Inhibited waxy starch and methods of use thereof

Abstract

To provide an inhibited waxy starch and a method for using the same. The present invention provides an inhibited waxy starch based on corn, wheat, or tapioca, having an amylopectin content in the range of 90-100% and a sedimentation volume in the range of 10-50 ml / g; the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has no more than 48.5% medium-chain branches with a chain length of 13-24 as measured by the valley-to-valley method, and the starch is not pregelatinized. Methods for using the starch material in foods are also described.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 434,921, filed December 15, 2016, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Field of the Disclosure The present disclosure relates generally to starch products. More particularly, the present disclosure relates to inhibited waxy starches and methods related thereto, including methods of using them.

[0003] Technical background Waxy starch is starch that has a high percentage of polysaccharide content in the form of amylopectin, i.e., as opposed to a mixture of amylopectin and amylose as in non-waxy starches. Waxy starches can provide a number of desirable properties to a variety of food products. For example, waxy starches, such as waxy corn starch and waxy tapioca starch, can provide desirable texture and thickness to food products such as bakery fillings (e.g., fruit fillings for pies), doughs, batters, sauces such as cheese sauces, and gravies. Waxy starches typically provide a higher viscosity than the corresponding non-waxy starches.

[0004] However, native starch is not usually resistant to the extreme conditions encountered during food processing, such as high temperatures and their high shear stresses. Moreover, native waxy starch is usually unable to retain the desired texture and rheological safety over a long shelf life, especially under refrigeration and / or freeze-thaw conditions. Chemical modification to produce hydroxypropylated or acetylated starch is often necessary to give starch the desired safety for food applications. However, chemical modification requires additional process steps and costs, and perhaps more importantly is considered undesirable by consumers. Summary of the Invention [Means for solving the problem]

[0005] One aspect of the disclosure is an inhibited waxy starch based on corn, wheat, or tapioca having an amylopectin content in the range of 90-100%; and a sedimentation volume in the range of 10-50 mL / g; the amylopectin fraction of said inhibited waxy starch based on corn, wheat, or tapioca having no more than 48.5% medium chain branches with chain lengths of 13-24 (i.e., degree of polymerization of branched chains) as measured by the valley-to-valley method (i.e., as described herein), and said starch is not pregelatinized. For example, in certain embodiments, the amylopectin fraction of said inhibited waxy starch based on corn, wheat, or tapioca has no more than 48.0% medium chain branches with chain lengths of 13-24 as measured by the valley-to-valley method. In certain embodiments, the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has 46.0%-48.5%, 46.5%-48.5%, 47.0%-48.5%, 46.0%-48.0%, 46.5%-48.0% or 47.0%-48.0% medium chain branches with chain lengths of 13-24 as measured by the valley-to-valley method.

[0006] Yet another aspect of the present disclosure is an inhibited waxy starch based on corn, wheat, or tapioca having an amylopectin content in the range of 90-100% as specifically described herein; and a sedimentation volume in the range of 10-50 mL / g; the amylopectin fraction of said inhibited waxy starch based on corn, wheat, or tapioca having at least 28.0% short chain branches with chain lengths of 6-12 as measured by the Valley to Valley method (i.e., as described herein), and said starch is not pregelatinized. For example, in certain embodiments, the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has at least 28.5% short chain branches with chain lengths of 6-12 as measured by the Valley to Valley method. In certain embodiments, the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has between 28.0% and 31.0%, 28.0% and 30.5%, 28.0 and 30.0%, 28.5% and 31.0%, 28.5% and 30.5%, or 28.5% and 30.0% short chain branches with chain lengths of 6 to 12 as measured by the valley-to-valley method.

[0007] Yet another embodiment of the present disclosure is an inhibited waxy starch based on corn, wheat or tapioca having an amylopectin content in the range of 90-100% as specifically described herein; and a sedimentation volume in the range of 10-50 mL / g; and a (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio of 25.5% or less as measured by the valley to valley method, where DP13-24 is the amount of medium chain branches with chain lengths of 13 to 24 in the amylopectin fraction of said inhibited waxy starch based on corn, wheat or tapioca, and DP6-12 is the amount of short chain branches with chain lengths of 6 to 12 in the amylopectin fraction of said inhibited waxy starch based on corn, wheat or tapioca, both measured as described herein, and wherein said starch is not pregelatinized. For example, in certain embodiments, the ratio (DP13-24 - DP6-12) / (DP13-24 + DP6-12) is 25.0% or less, or even 24.5% or less, as measured by the valley-to-valley method. In certain embodiments, the ratio (DP13-24 - DP6-12) / (DP13-24 + DP6-12) is 22.0% to 25.5%, 22.0% to 25.0%, 22.0% to 24.5%, 22.5% to 25.5%, 22.5% to 25.0%, 22.5% to 24.5%, 23.0% to 25.5%, 23.0% to 25.0%, or 23.0% to 24.5%, as measured by the valley-to-valley method.

[0008] Yet another aspect of the present disclosure is an inhibited waxy starch based on corn, wheat, or tapioca having an amylopectin content in the range of 90-100%; and a sedimentation volume in the range of 10-50 mL / g; the amylopectin fraction of said inhibited waxy starch based on corn, wheat, or tapioca having no more than 54.5% medium chain branches with a chain length of 13-24 (i.e., degree of polymerization of the branched chains) as measured by a drop-to-baseline method (i.e., as described herein), and said starch is not pregelatinized. For example, in certain embodiments, the amylopectin fraction of said inhibited waxy starch based on corn, wheat, or tapioca has no more than 54.0% medium chain branches with a chain length of 13-24 as measured by a drop-to-baseline method. In certain embodiments, the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has 52.0-54.5%, 52.5-54.5%, 53.0-54.5%, 52.0-54.0%, 52.5-54.0% or 53.0%-54.0% medium chain branches with chain length of 13-24 as measured by the drop-to-baseline method.

[0009] Yet another aspect of the present disclosure is an inhibited waxy starch based on corn, wheat, or tapioca, as specifically described herein, having an amylopectin content in the range of 90-100%; and a sedimentation volume in the range of 10-50 mL / g; the amylopectin fraction of said inhibited waxy starch based on corn, wheat, or tapioca has at least 30.5% short chain branches with chain lengths of 6-12 as measured by the drop-to-baseline method (i.e., as described herein), and said starch is not pregelatinized. For example, in certain embodiments, the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has at least 31.0% short chain branches with chain lengths of 6-12 as measured by the drop-to-baseline method. In certain embodiments, the amylopectin fraction of the inhibited waxy starch based on corn, wheat, or tapioca has 30.5%-33.5%, 30.5%-33.0%, 30.5%-32.5%, 31.0%-33.5%, 31.0%-33.0% or 31.0-32.5% short chain branches with chain lengths of 6-12 as measured by the drop-to-baseline method.

[0010] Yet another embodiment of the present disclosure is an inhibited waxy starch based on corn, wheat or tapioca as specifically described herein having an amylopectin content in the range of 90-100%; and a sedimentation volume in the range of 10-50 mL / g; wherein the (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio is less than or equal to 28.0% as measured by the drop-to-baseline method, where DP13-24 is the amount of medium chain branches with chain lengths of 13-24 in the amylopectin fraction of said inhibited waxy starch based on corn, wheat or tapioca, and DP6-12 is the amount of short chain branches with chain lengths of 6-12 in the amylopectin fraction of said inhibited waxy starch based on corn, wheat or tapioca, both measured as described herein, and wherein said starch is not pregelatinized. For example, in certain embodiments, the (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio is 27.5% or less, or even 27.0% or less, as measured by the drop-to-baseline method. In certain embodiments, the (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio is 24.5% to 28.0%, 24.5% to 27.5%, 24.5% to 27.0%, 25.0% to 28.0%, 25.0% to 27.5%, 25.0% to 27.0%, 25.5% to 28.0%, 25.5% to 27.5%, or 25.5% to 27.0%, as measured by the drop-to-baseline method.

[0011] Yet another aspect of the present disclosure is an inhibited waxy tapioca starch having an amylopectin content in the range of 90-100%; and a sedimentation volume in the range of 10-50 mL / g; the amylopectin fraction of said inhibited waxy tapioca starch having substantially more medium chain branches with chain lengths of 13-24 than native waxy rice starch, but substantially less medium chain branches with chain lengths of 13-24 than native waxy corn starch, said starch not being pregelatinized. For example, in certain embodiments, the amylopectin fraction of the inhibited waxy tapioca starch has a DP13-24 value at least 2 percentage points higher, at least 3 percentage points higher, or even at least 4 percentage points higher than the DP13-24 value for native waxy rice starch. And in certain embodiments, the amylopectin fraction of the inhibited waxy tapioca starch has a DP13-24 value that is at least 2 percentage points lower, or even at least 3 percentage points lower, than the DP13-24 value for native waxy maize starch. In certain such embodiments, the branch length is measured by the valley-to-valley method. In other such embodiments, the branch length is measured by the drop-to-baseline method. [Brief description of the drawings]

[0012] [Figure 1] 1 is a graph showing the DP13-24 fraction of example starches of the present disclosure compared to conventional starches as measured by the Valley to Valley method. [Diagram 2] 1 is a graph showing the (DP13-24-DP6-12) / (DP13-24+DP6-12) ratio of example starches of the present disclosure compared to conventional starches as measured by the Valley to Valley method. [Diagram 3] 1 is a photograph of the opacity standards used in the experiments described in the Examples. [Figure 4] 1 is a diagram illustrating the syneresis experiments performed in the examples. [Diagram 5]1 is a set of photographs for the standard for graininess used in the experiments described in the Examples. [Figure 6] 1 is a set of bar graphs showing mean values ​​of opacity, syneresis, and particulateness over time for the freeze-thaw experiments described in the Examples. [Figure 7] 1 is a set of bar graphs showing mean values ​​of opacity, syneresis, and particulateness over time for the freeze-thaw experiments described in the Examples. [Figure 8] 1 is a set of bar graphs showing mean values ​​of opacity, syneresis, and particulateness over time for the freeze-thaw experiments described in the Examples. [Figure 9] 1 is a graph showing the change in firmness after three freeze-thaw cycles versus the (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio measured by the valley-to-valley method in the experiments described in the Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The inventors have determined that starches having such properties (and in some embodiments, other properties described herein) can be particularly useful in that they are inhibited and do not necessarily have to be classified as "modified" starches despite having favorable stability properties. For example, the starches of the present disclosure can provide desirable freeze-thaw safety, desirable refrigerated storage safety, and / or desirable storage safety.

[0014] Those skilled in the art understand that various native starches have different relative amounts of the two major components of starch polysaccharides, amylose (a linear, alpha-1,4-linked polyglucoside) and amylopectin (a branched alpha-1,4-linked polyglucoside with alpha-1,6-linked branch points). So-called "waxy" starches have at least 90% amylopectin (i.e., the total amount of amylose and amylopectin). Typical non-waxy starches have amylopectin in amounts ranging from 70-85%. In certain embodiments, the inhibited waxy starches based on corn, wheat, or tapioca specifically described herein have amylopectin contents ranging from 95-100%. In other embodiments, the inhibited waxy starches based on corn, wheat or tapioca specifically described herein have an amylopectin content of at least 99%, or at least 99.9%. High amylopectin provides waxy starches with different properties than non-waxy starches, such as higher viscosity, longer and more cohesive paste formation, and higher resistance to retrogradation.

[0015] In certain embodiments of the inhibited waxy starch based on corn, wheat or tapioca specifically described herein, the inhibited waxy starch is waxy tapioca starch (also known as cassava waxy starch). In other embodiments of the inhibited waxy starch based on corn, wheat or tapioca specifically described herein, the inhibited waxy starch is waxy corn starch (i.e. waxy maize starch). In other embodiments of the inhibited waxy starch based on corn, wheat or tapioca specifically described herein, the inhibited waxy starch is waxy wheat starch (i.e. waxy wheat starch). Those skilled in the art can distinguish between different starch 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 stained with iodide, and use the size and shape of the observed granules to determine the type of starch. Those skilled in the art will appreciate that different types of starch from different sources can have different textural and rheological properties and therefore may be desirable for use in different food applications.

[0016] The inhibited waxy starches based on corn, wheat or tapioca of the present invention can have various sedimentation volumes ranging from 10 to 50 mL / g. For example, in certain embodiments, the inhibited waxy starches based on corn, wheat or tapioca specifically described herein have sedimentation volumes ranging from 15 to 40 mL / g. In other embodiments, the inhibited waxy starches based on corn, wheat or tapioca specifically described herein have sedimentation volumes ranging from 18 to 35 mL / g. In various additional embodiments, the inhibited waxy starches based on corn, wheat or tapioca specifically described herein have sedimentation volumes ranging from 10 to 40 mL / g, or 10 to 35 mL / g, or 15 to 50 mL / g, or 15 to 35 mL / g, or 18 to 50 mL / g, or 18 to 40 mL / g. In yet other embodiments, the inhibited waxy starch based on corn, wheat, or tapioca specifically described herein has a viscosity of 10-45 mL / g, or 10-30 mL / g, or 10-25 mL / g, or 10-20 mL / g, or 15-45 mL / g, or 15-30 mL / g, or 15-25 mL / g, or 15-20 mL / g, or 20-50 mL / g, or 20-45 mL / g, or 20-40 mL / g, or 20-35 mL / g. L / g, or 20-30 mL / g, or 20-25 mL / g, or 25-50 mL / g, or 25-45 mL / g, or 25-40 mL / g, or 25-35 mL / g, or 25-30 mL / g, or 30-50 mL / g, or 30-45 mL / g, or 30-40 mL / g, or 30-35 mL / g, or 35-50 mL / g, or 35-45 mL / g, or 35-40 mL / g, or 40-50 mL / g. One skilled in the art will appreciate that the sedimentation volume is a measure of the degree of inhibition of the starch and will select the desired sedimentation volume range for a particular end use application of the inhibited corn, wheat or tapioca based waxy starches described herein.

[0017] As used herein, the settling volume is the volume occupied by 1 g of cooked starch (dry basis) in 100 g of salted buffer solution (i.e., total amount, including starch). This value is also known in the art as the "swelling volume." As used herein, "salted buffer solution" refers to a solution prepared by 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 Rikka Chemical Co.) to fill the flask at least halfway; c) Stir until the sodium chloride dissolves; d) Add additional RVA pH 6.5 buffer to bring the final volume to 2 liters.

[0018] Sedimentation volumes as described herein are measured by cooking starch at 5% solids in salted buffer solution by first suspending the container containing 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 allowing the paste to remain at 95°C for 20 minutes. The container is removed from the bath and allowed to cool on the bench. The resulting paste is brought to the initial weight by adding water (i.e., to replace any evaporated water) and mixing well. 20.0 g of paste (containing 1.0 g starch) is weighed into a 100 mL graduated cylinder containing salted buffer solution, and the total weight of the mixture in the cylinder is brought to 100 g with buffer. The cylinder is allowed to stand for 24 hours. The volume occupied by the starch sediment (i.e., as read off the cylinder) is the sedimentation volume for 1 g of starch, i.e., in mL / g.

[0019] The present inventors have determined that inhibited waxy starches based on corn, wheat or tapioca having a particular branch chain length distribution may provide particularly desirable properties. Thus, in the particular inhibited waxy starches based on corn, wheat or tapioca of the present disclosure, the amylopectin fraction has less than 48.5% medium chain branches with a chain length of 13-24, and / or at least 28% short chain branches with a chain length of 6-12, and / or a (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio of less than 25.5%, all as measured using the valley-to-valley method described herein.

[0020] The inventors have also determined that inhibited waxy starches based on corn, wheat or tapioca having a particular branch chain length distribution may provide particularly desirable properties. Thus, in the particular inhibited waxy starches based on corn, wheat or tapioca of the present disclosure, the amylopectin fraction has less than 54.5% medium chain branches with a chain length of 13-24, and / or at least 30.5% short chain branches with a chain length of 6-12, and / or a (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio of less than 28.0%, all as measured using the drop-to-baseline method described herein.

[0021] The present inventors have also determined that an inhibited waxy starch based on tapioca having a particular branch chain length distribution may provide particularly desirable properties. Thus, in the particular inhibited waxy tapioca starch of the present disclosure, the amylopectin fraction has substantially more medium chain branches with chain lengths of 13-24 than native waxy rice starch, but substantially fewer medium chain branches with chain lengths of 13-24 than native waxy corn starch. As used herein, "native waxy corn starch" is starch derived from the endosperm of a waxy corn plant that does not contain the recessive sugary-2 (su2) allele, as described in U.S. Patent No. 5,954,883, the entire contents of which are incorporated herein by reference. As used herein, native waxy rice starch is native waxy rice starch from waxy rice varieties such as Taichung Waxy 1, Taichung Waxy 70, Tachimemochi and Tainung Sen Waxy 2. In certain embodiments, the DP13-24 value for the inhibited waxy tapioca starch of the present invention is at least 2 percentage points higher, at least 3 percentage points higher, or even at least 4 percentage points higher than the DP13-24 value for native waxy rice starch. In certain embodiments, the DP13-24 value for the inhibited waxy tapioca starch of the present invention is at least 2 percentage points lower, or even at least 3 percentage points lower than the DP13-24 value for native waxy corn starch. Comparing the DP13-24 values ​​for comparative waxy rice and waxy corn starches with the D13-24 values ​​for the inhibited waxy tapioca starches of the present disclosure provides an alternative method for identifying certain desirable starches. Notably, when making such comparisons, certain measurement artifacts can be controlled. In certain such embodiments, the chain length is determined by the valley-to-valley method described herein. In other such embodiments, the chain length is determined by the drop-to-baseline method described herein.

[0022] Such starches can have a non-cohesive, smooth texture when cooked or gelatinized, and can exhibit rheological and textural stability over the desired shelf life, as well as resistance to processing conditions (e.g., heat, shear, and / or extremes of pH), and even under freezing and / or freeze / thaw conditions.

[0023] In the valley-to-valley method, the branch length of the amylopectin fraction is measured by first exhaustively debranching the amylopectin using isoamylase (from Pseudomonas sp., EC 3.2.1.68, with an isoamylase activity on oyster glycogen of 240 U / mg, alpha amylase activity on reduced maltohebutose of less than 0.001 U / mg, maltase activity on maltose of less than 0.001 U / mg, and exo-alpha-glucanase activity on linear alpha-1,4-maltodextrin of less than 0.000001 U / mg) at pH 4.0 and 45° C. for 16 hours. A fresh acetic acid solution (i.e., not stored at 4° C. for more than 5 days) 100 mM at pH 4.0 is used for debranching. Isoamylase can be purchased from Megazyme, Wicklow, Ireland. Specifically, debranching is performed as follows: 1. Weigh 10 mg of waxy starch into the bottom of a glass test tube (Fisher, #14-962-26G). Add 3 ml of Milli-Q water and cap the tube. Prepare duplicate samples. 2. Heat the test tube containing the sample in boiling water for 1 hour, swirling at intervals. 3. Cool the test tube to room temperature. Add 2 ml of acetate buffer (pH 4.0) and mix well. 4. Add 10 ul of isoamylase (5 U), place a star-shaped stir bar into each tube, mix well, and cap. 5. Incubate samples in a 45°C heating block with constant agitation for at least 16 hours. 6. Heat the sample at 100°C for 30 minutes to inactivate the enzyme. 7. Allow the samples to cool to 40°C and filter through a 0.45 μm nylon syringe filter into an autosampler vial.

[0024] Characterization of debranched waxy starch is performed by HPAE-PAD (high performance anion exchange chromatography with pulsed amperometric detection) on a Dionex ICS-3000 (Dionex, Sunnyvale, CA). A Dionex CarboPac PA1 analytical column (4 × 250 mm) is used with a CarboPac PA2 guard column (4 × 50 mm). The eluents used for the separation were 150 mM NaOH (eluent A) and 150 mM NaOH containing 500 mM NaOAc (eluent B) prepared in degassed 18 MΩ·cm water and then filtered through a 0.2 μm membrane filter. The gradient program for the separation was as follows: 0–5 min at 60% A, 5–20 min at 60%–40% A, 20–50 min at 40%–20% A, and 50–55 min at 20% A. As will be understood by those skilled in the art, "60%A" refers to an eluent mixture of 60% eluent A and 40% eluent B. The injection volume of the sample solution is 10ul. Each experiment was performed at 30°C with a flow rate of 1.2ml / min. The working electrode is gold and the reference electrode is silver-silver chloride. The waveform is "Gold Standard PAD". The column is equilibrated and regenerated as follows: the system is equilibrated at 100%A for 30 minutes before injection and then at 60%A for at least 30 minutes. After every 5 sample injections, the column is regenerated at 100%A for 30 minutes, then equilibrated at 60%A for 30 minutes, and then the retention time is checked with 5ppm DP1-7 mixed standard solution. Sugar standards with degrees of polymerization from 1 to 7 can be purchased, for example, from Sigma Aldrich.

[0025] To analyze the data with the valley-to-valley analytical method, calculate the peak area by integrating the peaks valley-to-valley. Chain length distributions are expressed as a percentage of the total peak area from DP6 to DP53, ignoring the detector response that changes with DP. Chain length distributions between DP6 and DP12 are summarized as "DP6-12". Chain length distributions between DP13 and DP24 are summarized as "DP13-24". DP6-12 and DP13-24 of the three replicate experiments should have a %RSD lower than 2%.

[0026] To analyze the data with the drop-to-baseline analysis method, starch samples (20 mg, dry basis) are mixed with 10 ml of acetate buffer (0.01 M, pH 4) and subsequently cooked in a boiling water bath for 1 h. After cooling to 50°C, the gelatinized starch is debranched by adding 20 ul of isoamylase (Megazyme, Wicklow, Ireland). Starch debranching is allowed to proceed overnight (≥12 h) before the enzyme is inactivated by heating the samples in a boiling water bath for 30 min. After cooling to room temperature, a pulsed amperometric detector and CarboPac TM Samples of 1-1.5 ml were passed through a 45 μm filter before injection into the AS-DV autosampler of an HPAEC (Dionex ICS-3000, Sunnyvale, CA) equipped with a PA1 analytical column. Samples were eluted with a gradient program of 40% at 0 min, 50% at 2 min, 60% at 10 min, and 80% at 40 min of eluent B, where eluent A was 100 mM sodium hydroxide in water and eluent B was 150 mM sodium hydroxide in water containing 500 mM sodium acetate. The flow rate and separation temperature were maintained at 1 ml / min and 25°C, respectively, during the run. Peaks were resolved using a Chromeleon TMThe areas were integrated according to an automatically generated baseline using version 6.8 (Thermo Fisher Scientific, Waltham, MA). The relative area% of each detectable DP, expressed as the area of ​​each peak in the chromatogram as a percentage of the total area of ​​all peaks, was calculated using Chromeleon TM As mentioned above, the chain length distribution is expressed as a percentage of the total peak area from DP6 to DP53, ignoring the detector response which varies with DP. The chain length distribution between DP6 and DP12 is summarized as "DP6-12". The chain length distribution between DP13 and DP24 is summarized as "DP13-24". Peaks are confirmed using standards from Sigma-Aldrich, St. Louis, MO.

[0027] Those skilled in the art will appreciate that the branch chain length distribution of the amylopectin fraction of the waxy starch feedstock used to produce the inhibited waxy starch based on corn, wheat or tapioca can be substantially reflected in the branch chain length distribution of the amylopectin fraction of the inhibited waxy starch based on corn, wheat or tapioca. In the various methods for producing inhibited waxy starch based on corn, wheat or tapioca described herein, the process conditions will not substantially change the branch chain length distribution of the amylopectin fraction. In certain embodiments, for example, when using a particular waxy tapioca starch as the feedstock, the waxy starch feedstock will have a desired distribution of medium chain branches, as described above. However, in other embodiments, for example when certain waxy maize starches or waxy wheat starches are used as feedstocks, the waxy starch feedstock may be treated to reduce the relative amount of medium chain branches with chain lengths of 13 to 24 and / or to increase the relative amount of short chain branches with chain lengths of 6 to 12. Such treatments may be carried out, for example, using enzymatic methods.

[0028] The inhibited waxy starches based on corn, wheat or tapioca described herein can be produced with relatively low color development. For example, certain embodiments of the inhibited waxy starches based on corn, wheat or tapioca described herein are low color development, 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 low color development, i.e., have a Yellowness Index of less than 8 (e.g., 3-8 or 5-8). The Yellowness Index is measured by ASTM E313.

[0029] In particular, the inhibited waxy starch based on corn, wheat or tapioca described herein can be produced without many of the conventional chemical modifiers used to produce conventional modified and / or inhibited starches. Thus, in certain preferred embodiments, the inhibited waxy starch based on corn, wheat or tapioca described herein can be labeled as a so-called "clean label" starch. For example, in certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca described herein is not hydroxypropylated. In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca described herein is not acetylated. In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca described herein is not carboxymethylated. In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca described herein is not hydroxyethylated. In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca specifically described herein is not phosphorylated. In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca specifically described herein is not succinylated (e.g., not octenyl succinylated). In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca specifically described herein is not cationic or zwitterionic.

[0030] Similarly, in certain embodiments, the inhibited waxy starches based on corn, wheat, or tapioca described herein can be produced without the use of cross-linking agents commonly used in starch inhibition. For example, in certain embodiments, the inhibited waxy starches based on corn, wheat, or tapioca described herein are not cross-linked with phosphate (e.g., with phosphorus oxychloride or metaphosphate). In certain embodiments, the inhibited waxy starches based on corn, wheat, or tapioca described herein are not cross-linked with adipate. In certain embodiments, the inhibited waxy starches based on corn, wheat, or tapioca described herein are not cross-linked with epichlorohydrin. In certain embodiments, the inhibited waxy starches based on corn, wheat, or tapioca described herein are not cross-linked with acrolein.

[0031] And, the corn-, wheat-, or tapioca-based inhibited waxy starches of the present invention (e.g., having the above-mentioned yellowness index) can, in certain embodiments, be produced without the use of other harsh chemical treatments common in the art. For example, in certain embodiments, the corn-, wheat-, or tapioca-based inhibited waxy starches specifically described herein are not bleached or oxidized by hydrogen peroxide or hypochlorite. Of course, in other embodiments, hydrogen peroxide or hypochlorite can be used to provide better color development to the corn-, wheat-, or tapioca-based inhibited waxy starches described herein.

[0032] In certain embodiments, the inhibited waxy starch based on corn, wheat or tapioca of the present invention can be produced without dextrinization and thus does not contain significant amounts of repolymerized branched chains typical of dextrins.Accordingly, in such embodiments, the inhibited waxy starch based on corn, wheat or tapioca specifically described herein is substantially free of 1,2- and 1,3-branching (e.g., less than 1% each).Such branching can be determined using nuclear magnetic resonance techniques known to those skilled in the art.

[0033] The corn, wheat or tapioca based inhibited waxy starches of the present invention can have a variety of viscosities as measured by a Rapid Visco Analyzer (RVA). For example, in certain embodiments, the corn, wheat or tapioca based inhibited waxy starches specifically described herein can have a viscosity as measured by RVA in the range of 50-1500 cP. In such certain embodiments, the viscosity as measured by RVA can be in the range of 50-1000 cP, 50-850 cP, 50-700 cP, 50-500 cP, 50-400 cP, 50-300 cP, 50-200 cP, 100-1100 cP, 100-1000 cP, 100-850 cP, 100-700 cP, 100-500 cP, 100-400 cP, , 100-300 cP, 200-1100 cP, 200-1000 cP, 200-850 cP, 200-700 cP, 200-500 cP, 400-1100 cP, 400-1000 cP, 400-850 cP, 400-700 cP, 600-1100 cP or 600-850 cP, 700-1500 cP or 700-1300 cP. Viscosity is measured by RVA at 5% solids in pH 6.5 phosphate buffer in 1% NaCl at a stirring speed of 160 rpm. The initial temperature of the analysis is 50°C; the temperature is linearly increased to 90°C over 3 minutes, then held at 95°C for 20 minutes, then linearly decreased 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 a time of about 2-5 minutes, the measured final viscosity is higher than the pasting peak viscosity. If no pasting peak is present, the viscosity is plateau or increases during the 95°C hold.

[0034] As mentioned above, the corn, wheat or tapioca based inhibited waxy starches of the present invention are not pregelatinized.

[0035] In certain embodiments, the inhibited waxy starches based on corn, wheat or tapioca of the present invention substantially maintain intact granules upon cooking. Particle size, as used herein, is measured by cooking the starch at 5% solids in a salted buffer solution by suspending the container containing 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 allowing the paste to remain at 95°C for an additional 20 minutes, and then allowing the paste to cool to room temperature. After cooking in this manner, swollen but intact granules can be observed under a microscope. Those skilled in the art will appreciate that minor deviations from particle size are acceptable. For example, in certain embodiments of the inhibited waxy starches based on corn, wheat or tapioca specifically described herein, no more than 30% of the starch granules are damaged upon cooking (i.e., as explained above for particle size). In certain such embodiments, no more than 20%, or even no more than 10% of the starch granules are damaged upon cooking (i.e., as explained above for particle size). One of ordinary skill in the art can view the starch granules under a microscope (e.g., stained) as is conventional in the art to determine whether the starch granules remain intact.

[0036] Certain desirable embodiments of the inhibited waxy starches based on corn, wheat or tapioca described herein are substantially digestible. For example, in certain embodiments of the inhibited waxy starches based on corn, wheat or tapioca described herein, the amount of fiber is less than 10% as determined by AOAC 2001.03. In certain such embodiments, the amount of fiber is less than 5%, or even less than 2%.

[0037] As mentioned above, the starches of the present invention are inhibited. As used herein, the term "inhibited starch" refers to starches that exhibit "process resistance". As used herein, the term "process resistance" means that the starch particles swell in water when cooked, but substantially retain their particulate properties throughout the process. Process resistant starches resist degradation into fragments and resist dissolution during processing. Inhibited starches can vary in their degree of inhibition, characterized by their observed microscopic examination and swelling volume. The degree of inhibition can be assessed by cooking the starch in water (typically cooked at 95°C for 30 minutes with hand stirring for the first 6 minutes) and then observing the cook under a microscope. Uninhibited starches will have unusual granules and debris, as they tend to dissolve in water during cooking. Inhibited starches will show swollen, intact particles under a microscope, highly inhibited starches will show small, dark particles, and slightly inhibited starches will show large, light particles. Alternatively, the degree of inhibition can be assessed by measuring the sedimentation volume of the starch as described above.

[0038] The corn, wheat or tapioca based inhibited waxy starches of the present invention can be produced using a variety of methodologies. A variety of waxy starch feedstocks can be used (e.g., natural starches such as waxy tapioca starch, waxy corn starch, or any other waxy starch described herein). The waxy starch feedstock can be pretreated, for example, to reduce the amount of lipid and / or protein present in the starch, as is conventional in the art.

[0039] In a particular embodiment, the inhibited waxy corn, wheat or tapioca based starches of the present invention are produced using the methods described in International Patent Application Publication No. WO 2013 / 173161, the entire contents of which are incorporated herein by reference. Thus, the method for producing the starches described herein includes the steps of: a) heating non-pregelatinized granular waxy starch in an alcoholic medium in the presence of a base at a temperature of at least 35°C; b) neutralizing the base with an acid; c) separating the granular waxy starch from the alcohol medium; and d) removing the alcohol solvent from the waxy granular starch, for example by heating or steam. The alcoholic medium generally comprises at least one alcohol, in particular a C1-C4 monoalcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol, etc. One or more other substances may be present in the alcoholic medium, such as a non-alcoholic organic solvent (in particular one that is miscible with alcohol) and / or in water. However, in one embodiment of the above method, the alcoholic medium does not contain any solvent other than alcohol and water. For example, aqueous alcohol can be used to advantage. The alcoholic medium can, for example, comprise 30% to 100% by weight of alcohol (e.g., ethanol) and 0% to 70% by weight of water. In one embodiment, the alcoholic medium comprises 80% to 96% by weight of alcohol (e.g., ethanol) and 4% to 20% by weight of water, the total amount of alcohol and water being equal to 100%. In another embodiment, the alcoholic medium comprises 90% to 100% by weight of alcohol (e.g., ethanol) and 0% to 10% by weight of water, the total amount of alcohol and water being equal to 100%. In other embodiments, 10% or less by weight or 15% or less by weight water is present in the alcohol medium. The amount of alcohol medium relative to the starch is not considered critical, but generally, for convenience and ease of processing, sufficient alcohol medium is present to provide a stirrable and / or pumpable slurry. For example, the weight ratio of starch:alcohol medium can be from about 1:2 to about 1:6.

[0040] In certain processes, at least some amount of treating agent (base and / or salt) is present when the waxy starch feedstock is heated in the alcohol medium. However, in contrast to previously known starch modification processes, it is advantageous not to use large amounts of treating agent (relative to the starch) to achieve effective inhibition of the starch. This simplifies the subsequent processing of inhibited waxy starch based on corn, wheat or tapioca and reduces potential production costs. Typically, at least 0.5% by weight of treating agent (based on the dry weight of the starch used) is used, but in other embodiments at least 1% or more, 2%, at least 3%, at least 4%, or at least 5% by weight of treating agent is present. For economic reasons, typically no more than 10% or 15% by weight of treating agent is present.

[0041] Generally, the mixture of starch, alcohol medium and treating agent is in the form of a slurry. In certain embodiments, it may be desired to adjust the pH of the slurry to a particular value. Measuring the pH of such a slurry may be difficult due to the presence of alcohol. In an embodiment where a base is added to make the slurry basic, the appropriate amount of base can be determined as if the slurry were a starch slurry in deionized water alone, and then scaled up with the actual amount while maintaining the same ratio of base to starch.

[0042] The slurry can be, for example, neutral (pH 6-8) or basic (pH greater than 8). In one embodiment, the pH of the slurry is at least 6. In another embodiment, the pH of the slurry is at least 7. In another embodiment, the pH of the slurry is 12 or less. In other embodiments, the pH of the slurry is 6-10, 7.5-10.5, or 8-10. In yet other embodiments, the pH of the slurry is 5-8 or 6-7.

[0043] Treatment of starch with an alcohol treating agent can be accomplished by first placing the starch in an alcohol medium and then adding the treating agent (e.g., base and / or salt). Alternatively, the treating agent can be mixed with the alcohol medium first and then contacted with the starch. The treating agent can be formed in situ, such as by separate addition of a base and an acid that react to form a salt that functions as the treating agent.

[0044] Suitable bases for use in the above process include, but are not limited to, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide, calcium hydroxide, and sodium hydroxide.

[0045] Salts suitable 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 between 6 and 8). Particularly useful are alkali metal-containing salts, as well as salts (e.g., sodium or potassium salts) of organic acids, 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.

[0046] Mixtures of different treating agents can be used, for example, starch can be heated in an alcohol medium in the presence of both at least one base and at least one salt.

[0047] The starch, alcohol medium and treating agent are heated for a time and temperature effective to inhibit the starch to the desired degree. Generally, a temperature above room temperature (i.e., 35°C or higher) will be necessary. At the same time, extremely high temperatures should be avoided. The heating temperature may be, for example, 35°C to 200°C. Generally, temperatures of 100°C to 190°C, 120°C to 180°C, or 130°C to 160°C, or 140°C to 150°C will be sufficient. The heating time is generally at least 5 minutes but not more than 20 hours, usually 40 minutes to 2 hours. Generally, the desired level of starch inhibition can be achieved more quickly as the heating temperature is increased.

[0048] The specific conditions of treatment time, treatment temperature, and ratios of the components of the mixture of starch, alcohol medium, and treating agent are generally selected so that the starch does not gelatinize to any significant extent, i.e., the starch remains in a non-pregelatinized state, as explained above.

[0049] If the temperature selected for the heating step exceeds the boiling point of one or more components of the alcohol medium, it may be advantageous to carry out the heating step in a vessel or other device that can be pressurized. The treatment can be carried out in a confined area to maintain the alcohol medium in a liquid state. Additional positive pressure can be used, but is generally not necessary. The starch can be slurried in the alcohol medium with the treating agent under conditions of high temperature and pressure and treated for a time sufficient to change the viscosity characteristics of the starch. Such treatment can be carried out in a batch stirred tank reactor or a continuous tubular reactor, although other suitable processing techniques will be apparent to those skilled in the art. In another embodiment, the starch can be in the form of a bed in a tubular reactor, and the mixture of alcohol medium and treating agent is passed through such bed (optionally continuously), and the bed is maintained at the desired temperature, resulting in inhibition of the starch.

[0050] In embodiments where a base is used as the treating agent, the mixture of starch, alcohol medium and base, once the heating step is completed, can be mixed with one or more acids for the purpose of neutralizing the base. Suitable acids for use in such a neutralization step include, but are not limited to, organic carboxylic acids, such as itaconic acid, malonic acid, lactic acid, tartaric acid, oxalic acid, fumaric acid, aconitic acid, succinic acid, oxalosuccinic acid, glutaric acid, ketoglutaric acid, malic acid, citric acid, fatty acids and salts of combinations thereof, and other types of acids, such as uric acid. If the inhibited starch is intended for use as a food ingredient, the acid should generally be selected to be one that is acceptable for such use under applicable regulations. Generally, sufficient acid is added to lower the pH of the mixture to about neutral to slightly acidic, e.g., a pH of about 5 to about 7 or about 6 to about 6.5.

[0051] Neutralization with acid can be carried out at any suitable temperature. In one embodiment, the slurry of starch, base and alcohol medium is allowed to cool from the heating temperature used to about room temperature (e.g., about 15°C to 30°C) before mixing with the acid used for neutralization. The neutralized mixture can then be further processed to separate the inhibited starch from the alcohol medium, as described below. However, in another embodiment, the starch slurry is further heated following base neutralization. It has been found that such further heating can alter the rheological properties of the resulting inhibited starch, as compared to the rheological properties of a similarly prepared starch that has not been heated after base neutralization.

[0052] Generally, it is advantageous to carry out such further heating steps at temperatures above room temperature (i.e. above 35°C). At the same time, very high temperatures should be avoided. The heating temperature may be, for example, between 35°C and 200°C. Generally, temperatures between 100°C and 190°C, between 120°C and 180°C, or between 130°C and 160°C, or between 140°C and 150°C will be sufficient. The heating time is generally at least 5 minutes but not more than 20 hours, usually between 40 minutes and 2 hours.

[0053] The mixture of starch and alcohol medium can be processed to separate the starch from the alcohol medium. Conventional methods for recovering particulate solids from liquids such as filtration, decantation, sedimentation or centrifugation can be adapted for such purposes. The separated starch can be washed with additional alcohol medium and / or alcohol and / or water to remove any undesirable water-soluble impurities. In one embodiment, neutralization of residual base is achieved by washing the recovered starch with an acidified liquid medium. Drying of the separated starch will provide an inhibited non-pregelatinized granular starch according to the invention. For example, this can be done at relatively high temperatures (e.g., 30°C to 60°C) in suitable equipment such as an oven or fluidized bed reactor or dryer or mixer. To facilitate removal of volatile materials (e.g., water, alcohol) from the starch, vacuum and / or gas purge (e.g., nitrogen sweep) can be applied. The resulting dried inhibited non-pregelatinized granular starch can be crushed, ground, milled, screened or sieved or any other such technique to achieve a particular desired particle size. In one embodiment, the inhibited starch is in the form of a free-flowing granular material.

[0054] However, in one embodiment, the starch is applied to the desolventization step at significantly higher temperatures (e.g., above 80°C or above 100°C or above 120°C). However, excessively high temperatures should be avoided as they may cause denaturation or discoloration of the starch. Such a step not only reduces the amount of residual solvent (alcohol) in the product, but also provides the unexpected additional advantage of enhancing the degree of inhibition exhibited by the starch. The desolventization temperature may be, for example, from about 100°C to about 200°C. Typically, the temperature is between 120°C and 180°C or between 150°C and 170°C. The desolventization may be carried out in the presence or absence of steam. Steam treatment has been found to be advantageous in that it helps to minimize the degree of discoloration of the starch that may occur at such high temperatures. In one embodiment, steam is passed through a bed or cake of inhibited waxy starch based on corn, wheat, or tapioca. For all purposes, the starch desolventization method of U.S. Patent No. 3,578,498, incorporated herein by reference in its entirety, may be adapted for use. After steam treatment, the inhibited waxy starch based on corn, wheat, or tapioca may be dried (e.g., by heating in an oven or in a fluidized bed reactor at a temperature of about 30° C. to 70° C.) to reduce the residual moisture content.

[0055] In one embodiment, the treated starch recovered from the alcohol medium is initially provided with a total volatiles content of about 35% by weight or less, or about 15% by weight or less. This can be accomplished, for example, by first air-drying or oven-drying the recovered starch at a moderate temperature (e.g., 20° C.-70° C.) to the desired initial volatiles content. Live steam is then passed through the dried starch, maintaining the system at a temperature above the condensation point of the steam. A fluidized bed apparatus can be used to carry out such a steam desolventization step.

[0056] Generally, it will be desirable to carry out the desolventization under conditions effective to result in a residual alcohol content in the inhibited corn, wheat, or tapioca based waxy starch of less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight.

[0057] After being desolventized, the inhibited waxy corn, wheat, or tapioca based starch can be washed with water and then redried to further improve color and / or flavor and / or reduce moisture content.

[0058] Of course, one skilled in the art can use other methodologies to arrive at the starches described herein. Waxy starch feedstock can, for example, be pH adjusted and heated. pH adjustment can be achieved by contacting a pH adjuster with the starch; examples of pH adjusters include formic acid, propionic acid, butyric acid, oxalic acid, lactic acid, malic acid, citric acid, fumaric acid, succinic acid, glutaric acid, malonic acid, tartaric acid, itaconic acid, aconitic acid, oxalosuccinic acid, ketoglutaric acid, fatty acids and carbonic acid, as well as their salts (e.g. potassium and / or sodium salts, which can be generated in situ by neutralization of the acidity). The pH adjuster can be contacted with the starch feedstock in any convenient manner, for example, as a slurry in a liquid (e.g., water, an alcohol including an aqueous alcohol such as aqueous ethanol (e.g., as described above including ethanol or isopropanol) or another solvent); in dry form; in wet form (e.g., a mist in a solvent (e.g., water, aqueous ethanol or another solvent); or in the form of a starch wet dough (e.g., with water, aqueous ethanol or another solvent). Also, when an alkali metal salt of an acid is used, for example, the acid and the alkali metal hydroxide or carbonate can be added in a separate step and formed in situ.

[0059] A pH adjustment can be performed and various pH values ​​calculated. For example, in certain embodiments and as described in WO 2013 / 173161, a pH adjustment can be performed and a pH in the range of 7-10 can be calculated. In other alternative embodiments, a pH adjustment can be performed and a pH in the range of 3-7 can be calculated, for example, 3-6, or 3-5, or 3-4, or 4-7, or 4-6, or 4.5-7, or 4.5-6, or 5-7, or 5-6, or about 3, or about 3.5, or about 4, or about 4.5, or about 5, or about 5.5, or about 6, or about 6.5, or about 7. If the pH adjustment is performed in a slurry, the pH of the slurry is the relevant pH. If the pH adjustment is performed in a substantially non-liquid form (e.g., dough or wet solids), the pH of 38% solid material in water is the relevant pH. The amount of pH adjuster relative to the starch can vary, for example, from 0.05 to 30% by weight, e.g., 0.05 to 20% by weight, 0.05 to 10% by weight, 0.05 to 5% by weight, 0.05 to 2% by weight, 0.05 to 1% by weight, 0.05 to 0.5% by weight, 2 to 30% by weight, 0.2 to 20% by weight, 0.2 to 10% by weight, 0.2 to 5% by weight, 0.2 to 2% by weight, 0.2 to 1% by weight, 1 to 30% by weight, 1 to 20% by weight, 1 to 10% by weight, 1 to 5% by weight, 5 to 30% by weight, or 5 to 20% by weight, based on dry solids. Desirably, the pH adjuster is thoroughly mixed with the starch feedstock. This will require different process conditions depending on the form in which the pH adjustment is performed. If the pH adjustment is performed in a slurry, simply stirring the slurry for a few minutes is sufficient. If the pH adjustment is done in a drier form (e.g., wet solids or dough), a more substantial contacting procedure may be desired. For example, if the pH adjuster solution is sprayed onto a dry starch feedstock, mixing for about 30 minutes followed by storage for at least several hours may be desired. To provide uniform inhibition, it is desirable to provide a uniform pH adjuster distribution throughout the starch, i.e., at the granule level.

[0060] After contacting the pH adjusting agent with the starch, the starch can be heated (i.e., while still in contact with the pH adjusting agent). The starch can be heated in a variety of forms. For example, the starch can be heated in an alcohol or non-aqueous solvent slurry (e.g., under pressure if the boiling point of the solvent is not sufficiently higher than the heating temperature); as a dough of starch, water and a non-aqueous solvent to inhibit granule swelling (e.g., as disclosed in WO 2013 / 173161); or in a dry state (the solvent can be removed using conventional techniques such as, for example, filtration, centrifugation and / or heat-drying as described above for WO 2013 / 173161). The starch can be dried, for example, to a moisture level of less than 5% before further heating. For such drying, relatively low temperatures can be used, for example, 40-80°C, or 40-60°C, or about 50°C. Vacuum can also be used in the drying step. The starch may be dried as a result of the heating process (see below); a separate drying step is not necessary.

[0061] The dry starch may be heated at a temperature ranging from 100 to 200°C. For example, in certain methods, the heating temperature is 120 to 160°C. In various other methods, the heating temperature is 120 to 180°C, or 120 to 160°C, or 120 to 140°C, or 140 to 200°C, or 140 to 180°C, or 140 to 160°C, or 160 to 200°C, or 160 to 180°C, or 180 to 200°C. The starch may be heated several times. The starch may be heated for a period of time ranging, for example, from 20 seconds to 20 hours. Typical heating times range from 10 minutes to 2 hours. Longer heating times and / or higher heat treatment temperatures may be used to provide more inhibition. The material is desirably heated uniformly. The starch may be heated under pressure or in a mass flow bin or similar device to maintain the desired moisture content.

[0062] Certain methods described herein may be carried out, for example, without the use of alcohol in the liquid medium for said contacting with pH adjustment. In certain particularly desirable methods, water is used as the medium for pH adjustment. Thus, in certain desirable embodiments, the inhibited waxy starch based on corn, wheat, or tapioca contains less than 500 ppm of alcohol solvent, for example, less than 500 ppm of ethanol. For example, in various embodiments, the inhibited waxy starch based on corn, wheat, or tapioca contains less than 100 ppm, less than 50 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppm of alcohol solvent, for example, less than 100 ppm, less than 50 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppm of ethanol.

[0063] After the cooked starch is cooled, it can be used as is or further processed in a manner conventional in the art. For example, the starch can be washed to provide a whiter color and a more pleasant flavor. When a non-aqueous solvent is used, it is desirable to remove as much of the solvent as possible. However, if a relatively low level of pH adjuster is used, the final product can meet reasonable pH and ash targets without further washing.

[0064] As one of ordinary skill in the art will appreciate, the starch feedstock can be purified, for example, by conventional methods, for example, to reduce undesirable flavors, odors and colors inherent in the starch or otherwise present. For example, impurities can be reduced using methods such as washing (e.g., alkaline washing), steam stripping, ion exchange steps, dialysis, filtration, bleaching, e.g., with chlorite, enzymatic modification (e.g., to remove proteins), and / or centrifugation. One of ordinary skill in the art will appreciate that such purification operations can be performed at various suitable points in the process.

[0065] Yet another aspect of the present disclosure is a pregelatinized starch produced by a process comprising gelatinizing and drying an inhibited waxy corn, wheat, or tapioca based starch as described herein (i.e., in the substantial absence of other food ingredients to provide a material that is at least 95% by weight, or even at least 99% by weight, on a dry solids basis, pregelatinized starch).Those skilled in the art will use conventional pregelatinization methods.

[0066] The starches described herein can be used, for example, as thickeners or viscosifiers to increase the viscosity of fluid or semi-solid compositions. One problem with conventional starches is that upon storage, e.g., upon long-term storage, upon storage at low temperatures, or upon storage undergoing freeze / thaw cycles, the starch can become dehydrated as a result of intermolecular associations and can irreversibly lose water through a process known as syneresis. This can significantly reduce the texture and crispness of the food. Advantageously, when a food containing the starch of the present disclosure is cooked and cooled to a desired storage temperature, it can maintain its textural attributes for an extended period of time throughout its shelf life and can withstand temperature fluctuations during storage (e.g., freeze-thaw cycles). Thus, food containing the starch described herein can be substantially freeze-thaw stable, substantially refrigeration stable, and / or substantially storage stable. In certain embodiments specifically described herein, the inhibited waxy starch has one or more of the following: 1) a granularity of 4 or less after three freeze-thaw cycles, 2) a syneresis of 5 or less, or even 3 or less after three freeze-thaw cycles, and 3) a hardness change of 2 or less after three freeze-thaw cycles, all of which are measured as described in the Examples below.

[0067] Thus, another aspect of the present invention is a method for producing a food product. The method includes cooking a starch as described herein in the presence of water, and providing the cooked starch in combination with one or more other food ingredients. For example, the starch as described herein can be combined with one or more other food ingredients, including water, to cook the starch-food ingredient combination. In certain embodiments, the method includes pasteurization, retort processing, kettle or batch cooking, or ultra-high temperature processing. The starch can alternatively be cooked separately and later combined with one or more food ingredients.

[0068] The food products can include, for example, tomato-based products, sauces such as gravies, white sauces or cheese sauces, soups, puddings, salad dressings (e.g., pourable or spoonable), yogurt, sour cream, puddings, custards, cheese products, fruit fillings or toppings, cream fillings or toppings, syrups (e.g., light syrups), beverages (e.g., dairy beverages), glazes, condiments, confectionery, pasta, frozen foods, cereals, or soups. A variety of cooking methods can be used, such as pasteurization, retort processing, kettle cooking, batch cooking, and ultra-high temperature processing.

[0069] The starches described herein may also be used to modify the properties of solid foods, such as confectionery bakery products, for example, by acting as an anti-scalant to provide a softer product that retains a fresher texture after storage. Thus, in other embodiments, the food product is a confectionery bakery product, such as bread, pastry, pie crust, donut, cake, biscuit, cookie, cracker, or muffin. In such embodiments, cooking may include baking. In some embodiments, the use of the starches described herein in confectionery bakery products (i.e., their doughs or doughs) may help reduce staling. In other embodiments, the starch may be included in, for example, the filling inside the confectionery bakery product.

[0070] The starch of the present invention can be used to advantage to produce a variety of other food products. For example, food products in which the starch of the present invention is useful include thermally processed foods, acidic foods, dry mixes, refrigerated foods, frozen foods, extruded foods, oven-cooked foods, stove-cooked foods, microwaveable foods, full-fat or low-fat foods, and foods with low water activity. Food products in which the starch of the present invention is particularly useful are foods that require a thermal processing step, such as pasteurization, retort processing, high-temperature short-time processing, or ultra-high temperature (UHT) processing. The starch of the present invention is particularly useful in food applications that require stability over all processing temperatures, including cooling, freezing, and heating.

[0071] Based on the processed food preparation, the practitioner can readily select the amount and type of starch of the present invention needed to provide the desired texture as well as the requisite thickness and gelling viscosity in the finished food product. Generally, the starch is used in an amount of 0.1 to 35%, e.g., 0.5 to 6.0%, by weight of the food product.

[0072] Among the foods that may be improved by use of the starches of the present invention are highly acidic foods (pH<3.7) such as fruit based pie fillings, baby foods; acidic foods (pH 3.7-4.5) such as tomato based products; weakly acidic foods (pH>4.5) such as gravies, sauces and soups; stove cooked foods such as sauces, gravies and puddings; ready to eat foods such as puddings; pourable and spoonable salad dressings; refrigerated foods such as dairy or dairy-like products (e.g., yogurt, sour cream and cheese); frozen foods such as frozen desserts and frozen dinners; microwaveable foods such as frozen dinners; liquid products such as diet and hospital foods; dry mixes for the manufacture of confectionery and bakery products, gravies, sauces, puddings, baby foods, hot cereals, and the like; and dry mixes for predusting foods prior to dough cooking and frying.

[0073] In another embodiment, the food product is a confectionery.

[0074] 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 present invention, the starches are used in foods selected from baked foods, breakfast cereals, anhydrous coatings (e.g., ice cream compound coatings, chocolate), dairy products, confectionery, 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, meats and fish, dried fruits, baby foods, and doughs and coatings. The starches described herein can also be used in a variety of medical foods. The starches described herein can also be used in pet foods.

[0075] The starches of the present invention can also be used in a variety of non-food end uses where chemically modified (crosslinked) inhibited starches are traditionally utilized, such as cosmetics and personal care products, paper, packaging, pharmaceutical formulations, adhesives, etc.

[0076] Desirably, the starches of the present disclosure can provide superior properties, such as freeze-thaw safety, in combination with good digestive resistance. The inventors have determined that, unlike many highly modified starches, the starches described herein can be sufficiently inhibited to provide desirable properties, such as desirable viscosity characteristics and desirable freeze-thaw resistance, without becoming resistant to digestion or otherwise causing digestive intolerance, and even at the required storage conditions.

[0077] For example, in certain desirable embodiments specifically described herein, the starches of the present disclosure have one or more (e.g., two or more, or all three) of the following:

[0078] a) A desirable viscosity, for example a viscosity in the range of 50 to 1500 cP as measured by RVA. In certain such embodiments, the viscosity as measured by RVA is 50 to 1000 cP, 50 to 850 cP, 50 to 700 cP, 50 to 500 cP, 50 to 400 cP, 50 to 300 cP, 50 to 200 cP, 100 to 1100 cP, 100 to 1000 cP, 100 to 850 cP, 100 to 700 cP, 100 to 500 cP, 100 to 400 cP , 100-300cP, 200-1100cP, 200-1000cP, 200-850cP, 200-700cP, 200-500cP, 400-1100cP, 400-1000cP, 400-850cP, 400-700cP, 600-1100cP or 600-850cP, 700-1500cP or 700-1300cP range;

[0079] b) desirable freeze-thaw behavior, such as one or more of: 1) granularity of 4 or less after three freeze-thaw cycles; 2) syneresis of 5 or less, or even 3 or less after three freeze-thaw cycles; 3) hardness change of 2 units or less after three freeze-thaw cycles; and

[0080] c) Good digestive tolerance.

[0081] Another aspect of the present invention is a dry mix comprising the starch described herein in admixture with one or more food ingredients.When the dry mix is ​​cooked (i.e., in the presence of water), it may take longer to gel, and therefore may allow more time to maintain the cooked product, transport the cooked product (e.g., by pumping), and fill the cooked product into a container before the cooked product begins to gel.The dry mix may be, for example, a dry mix for confectionery bakery products, such as bread, pastry, pie crust, donut, cake, biscuit, cookie, cracker, or muffin.

[0082] Further explanation is provided below with reference to examples.

[0083] Example 1 - Viscosity and Sedimentation Volume of Inhibited Waxy Starch The waxy starch feedstock is pH adjusted using any of the following pH adjusters: formic acid, propionic acid, butyric acid, oxalic acid, lactic acid, malic acid, citric acid, fumaric acid, succinic acid, glutaric acid, malonic acid, tartaric acid, itaconic acid, aconitic acid, oxalosuccinic acid, ketoglutaric acid, and carbonic acid, as well as their salts (e.g., potassium and / or sodium salts, which may be generated in situ by neutralization of the acidity). The pH adjuster is contacted with the starch feedstock in a slurry in liquid (e.g., water) under stirring for several minutes. The pH adjustment can be performed in a pH range between 3.5 and 7.0. The amount of pH adjuster relative to the starch can vary, for example, between 0.01 and 30% by weight based on the dry solids weight of the starch. After contacting the pH adjuster with the starch, the starch (i.e., while still in contact with the pH adjuster) is dried to a moisture level of less than 1% before being further heated, and the dried starch is heated at a temperature in the range of 100-200°C for a period of time, e.g., in the range of 20 seconds to 20 hours.

[0084] Native waxy maize starch and native waxy tapioca starch have an amylopectin content of 90% or greater per information provided by the supplier. Sedimentation volume and RVA viscosity data for both native and inhibited waxy starches are provided in Table 1 below. Samples 1-4 were made using native waxy tapioca starch as the starting material and Samples 5-7 were made using native waxy maize starch as the starting material. The sedimentation volume range of greatest interest for food applications is generally believed to be 20-35 mL / g. [Table 1]

[0085] Viscosity is measured by RVA at 5% solids in salted buffer solution at an agitation speed of 160 rpm. The initial temperature for the analysis is 50°C; the temperature is linearly increased to 90°C over 3 minutes, then held at 95°C for 20 minutes, then linearly decreased to 50°C over 3 minutes, then held at 50°C for 9 minutes. Viscosity is measured throughout the heating and cooling cycle, and the viscosity at the end of the cycle is reported as the RVA viscosity. In contrast to native waxy starches, samples 1-7 do not have a significant peak at the beginning of the RVA curve and retain stable viscosity at high temperatures.

[0086] Example 2 Branch Chain Length Distribution Analysis - Valley-to-Valley Method The branch length distribution was determined as described above for the native or inhibited waxy starches described herein using the valley-to-valley method. The results are shown in Figures 1 and 2, which show that the inhibited waxy tapioca starches of the present disclosure have an amylopectin fraction with DP13-24 of 48.0% or less, while the other inhibited starches have an amylopectin fraction with DP13-24 of more than 48.5%; the inhibited waxy tapioca starches of the present disclosure have a (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio of less than 25.0%, while the other inhibited starches have a (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio of more than 25.5%. Detailed data is provided in the table below, with reproductions provided for each material. [Table 2]

[0087] Example 3 - Freeze-thaw stability of inhibited waxy starch A series of experiments were conducted to investigate various textural attributes related to freeze-thaw safety of the starches of the present disclosure. To evaluate the texture properties, various starches of the present invention and commercially available corn, wheat, or tapioca based inhibited waxy starches were cooked in deionized water at 5% solids by suspending the containers (i.e., glass jars) containing the slurry in a 95°C water bath and stirring with a glass rod or metal spatula for 8 minutes, followed by covering the containers and allowing the paste to remain at 95°C for 20 minutes. The containers were removed from the bath and allowed to cool on the bench. The resulting paste was brought to initial weight by adding water (i.e., to replace any evaporated water) and mixing well. The glass jars used for the first, second, and third freeze-thaw cycles were placed in a freezer (-18°C) without touching the jars and without the jars being in a container or box or otherwise insulated. The glass jars were allowed to rest overnight (16-18 hours). The samples were removed from the freezer and placed on a laboratory countertop without touching the glass bottle. The glass bottle was allowed to warm to room temperature for at least 6 hours. This completed the first freeze-thaw cycle. The samples that had undergone the second and third freeze cycles were returned to the freezer for repeated freezing and thawing steps. The samples were evaluated by panelists on the day of cooking and after each of the three freeze / thaw cycles. The starches investigated were Sample 6; Comparative Starch A; and Sample 2, described in Table 2. Comparative Starch A is a modified waxy maize starch, produced by esterification with acetic anhydride and adipic anhydride, with acetyl groups being 1.2-1.5% by weight of the starch and adipic acid groups being 0.1% by weight of the starch.

[0088] Panelists rated opacity, hardness, syneresis and graininess as described below. Each attribute was graded on a 15 point line scale. References for the different grades were provided to each group.

[0089] Hardness was determined by comparison with commercially available products: ● Hardness 3 - Suave Creamy almond & verbena Body Wash ● Hardness 7-Shea Moisture Coconum & Hibiscus Curling Gel Souffle w / Agave Nectar & Flax Seed Oil ● Hardness 11 - Garnier Power Putty Surfer Hair

[0090] To determine hardness, the test starch and reference product were poked 2-3 times using the back of a spoon; the resistance of the test starch against the spoon was evaluated against that of the reference product. A higher number indicates a higher hardness.

[0091] Opacity was determined by comparing the test starch in a 250 ml beaker in front of approximately 1 inch of a black background with the photograph in Figure 3. Higher numbers indicate higher opacity.

[0092] Syneresis was determined by holding a plastic spoon at a 45 degree angle to the test sample surface, gently pressing down about halfway down the test sample, and observing from the side how much fresh water was squeezed out in 3 seconds. The level of syneresis was determined by comparing with the photograph in Figure 4.

[0093] Granularity (i.e., surface granularity) was determined by observing the top surface of the test starch and comparing this to the photograph in FIG.

[0094] 6-8 provide bar graphs showing the average values ​​for the three tested attributes for each product (Sample 6, Comparative Starch A; and Sample 2, respectively) during the progression of freeze / thaw cycles. Unlike Sample 6 and Comparative Starch A, the inhibited waxy tapioca starch of the present disclosure (Sample 2) exhibited good freeze / thaw safety.

[0095] Figure 9 demonstrates the correlation between the above ratio and the freeze-thaw safety of starch. The change in hardness after three freeze-thaw cycles is a measure of starch safety and is calculated as the difference between the hardness after three freeze-thaw cycles and that of the fresh sample divided by the total scale of the vote, which was 15 as above. When the ratio is below 25.5%, the hardness change is negligible; when the ratio is above 25.5%, the hardness change is significant, indicating poor freeze-thaw safety.

[0096] Example 4 Branch Chain Length Distribution Analysis-Drop to Baseline Method Branch length distribution was measured using the drop-to-baseline method as described above for the inhibited waxy tapioca starches described herein and for the commercially available inhibited starches; data are the average of duplicate experiments. The results are shown in the table below, which shows that the inhibited waxy tapioca starch of the present disclosure has an amylopectin fraction of DP13-24 equal to or less than 54.5%, while other commercially available inhibited starches have an amylopectin fraction of DP13-24 greater than 54.5%; the inhibited waxy tapioca starch of the present disclosure has an amylopectin fraction of DP6-12 equal to or less than 30.5%, while other commercially available inhibited starches have an amylopectin fraction of DP6-12 less than 30.5%; the inhibited waxy tapioca starch of the present disclosure has a (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio of equal to or less than 28.0%, while other commercially available inhibited starches have an amylopectin fraction of (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio. [Table 3]

Claims

1. 1. An inhibited waxy starch based on tapioca, an amylopectin content of at least 99%; and a sedimentation volume in the range of 20 to 35 mL / g; the amylopectin fraction of said tapioca-based inhibited waxy starch has a range of 52.0% to 54.5% medium chain branches with chain lengths of 13 to 24 as measured by the drop-to-baseline method; and / or the amylopectin fraction of said tapioca-based inhibited waxy starch has a range of 31.0% to 33.5% short chain branches with chain lengths of 6 to 12 as measured by the drop-to-baseline method; and / or the ratio (DP13-24-DP6-12) / (DP13-24+DP6-12) is in the range of 24.5% to 27.5%, where DP13-24 is the amount of medium chain branches with chain lengths of 13 to 24 in the amylopectin fraction of said tapioca-based inhibited waxy starch as measured by the drop-to-baseline method, and DP6-12 is the amount of short chain branches with chain lengths of 6 to 12 in the amylopectin fraction of said tapioca-based inhibited waxy starch as measured by the drop-to-baseline method; and The tapioca-based inhibited waxy starch is produced by adjusting an aqueous slurry of tapioca starch feedstock to a pH in the range of 3.5 to 7.0, followed by drying the slurry to a moisture level of less than 1% to produce a dried starch, and heating the dried starch at a temperature in the range of 100 to 200° C.; The tapioca-based inhibited waxy starch is not hydroxypropylated, not acetylated, not carboxymethylated, not hydroxyethylated, not phosphorylated, not succinylated, not cationic or zwitterionic, not cross-linked with phosphate, not cross-linked with adipate, not cross-linked with epichlorohydrin, and not cross-linked with acrolein; and The starch is a non-gelatinized, tapioca-based, inhibited waxy starch.

2. 2. The tapioca-based inhibited waxy starch according to claim 1, wherein the amylopectin fraction of said tapioca-based inhibited waxy starch has 52.5% to 54.5% medium chain branches with chain lengths of 13 to 24 as measured by the drop-to-baseline method.

3. 3. The tapioca-based inhibited waxy starch according to claim 1 or 2, wherein the amylopectin fraction of said tapioca-based inhibited waxy starch has 31.0%-33.0% or 31.0-32.5% short chain branches with chain length 6-12 as measured by the drop-to-baseline method.

4. 4. The tapioca-based inhibited waxy starch according to any one of claims 1 to 3, wherein the (DP13-24 - DP6-12) / (DP13-24 + DP6-12) ratio is 24.5% to 27.0%, 25.0% to 27.5%, 25.0% to 27.0%, 25.5% to 27.5%, or 25.5% to 27.0%, wherein DP13-24 is the amount of medium chain branches with a chain length of 13 to 24 in the amylopectin fraction of the inhibited tapioca-based waxy starch as measured by the drop-to-baseline method, and DP6-12 is the amount of short chain branches with a chain length of 6 to 12 in the amylopectin fraction of the inhibited tapioca-based waxy starch as measured by the drop-to-baseline method.

5. 5. The tapioca-based inhibited waxy starch according to any one of claims 1 to 4, wherein the amylopectin fraction has substantially more medium chain branches with chain lengths of 13 to 24 than native waxy rice starch, but substantially less medium chain branches with chain lengths of 13 to 24 than native waxy maize starch.

6. 6. The tapioca-based inhibited waxy starch according to any one of claims 1 to 5, having a yellowness index of 3 to 10.

7. 7. The tapioca based inhibited waxy starch according to any one of claims 1 to 6, wherein the tapioca based inhibited waxy starch is not bleached or oxidized by hydrogen peroxide or hypochlorite.

8. 8. The tapioca-based inhibited waxy starch according to any one of claims 1 to 7, wherein the tapioca-based inhibited waxy starch has less than 10% fibre.

9. 9. The tapioca-based inhibited waxy starch according to any one of claims 1 to 8, wherein the tapioca-based inhibited waxy starch has a viscosity in the range of 50 to 1500 cP in RVA test.

10. 10. The tapioca-based inhibited waxy starch according to any one of claims 1 to 9, wherein not more than 20% of the starch granules are damaged during cooking.

11. An inhibited waxy starch based on tapioca according to any one of claims 1 to 10, having good digestive resistance.

12. The tapioca-based inhibited waxy starch according to any one of claims 1 to 11, having one or more of the following: 1) graininess of 4 or less after 3 freeze-thaw cycles, 2) syneresis of 5 or less after 3 freeze-thaw cycles, and 3) hardness change of 2 units or less after 3 freeze-thaw cycles.

13. 13. A method for producing a food product comprising the steps of cooking an inhibited waxy tapioca-based starch according to any one of claims 1 to 12 in the presence of water and providing said starch in combination with one or more other food ingredients.

14. A food product comprising the tapioca-based inhibited waxy starch according to any one of claims 1 to 12 in cooked form.

15. the food product is a tomato-based product, a sauce such as gravy, white sauce or cheese sauce, a soup, a pudding, a salad dressing (e.g., pourable or spoonable), yogurt, sour cream, pudding, custard, a cheese product, a fruit filling or topping, a cream filling or topping, a syrup (e.g., a light syrup), a beverage (e.g., a dairy beverage), a glaze, a condiment, a confectionery, a pasta, a frozen food, a cereal, or a soup, or a confectionery or bakery product (e.g., bread, pastry, pie crust, donut, cake, biscuit, cookie, cracker, or muffin); and / or selected from thermally processed foods, acidic foods, dry mixes, refrigerated foods, frozen foods, extruded foods, ovenable foods, stovetop foods, microwaveable foods, full or low fat foods, and foods with low water activity, and / or high acid foods (pH<3.7) such as fruit based pie fillings, baby foods, etc; acidic foods (pH 3.7-4.5) such as tomato based products; low acid foods (pH>4.5) such as gravies, sauces and soups; stovetop foods such as sauces, gravies and puddings; ready-to-eat foods such as puddings; pourable and spoonable salad dressings; refrigerated foods such as dairy or similar dairy products (e.g., yogurt, sour cream and cheese); frozen desserts and frozen dinners, etc.

15. The method or food of claim 13 or 14, which is selected from frozen foods; microwaveable foods such as frozen dinners; liquid products such as diet products and hospital foods, and / or is selected from baked foods, breakfast cereals, anhydrous coatings (e.g. ice cream compound coatings, chocolate), dairy products, confectionery, 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, meats and fish, dried fruit, baby foods and doughs and batters, and / or is a medical food or a pet food.

16. A dry mix comprising the tapioca-based inhibited waxy starch according to any one of claims 1 to 12 in admixture with one or more additional dry food ingredients.

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