KR20010050764A - Highly resistant granular starch - Google Patents

Abstract

PURPOSE: A highly resistant granular starch and its production method are provided, which starch has high resistance to enzymes, dietary fibers, a proprietary molecular weight distribution, high melting point and high heat of gelatinization that suggests excellent processing tolerance (ΔH). CONSTITUTION: The highly resistant granular starch is produced by heating a high-amylose starch that contains at least 40 wt% of amylose under the moisture and temperature condition to allow the granule of starch not to be decomposed and the starch to be birefringent, preferably at a moisture of about 10-80 wt% and a temperature of about 60-160 deg.C; digesting the amorphous area with α-amylase or a chemical reagent. The highly resistant granular starch is characterized by a granular structure; a molecular weight of about 2,000 to 80,000 dalton; an initiation melting point of at least about 90 deg.C; a peak melting point of at least about 110 deg.C; and a heat of gelatinization of at least about 20 J/g.

Description

High Resistance Granule Starch {HIGHLY RESISTANT GRANULAR STARCH}

The present invention relates to highly resistant granulated starch, a method for preparing such starch, and its use.

The present invention relates to high-resistant granular starch having a high content of dietary fiber, wherein the high-resistant granular starch can be prepared by selectively heat-moisture treating high-amylose starch and then treating with amylase. The present invention also relates to the use of such highly resistant granulated starch in food products.

Starch, a complex carbohydrate, consists of two types of polysaccharide molecules. One is amylose, which is a generally straight-chain flexible polymer consisting of D-anhydroglucose units linked by alpha-1,4-D-glucoside bonds, and the other is alpha-1,6. Amylopectin, a straight-chain branched polymer linked by a -D-glucoside bond. Starch is mostly broken down in the small intestine by alpha-amylase enzymes. Alpha-amylase hydrolyzes alpha-1,4-D-glucoside linkages, but does not hydrolyze alpha-1,6-D-glucoside linkages, so hydrolysis of amylopectin fragments is not complete.

Some starches are transformed into starches that are resistant to pancreatic amylase by processing, which is simply referred to as resistant starch. Resistant starch can tolerate the breakdown of the pancreas by alpha-amylase and absorption in the small intestine, but it passes through the large intestine to ferment by the microorganisms of the colon to become short-chain fatty acids and gases. According to the research literature, fermentation of such resistant starch by the bacteria in the colon has several desirable effects, including the health of the colon and reduces the chance of developing diverticulosis and colon cancer. In addition, since the resistant starch is not used until reaching the large intestine fermented with short-chain fatty acids, the caloric value is low, and it is reported that it is useful as a dietary fiber in view of these characteristics.

In this document, resistant starch (RS) is classified into four categories according to the cause of resistance. RS1 is a starch that is physically inaccessible because it is trapped into granules within the protein matrix or the cell wall of the plant. RS2 is granulated starch that can withstand the degradation of the pancreas by alpha-amylase. RS3 is a nongranular degenerated starch formed by heating / moisture treatment of starch or whole food. RS4 resists degradation by alpha-amylase and is a chemically modified starch including acetylated hydroxy propylated or cross-linked starch.

Various methods have been reported for producing various types of resistant starch. US Patent No. 5,593,503 describes a process for preparing RS2-type resistant starch; US Pat. Nos. 5,281,276 and 5,409,542 describe methods for preparing RS3-type resistant starch; U. S. Patent No. 5,855, 946 describes a process for preparing RS4-type resistant starch.

However, these resistant starches are not very resistant unless they are highly crosslinked, and commercially available tolerant starches are typically about 35-65% resistant. Because of the availability of resistant starches, highly resistant starches that are not chemically modified are becoming important and of greater value.

U.S. Pat. Nos. 5,051,271 and WO90 / 15147 describe high tolerant starches. However, the highly resistant starch is not in the form of granules.

The inventors have found that highly resistant granular starch can be prepared and that such starch has unique and useful properties.

It is an object of the present invention to provide highly resistant granular starch with a high content of dietary fiber.

1 is a molecular weight distribution of the highly resistant granulated starch, heat-treated resistant granular starch, and heat-treated high resistant granular starch of the present invention prepared from high amylose starch stock.

Highly tolerant granular starches can be prepared having unique and useful properties including high resistance, high dietary fiber, unique molecular distribution, high melting point, and large heat of gelatiniztion (delta H). For example, such starch may be heated by heating high amylose starch having an amylose content of at least 40% by weight at percent moisture and temperature at which the granularity of the starch is not destroyed, followed by, for example, amorphous using alpha-amylase or chemical reagents. It can be prepared by decomposing the site.

The invention also relates to foods containing high tolerant granular starch having a high content of dietary fiber, in particular high tolerant granular starch prepared using heat-moisture treatment as described herein.

As used herein, "tolerant starch (RS)" refers to starch and starch degradation products in the general sense that are not absorbed in the small intestine of healthy people. Resistant starch is defined herein as measured by alpha amylase treatment of the pancreas in the tests described below. As used herein, "total content of dietary fiber (TDE)" is defined as measured by the method introduced by Prosky et al. In Association of Official Analytical Chemist (AOAC) 68: 677 (1985).

The starch used to prepare the alpha-amylase resistant granular starch may be any natural amylose-containing starch derived from natural raw materials. As used herein, natural starch refers to that which occurs in nature. Also suitable are starches derived from plants made by standard breeding methods including hybrid breeding, translocation, inversion, transformation, or by engineering genes or chromosomes to include variants. Starches derived from plants grown from induced mutations and variants of the compositions that can be prepared by known standard mutation methods are also useful in the present invention.

Typical starch ingredients are cereals, tubers, roots, legumes, and fruits. Natural raw materials may be corn, peas, potatoes, sweet potatoes, bananas, barley, and rice, sago, amaranth, tapioca, arrowroot, canna, sugar cane, and goamylose varieties. By “high amylose” starch is meant herein starch containing at least 40% by weight of amylose. High amylose starch has been found to be most preferred in the present invention.

Starch consists of two classes, linear and branched. Starch belonging to the straight chain class is called amylose, and starch belonging to the branched chain class is called amylopectin. Starches derived from different raw materials will have relatively different ratios for amylose and amylopectin components. Some plants were genetically developed so that one is far superior to the other. For example, several varieties of corn, which typically contain about 22-28% by weight of amylose, have been developed to produce starch consisting of at least 40% amylose. Such hybrids are called Goamylose varieties.

High amylose maize hybrids have been developed to naturally provide high amylose starches and have been on the market since about 1963. Preferred high amylose starches for the present invention are starches having an amylose content of at least 40% by weight, preferably at least 65% by weight.

Starch materials useful in the present invention may include high amylose milling, wherein the starch component of the flour contains at least 40% by weight amylose. The term starch, as used throughout this specification, refers to milling, where the amylose content of the milling in this specification and claims refers to the amylose content of the starch component of the milling (eg , 40% by weight amylose based on the starch content in the mill). Typically, such milling comprises protein (about 8-13% by weight), lipids (up to about 3% by weight), and high amylose starch (about 80-90% by weight).

Other useful high amylose starches include substantially pure starch extracted from plant sources having an amylose extender genotype, which comprises up to 10% by weight amylopectin. Starches useful as starch feedstocks, when measured by butanol fractionation / exclusion chromatography, may contain at least 75% by weight of amylose, optionally at least 85% by weight of amylose (ie, normal amylose) as a gene complex of germ plasm extracts. Containing plant breeding groups, particularly those derived from corn. The starch further comprises up to 10 wt%, optionally up to 5 wt% amylopectin, and about 8 to 25 wt% low molecular weight amylose. Starch is preferably extracted in a substantially pure form derived from the milled product of a starch-containing plant having a recessive amylose-extended genotype linked to many amylose-extension modified genes. Such starches and methods for their preparation are described in US Pat. No. 5,300,145, which is incorporated herein by reference.

To prepare the resistant granular starch of the present invention, a starch raw material having a predetermined amount of water or moisture content and heated to a predetermined temperature is required. Treatment of starch under these conditions produces a resistant granular starch having a high total content of dietary fibers, as described below.

Starch is heat treated at a moisture content and at a temperature such that the granular nature of the starch is not broken. Typically, the total moisture and water content of the starch to be heated will be about 10 to 80% by weight, preferably 20 to 45% by weight, more preferably about 30 to 40% by weight, based on the weight of the dried starch. In particular, the relative levels of this moisture are maintained for a significant period of the heating step.

Typically, starches having a defined moisture content are heated at a temperature of about 60 to 160 ° C, preferably about 90 to 120 ° C. The most preferred temperature may vary depending on the starch's water content as well as the specific starch and their amylose content, but it is important that the starch remains in the granular state and does not lose birefringence properties. In addition, the heating time may vary depending on the moisture content and the heating temperature as well as the degree of starch used, their amylose content, and the total amount of dietary fiber required. Typical heating times will be about 0.5 to 24 hours, preferably about 1 to 4 hours.

The most preferred conditions for treating starch to increase the total content of dietary fibers are those in which the granule structure of the starch is not broken and the granules can still maintain birefringence. In addition, when a granular structure is observed under polarized light, a distinct maltese cross occurs. However, under some conditions of high moisture content and temperature, the starch granules may partially expand, but crystallinity is not completely destroyed. Under these conditions, the starch granules will not be completely destroyed and the total dietary fiber will increase according to the present invention. Thus, "granular starch" as used herein means a starch that predominantly retains their granular structure and has some crystallinity, for example starch, which retains birefringence and exhibits distinct malt crossover under polarized light.

In addition, other methods known in the art, such as those described in US Pat. No. 5,849,090, can be used to artificially produce resistant granular starch.

After producing resistant granular starch, residual amorphous sites are removed. This can be done using degradation by alpha-amylase or by treating at least one chemical reagent. Such chemical reagents include, but are not limited to, organic and inorganic acids including hydrochloric acid and sulfuric acid and derivatives thereof.

Enzymatic hydrolysis of the heat treated starch is carried out by methods known in the art. The amount of enzyme used depends not only on the degree of hydrolysis, but also on the type and activity of the enzyme and the raw materials used. Typically, the enzyme is used in an amount of about 0.01 to 2.0% by weight, preferably about 0.5 to 1.5% by weight, based on the weight of the starch.

The optimum temperature for the activity of the enzyme varies greatly depending on the enzyme used. The rate of degradation of the enzyme depends on factors known in the art, including the enzyme used, concentration of enzyme, concentration of substrate, pH, temperature, presence of inhibitor, and degree and type of modification. These factors can be adjusted to optimize the decomposition rate of the starch raw material.

Generally, the enzyme treatment is carried out in an aqueous slurry or buffer slurry containing about 5-40% starch solids, depending on the starch raw material to be processed. The content of solids in the present invention is preferably about 15 to 35%, more preferably about 18 to 25%. Typically, enzymatic digestion is carried out at the maximum solids content that can be carried out without reducing the reaction rate in order to facilitate drying of the subsequent starch composition. The method may be used an enzyme immobilized on a solid carrier.

Enzyme treatment can also be carried out under conditions of high solids content. In the process described in EP 806 434, a single-phase powder mixture is prepared without starch, water (generally no more than 35% by weight based on the weight of the starch), enzyme free visible water phase. And mix the enzyme in a sufficient amount to heat activate.

The pH and temperature of the reaction should be adjusted to provide effective enzymatic hydrolysis. These factors are determined by the enzyme used and are known in the art. Generally, a temperature of about 22 to 65 ° C., preferably about 30 to 45 ° C., is used. In general, the pH is adjusted to about 3.5 to 7.5, preferably about 4.5 to 7.5 using methods known in the art.

Enzyme reactions continue until the desired level of resistance is reached. In general, a significant portion of the amorphous portion of the starch is degraded, resulting in high resistance, preferably at least about 75% by weight, more preferably at least about 80% by weight of starch.

In general, the enzymatic reaction will be carried out over about 0.1 to 24 hours, more preferably about 0.5 to 6 hours. The reaction time depends on the reaction factors such as the type of starch and enzyme used, the amount of enzyme used, the solids ratio, the pH, and the temperature.

Enzymatic digestion may then be terminated by methods known in the art, such as acid inactivation or base inactivation. For example, acid inactivation can be performed by adjusting the pH to 2.0 or less for at least 30 minutes. In general, heat required for inactivation of enzymes gelatinizes starch, so heat inactivation is not desirable when granulated starch is desired.

In addition, the hydrolysis of starch may be carried out by the addition of chemical reagents, in particular hydrochloric acid or sulfuric acid. Typically, acid hydrolysis is performed by adding acid to the aqueous starch slurry with stirring at a temperature slightly below room temperature to the gelatinization temperature of the starch and stirring until the desired level of resistance is reached. Then, the acid is neutralized using a neutralizing base such as Na ₂ CO ₃ or NaOH. Acid hydrolysis methods and conditions are well known in the art, which include Modified Starches, OP Wurzburg; Properties and Use, CRC Press Inc. (1986) Baca Raton, FL pp. 17-24.

After hydrolysis using enzymes or chemical reagents, the starch is filtered to remove soluble material, optionally washed, and then air dried to reach water equilibrium or dried using a flash dryer or other drying means. Can be.

Starch may be modified by treatment of a sample or mixture of samples that provides modifications that do not destroy the granularity of the starch. Chemical modification is carried out on the starch feed before and after heat treatment and / or before and after hydrolysis. Chemical modifications include crosslinking starch, acetylated and organic esterified starches, hydroxyethylated and hydroxypropylated starches, phosphorylated and inorganic esterified starches, cationic, anionic, nonionic, and zwitterionic starches, and starch starches. Mythological and substituted succinate derivatives. Such modifications are known in the art and are described, for example, in Modified Starches: Properties and Use, Ed. Wurzburg, CRC Press, Inc., Florida (1986). Other useful modifications and modifications are described in US Pat. Nos. 4,626,288, 2,613,206, and 2,661,349, which are incorporated herein by reference.

Heat treated and hydrolyzed chemically modified or unmodified starch products will have a birefringence upon microscopic observation and will have a granular structure exhibiting malt crossover when viewed under polarized light. The resistant granular starch product will have a total dietary fiber content of at least about 20% by weight, preferably at least about 40% by weight, more preferably at least about 50% by weight. In addition, the resistant granular starch product will have a resistant starch content of at least about 70% by weight, preferably at least about 80% by weight, based on the starch. The specific starch starting material of dietary fiber of resistant starch will vary depending on the conditions used.

The resulting starch product has a molecular weight peak of about 2,000 to 80,000 Daltons, preferably about 5,000 to 20,000 Daltons.

In addition, the resulting granular starch product exhibits a high starting melting point, peak melting point, and ending melting point as well as high heat of gelatinization (delta H) when measured according to differential scanning calorimetry (DSC), as compared to natural granular starch having high resistance. In particular, the starch obtained has an initial melting point of at least about 90 ° C., preferably at least about 95 ° C., and a peak melting point of at least about 110 ° C., preferably at least about 120 ° C., and at least about 20 J / g delta H. Have High melting point and delta H means high process resistance. Thus, the starch obtained will at least maintain, or in some cases increase, their resistance and overall dietary fiber under conventional processing temperatures and shears during processing.

The resistant granular starch of the present invention may be used in foods or beverages (collectively, foodstuffs) for the purpose of preserving whole dietary fiber and resistant starch and lowering calories. Typical foodstuffs include cereals such as instant, inflated or expanded cereals, cereals cooked before meals; Baked goods such as breads, crackers, cookies, cakes, muffins, rolls, pastries, and other ground ingredients; pasta; beverage; Fried foods and coated foods; snack; And fermented dairy products such as yoghurt, cheese, and sour cream.

The content of resistant granular starch and dietary fiber added and used in a given food will most likely be determined to be functionally resistant. In other words, the content of resistant granular starch and dietary fiber used will be to an acceptable level when sensory evaluation of food products. In general, resistant granular starch may be used in food products in an amount of about 0.1 to 5.0% by weight, preferably about 1 to 25% by weight.

Resistant granular starch of the present invention can be used in pharmaceuticals or nutritional supplements, including prebiotic and synbiotic compositions, diabetic foods and supplements, dietary foods, glycerinmic reaction foods, tablets and other pharmaceutical forms However, it is not limited to these. Probiotic compositions are non-digestible food ingredients that have a good effect on the host by selectively promoting the growth and activity of many bacteria, one or more of which are limited in colon. The symbiotic composition may be in the form of yoghurt, a capsule infused into a host animal, including humans, in which the probiotic is used with a live microbial food supplement. Live microbial food supplements have a good effect on host animals by improving the host's intestinal microbial balance.

Such live microbial food supplements may include, but are not limited to, yeasts such as Saccharomyces and bacteria such as Bifobacterium, Bacteriodes, Clostridium, Fusobacterium, Propionibacterium, Streptococcus, Enterococcus, Lactococcus, Staphylococcus, Peptostreptococcus, and Lactobacillus.

Example

The following examples are intended to illustrate the present invention in more detail, and the present invention is not limited to these examples. Unless otherwise indicated, all parts and percentages are by weight and all temperatures are in degrees Celsius (° C.).

In the examples, the following components were used.

HYLON ™ Starch, a product of National Starch and Chemical.

Pancreatin, product # P-7545, product of Sigma Chemical.

In the examples, the following test method was used.

A. Resistant Starch Measurement

The content of resistant starch was determined in the following manner:

Sample manufacture

(1) 2.0 g (dry weight) of test starch is placed in a jar.

(2) Add 0.05 M phosphate buffer containing 4% NaCl to make the total weight 42.0 g.

(3) Put the magnetic stirrer into the bottle, mix it evenly, and close the lid tightly.

(4) Equilibrate for 5 minutes in a stirring vessel at 37 ° C.

Blank Measurement

(1) Using a pipette, carefully place 1.0-1.5 ml of each sample into the microcentrifuge tube.

(2) Centrifuge at 10,000 rpm for 2 minutes.

(3) Measure a drop of supernatant soluble material using a zero point refractometer with DI water.

(4) Transfer the residual sample from the centrifuge tube to the bottle.

Enzyme addition

(1) 8 ml of 5% pancreatin is added and the timer is started.

(2) After mixing evenly, the lid is tightly closed and then cultured in a stirring vessel at 37 ° C.

Sampling method (after 6 hours)

(1) 1.5 ml of the sample is placed in a microcentrifuge tube using a pipette.

(2) Centrifuge at 10,000 rpm for 2 minutes.

(3) Measure the soluble substance of the supernatant using a zero point refractometer with deionized water. The amount of starch degraded can be calculated from the proportion of solubles. The content of undecomposed starch is the content of resistant starch.

B. Total Dietary Fiber Measurements

The content of total dietary fiber ("TDF") is measured using a Megazyme TDF Test Kit (commercially available from Megazyme Int. Ireland, Ltd.) utilizing the principles of AOAC method 985.29.

TDF Analysis Kit

Kits containing 200 assay reagents are from Megazyme and include:

1. Complete Method.

2. Thermostable α-amylase (20 mL) (Megazyme E-BLAAM).

3. Purified protease (20 mL) (Megazyme E-BSPRT).

4. Purified amyloglucosidase (2 × 20 mL) (150% concentration in other TDF kits) (Megazyme E-AMGDF).

Cellite ™ 545 (hereinafter “Celite”), acid washed in 100 g or 500 g packaging units (G-CEL100; or G-CEL500, respectively).

Experiment apparatus:

dispenser

a. 95% ethanol-280 ± 2.0 ml

b. 78% ETOH, 95% ethanol, and acetone-10 ± 0.5 ml

c. Buffer solution-50 ± 0.5 ㎖

reagent:

1.phosphate buffer, 0.08 M, pH 6.0:

1,400 g of sodium phosphate anhydrate (Na ₂ HPO ₄ ) (or 1.753 g of diglycerate) and 9.68 g of Na phosphate monovalent base monohydrate (NaH ₂ PO ₄ ) (or 10.94 g of dihydrate) Is dissolved in approximately 700 ml of distilled water. Check the pH using a pH meter.

2. Sodium hydroxide solution, 0.275 N:

In a 1 L flask, 11.00 g of ACS NaOH is dissolved in approximately 700 ml of distilled water, cooled and diluted with water using a suitable method.

3. hydrochloric acid solution, 0.325 N:

The known titer mother liquor (ie 325 mL of 1.0 N HCl) is diluted with water in a 1 L flask.

Experimental procedure:

Sample manufacture

The total dietary fiber should be measured on the basis of dry low fat or nonfat samples. The sample is homogenized and dried overnight in a 70 ° C. vacuum oven. Cool in desiccator, reweigh and record weight loss by drying. Dry samples are dry-milled to 0.3-0.5 mesh size. If the sample cannot be heated, it is milled and then freeze-dried. Before grinding, if the fat content is high (<10%), 25 ml (per g of sample) petroleum ether is used to remove fat three times. When analyzing a mixed diet, always extract the fat before measuring the total dietary fiber.

Record the weight loss due to fat. The final percentage of dietary fiber measurements are corrected for moisture and fat removed. Dry-mill samples are stored in a closed jar in the desiccator until analysis is made.

Experiment method

1. 1 g of sample was weighed twice, accurately measured at 0.1 mg and placed in a 400 ml long beaker. The weights of the samples should differ by less than 20 mg from each other. 50 ml of phosphate buffer (pH 6.0) are added to each beaker and the pH is measured using a pH meter. Adjust the pH to 6.0 ± 0.1.

2. Add 50 L of heat-stable α-amylase solution.

3. Cover the beaker with aluminum foil and place in boiling water bath for 15 minutes. Stir slowly at 5 minute intervals.

Note: If there is a large number of beakers in the bath and it is difficult to raise the internal temperature of the beaker content to 100 ° C, increase the incubation time. Use a thermometer indicating 15 minutes at 100 ° C. A boiling water bath should be enough for about 30 minutes.

4. Cool the solution to room temperature.

5. Adjust the pH to 7.5 ± 0.1 by adding 10 ml of 0.275 N NaOH solution. Check the pH using a pH meter.

6. Add 100 L of protease solution.

7. Cover the beaker with aluminum foil and incubate at 60 ° C. for 30 minutes with constant speed.

8. After cooling, adjust the pH to 4.5 ± 0.2 by adding 10 ml of 0.325 N HCl solution and check the pH using a pH meter.

9. Add 200 L amyloglucosidase, cover with aluminum foil, and incubate for 30 minutes with stirring at 60 ° C. at constant speed.

10. Add 280 mL of 95% ethanol (“EtOH”) preheated to 60 ° C. (volume before heating). Stabilize for 60 minutes at room temperature.

11. After weighing the crucible containing Celite, wet the bed in the crucible with 78% EtOH and dispense from the wash bottle.

12. Add a solution that absorbs Celite like a flat mat over the molten glass. The solution is maintained and the precipitate by enzymatic digestion is transferred quantitatively into the crucible.

13. Wash the residue continuously using 20 ml 78% EtOH, 10 ml 95% EtOH (twice), and 10 ml acetone (twice). In some cases, a gum may form that traps the liquid in the residue during filtration. Injecting the filtrate at regular intervals can reduce the filtration time.

14. The crucible containing the residue is dried overnight in a 70 ° C. vacuum oven or 150 ° C. air oven.

15. After cooling in the desiccator, weigh in approximately 0.1 mg increments. The weight of the residue is determined by weighing Celite excluding the crucible.

16. Analyze proteins for residues obtained from two sets of samples using AACC method 46-13 using N × 6.25 as conversion factor.

17. Incinerate the pair of second residue samples at 525 ° C. for 5 hours. Cool in desiccator and weigh in 0.1 mg increments. The weight of ash is measured by weighing Celite excluding the crucible.

Calculation

Uncorrected Average Blank Residue (UBAR)

= Average blank residue (in mg) of a pair of blanks (obtained in step 15)

Blank Protein Residues (BPR)

= UABR × (% of protein) in the blank (obtained in step 16) / 100

Blank Ash Residue (BAR)

= Ratio of ash in the UABR x (obtained in step 17) blank (%) / 100

Calibration Blank (CB) = UABR-BPR-BAR

Uncorrected Average Sample Residue (USAR)

= Average sample residue (in mg) of a pair of samples (obtained in step 15)

Sample Protein Residue (SPR)

=% Of protein in USAR x (obtained in step 16) sample / 100

Sample Ash Residue (SAR)

= USAR x (% ash) / 100 in sample (obtained in step 17)

Calibration Sample Residue (CSR) = USAR-SPR-SAR-CB

TDF Percentage = 100 × CSR / Sample mg

C. Differential Scanning Calorimetry ("DSC") Measurement

Differential scanning calorimetry was performed in Perkin-Elemer DSC-7 (Norwalk, Ct, U.S.A.). The apparatus was calibrated using indium. Samples with a starch to water ratio of 1: 3 (approximately 10 mg of starch) were prepared and heated from 5 ° C. to 160 ° C. at a rate of 10 ° C./min. As a control, a stainless-steel pan containing nothing was used.

Example 1 Preparation of High Resistance Heat-Treated Granule Starch

a. At room temperature, a sample of HYLON ™ starch (moisture = 10.6%) was mixed with a sufficient amount of water to bring the total water content to 38%. The temperature was raised to about 210 ° F. and the temperature of the sample was maintained at that temperature for 2 hours while maintaining the moisture content of the system. The heat-treated starch obtained was dried to contain about 12% moisture and then cooled.

200 g of heat-treated starch sample were diluted with 4400 mL of 0.05 NaH ₂ PO ₄ containing 4% NaCl. The pH was adjusted to 6.9 and the temperature was adjusted to 37 ° C. 0.8 wt% pancreatin (based on the weight of the starch sample) was added. After 8 hours, the enzyme was inactivated, and then the sample was filtered, washed and dried and ground to size through a 40 mesh sieve.

b. Example 1a was repeated using low amylopectin starch prepared according to US Pat. No. 5,300,145. However, the moisture content during the heat-treatment was maintained at 20%, and the heat-treatment process was performed at 260 ° F. for 3 hours.

Example 2 Preparation of High Resistance Heat-Treated Granule Starch

a. 200 g of HYLON (R) starch (water = 10.6%) sample was diluted using 4400 mL of 0.05 NaH ₂ PO ₄ containing 4% NaCl. The pH was adjusted to 6.9 and the temperature was adjusted to 37 ° C. 0.8 wt% pancreatin (based on the weight of the starch sample) was added. After 8 hours, the enzyme was inactivated, and then the sample was filtered, washed and dried to a size that passed through a 40 mesh sieve.

b. The procedure of Example 2a was repeated using low amylopectin starch prepared according to US Pat. No. 5,300,145.

Example 3 Preparation of Heat-treated Granulated Starch

a. At room temperature, a sample of HYLON ™ starch (moisture = 10.6%) was mixed with a sufficient amount of water to bring the total water content to 38%. The temperature was raised to about 210 ° F. and the temperature of the sample was maintained at that temperature for 2 hours while maintaining the moisture content of the system. The heat-treated starch obtained was dried to contain about 12% moisture and then cooled.

b. The procedure of Example 3a was repeated using low amylopectin starch prepared according to US Pat. No. 5,300,145. However, the moisture content during the heat-treatment was maintained at 20%, and the heat-treatment process was performed at 260 ° F. for 3 hours.

Example 4-Comparison of Resistant Starches

The total content of dietary fiber, the content of resistant starch, the starting melting point, the peak melting point, the ending melting point, and the heat of gelatinization for the resistant starches of Examples 1a, 2a, and 3a were measured and the results are listed in the table below.

Sample TDF% RS% T _start (℃) T _peak (℃) T _termination (℃) ΔH (j / g) Example 1a 50 90 99.6 121.5 158.5 33.1 Example 2a 14 80 74.4 96.4 126.2 17.2 Example 3a 62 54 94.7 107.3 132.5 19.8

The data recorded in the table above show that when enzymatically digesting high purity heat-treated starches, highly resistant starch (Example 1a) is produced with desirable properties. For example, Example 1a showed a significantly higher onset melting point than undecomposed heat-treated starch (Example 3a) or high purity resistant starch made from natural starch (Example 2a).

The present invention provides highly resistant granular starch having a high content of dietary fiber and having unique and useful properties including unique molecular distribution, high melting point, and large heat of gelatinization.

Claims (21)

Highly resistant starch with the following characteristics: a) granular structure; b) a molecular weight peak of about 2,000 to 80,000 daltons; c) an onset melting point of at least about 90 ° C .; d) a peak melting point of at least about 110 ° C .; And e) heat of gelatinization of at least about 20 J / g. The method of claim 1, High tolerant starch having a molecular weight peak of about 5,000 to 20,000 Daltons. The method according to claim 1 or 2, High tolerant starch having an onset melting point of at least about 95 ° C. The method according to any one of claims 1 to 3, High resistant starch having a peak melting point of at least about 120 ° C. The method according to any one of claims 1 to 4, High resistance starch, wherein said starch has a resistant starch content of at least about 80% by weight. In the method for producing high resistant granular starch having a high total content of dietary fiber, a) heating a high amylose starch having an amylose content of at least 40% by weight under complex moisture and temperature conditions such that the starch remains granular and is birefringent. The total moisture content of the starch is about 10 to 80% by weight and the temperature is about 60 to 160 ° C; And b) removing the amorphous site Wherein the resistant granular starch obtained comprises at least about 20% dietary fiber total content and at least about 80% resistant starch content. The method of claim 6, A method for producing highly tolerant granular starch, wherein the step of removing the amorphous site is carried out by a step of treating with alpha-amylase. The method of claim 6, A method for producing highly resistant granular starch, wherein the step of removing the amorphous portion comprises treating with at least one chemical reagent. The method according to any one of claims 6 to 8, High amylose starch has a total moisture content of about 20 to 45%, wherein the starch is heated at a temperature of about 90 to 120 ℃. The method according to any one of claims 6 to 9, A method for producing highly resistant granulated starch, wherein the high amylose starch is the high amylose corn starch. The method according to any one of claims 6 to 10, A method for producing highly resistant granular starch, in which high amylose starch is chemically modified. The method according to any one of claims 6 to 11, High amylose starch has a total moisture content of about 20 to 45%, wherein the heating step is carried out at a temperature of about 90 to 120 ℃. The method according to any one of claims 6 to 12, High amylose starch has a total moisture content of about 30 to 40% by weight, wherein the heating step is performed at a temperature of about 90 to 120 ℃. The method according to any one of claims 6 to 13, A method of preparing high resistance granule starch, wherein the high amylose starch has an amylose content of at least 65% by weight. The method according to any one of claims 6 to 14, A method of making highly resistant granular starch, wherein the high amylose starch product has a total content of dietary fiber of at least 40%. The method according to any one of claims 6 to 15, High amylose starch is a largely pure starch extracted from a plant source with an amylose extender genotype and is less than 10% when measured using butanol fractionation / exclusion chromatography measurement. A method of producing high-resistant granulated starch containing amylopectin. Resistant granular starch product prepared by the method of any one of claims 6-16. A food product containing the resistant starch of any one of claims 1 to 5 and having a total content of dietary fiber of at least 20%. A food product containing resistant granular starch prepared by the method of any one of claims 6 to 17 and having a total content of dietary fiber of at least 20%. The method of claim 18 or 19, Foodstuffs selected from the group consisting of cereals, breads, crackers, cookies, cakes, pastas, beverages, fried and coated foods, snacks, and fermented dairy products. The method of claim 1, A resistant starch having a molecular weight peak of about 5,000 to 20,000 Daltons, a starting melting point of at least about 95 ° C., a peak melting point of at least about 120 ° C., and a resistant starch content of at least about 80% by weight.