0.2 to 5 microns, or 0.5 to 100 microns, or 0.5 to 50 microns, or 0.5 to 25 microns, or 0.5 to 15 microns, or 0.5 to 5 microns. Embodiment 52. The emulsion or method of any one of embodiments 45 to 51, wherein the aqueous phase is present in the emulsion in an amount in the range of at least 30% by weight, such as at least 35% by weight, or at least 40% by weight, or at least 45% by weight, or at least 50% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight. Embodiment 53. The emulsion or method of any one of embodiments 45 to 52, wherein the hydrophobic phase is present in the emulsion in an amount ranging from 0.5 to 70% by weight, such as from 0.5 to 50% by weight, or from 0.5 to 35% by weight, or from 0.5 to 15% by weight. Embodiment 54. A food or beverage product comprising an emulsion according to any one of embodiments 45, 46, or 49-53. Embodiment 55 The food or beverage product of embodiment 54, wherein the food is a gravy, a sauce (e.g., mayonnaise, white sauce, or cheese sauce), a soup, or a stew. Embodiment 56 The food or beverage product of embodiment 54, wherein the food or beverage product is a dressing (e.g., pourable or spoonable), such as a salad dressing. Embodiment 57 The food or beverage product of embodiment 54, wherein the food or beverage product is a dairy product, such as yogurt, sour cream, ice cream, or ice milk. Embodiment 58. The food or beverage product of embodiment 54, wherein the food or beverage product is a dairy substitute, such as a non-dairy creamer, a plant-based milk (such as oat milk, soy milk, or nut milk), or a food or beverage based thereon (e.g., an ice cream analog based on such milk), or a margarine. Embodiment 59. The food or beverage product of embodiment 54, wherein the food or beverage product is a cream filling or custard. Embodiment 60. A food or beverage product according to embodiment 54, wherein the food or beverage product is a confectionery, for example chocolate. Embodiment 61 The food or beverage product of embodiment 54, wherein the food or beverage product is a mousse. Embodiment 62 The food or beverage product of embodiment 54, wherein the food or beverage product is a smoothie or shake. Embodiment 63. A personal care composition or a nutraceutical composition or a pharmaceutical composition comprising an emulsion according to any one of embodiments 45, 46 or 49-53.

[0066] While various embodiments and aspects of the present invention have been shown and described herein, it will be apparent to those skilled in the art that such embodiments and aspects are provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the present invention. It is understood that in implementing the structures and methods of the present invention, various alternatives to the embodiments specifically described herein may be employed.

Claims

1. Waxy tapioca starch, Amylopectin content in the range of 90-100%, and It has a degree of octenyl succinylation of at least 1.0% by weight based on dry solids content, Here, The aforementioned starch is not inhibited, and The aforementioned starch is waxy tapioca starch that is gelatinized.

2. Waxy tapioca starch, Amylopectin content in the range of 90-100% by weight, and It has a degree of octenyl succinylation of at least 1.0% by weight based on dry solids content, Here, The starch is uninhibited waxy tapioca starch.

3. The waxy tapioca starch according to claim 1, having an amylopectin content of at least 99%.

4. The waxy tapioca starch according to claim 1, wherein the starch has an octenyl succinylation degree of at least 1.6% by weight.

5. The waxy tapioca starch according to claim 1, wherein the starch has an octenyl succinylation degree in the range of 1.0 to 5.0% by weight.

6. The waxy tapioca starch according to claim 1, wherein the starch has an octenyl succinylation degree in the range of 1.0 to 3.0% by weight.

7. The waxy tapioca starch according to claim 1, having a maximum water fluidity of 70 mL.

8. The waxy tapioca starch according to claim 1, having a water fluidity of at least 60 mL.

9. The waxy tapioca starch according to claim 1, wherein the starch has not been diluted.

10. The waxy tapioca starch according to claim 1, wherein the starch is diluted.

11. The waxy tapioca starch according to claim 1, wherein the starch does not have a measurable sedimentation capacity in the range of 1 to 70 mL / g.

12. The waxy tapioca starch according to claim 1, wherein the waxy tapioca starch is not hydroxypropylated, not acetylated, not carboxymethylated, not hydroxyethylated, not phosphorylated, and is neither cationic nor amphoteric.

13. Octenyl succinylated waxy tapioca starch, A step of providing a waxy tapioca slurry at a basic pH, The step of adding octenyl succinic anhydride to the slurry, A step to maintain the basic pH of the slurry, and Octenyl succinylated waxy tapioca starch is produced by a process comprising the step of mixing a slurry for a sufficient amount of time to obtain octenyl succinylated waxy tapioca starch.

14. A method for producing octenyl succinylated waxy tapioca starch, A step of providing a waxy tapioca slurry at a basic pH, The step of adding octenyl succinic anhydride to the slurry, A step to maintain the basic pH of the slurry, and A method for producing octenyl succinyl waxy tapioca starch, comprising the step of mixing a slurry for a sufficient amount of time to obtain octenyl succinyl waxy tapioca starch.

15. An emulsion comprising an emulsion phase which is a hydrophobic phase emulsified in an aqueous phase, and stabilized with gelatinized starch which is a gelatinization product of waxy tapioca starch, wherein the waxy tapioca starch is Amylopectin content in the range of 90-100%, and It has a degree of octenyl succinylation of at least 1.0% by weight based on dry solids content, Here, The aforementioned starch is an uninhibited emulsion.

16. An emulsion comprising an emulsion phase which is a hydrophobic phase emulsified in an aqueous phase, and stabilized with gelatinized starch which is a gelatinization product of waxy tapioca starch, wherein the waxy tapioca starch is Amylopectin content in the range of 90-100%, and It has a degree of octenyl succinylation of at least 1.0% by weight based on dry solids content, Here, The aforementioned starch is not inhibited, The gelatinized starch is the gelatinized starch described in claim 1, in an emulsion.

17. A method for producing an emulsion according to claim 16, comprising the step of mixing a hydrophobic phase, an aqueous phase, and waxy tapioca starch according to any one of claims 1 to 13 under conditions sufficient to form an emulsion.

18. The method according to claim 17, further comprising the step of gelatinizing the waxy tapioca starch.

19. The method according to claim 16, wherein the waxy tapioca starch is present in the emulsion in an amount in the range of at least 1% by weight of the hydrophobic phase.

20. The method according to claim 16, wherein the average emulsion droplet size of the emulsion (i.e., the average emulsion droplet size of the emulsion phase) is in the range of 0.2 to 100 microns.

21. The method according to claim 16, wherein the aqueous phase is present in the emulsion in an amount of at least 30% by weight, and the hydrophobic phase is present in the emulsion in an amount of 0.5 to 70% by weight.

22. A food or beverage product comprising the emulsion according to any one of claims 15, 16, 19 to 21.

23. The aforementioned food items include gravy, sauces (e.g., mayonnaise, white sauce, or cheese sauce), soups, or stews; The food or beverage product according to claim 22, which is a dressing, for example, a salad dressing (for example, one that can be poured or scooped with a spoon); a dairy product, for example, yogurt, sour cream, ice cream or ice milk; a dairy substitute, for example, a non-dairy creamer, plant-based milk (for example, oat milk, soy milk or nut milk) or a food or beverage based thereon (for example, an ice cream-like product based on such milk), or margarine; a cream filling or custard; confectionery, for example, chocolate, mousse; or a smoothie or shake.

24. A personal care composition, nutritional supplement composition, or pharmaceutical composition comprising the emulsion described in any one of claims 15, 16, and 19 to 21.

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