CN109748978B - High-temperature stable slowly digestible starch and preparation method thereof - Google Patents
High-temperature stable slowly digestible starch and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method for slowly digesting starch at a high temperature and stability, slowly digestible starch at a high temperature and stability and application thereof. The preparation method of the high-temperature stable slowly digestible starch is characterized by comprising the following gelatinization steps: gelatinizing raw material starch, water and hydrophilic colloid to obtain a gelatinized starch mixture; a separation step: separating the obtained gelatinized starch mixture to obtain the high-temperature stable slowly-digested starch. The preparation method of the invention not only effectively solves the problem of unstable high-temperature processing of slowly digestible starch prepared by the traditional method, but also can effectively overcome the long-term aging and retrogradation of the starch. In addition, the preparation method of the invention obtains starch products with high freeze-thaw stability, and is beneficial to expanding the application of the slowly digestible starch in various fields.
Description
Technical Field
The invention relates to a method for slowly digesting starch at a high temperature and stability, slowly digestible starch at a high temperature and stability and application thereof.
Background
In recent years, the spectrum of human diseases has been shifting to chronic diseases due to changes in dietary structure caused by the accelerated pace of social life and the accelerated progress of aging in the world. Diabetes mellitus, a common chronic disease, is currently growing at an alarming rate, and particularly type II diabetes mellitus has become one of three chronic diseases that seriously affect the physical and mental health of human beings. Recent reports from the international diabetes association show that there are nearly 2 billion diabetic patients worldwide and this number will reach 3 billion by 2025. With the development of economic society of China, the number of diabetic patients in China also rapidly increases. According to IDF statistics, the number of diabetic patients in China reaches 1.1 hundred million by 2015, which is the first in the world. Therefore, the treatment and prevention of diabetes has become one of the most important public health problems in our country.
The digestion of starch, which is a main component of the dietary structure of rice or wheat as a staple food, is closely related to the carbohydrate metabolism of diabetes patients. According to the in vitro determination of starch digestibility, as established by Englyst, a british physiologist, starch can be classified as fast-digestible starch (RDS), slow-digestible starch (SDS) and Resistant Starch (RS). Fast digestion of starch causes a drastic rise and fall of postprandial blood glucose. Although resistant starch does not produce glucose, it has a poor mouthfeel when consumed. The slowly digestible starch is slowly digested and absorbed, so that the balance of blood sugar is facilitated, and the oxidative stress effect of oxygen free radicals generated by stimulating mitochondria by high-concentration blood sugar on cell membranes and DNA is relieved. Therefore, the research on how to prepare high-quality slowly digestible starch has important nutritional significance. Since the heat treatment of starch-based foods before consumption tends to destroy the properties of the slowly digestible starch in the raw starch, the purpose of slowly digesting starch can only be achieved by changing the molecular structure of the starch.
Currently, there are no commercially available slowly digestible starch products, and most of the slowly digestible starches are still in the research and development stage of laboratories, mainly by physical methods, chemical methods, enzymatic methods, microencapsulation and the like. The related patents mainly include: CN201010228265.9, CN201510405930.X, CN201410778564.8, CN201010142421.X, CN201110112582.9 and the like. The main drawbacks of the above process are: the slow-digestion starch obtained by a physical method has low content, weak heat-resisting processing capacity, complex process, high energy consumption and high equipment requirement; the chemical method introduces a chemical reagent in the process of obtaining the slowly digestible starch, so that certain potential safety hazards exist for the health of a human body; the enzyme method modification has complex process, higher requirement on equipment, high price, low market investment rate and difficult industrial production; the microcapsule method utilizes the characteristic that hydrophilic colloid is not easy to be enzymolyzed, but the obtained starch is difficult to be gelatinized, so that the application of the starch is limited.
Disclosure of Invention
The invention discloses a method for preparing high-temperature stable slowly digestible starch by using hydrophilic colloid and starch, the high-temperature stable slowly digestible starch and application thereof. The preparation method of the invention not only effectively solves the problem of unstable high-temperature processing of slowly digestible starch prepared by the traditional method, but also can effectively overcome the long-term aging and retrogradation of the starch. In addition, the preparation method of the invention obtains starch products with high freeze-thaw stability, and is beneficial to expanding the application of the slowly digestible starch in various fields.
The invention provides a preparation method of high-temperature stable slowly digestible starch, which is characterized by comprising the following steps:
pasting: gelatinizing raw material starch, water and hydrophilic colloid to obtain a gelatinized starch mixture;
a separation step: separating the obtained gelatinized starch mixture to obtain the high-temperature stable slowly-digested starch.
According to the preparation method of the present invention, the step of gelatinizing further comprises a water removal step of: the resulting gelatinized starch mixture is freed of water.
According to the production method of the present invention, a redissolution step is further included after the water removal step: the solute obtained after removal of water is redissolved.
According to the preparation method of the invention, the gelatinization step is carried out at a pH of 11 or more.
According to the preparation method, the step of gelatinization comprises the step of carrying out at the water temperature of 50-100 ℃, preferably at the water temperature of 53-98 ℃, more preferably at the water temperature of 55-96 ℃, and even more preferably at the water temperature of 58-95 ℃.
According to the preparation method, the ratio of the hydrophilic colloid, the raw material starch and the water is 0.005-1.2: 1:10 to 120 (w/w), preferably 0.008 to 1.1: 1: 11 to 110 (w/w), more preferably 0.01 to 1: 1: 12 to 100 (w/w), and more preferably 0.03 to 0.3: 1: 20 to 100 (w/w).
According to the preparation method, the temperature is raised to 50-100 ℃, and the mixture is stirred for 5-10 min, so that the starch is gelatinized.
According to the preparation method, the temperature is raised to 53-98 ℃, preferably to 55-96 ℃, and more preferably to 58-95 ℃.
According to the preparation method of the invention, the zero-cut viscosity of the gelatinized starch mixture is obtainedη 0≤2000cP。
According to the preparation method of the invention, the zero-cut viscosity of the gelatinized starch mixture is obtainedη 0≤1000cP。
According to the preparation method of the present invention, the hydrocolloid is selected from at least one of a natural hydrocolloid, a physically modified hydrocolloid, a chemically modified hydrocolloid, or an enzymatically modified hydrocolloid.
According to the preparation method of the invention, the hydrophilic colloid is selected from at least one of curdlan, gellan gum, konjac gum, sodium alginate, carboxymethyl curdlan and a compound of the colloid.
According to the preparation method of the present invention, the raw starch is selected from at least one of corn starch, wheat starch, rice starch, potato starch, tapioca starch, sweet potato starch, mung bean starch, chickpea starch, sorghum starch, sago starch, canna starch, banana starch, apple starch, peach starch, yam starch, lotus root starch, rice flour, wheat flour, corn flour, potato flour, tapioca flour, sweet potato flour, mung bean flour, chickpea flour, sorghum flour, sago flour, banana flour, yam flour, lotus root flour, banana flour, apple flour or peach flour.
According to the preparation method of the invention, the hydrophilic colloid is curdlan, and the pH value in the gelatinization step and the water removal step is more than or equal to 11.
According to the inventionThe preparation method comprises the steps that the hydrophilic colloid is gellan gum or sodium alginate, and the ion R in the gelatinization step2+The ratio of the amount of the sodium alginate to the amount of the gellan gum or the sodium alginate is more than or equal to 0.05M percent and less than or equal to the ion R2+Gellan gum or sodium alginate less than or equal to 0.5M%, M is the molecular weight of divalent cation, R2+Is selected from Ca2+、Mg2+Or Zn2+。
According to the preparation method of the invention, the ion R is obtained by adding calcium salt, magnesium salt or zinc salt into the reaction solution2+The amount of (c).
According to the preparation method of the invention, the hydrophilic colloid is carboxymethyl curdlan: the degree of substitution is less than or equal to 0.2.
According to the preparation method of the invention, the hydrophilic colloid is a compound of carrageenan and konjac glucomannan, and the pH value in the gelatinization step is more than or equal to 10.
According to the preparation method, in the compound of the carrageenan and the konjac glucomannan, the ratio of the carrageenan to the konjac glucomannan is not less than 0 in terms of weight ratio: the ratio of konjac glucomannan to konjac gum is less than or equal to 0.6: 1.
According to the preparation method of the present invention, in the water removal step, the reaction solution is volatilized at a temperature of 80 to 100 ℃ for 30 to 120 seconds.
According to the production method of the present invention, in the redissolution step, the volatile matter obtained in the water removal step is dispersed and dissolved in water, and the precipitate obtained after centrifugation is freeze-dried.
According to the preparation method, the volatile matter obtained in the water removing step is dispersed and dissolved in water with the temperature of 80-100 ℃.
According to the preparation method, the mixture is centrifuged at 4000-8000 rpm for 3-6 min.
According to the preparation method, the freeze drying is carried out for 12-24 hours.
According to the preparation method of the invention, a hydrogen bond breaking agent is added in the pasting step.
According to the production method of the present invention, the hydrogen bond disrupting agent is selected from at least any one of an electrolyte and a chemical agent.
According to the production method of the present invention, anions of the electrolyteHaving OH groups-Salicylic acid radical, CNS-、I-、Br-、NO3 -、Cl-Tartrate, citrate or SO4 2-Any one of the above.
According to the production method of the present invention, the cation of the electrolyte has Li+、Na+、K+、NH4 +、Mg2+Any one of the above.
According to the preparation method of the invention, the hydrogen bond disruptor is selected from NaOH, LiOH, KOH, Mg (OH)2Lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, magnesium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、Mg(CNS)2、LiI、NaI、KI、NH4I、MgI2、LiBr、NaBr、KBr、NH4Br、MgBr2、LiNO3、NaNO3、KNO3、NH4NO3、Mg(NO3)2、LiCl、NaCl、KCl、NH4Cl、MgCl2Lithium tartrate, sodium tartrate, potassium tartrate, sodium citrate, potassium citrate, lithium citrate, Li2SO4、K2SO4、Na2SO4Preferably selected from NaOH, LiOH, KOH, Mg (OH)2Lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, magnesium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、Mg(CNS)2、LiI、NaI、KI、NH4I、MgI2、LiBr、NaBr、KBr、NH4Br、MgBr2、LiNO3、NaNO3、KNO3、NH4NO3、Mg(NO3)2、LiCl、NaCl、KCl、NH4Cl、MgCl2More preferably selected from NaOH, LiOH, KOH, lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、LiI、NaI、KI、NH4I、LiBr、NaBr、KBr、NH4Br、 LiNO3、NaNO3、KNO3、NH4NO3Any one of the above.
According to the preparation method of the invention, the addition amount of the hydrogen bond disruptor is 0.001-1 mol/L, preferably 0.003-0.9 mol/L, more preferably 0.005-0.85 mol/L, and further preferably 0.01-0.8 mol/L.
The present invention provides a high-temperature stable slowly digestible starch characterized in that the degree of hydrogen bonding represented by the following formula is 20 to 60 wt%,
degree of hydrogen bonding: xb= (1+αAfm2/Abm1)-1×100%。
In the formula, alpha is molar absorption coefficient, and a constant is 3.5; a. thefIs 3000-4000 cm in the infrared spectrum of a starch raw material-1Absorbance of the maximum absorption peak in the range, AbThe sample to be detected is 3000-4000 cm-1Absorbance of the maximum absorption peak in the range; m is1M is the sample mass to be measured2For the analysis of pure corn starch quality.
According to the high-temperature stable slowly digestible starch of the present invention, the hydrogen bonding degree is 20.5 wt% to 50 wt%, preferably 21 wt% to 45 wt%, more preferably 21.5 wt% to 40 wt%, and even more preferably 22 wt% to 35 wt%.
The high-temperature stable slowly digestible starch according to the present invention has a content of slowly digestible starch of 30 wt% or more, preferably 30 wt% to 99.9 wt%, more preferably 30.3 wt% to 80 wt%, even more preferably 31 wt% to 70 wt%, particularly preferably 31.5 wt% to 60 wt%, and most preferably 32 wt% to 55 wt%, based on the total amount of the high-temperature stable slowly digestible starch.
According to the high-temperature stable slowly digestible starch, after high-temperature processing, the SDS retention rate is more than 97%, preferably 97.3-99.9%, more preferably 98-99.9%, and even more preferably 98.3-99.9%.
The high-temperature stable slowly digestible starch has the maximum aging degree of 0.2-0.4.
According to the high-temperature stable slowly digestible starch, the water precipitation rate is 20-48%.
The high temperature stable slowly digestible starch according to the invention comprises a hydrocolloid.
The high temperature stable slowly digestible starch according to the invention, the hydrocolloid is selected from at least one of a natural hydrocolloid, a physically modified hydrocolloid, a chemically modified hydrocolloid or an enzymatically modified hydrocolloid.
According to the high-temperature stable type slowly digestible starch, the hydrophilic colloid is selected from at least one of curdlan, gellan gum, konjac gum, sodium alginate, carboxymethyl curdlan and a compound of the colloid.
According to the high-temperature stable slowly digestible starch, the colloid compound is a konjac gum compound.
According to the high-temperature stable slowly digestible starch, the konjac gum compound is a carrageenan and konjac gum compound.
According to the high-temperature stable slowly digestible starch, in the compound of the carrageenan and the konjac glucomannan, the ratio of the carrageenan to the konjac glucomannan is not less than 0 and not more than carrageenan by weight: the ratio of konjac glucomannan to konjac gum is less than or equal to 0.6: 1.
The invention provides application of high-temperature stable slowly digestible starch in preparation of food, beverage, health-care product, medicine and feed.
According to the use of the present invention, the high temperature stable slowly digestible starch is the high temperature stable slowly digestible starch prepared by the preparation method of the present invention or the high temperature stable slowly digestible starch.
The high-temperature stable slowly digestible starch prepared by the preparation method of the high-temperature stable slowly digestible starch is provided.
The invention provides a starch composition comprising the high temperature stable slowly digestible starch of the invention.
The present invention provides a product comprising a high temperature stable slowly digestible starch according to the invention and/or a starch composition according to the invention, preferably a food, beverage, nutraceutical, pharmaceutical and/or feed.
The invention provides an auxiliary material for food, medicine and/or feed, which comprises the high-temperature stable slowly digestible starch and/or the starch composition.
Effects of the invention
According to the preparation method of the high-temperature stable slowly digestible starch, the slowly digestible starch with high temperature stability is prepared, so that the problem of unstable high-temperature processing of the slowly digestible starch prepared by the traditional method is solved. The high-temperature stable slowly digestible starch has slow digestibility, freeze-thaw stability and ageing resistance, and can remarkably widen the application range of the starch. The preparation method of the high-temperature stable slowly digestible starch can prepare the high-temperature stable slowly digestible starch with high yield, and has the advantages of simple and clean process, low requirement on equipment and low cost, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a FT-IR plot of slowly digestible starch prepared with curdlan and starch (0: 100; 1:100; 3: 100) at different ratios.
FIG. 2 is a FT-IR plot of slowly digestible starch prepared with different ratios of gellan gum to starch (0: 100; 1:100; 1: 1).
FIG. 3 is a FT-IR plot of slowly digestible starch prepared with different ratios of carboxymethyl curdlan to starch (0: 100; 1:100; 1: 1).
FIG. 4 is a FT-IR plot of slowly digestible starch prepared with different ratios of carrageenan and konjac gum mixture to starch (0: 100; 1:100; 1: 1).
Detailed Description
Preparation method of high-temperature stable slowly digestible starch
The preparation method of the high-temperature stable slowly digestible starch is characterized by comprising the following steps: pasting: gelatinizing raw material starch, water and hydrophilic colloid to obtain a gelatinized starch mixture; a separation step: separating the gelatinized starch mixture to obtain the high-temperature stable slowly digestible starch.
In the preparation method of the invention, Gelatinization (Gelatinization) refers to Gelatinization of starch, and is characterized in that starch grains are swelled and collapsed to form a viscous and uniform transparent paste solution after the starch is mixed in water and heated to reach a certain condition.
The gelatinization nature of starch is that water enters into microcrystalline bundles, the association state among starch molecules is broken up, the starch molecules lose the original orientation arrangement and become a disordered state, and the starch is dispersed in water to form a colloidal solution. Thus, starch gelatinization can occur in all ways that disrupt the hydrogen bonding between starches. After the starch milk is heated, starch grains begin to be destroyed within a certain temperature range, the crystal structure disappears, the volume is expanded, the viscosity rises sharply, and the starch is viscous paste, so that the non-crystalline starch is obtained. The gelatinization temperature of each starch varies depending on the kind of raw material, the size of starch grains, and the like. The temperature required for gelatinization of the starch to occur is referred to as the gelatinization temperature. Refers to the temperature at which birefringence (polarizing cross) disappears. The gelatinization temperature is not a point but a range of temperatures. The temperature at which the starch granules begin to swell is called the onset gelatinization temperature. The temperature at which the starch paste is formed is called the gelatinization end temperature. The gelatinization temperature of starch must reach a certain degree, the gelatinization temperature of different starches is different, the particle size of the same starch is different, the gelatinization temperature is different, the gelatinization is carried out before the particle size is large, and the gelatinization is carried out after the particle size is small. In addition to heat, some hydrogen bond disrupting agents may also promote starch gelatinization, lowering the gelatinization temperature, such as by adding hydrogen bond disrupting agents (e.g., electrolytes or chemical agents such as urea, guanidinium, dimethylsulfoxide, etc.) to the starch milk.
The ability of different electrolytes to promote starch gelatinization is different, and the order of promoting starch gelatinization by anions is: OH group-Salicylic acid radical > CNS-＞I-＞Br-＞NO3 -＞Cl-Tartrate > citrate > SO4 2-The order in which the cations promote gelatinization is: li+＞Na+＞K+＞NH4 +＞Mg2+. Therefore, the hydrogen bond disruptor is preferably NaOH, LiOH, KOH, Mg (OH)2Lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, magnesium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、Mg(CNS)2、LiI、NaI、KI、NH4I、MgI2、LiBr、NaBr、KBr、NH4Br、MgBr2、LiNO3、NaNO3、KNO3、NH4NO3、Mg(NO3)2、LiCl、NaCl、KCl、NH4Cl、MgCl2Lithium tartrate, sodium tartrate, potassium tartrate, sodium citrate, potassium citrate, lithium citrate, Li2SO4、K2SO4、Na2SO4More preferably NaOH, LiOH, KOH, Mg (OH)2Lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, magnesium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、Mg(CNS)2、LiI、NaI、KI、NH4I、MgI2、LiBr、NaBr、KBr、NH4Br、MgBr2、LiNO3、NaNO3、KNO3、NH4NO3、Mg(NO3)2、LiCl、NaCl、KCl、NH4Cl、MgCl2Particularly preferred are NaOH, LiOH, KOH, lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, LiCNS, NaCNS, KCNS, and NH4CNS、LiI、NaI、KI、NH4I、LiBr、NaBr、KBr、NH4Br、 LiNO3、NaNO3、KNO3、NH4NO3。
The gelatinization temperature of the starch is gradually reduced with the increase of the concentration of the hydrogen bond disruptor (electrolyte or chemical agent), so that the starch can be gelatinized at room temperature under the condition of high concentration of the hydrogen bond disruptor (electrolyte or chemical agent). Therefore, the amount of the hydrogen bond-disrupting agent added is generally 0.001 to 1mol/L, preferably 0.003 to 0.9mol/L, more preferably 0.005 to 0.85mol/L, and particularly preferably 0.01 to 0.8 mol/L. In addition, the pressure borne by the starch milk in the gelatinization process is also a factor influencing the gelatinization of the starch, and the gelatinization temperature of the starch is gradually reduced along with the increase of the pressure borne by the starch.
In the preparation method of the invention, the gelatinization step is carried out at a temperature which is higher than the gelatinization starting temperature of starch and is not higher than 100 ℃, and the gelatinization starting temperature of starch can be determined by the method in GB-T14490-2008.
In the preparation method of the present invention, the gelatinizing step may be selected from one or more of: a) gelatinizing starch with water at a temperature higher than the gelatinization temperature of the starch to obtain gelatinized starch, and contacting with a hydrophilic colloid or an aqueous solution of the hydrophilic colloid to obtain a gelatinized starch mixture; b) contacting starch, water and hydrophilic colloid, and gelatinizing at a temperature higher than the gelatinization temperature of the starch to obtain a gelatinized starch mixture; c) contacting water with hydrophilic colloid to form hydrophilic colloid solution, and contacting and gelatinizing the hydrophilic colloid solution with starch at the temperature higher than the gelatinization starting temperature of the starch to obtain gelatinized starch mixture; d) contacting starch, water or an aqueous solution containing a hydrogen bond breaking agent with a hydrophilic colloid, and gelatinizing under the condition of normal pressure or high pressure and the temperature higher than the gelatinization temperature of the starch to obtain a gelatinized starch mixture; c) contacting water or water solution containing hydrogen bond disruptor with hydrophilic colloid to form hydrophilic colloid solution, and contacting with starch and gelatinizing at a temperature higher than starch gelatinization temperature under normal pressure or high pressure to obtain gelatinized starch mixture.
In the preparation method of the present invention, a water removal step is further included after the gelatinization step: the resulting gelatinized starch mixture is freed of water. In the water removal step, the reaction solution is evaporated in 30 to 120 seconds at a temperature of 80 to 100 ℃.
In the production method of the present invention, a redissolution step is further included after the water removal step: the solute obtained after removal of water is redissolved. In the redissolution step, the volatile matter obtained in the water removal step is dispersed and dissolved in water, and the precipitate obtained after centrifugation is freeze-dried. The amount of water used in the redissolution step is not particularly limited, and is preferably the same as the amount of water used in the gelatinization step. Preferably, the volatile matter obtained in the water removing step is dispersed and dissolved in water at 80-100 ℃. Preferably, the centrifugation is carried out at 4000 to 8000rpm for 3 to 6 min. Preferably, the freeze drying is carried out for 12-24 hours.
After freeze-drying, the powder is pulverized and sieved (e.g., 100 mesh standard sieve) according to conventional methods.
The step of gelatinizing comprises the steps of stirring for 5-10 min at a pH of more than or equal to 11 or at a temperature of 50-100 ℃, preferably 53-98 ℃, more preferably 55-96 ℃, and particularly preferably 58-95 ℃, and/or raising the temperature to 50-100 ℃, preferably 53-98 ℃, more preferably 55-96 ℃, and particularly preferably 58-95 ℃ to gelatinize the starch.
In the step of gelatinizing, the ratio of the hydrophilic colloid to the raw starch to the water is 0.005-1.2: 1:10 to 120 (w/w), preferably 0.008 to 1.1: 1: 11 to 110 (w/w), more preferably 0.01 to 1: 1: 12 to 100 (w/w), and particularly preferably satisfies the following requirements of 0.03 to 0.3: 1: 20 to 100 (w/w). In a particular embodiment of the invention, the ratio of the hydrocolloid, the starting starch and the water satisfies 0.01: 1:100 (w/w), 0.03: 1:10 (w/w), 0.01: 1:100 (w/w), 1: 1:100 (w/w), 0.01: 1:100 (w/w), 1: 1:100 (w/w), 0.01: 1:100 (w/w), 1: 1:100 (w/w).
Gelatinizing the raw starch, water and hydrocolloid to obtain a gelatinized starch mixture with zero-cut viscosityη 02000cP or less, preferablyη 01000cP or less, more preferably 1000cP or lessη 0950cP or less, and further preferably 950cP or lessη 0Less than or equal to 900 cP. In a particular embodiment of the invention, the gelatinized starch mixture obtained has a zero-cut viscosityη 0491cP, 496cP, 513cP, 527cP, 938cP, 947cP, 8656cP, 1825 cP.
In the present invention, the hydrocolloid is selected from natural hydrocolloids, physically modified hydrocolloids, chemically modified hydrocolloids. At least one of the hydrocolloids being enzymatically modified. Preferably, the hydrophilic colloid is at least one selected from curdlan, gellan gum, konjac gum, sodium alginate, carboxymethyl curdlan and a compound of the colloid.
The hydrophilic colloid is a hydrophilic colloid hydrate, and can generate no macroscopic flow (macroscopic non-flow) when being heated to 100 ℃ from room temperature. Which can maintain a hydrocolloid hydrate such as a hydrogel or the like in a solid-like state under a high temperature condition.
The "macroscopic flow" and "macroscopic non-flow" refer to the liquid-like flow or solid-like static properties when the liquid-like flow or the solid-like static properties are displayed when the liquid-like flow or the solid-like static properties are statically placed. By "macroscopically non-flowing" is meant that the hydrocolloid hydrate does not flow or cast when placed at rest. The specific determination method can adopt a dynamic test method of a rheometer, wherein the "macroscopic flow" is represented by the storage modulus G '> loss modulus G' of a sample in a tested frequency range, and the "macroscopic flow" is represented by the storage modulus G '< loss modulus G' in the tested frequency range.
By a formulation of colloids is meant a mixture resulting from mixing two or more colloids together, the resulting mixture having properties not possessed by each individual colloid prior to mixing. For example, the compound of carrageenan and konjac glucomannan, wherein the proportion of carrageenan to konjac glucomannan is 0 ≤ carrageenan: the ratio of konjac glucomannan to konjac gum is less than or equal to 0.6: 1.
In the present invention, the raw starch is selected from at least one of corn starch, wheat starch, rice starch, potato starch, tapioca starch, sweet potato starch, mung bean starch, chickpea starch, sorghum starch, sago starch, canna starch, banana starch, apple starch, peach starch, yam starch, lotus root starch, rice flour, wheat flour, corn flour, potato flour, tapioca flour, sweet potato flour, mung bean flour, chickpea flour, sorghum flour, sago flour, banana flour, yam flour, lotus root flour, banana flour, apple flour, or peach flour.
In a preferred embodiment of the invention, the hydrocolloid is curdlan and the pH during the gelatinisation step and the water removal step is ≥ 11. Adding alkaline component into the added water to make pH greater than or equal to 11. The alkaline component is, for example, a hydroxide of an alkali metal such as sodium hydroxide, potassium hydroxide, or the like. The reaction may be carried out by directly using an aqueous solution of an alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide, etc.).
In a preferred embodiment of the invention, the hydrocolloid is gellan gum or sodium alginate and the ion R in the gelatinisation step is2+The ratio of the amount of the sodium alginate to the amount of the gellan gum or the sodium alginate is more than or equal to 0.05M percent and less than or equal to the ion R2+Gellan gum or sodium alginate less than or equal to 0.5M%, and M is divalent cationQuantum, R2+Is selected from Ca2+、Mg2+Or Zn2+. The ion R is obtained by adding calcium salt, magnesium salt or zinc salt into the reaction solution2+The amount of (c).
In a particular embodiment of the invention, the hydrocolloid is gellan gum and the divalent cation is Ca2+，Ca2 +Gellan gum =2% or Ca2+Gellan gum = 19.8%.
In a preferred embodiment of the invention, the hydrocolloid is carboxymethyl curdlan: the degree of substitution is less than or equal to 0.2. "degree of substitution" refers to the average number of hydroxyl groups on each curdlan macromolecule glucose residue ring that are substituted with carboxymethyl groups. The specific test method comprises the following steps: acidimetry, ashing, conductivity, nuclear magnetic resonance, and the like. In a specific embodiment of the invention, the degree of substitution of the carboxymethyl curdlan is 0.15 or 0.2.
In a preferred embodiment of the invention, the hydrophilic colloid is a compound of carrageenan and konjac gum, and the pH value in the gelatinization step is more than or equal to 10. In the carrageenan and konjac glucomannan compound, the ratio of carrageenan to konjac glucomannan is not less than 0 in terms of weight ratio: the ratio of konjac glucomannan to konjac gum is less than or equal to 0.6: 1.
In a specific embodiment of the present invention, in the gelatinization step, the pH =10, and in the carrageenan-konjac glucomannan composition, the ratio of carrageenan to konjac glucomannan is, in terms of weight ratio, carrageenan: konjac gum =0.3: 1.
The preparation method of the high-temperature stable slowly digestible starch can prepare the high-temperature stable slowly digestible starch with high yield. The yield by the preparation method of the invention is 60-95%, preferably 62-91%. In a specific embodiment of the invention, the yield by the preparation process of the invention is 62.8%, 64.3%, 65.6%, 65.8%, 81.8%, 85.5%, 87.4%, 90.2%.
The method for preparing the high-temperature stable slowly digestible starch of the present invention can be used for preparing the high-temperature stable slowly digestible starch of the present invention.
In the preparation method of the high-temperature stable slowly digestible starch, the starch and the hydrophilic colloid form an intermolecular winding state in a gelatinized state, and the state is maintained to solidify a compound of the hydrophilic colloid and the starch (namely, the compound forms macroscopic immobile liquid by adjusting pH and ionic strength), and the slowly digestible starch is obtained by separation and drying.
High-temperature stable slowly digestible starch
The high-temperature stable slowly digestible starch of the present invention is characterized in that the degree of hydrogen bonding represented by the following formula is 20 to 60 wt%,
degree of hydrogen bonding:X b= (1+αA fm2/A bm1)-1×100%。
in the formula, alpha is molar absorption coefficient, and a constant is 3.5;A fis 3000-4000 cm in infrared spectrum of starch raw material-1The absorbance of the maximum absorption peak in the range,A bthe sample to be detected is 3000-4000 cm-1Absorbance of the maximum absorption peak in the range; m is1M is the mass of the sample to be measured2For the analysis of pure corn starch quality.
The degree of hydrogen bonding refers to the weight fraction of hydrogen bonding functional groups in the sum of free functional groups and hydrogen bonding functional groups. In an infrared spectrogram, 3000-4000 cm-1The maximum absorption peak in the range is the absorption peak of the hydroxyl group for stretching vibration. In a system mainly composed of a certain compound, when a physicochemical reaction is carried out, a free hydroxyl group is converted into an associated hydrogen-bonded hydroxyl group, the position of the maximum absorption peak of the free hydroxyl group undergoes a blue shift and moves to the direction of the hydrogen-bonded hydroxyl group in a low wave number direction, and it is considered that the free hydroxyl group is converted into the associated hydrogen-bonded hydroxyl group when the blue shift range is generally 5 to 50 wave numbers. In this case, Af is defined to be 3000 to 4000cm-1In the range, the absorbance of the free hydroxyl group in the compound at the absorption peak of stretching vibration; ab is defined to be 3000-4000 cm-1Within the range, the absorption peak position of free hydroxyl in the compound system is blue-shifted, and the formed hydrogen bonding hydroxyl stretches and contracts to vibrate and absorb the absorbance of the absorption peak. To simplify the operation, the starch feedstock (in one embodiment, employed) is used in the present inventionAnalytically pure corn starch) in the range of 3000-4000 cm-1The maximum absorption peak in the range is defined as the absorbance of the free hydroxyl group (II) ((III))A f ) (ii) a Pretreating a sample at 3000-4000 cm-1The maximum absorption peak when blue shift of 5-50 wave numbers occurs in the range is defined as the absorbance of hydrogen bonded hydroxyl group (A b ）。
The degree of hydrogen bonding of the high-temperature stable slowly digestible starch of the present invention is preferably 20.5 to 50 wt%, more preferably 21 to 45 wt%, still more preferably 21.5 to 40 wt%, and particularly preferably 22 to 35 wt%.
In a particular embodiment of the invention, the high temperature stable slowly digestible starch of the invention has a degree of hydrogen bonding of 22.6 wt%, 23.3 wt%, 23.7 wt%, 26.7 wt%, 31.6 wt%, 31.7 wt%, 32.3 wt%, 34.8 wt%.
The content of the slowly digestible starch is more than 30 wt% based on the total weight of the high temperature stable slowly digestible starch. In a preferred embodiment of the present invention, the high-temperature stable slowly digestible starch has a slowly digestible starch content of 30 wt% to 99.9 wt%, preferably 30.3 wt% to 80 wt%, more preferably 31 wt% to 70 wt%, even more preferably 31.5 wt% to 60 wt%, and particularly preferably 32 wt% to 55 wt%.
The slowly digestible starch is insoluble precipitate formed by a starch molecular chain and the hydrophilic colloid molecular chain through hydrogen bond action in a high-temperature water solution environment.
In a specific embodiment of the invention, the high temperature stable slowly digestible starch of the invention has a slowly digestible starch content of 30.3 wt.%, 31.6 wt.%, 32.3 wt.%, 33 wt.%, 48.7 wt.%, 49.7 wt.%, 52.4 wt.%.
After the high-temperature stable slowly digestible starch is processed at high temperature, the retention rate of the Slowly Digestible Starch (SDS) is more than 97%, preferably the retention rate of the SDS is 97.3-99.9%, more preferably the retention rate of the SDS is 98-99.9%, and even more preferably the retention rate of the SDS is 98.3-99.9%. The high-temperature processing is, for example, processing in which the starch is sufficiently gelatinized at 100 ℃ under an environment of 0.1MPa so that the gelatinization degree of the starch becomes 100%.
In a specific embodiment of the invention, the high temperature stable slowly digestible starch of the invention has a retention rate of the Slowly Digestible Starch (SDS) after high temperature processing of 97.3%, 97.4%, 97.5%, 98.3%, 98.7%, 98.8%.
The maximum aging degree of the high-temperature stable slowly digestible starch is 0.2-0.4. In a specific embodiment of the invention, the high temperature stable slowly digestible starch of the invention has a maximum retrogradation degree of 0.24, 0.25, 0.28, 0.32, 0.33, 0.35, 0.36.
The water precipitation rate of the high-temperature stable slowly digestible starch is 20-48%. In a specific embodiment of the invention, the water extraction rate of the high temperature stable slowly digestible starch of the invention is 26.7%, 34.4%, 35.1%, 35.6%, 40.3%, 42.5%, 44.3%, 46.3%.
The high-temperature stable slowly digestible starch contains hydrophilic colloid. The hydrocolloid is selected from a natural hydrocolloid, a physically modified hydrocolloid, a chemically modified hydrocolloid. At least one of the hydrocolloids being enzymatically modified. Preferably, the hydrophilic colloid is at least one selected from curdlan, gellan gum, konjac gum, sodium alginate, carboxymethyl curdlan and a compound of the colloid.
By a formulation of colloids is meant a mixture resulting from mixing two or more colloids together, the resulting mixture having properties not possessed by each individual colloid prior to mixing. For example, the compound of carrageenan and konjac glucomannan, wherein the proportion of carrageenan to konjac glucomannan is 0 ≤ carrageenan: the ratio of konjac glucomannan to konjac gum is less than or equal to 0.6: 1.
The high-temperature stable slowly digestible starch of the present invention may be prepared by the above-described method of preparing a high-temperature stable slowly digestible starch of the present invention.
High temperature stable slow digestion starch composition
The high-temperature stable slowly digestible starch composition of the present invention comprises the above-described high-temperature stable slowly digestible starch of the present invention.
Use of
The high-temperature stable slowly digestible starch, the high-temperature stable slowly digestible starch prepared by the preparation method of the high-temperature stable slowly digestible starch and the high-temperature stable slowly digestible starch composition can be used in food, beverage, health products, medicines and/or feeds and used as auxiliary materials of the food, the medicines and/or the feeds.
The high-temperature stable slowly digestible starch has a hydrogen bonding degree of 20-60 wt%. Starch molecules are bonded with the high-temperature non-flowing hydrophilic colloid through hydrogen bond action, and on one hand, the action can generate more slowly digested starch; meanwhile, the slowly digestible starch can be endowed with certain high-temperature stability, so that the slowly digestible starch can be retained to the greatest extent after the slowly digestible starch is processed into food. In addition, the hydrogen-bonded high-temperature non-flowing hydrophilic colloid can inhibit the aging and the reversion of the starch, and simultaneously, the product has better freeze-thaw resistance stability, so that the application of the slowly digestible starch in various fields can be further expanded. The application of the invention can relate to a plurality of fields, such as baked food, fast food, candy, seasoning, dairy products, special food for athletes, food for diabetics, weight-losing food, oral small intestine targeted controlled-release film coating material, other specific health-care functional food and feed, and the like.
Examples
The following examples are further illustrative of the present invention, but the present invention is not limited to the following. The embodiments in the present description are only for illustrating the present invention, and do not limit the scope of the present invention. The scope of the present invention is defined only by the appended claims, and any omissions, substitutions, and changes in the form of the embodiments disclosed herein that may be made by those skilled in the art are intended to be included within the scope of the present invention.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. In the following examples, various starting materials were used, and unless otherwise specified, conventional commercially available products were used. In the description of the present invention and the following examples, "%" represents weight percent unless otherwise specified.
The detection method employed in the present invention is as follows.
Yield of slowly digested starch: yield Y (%) = mass of dry matter obtained by reaction/(mass of original starch dry basis + mass of hydrophilic colloid) × 100%
Starch digestibility: the Englyst method was used.
Raw starch sample: 200mg of starch sample is placed in a test tube, 15ml of sodium acetate buffer solution with pH5.2 is added, 10ml of mixed enzyme solution (containing fungal alpha-amylase (3500U/ml), glucoamylase (100U/ml) and calcium chloride (10 mM) is added), the mixture is placed in a constant temperature water bath at 37 ℃ for oscillation, after hydrolysis is carried out for 20 and 120min, the content of generated glucose is measured by a glucose kit at 505nm through colorimetry, and the content of Slowly Digested Starch (SDS) is calculated according to the difference.
Starch samples after high temperature processing: taking 10g of raw starch sample, placing in a high-temperature and high-pressure environment with the temperature of 100 ℃ and the pressure of 0.1MPa, fully gelatinizing for 10min to enable the gelatinization degree to reach 100%, and freeze-drying the obtained sample. After freeze-drying, the sample is detected by Slowly Digestible Starch (SDS) in the same way as the original starch.
SDS Retention C (%) = SDS content of starch after high-temperature processing/SDS content of native starch × 100%
Zero-shear viscosity of the reaction Systemη 0: the zero-cut viscosity of the reaction system was measured by a rheometer model Anton Par Physica MCR 301. According to the temperature condition when the starch and colloid mixed system is gelatinized, a flat plate mode is adopted, the diameter of the flat plate is 25mm, and the shearing rate range is 0.01-1000S-1The viscosity at which the shear rate at the earlier stage approaches zero is recorded.
Evaluation of aging Property: differential scanning calorimetry (DSC method). The method specifically comprises the following steps: accurately weighing 2mg of sample, placing 4ul of deionized water in a crucible, sealing, balancing at room temperature for 24h, taking an empty crucible as reference, and carrying out temperature scanning within the range of 20-100 ℃ at the scanning speed of 10 ℃/min. The maximum aging Degree (DR) is the ratio of the melting enthalpy of the aged crystal to the gelatinization enthalpy.
Evaluation of freeze-thaw stability: the water-separating rate was determined by referring to the Muadklay method. 30ml of 10% (w/v) starch paste was poured into a 50ml centrifuge tube, stored at-20 ℃ for 22h, then thawed in a water bath at 30 ℃ for 2h, and the cycle was repeated 5 times. The sample was centrifuged at 4500rpm for 15min, the supernatant was discarded, the mass of the precipitate was weighed and the experiment was repeated 3 times.
The calculation formula is as follows: water Separation Rate (SR) = (total sample weight-precipitate weight)/total sample weight × 100%
Analysis of degree of hydrogen bonding:
(A) pretreatment: taking a certain amount of sample to be tested, stirring and dissolving the sample in water at 70-100 ℃ to prepare a solution with the concentration of more than 0 and less than or equal to 10%, centrifuging the solution at 4000-10000 rpm for 3-10 min, and freeze-drying the precipitate in a freeze dryer for 12-24h to obtain the sample to be tested.
(B) Fourier transform infrared spectrometer analysis:
weighing m1Gram of sample to be tested and m2Gram starch (analytically pure corn starch), preparing a sample slice to be detected by adopting a KBr tabletting method, placing the slice in a sample cell, taking air as a reference, scanning for 32 times by using a DTGS detector, and enabling the resolution to be 4cm-1. And (4) carrying out infrared spectrum measurement on the obtained sample, and calculating the degree of hydrogen bonding.
Degree of hydrogen bonding:X b= (1+αA fm2/A bm1)-1×100%。
in the formula, alpha is a molar absorption coefficient, and a constant is 3.5;A fis 3000-4000 cm in the infrared spectrum of a starch raw material-1The absorbance of the maximum absorption peak in the range,A bthe sample to be detected is 3000-4000 cm-1Absorbance of the maximum absorption peak in the range; m is1M is the sample mass to be measured2For the analysis of pure corn starch quality.
Carrageenin: san Ei Gen F.F.I. carrageenan (SAN SUPPORT G-16) Japan; konjac glucomannan: japan San Ei Gen F.F.I. Konjac Gum (VIS TOP D-2134)); gellan gum: fufeng group LG 2016123170; sodium alginate: national drug group chemical agents ltd k 20100312; curdlan: jiangsu Dongsheng food science and technology ltd; corn starch: shandong Zhucheng corn development, Inc.; other chemical reagents are purchased from chemical reagents of national drug group, ltd; guar gum: shanghai Xibao Biotechnology Ltd., AJA 0082G.
Examples 1 to 1
0.01g curdlan was taken and dissolved in 100ml of NaOH solution with pH =11 with stirring at room temperature. And (3) putting another 1g of corn starch into curdlan aqueous solution, heating to 90 ℃, and fully stirring for 8 min. Under these conditions, the solution was heated rapidly to 100 ℃ and the solvent was rapidly evaporated within 50 s. Dispersing the solute in 100ml water at 85 deg.C, adjusting pH of the mixed solution to 7 with 0.5mol/L citric acid solution, centrifuging at 6000rpm for 6min under high temperature environment, drying the precipitate in a freeze dryer for 24 hr, pulverizing, and sieving with 100 mesh standard sieve.
Examples 1 to 2
The experimental conditions were the same as in example 1-1, except that the curdlan was added in an amount of 0.3g and the corn starch was added in an amount of 10 g.
Comparative example 1-1
The experimental conditions were the same as in example 1-1, except that the amount of corn starch added was 10 g.
Comparative examples 1 to 2
The experimental conditions were the same as in examples 1-2 except that curdlan was added in an amount of 0.5 g.
Comparative examples 1 to 3
The experimental conditions were the same as in example 1-1, except that the amount of corn starch added was 15 g.
Comparative examples 1 to 4
Experimental conditions were the same as in example 1-2, except for the initial stage, 0.3g of curdlan was dissolved in 100ml of deionized water at room temperature with stirring.
Comparative examples 1 to 5
Experimental conditions were the same as in example 1-1 except for the initial stage, 0.01g curdlan was dissolved in a citric acid solution of pH =4 with stirring at room temperature.
Comparative examples 1 to 6
0.3g curdlan was taken and dissolved in 100ml of NaOH solution with pH =11 with stirring at room temperature. And placing another 10g of corn starch in curdlan aqueous solution, and fully stirring for 8 min. Adjusting pH of the mixed solution to 7 with 0.5mol/L citric acid solution, drying in a freeze dryer for 24 hr, pulverizing, and sieving with 100 mesh standard sieve.
Comparative examples 1 to 7
0.3g curdlan was taken and dissolved in 100ml of NaOH solution with pH =11 with stirring at room temperature. And placing another 10g of corn starch in curdlan aqueous solution, and fully stirring for 8 min. Heating the above solution to 100 deg.C rapidly, volatilizing the solvent rapidly within 50s, pulverizing, and sieving with 100 mesh standard sieve.
As can be seen from FIG. 1, in the slowly digestible starch prepared from curdlan and starch, hydrogen bonding is generated between curdlan molecular chains and starch molecular chains (3430 cm)-1The absorption peaks of the associated hydroxyl groups at the left and right sides are blue-shifted, and the peak intensity becomes large).
Watch (A)
Comparing the above examples, it can be seen that when the curdlan content is too low (comparative example 1-1), the yield of the prepared SDS starch is low, the SDS contains too little colloid, the enzyme has enough attack sites, and the digestion-inhibiting effect is weak; when curdlan or starch is excessive (comparative examples 1-2 and 1-3), the solution viscosity is too high, so that the molecular chain in the solution is difficult to move, the bonding amount of the starch molecular chain and the colloid molecular chain is small, most of the starch molecular chain and the colloid molecular chain are bonded by themselves in the solution environment, and SDS (sodium dodecyl sulfate) is also less; the increase of SDS can only be really realized when curdlan and starch are in a proper proportion range (examples 1-1 and 1-2). For the DR value, the aging of the starch can be delayed after the curdlan is added, and the aging of the starch is inhibited mainly because the combination of molecular chains of the curdlan and the starch blocks the combination of the molecular chains of the starch. Meanwhile, the water precipitation rate is gradually reduced along with the addition of the curdlan, which is mainly consistent with the fact thatCurdlan inhibits starch retrogradation and is associated with excellent water retention. Degree of hydrogen bondingX bAlthough comparative examples 1-1 and 1-2 are also large, they are mostly generated by binding of colloids themselves, and thus do not contribute much to SDS. In comparative examples 1-4, 1-5, 1-6 and 1-7, SDS was measured to be significantly lower because the SDS substance could not be separated from the product due to the difference in reaction conditions and preparation process.
Example 2-1
0.01g of gellan gum was dispersed and dissolved in 100ml of 85 ℃ water. Another 1g of corn starch is put into the high-temperature water solution of gellan gum and fully stirred for 7 min. 0.0055g of calcium chloride was weighed and added to the above high-temperature aqueous solution (Ca)2+: gellan = 19.8%), stirring was continued for 2 min. Maintaining the high temperature environment, and quickly evaporating the solution within 100 s. Dispersing the obtained volatile matter in 100ml water at 95 deg.C, centrifuging at 4000rpm for 4min at high temperature, drying the precipitate in freeze dryer for 20 hr, pulverizing, and sieving with 100 mesh standard sieve.
Examples 2 to 2
The experimental conditions were the same as in example 2-1, except that the amount of gellan gum added was 1g and the amount of calcium chloride added was 0.055g (Ca)2+: gellan = 2%).
Comparative example 2-1
The experimental conditions were the same as in example 2-1, except that the amount of corn starch added was 10 g.
Comparative examples 2 to 2
The experimental conditions were the same as in example 2-2, except that the amount of corn starch added was 0.8 g.
Comparative examples 2 to 3
The experimental conditions were the same as in example 2-2, except that the amount of corn starch added was 15 g.
Comparative examples 2 to 4
Experimental conditions were the same as in example 2-2, except that the amount of calcium chloride added was 0.02g (Ca)2+: gellan gum<2%）。
Comparative examples 2 to 5
1g of gellan gum was dispersed and dissolved in 100ml of 85 ℃ water. Another 1g of corn starch is put into the high-temperature water solution of gellan gum and filled withStirring for 7 min. 0.055g of calcium chloride was weighed out and added to the above high temperature aqueous solution (Ca)2+: gellan = 2%), and stirring is continued for 2 min. Cooling to room temperature, drying the obtained material in a freeze dryer for 20h, pulverizing, and sieving with 100 mesh standard sieve.
Comparative examples 2 to 6
1g of gellan gum was dispersed and dissolved in 100ml of 85 ℃ water. Another 1g of corn starch is put into the high-temperature water solution of gellan gum and fully stirred for 7 min. 0.055g of calcium chloride was weighed out and added to the above high temperature aqueous solution (Ca)2+: gellan = 2%), and stirring is continued for 2 min. Maintaining the high temperature environment, and quickly evaporating the solution within 100 s. Pulverizing, and sieving with 100 mesh standard sieve.
As can be seen from FIG. 2, in the slowly digestible starch prepared from gellan gum and starch, hydrogen bonding (3430 cm) is generated between gellan gum molecular chains and starch molecular chains-1Absorption peaks of the associated hydroxyl groups at the left and right sides are blue-shifted, and the peak intensity is increased).
TABLE 2
Comparing the above examples, it can be seen that when the gellan gum content is too low (comparative example 2-1), the yield of the prepared SDS is low, and at the same time, the amount of thermally stable hydrophilic colloid around the starch is too small, and the enzyme has enough attack sites and weak digestion-inhibiting effect; when the gellan gum content is too high (comparative example 2-2), the starch molecule barrier effect is lacking between the gellan gum molecules, resulting in too high local concentration of gellan gum in the solution, and self-binding of gellan gum molecules, resulting in lower SDS yield and content. In addition, if the viscosity of the system is high, the collision bonding probability of starch and colloid molecules is affected, resulting in the generation of SDS with too low content (comparative examples 2-3). For DR value, the aging of starch can be delayed after adding gellan gum, and the aging of starch is inhibited mainly because the presence of gellan gum hinders the combination of starch molecular chains. Meanwhile, the water precipitation rate is gradually reduced along with the addition of the gellan gum, and is mainly related to the fact that the gellan gum inhibits the aging of starch and has excellent water retention. Degree of hydrogen bondingX bThe gellan gum and the starch can form hydrogen bond only when in a proper proportion range; when the gellan gum content is too large (comparative example 2-2), ionic bonding occurs by itself, hydrogen bonding with starch is restricted, and therefore the degree of hydrogen bonding is low. In comparative examples 2 to 4, SDS could not be obtained by the above-mentioned process because the concentration of the ionic crosslinking agent added was too low, resulting in failure to form a thermally irreversible gel. In comparative examples 2-5 and 2-6, the SDS-substance was not separated from the product due to the difference in reaction conditions and preparation process, so that the SDS content was significantly low.
Example 3-1
0.01g of carboxymethyl curdlan (degree of substitution = 0.15) was taken and dispersed in 100ml of 80 ℃ water. And (3) putting another 1g of corn starch in the high-temperature aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Maintaining the high temperature environment, and quickly evaporating the solution within 120 s. Dispersing the obtained volatile matter in 100ml water at 100 deg.C, centrifuging at 5000rpm for 6min at high temperature, drying the precipitate in freeze dryer for 16 hr, pulverizing, and sieving with 100 mesh standard sieve.
Examples 3 to 2
The experimental conditions were the same as in example 3-1 except that carboxymethyl curdlan (degree of substitution = 0.2) was added in an amount of 1 g.
Comparative example 3-1
The experimental conditions were the same as in example 3-1, except that the amount of corn starch added was 10 g.
Comparative example 3-2
The experimental conditions were the same as in example 3-2, except that the amount of corn starch added was 0.6 g.
Comparative examples 3 to 3
The experimental conditions were the same as in example 3-2, except that the amount of corn starch added was 15 g.
Comparative examples 3 to 4
The experimental conditions were the same as in example 3-2, except that the degree of substitution of carboxymethyl curdlan was 0.5.
Comparative examples 3 to 5
The experimental conditions were the same as in example 3-2, except that the degree of substitution of carboxymethyl curdlan was 1.
Comparative examples 3 to 6
1g of carboxymethyl curdlan (degree of substitution = 0.2) was taken and dispersed in 100ml of 80 ℃ water. And (3) putting another 1g of corn starch into the aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Cooling to room temperature, drying the obtained material in a freeze dryer for 16h, pulverizing, and sieving with a 100-mesh standard sieve.
Comparative examples 3 to 7
1g of carboxymethyl curdlan (degree of substitution = 0.2) was taken and dispersed in 100ml of 80 ℃ water. And (3) putting another 1g of corn starch in the high-temperature aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Maintaining the high temperature environment, and quickly evaporating the solvent within 120 s. Pulverizing, and sieving with 100 mesh standard sieve.
As can be seen from FIG. 3, in the slowly digestible starch prepared from carboxymethyl curdlan and starch, hydrogen bonding is generated between carboxymethyl curdlan molecular chains and starch molecular chains (3430 cm)-1The absorption peaks of the associated hydroxyl groups at the left and right sides are blue-shifted, and the peak intensity becomes large).
TABLE 3
Comparing the above examples, it is shown that when the carboxymethyl curdlan content is too low (comparative example 3-1), the yield of the prepared SDS is low, and at the same time, the thermally stable colloid around the starch is too small, and the enzyme has enough attack sites and weak digestion-inhibiting effect; when the content of the carboxymethyl curdlan is too high (comparative example 3-2), the barrier effect of starch molecules is lacked among carboxymethyl curdlan molecules, so that the local concentration of the carboxymethyl curdlan in the solution is too high, the carboxymethyl curdlan molecules are combined with each other, and the yield and the content of SDS are low. In addition, if the viscosity of the system is high, the collision bonding probability of starch and colloid molecules is affected, resulting in the generation of SDS with too low content (comparative example 3-3). For DR value, retrogradation of starch can be delayed after addition of carboxymethyl curdlan, mainly because the presence of carboxymethyl curdlan hinders starchThe combination of the molecular chain of the starch inhibits the aging of the starch. Meanwhile, the water separation rate is gradually reduced along with the addition of the carboxymethyl curdlan, and is mainly related to the aging inhibition of the carboxymethyl curdlan on the starch and the excellent water retention property. Degree of hydrogen bondingX bAlthough the comparative examples 3-1 and 3-2 are also large, they are mostly generated by binding of the colloid itself, and thus do not contribute much to SDS. In comparative examples 3-4 and 3-5, SDS was not obtained by the above-described process because the formation of a thermally irreversible gel was not achieved due to the large degree of substitution of carboxymethyl curdlan. In comparative examples 3-5 and 3-6, the SDS-substance was not separated from the product due to the difference in reaction conditions and preparation process, so that the SDS content was significantly low.
Example 4-1
Taking 0.01g of a mixture (W) of carrageenan and konjac gumCarrageenan：WKonjak glue=0.3: 1), dispersed and dissolved in 100ml of 95 ℃ water. And adding another 1g of corn starch into the high-temperature aqueous solution, and fully stirring for 5 min. The solution pH =10 was adjusted with 1M sodium carbonate solution and stirring was continued for 2 min. Maintaining the high temperature environment, and quickly evaporating the solvent within 30 s. Dispersing the obtained solute in 100ml water at 95 deg.C, adjusting pH of the mixed solution with 1mol/L acetic acid solution at high temperature, centrifuging at 7000rpm for 3min, drying the precipitate in a freeze dryer for 14h, pulverizing, and sieving with 100 mesh standard sieve.
Example 4-2
Experimental conditions were the same as in example 4-1, except that carrageenan/konjac gum mixture (W)Carrageenan：WKonjak glueAddition amount of =0.3: 1) was 1 g.
Comparative example 4-1
The experimental conditions were the same as in example 4-1, except that the amount of corn starch added was 10 g.
Comparative example 4-2
The experimental conditions were the same as in example 4-2, except that the amount of corn starch added was 0.6 g.
Comparative examples 4 to 3
The experimental conditions were the same as in example 4-2, except that the amount of corn starch added was 15 g.
Comparative examples 4 to 4
The experimental conditions were the same as in example 4-2, except that the reaction solution had a pH = 8.
Comparative examples 4 to 5
The experimental conditions were the same as in example 4-2, except that the reaction solution had a pH = 9.
Comparative examples 4 to 6
Taking 1g of mixture (W) of carrageenan and konjac glucomannanCarrageenan：WKonjak glue=0.3: 1), dispersed and dissolved in 100ml of 95 ℃ water. And adding another 1g of corn starch into the high-temperature aqueous solution, and fully stirring for 5 min. The pH of the solution was adjusted with 0.1M sodium hydroxide =13 and stirring was continued for 2 min. Cooling to room temperature, drying the obtained material in a freeze dryer for 14h, pulverizing, and sieving with 100 mesh standard sieve.
Comparative examples 4 to 7
Taking 1g of mixture (W) of carrageenan and konjac glucomannanCarrageenan：WKonjak glue=0.3: 1), dispersed and dissolved in 100ml of 95 ℃ water. And putting another 1g of corn starch in the high-temperature aqueous solution, and fully stirring for 5 min. The pH of the solution was adjusted with 0.1M sodium hydroxide =13 and stirring was continued for 2 min. Maintaining the high temperature environment, quickly volatilizing the solvent within 30s, pulverizing, and sieving with 100 mesh standard sieve.
As can be seen from FIG. 4, in the slowly digestible starch prepared from starch and the compound gum of carrageenan and konjac gum, hydrogen bonding is generated between the colloid molecular chains and the starch molecular chains (3430 cm)-1The absorption peaks of the associated hydroxyl groups at the left and right sides are blue-shifted, and the peak intensity becomes large).
TABLE 4
Comparing the above examples, it is found that when the contents of the carrageenan and konjac gum are too low (comparative example 4-1), the yield of the prepared SDS is low, and at the same time, the thermal stability colloid around the starch is too little, and the enzyme has enough attack sites and weak digestion inhibition effect; when the contents of carrageenan and konjac gum are too high (comparative example 4-2), the molecules of the compounded gum are deficientThe blocking effect of starch molecules causes the local concentration of colloid in the solution to be overhigh, and the colloid molecules are combined with each other, thereby causing the low yield and content of SDS. In addition, if the viscosity of the system is high, the collision bonding probability of starch and colloid molecules is affected, resulting in the generation of SDS with too low content (comparative example 4-3). For DR value, the aging of starch can be delayed after adding hydrophilic colloid, and the aging of starch is inhibited mainly because the hydrophilic colloid blocks the combination of starch molecular chains. Meanwhile, the water separating rate is gradually reduced along with the addition of the compound colloid, and is mainly related to the fact that the hydrophilic colloid inhibits the aging of starch and has excellent water retention property. Degree of hydrogen bondingX bAlthough comparative examples 4-1 and 4-2 are also large, they are mostly generated by binding of the colloid itself, and thus do not contribute much to SDS. In comparative examples 4-4 and 4-5, SDS could not be obtained by the above-mentioned process because the thermally irreversible gel could not be formed due to the excessively low pH of the system. In comparative examples 4-6 and 4-7, the SDS-substance was not separated from the product due to the difference in reaction conditions and preparation process, so that the SDS content was significantly low.
Example 5-1
0.01g of carboxymethyl curdlan (degree of substitution = 0.15) was taken and dispersed in 100ml of water at 58 ℃. And (3) putting 1g of cassava starch into the aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. The solution is heated to 100 ℃ and the solvent is quickly volatilized within 120 s. Dispersing the obtained volatile matter in 100ml water at 100 deg.C, centrifuging at 5000rpm for 6min under high temperature environment, drying the precipitate in freeze dryer for 16 hr, pulverizing, and sieving with 100 mesh standard sieve.
Examples 5 and 2
The experimental conditions were the same as in example 5-1, except that carboxymethyl curdlan (degree of substitution = 0.2) was added in an amount of 1g, and was dispersively dissolved in 100ml of 0.8mol/L aqueous NaSCN solution at 28 ℃.
Comparative example 5-1
The experimental conditions were the same as in example 5-1, except that the amount of tapioca starch added was 10 g.
Comparative example 5-2
The experimental conditions were the same as in example 5-2, except that the amount of tapioca starch added was 0.6 g.
Comparative examples 5 to 3
The experimental conditions were the same as in example 5-2, except that the amount of tapioca starch added was 15 g.
Comparative examples 5 to 4
The experimental conditions were the same as in example 5-2, except that the substitution degree of carboxymethyl curdlan was 0.5, and it was dispersed and dissolved in 100ml of a 0.1mol/L aqueous solution of LiI at 35 ℃.
Comparative examples 5 to 5
The experimental conditions were the same as in example 5-2 except that carboxymethyl curdlan having a degree of substitution of 1 was dispersed and dissolved in 100ml of 0.01mol/L aqueous solution of sodium salicylate at 55 ℃.
Comparative examples 5 to 6
Taking 1g carboxymethyl curdlan (degree of substitution = 0.2), dispersing and dissolving in 100ml 0.3mol/L KNO at 42 deg.C3In aqueous solution. And (3) putting 1g of cassava starch into the aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Cooling to room temperature, drying the obtained material in a freeze dryer for 16h, pulverizing, and sieving with 100 mesh standard sieve.
Comparative examples 5 to 7
1g of carboxymethyl curdlan (degree of substitution = 0.2) was dispersed and dissolved in 100ml of 0.06mol/L NaBr aqueous solution at 53 ℃. And (3) putting 1g of cassava starch into the aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Heating the solution to 100 deg.C, and volatilizing the solvent rapidly within 120 s. Pulverizing, and sieving with 100 mesh standard sieve.
Example 6-1
0.01g of carboxymethyl curdlan (degree of substitution = 0.15) was taken and dispersed in 100ml of water at 68 ℃. And adding 1g of rice starch into the aqueous solution of carboxymethyl curdlan, and stirring for 8 min. The solution is heated to 100 ℃ and the solvent is quickly volatilized within 120 s. Dispersing the obtained volatile matter in 100ml water at 100 deg.C, centrifuging at 5000rpm for 6min under high temperature environment, drying the precipitate in freeze dryer for 16 hr, pulverizing, and sieving with 100 mesh standard sieve.
Example 6 to 2
The experimental conditions were the same as in example 6-1 except that carboxymethyl curdlan (degree of substitution = 0.2) was added in an amount of 1g, and was dispersed and dissolved in 100ml of an aqueous solution adjusted to pH =12 with 0.1mol/L NaOH at room temperature.
Comparative example 6-1
The experimental conditions were the same as in example 6-1, except that the rice starch was added in an amount of 10 g.
Comparative example 6-2
The experimental conditions were the same as in example 6-2 except that the rice starch was added in an amount of 0.6 g.
Comparative examples 6 to 3
The experimental conditions were the same as in example 6-2 except that the rice starch was added in an amount of 15 g.
Comparative examples 6 to 4
The experimental conditions were the same as in example 6-2 except that the substitution degree of carboxymethyl curdlan was 0.5, and the carboxymethyl curdlan was dispersed and dissolved in 100ml of an aqueous solution having a pH =8 adjusted with 0.01mol/L NaOH at 63 ℃.
Comparative examples 6 to 5
The experimental conditions were the same as in example 6-2 except that the substitution degree of carboxymethyl curdlan was 1, and the carboxymethyl curdlan was dispersed and dissolved in 100ml of an aqueous solution having a 55 ℃ temperature adjusted to pH =9 with 0.05mol/L NaOH.
Comparative examples 6 to 6
1g of carboxymethyl curdlan (degree of substitution = 0.2) was taken and dispersed and dissolved in 100ml of an aqueous solution having a pH =10 adjusted with 0.1mol/L NaOH at 46 ℃. And (3) putting 1g of cassava starch into the aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Cooling to room temperature, drying the obtained material in a freeze dryer for 16h, pulverizing, and sieving with 100 mesh standard sieve.
Comparative examples 6 to 7
1g of carboxymethyl curdlan (degree of substitution = 0.2) was taken and dispersed and dissolved in 100ml of an aqueous solution adjusted at 30 ℃ to pH =11 with 0.1mol/L NaOH. And (3) putting 1g of cassava starch into the high-temperature aqueous solution of the carboxymethyl curdlan, and fully stirring for 8 min. Heating the solution to 100 deg.C, and volatilizing the solvent rapidly within 120 s. Pulverizing, and sieving with 100 mesh standard sieve.
Comparative example 1
1g of guar gum (hydrocolloid hydrate having macroscopic flow properties when heated from room temperature to 100 ℃) was weighed out and dispersed in 100ml of 90 ℃ water. And adding another 1g of corn starch into the high-temperature aqueous solution, and fully stirring for 9 min. Maintaining the high temperature environment, and quickly evaporating the solvent within 60 s. Dispersing the solute in 100ml water at 85 deg.C, centrifuging at 4000rpm for 4min at high temperature, drying the precipitate in a freeze dryer for 16h, pulverizing, and sieving with 100 mesh standard sieve.
Comparative example 2
The experimental conditions were the same as in comparative example 1 except that the hydrocolloid was replaced by carboxymethylcellulose.
Comparative example 3
Experimental conditions were the same as in comparative example 1 except that the hydrocolloid was replaced with a combination of guar gum and xanthan gum (W)Guar gum：WXanthan gum=1:1）。
Comparative example 4
Adding 1g of corn starch into a 100mL beaker, pouring 50mL of water, uniformly stirring, and adding 1g of sodium alginate to prepare a 1% sodium alginate solution. Preparing vegetable oil containing 1 ‰ span-80, slowly adding sodium alginate solution into vegetable oil under high speed dispersion of 13000r/min, emulsifying for 3min, slowly adding 10ml 2% CaCl under vortex stirring2And continuously stirring the solution, crosslinking and curing for 10min, and standing for 2 h. Suction filtration is carried out, and the mixture is washed by suction filtration with water and ethanol for 3 times. Vacuum drying to obtain starch granule.
Comparative example 5
5g of sodium alginate is dissolved in 50ml of water with stirring, and the solution is added into a flour-mixing machine filled with 100g of corn starch to be kneaded into dough. Then soaking the dough in 100ml of 2% CaCl2Standing the solution for 2 h. Taking out, drying in a freeze dryer for 16h, pulverizing, and sieving with a 100-mesh standard sieve.
Comparative example 6
1g of pectin is taken and dispersed in 100ml of water at 80 ℃. Another 1g of corn starch is put into the high-temperature aqueous solution of pectin and fully stirred for 8 min. Cooling to room temperature, drying the obtained material in a freeze dryer for 16h, pulverizing, and sieving with 100 mesh standard sieve.
Comparison of the above examples shows that for hydrocolloid hydrates which can macroscopically flow when heated from room temperature to 100 ℃, slowly digestible starch substances cannot be obtained by this method, since such colloids can be dissolved in aqueous solutions at high temperatures; in contrast, the microcapsule-coated slowly digestible starch prepared by the methods of comparative examples 4 and 5 has a limited entrapment rate, so that the product has a slow digestibility far lower than that of the product of the patent. Meanwhile, in comparative example 6, even though the treatment method of slowing down digestion is achieved by a colloid thickening method, the effect of realizing slow digestion is limited, and the content of SDS in the patent is far less.
Claims (54)
1. The preparation method of the high-temperature stable slowly digestible starch is characterized by comprising the following steps:
pasting: gelatinizing raw material starch, water and hydrophilic colloid to obtain a gelatinized starch mixture;
a separation step: separating the obtained gelatinized starch mixture to obtain high-temperature stable slowly-digestible starch,
a water removal step is also included after the gelatinization step: the water in the resulting gelatinized starch mixture is removed,
a redissolution step is also included after the water removal step: the solute obtained after the removal of water is redissolved,
in the water removal step, the reaction solution is evaporated in 30 to 120 seconds at a temperature of 80 to 100 ℃,
in the redissolution step, the volatile matter obtained in the water removal step is dispersed and dissolved in water at 80-100 ℃,
in the process for the preparation of the above-mentioned,
the hydrophilic colloid is curdlan, the pH value in the gelatinization step is more than or equal to 11, and the ratio of the hydrophilic colloid to the raw material starch to the water is 0.01-0.03: 1:10 to 100 (w/w); alternatively, the first and second electrodes may be,
the hydrophilic colloid is gellan gum, and ions R are added in the gelatinization step2+Ion R2+The ratio of the amount of the sodium alginate to the amount of the gellan gum is more than or equal to 0.05M percent of the ion R2+Gellan gum not more than 0.5M%, M is the molecular weight of divalent cation, R2+Is selected from Ca2+、Mg2+Or Zn2+The ratio of the hydrophilic colloid to the raw starch to the water is 0.008-1.1: 1: 20 to 100 (w/w); alternatively, the first and second electrodes may be,
the hydrocolloid is carboxymethyl curdlan: the substitution degree is 0.15-0.2, and the ratio of the hydrophilic colloid to the raw starch to the water is 0.008-1.1: 1: 20 to 100 (w/w); alternatively, the first and second electrodes may be,
the hydrophilic colloid is a compound of carrageenan and konjac glucomannan, the pH value in the gelatinization step is more than or equal to 10, and in the compound of carrageenan and konjac glucomannan, the ratio of carrageenan to konjac glucomannan is more than 0 in terms of weight ratio: the konjac glucomannan is not more than 0.6:1, and the ratio of the hydrophilic colloid to the raw starch to the water is 0.008-1.1: 1: 20 to 100 (w/w).
2. The method according to claim 1, wherein in the redissolution step, the volatile matter obtained in the water removal step is dispersed and dissolved in water, and the precipitate obtained after centrifugation is freeze-dried.
3. The preparation method according to claim 1 or 2, wherein the gelatinizing step comprises performing at a water temperature of 50 to 100 ℃.
4. The preparation method according to claim 3, wherein the gelatinizing step comprises performing at a water temperature of 53-98 ℃.
5. The preparation method according to claim 3, wherein the gelatinizing step is carried out at a water temperature of 55-96 ℃.
6. The preparation method according to claim 3, wherein the gelatinizing step is carried out at a water temperature of 58-95 ℃.
7. The method according to any one of claims 1 and 2, wherein the starch is gelatinized by heating to 50 to 100 ℃ and stirring for 5 to 10 min.
8. The method according to claim 7, wherein the temperature is raised to 53-98 ℃.
9. The method according to claim 7, wherein the temperature is raised to 55-96 ℃.
10. The method according to claim 7, wherein the temperature is raised to 58 to 95 ℃.
11. The method of claim 7, wherein the zero-cut viscosity η of the gelatinized starch mixture is obtained0≤2000cP。
12. The method of claim 7, wherein the zero-cut viscosity η of the gelatinized starch mixture is obtained0≤1000cP。
13. The production method according to claim 1 or 2, the raw starch is selected from at least one of corn starch, wheat starch, rice starch, potato starch, tapioca starch, sweet potato starch, mung bean starch, chickpea starch, sorghum starch, sago starch, canna starch, banana starch, apple starch, peach starch, yam starch, lotus root starch, rice flour, wheat flour, corn flour, potato flour, tapioca flour, sweet potato flour, mung bean flour, chickpea flour, sorghum flour, sago flour, banana flour, yam flour, lotus root flour, banana flour, apple flour, or peach flour.
14. The method according to claim 13, wherein the hydrophilic colloid is curdlan, and the pH in the gelatinizing step and the water removing step is not less than 11.
15. The production method according to claim 1 or 2, wherein when the hydrophilic colloid is gellan gum, the ion R is obtained by adding a calcium salt, a magnesium salt or a zinc salt to the reaction solution in the step of gelatinization2+The amount of (c).
16. The preparation method according to claim 1 or 2, wherein in the carrageenan-konjac glucomannan compound, the ratio of carrageenan to konjac glucomannan is as follows by weight: konjac gum =0.3: 1.
17. The method according to claim 2, wherein the centrifugation is performed at 4000 to 8000rpm for 3 to 6 min.
18. The method according to claim 2, wherein the freeze-drying is performed for 12 to 24 hours.
19. The production method according to claim 1 or 2, wherein a hydrogen bond disrupting agent is added in the gelatinization step.
20. The method of claim 19, wherein the hydrogen bond disrupting agent is selected from at least any one of an electrolyte and a chemical agent.
21. The production method according to claim 20, wherein an anion of the electrolyte has OH-Salicylic acid radical, CNS-、I-、Br-、NO3 -、Cl-Tartrate, citrate or SO4 2-Any one of the above.
22. The production method according to claim 21, the cation of the electrolyte has Li+、Na+、K+、NH4 +、Mg2+Any one ofAnd (4) seed preparation.
23. The method of claim 19, wherein the hydrogen bond disrupting agent is selected from NaOH, LiOH, KOH, Mg (OH)2Lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, magnesium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、Mg(CNS)2、LiI、NaI、KI、NH4I、MgI2、LiBr、NaBr、KBr、NH4Br、MgBr2、LiNO3、NaNO3、KNO3、NH4NO3、Mg(NO3)2、LiCl、NaCl、KCl、NH4Cl、MgCl2Lithium tartrate, sodium tartrate, potassium tartrate, sodium citrate, potassium citrate, lithium citrate, Li2SO4、K2SO4、Na2SO4Any one of the above.
24. The method of claim 19, wherein the hydrogen bond disrupting agent is selected from NaOH, LiOH, KOH, Mg (OH)2Lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, magnesium salicylate, LiCNS, NaCNS, KCNS, NH4CNS、Mg(CNS)2、LiI、NaI、KI、NH4I、MgI2、LiBr、NaBr、KBr、NH4Br、MgBr2、LiNO3、NaNO3、KNO3、NH4NO3、Mg(NO3)2、LiCl、NaCl、KCl、NH4Cl、MgCl2Any one of the above.
25. The method of claim 19, wherein the hydrogen bond disrupting agent is selected from NaOH, LiOH, KOH, lithium salicylate, sodium salicylate, potassium salicylate, ammonium salicylate, LiCNS, nanns, KCNS, NH4CNS、LiI、NaI、KI、NH4I、LiBr、NaBr、KBr、NH4Br、 LiNO3、NaNO3、KNO3、NH4NO3Any one of the above.
26. The method according to claim 19, wherein the hydrogen bond disrupting agent is added in an amount of 0.001 to 1 mol/L.
27. The preparation method according to claim 19, wherein the hydrogen bond breaking agent is added in an amount of 0.003 to 0.9 mol/L.
28. The method according to claim 19, wherein the hydrogen bond disrupting agent is added in an amount of 0.005 to 0.85 mol/L.
29. The preparation method according to claim 19, wherein the hydrogen bond disrupting agent is added in an amount of 0.01 to 0.8 mol/L.
30. A high temperature stable slowly digestible starch produced by the process of any one of claims 1 to 29.
31. The high temperature stable slowly digestible starch according to claim 30, wherein the degree of hydrogen bonding is 20 to 60 wt% as indicated by the formula,
degree of hydrogen bonding: xb= (1+αAfm2/Abm1)-1×100%
In the formula, alpha is molar absorption coefficient, and a constant is 3.5; a. thefIs 3000-4000 cm in infrared spectrum of starch raw material-1Absorbance of the maximum absorption peak in the range, AbThe sample to be measured is 3000-4000 cm-1Absorbance of the maximum absorption peak in the range; m is1M is the mass of the sample to be measured2For the analysis of pure corn starch quality.
32. The high temperature stable, slowly digestible starch according to claim 31, wherein the degree of hydrogen bonding is between 20.5 and 50 wt%.
33. The high temperature stable, slowly digestible starch according to claim 31, wherein the degree of hydrogen bonding is between 21 and 45 wt%.
34. The high temperature stable, slowly digestible starch according to claim 31 wherein the degree of hydrogen bonding is between 21.5 and 40 wt%.
35. The high temperature stable, slowly digestible starch according to claim 31 wherein the degree of hydrogen bonding is between 22 and 35 wt%.
36. A high temperature stable, slowly digestible starch according to claim 30 or 31 wherein the slowly digestible starch is present in an amount of more than 30 wt.% based on the total amount of the high temperature stable, slowly digestible starch.
37. A high temperature stable, slowly digestible starch according to claim 30 or 31 wherein the slowly digestible starch is present in an amount of from 30 to 99.9 wt% based on the total amount of high temperature stable, slowly digestible starch.
38. A high temperature stable, slowly digestible starch according to claim 30 or 31 wherein the slowly digestible starch is present in an amount of from 30.3 to 80 wt% based on the total amount of high temperature stable, slowly digestible starch.
39. A high temperature stable, slowly digestible starch according to claim 30 or 31 wherein the slowly digestible starch is present in an amount of 31 to 70 wt% based on the total weight of the high temperature stable, slowly digestible starch.
40. A high temperature stable, slowly digestible starch according to claim 30 or 31 wherein the slowly digestible starch is present in an amount of from 31.5 to 60 wt% based on the total amount of high temperature stable, slowly digestible starch.
41. A high temperature stable, slowly digestible starch according to claim 30 or 31 wherein the slowly digestible starch is present in an amount of from 32 to 55 wt% based on the total amount of high temperature stable, slowly digestible starch.
42. A high temperature stable, slowly digestible starch according to claim 30 or 31 having a retention of more than 97% after high temperature processing.
43. A high temperature stable slowly digestible starch according to claim 30 or 31 having a retention of 97.3% to 99.9% after high temperature processing.
44. A high temperature stable slowly digestible starch according to claim 30 or 31 having a slow digestible starch retention of 98% to 99.9% after high temperature processing.
45. A high temperature stable slowly digestible starch according to claim 30 or 31 having a slow digestible starch retention of 98.3% to 99.9% after high temperature processing.
46. A high temperature stable slowly digestible starch according to claim 30 or 31 having a maximum retrogradation degree of from 0.2 to 0.4.
47. A high temperature stable slowly digestible starch according to claim 30 or 31 having a water extraction rate of 20% to 48%.
48. Use of the high temperature stable slowly digestible starch prepared by the preparation method according to any one of claims 1 to 29 or the high temperature stable slowly digestible starch according to any one of claims 30 to 47 in the preparation of food, health products, pharmaceuticals and feed.
49. Use of the high temperature stable slowly digestible starch prepared by the method according to any one of claims 1 to 29 or the high temperature stable slowly digestible starch according to any one of claims 30 to 47 in the preparation of a beverage.
50. A starch composition comprising the high temperature stable, slowly digestible starch of any one of claims 30 to 47.
51. A product comprising the high temperature stable, slowly digestible starch of any one of claims 30 to 47 and/or the starch composition of claim 50.
52. The product according to claim 51, which is a food, nutraceutical, pharmaceutical and/or feed.
53. The product of claim 51 which is a beverage.
54. An adjuvant for food, pharmaceutical and/or feed comprising the thermostable slowly digestible starch according to any one of claims 30 to 47 and/or the starch composition according to claim 50.
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