Method for controlling starch retrogradation by using medium-high degree of polymerization linear sugar chain

Abstract

The application discloses a method for regulating starch retrogradation by using middle-high degree of polymerization linear sugar chains, and belongs to the technical field of physically modified starches. The method is characterized in that middle-high degree of polymerization linear sugar chains, such as maltotriose, maltotetraose, maltopentaose, maltohexaose and dextran with an average degree of polymerization of 9, 21 and 34, are added to starch. During the starch retrogradation process, the sugar chain molecules form hydrogen bonds with water or starch chains, or are entangled with amylopectin chains, thereby interfering with or promoting the crystallization of amylose and amylopectin, and achieving the purpose of regulating the starch retrogradation properties. Therefore, the application effectively regulates starch retrogradation by adding middle-high degree of polymerization linear sugar chains, and has important significance in the food industry.

Description

Technical Field

[0001] The invention relates to a method for regulating starch retrogradation by utilizing linear sugar chains with medium and high polymerization degrees, and belongs to the technical field of physically modified starch. Background Art

[0002] Natural starch is a semicrystalline polymer macromolecule primarily composed of amylose and highly branched amylopectin. During starch gelatinization, starch granules transition from an ordered, crystalline state to a disordered state. During cooling, the amylose and amylopectin chains recombine into an ordered structure, a process known as starch retrogradation. Starch retrogradation can be categorized as short-term retrogradation, with short-term retrogradation primarily characterized by amylose crystallization and lasting for hours, and long-term retrogradation primarily characterized by amylopectin recrystallization and lasting for days. As an important food ingredient, starch retrogradation can cause starch-based foods to become hard, lose elasticity, and lose flavor during storage, shortening their shelf life. Furthermore, this phenomenon is essential in the processing of traditional gel foods. For example, in the production of starch gel foods such as vermicelli, jelly, and fresh wet rice noodles, moderate retrogradation significantly improves the product's texture and sensory qualities. Therefore, effective starch retrogradation control can enhance the nutritional value and functionality of foods, as well as improve their structure and sensory quality, and is of great significance in the food industry.

[0003] Currently, the main methods for regulating starch retrogradation include physical, chemical, and enzymatic methods. The main advantage of physical methods is their simplicity and ease of application in industrial production. In previous studies, the small molecule sugars used to control starch retrogradation were mostly relatively rare sugars, such as inulin, trehalose, and Artemisia polysaccharide. Maltooligosaccharides have the same structural units as starch, and glucans also have a similar structure to starch. Moreover, some maltooligosaccharides and glucans can be produced industrially in large quantities and are inexpensive and readily available. Therefore, using them to modify starch and regulate starch retrogradation has certain industrial production and commercial value. Summary of the Invention

[0004] To address these issues, the present invention adds linear sugar chains with medium to high degrees of polymerization (DOPs), such as maltohexaose, maltoheptaose, maltooctaose, and glucans with average DOPs of 9, 21, and 34, to starch. During starch retrogradation, the sugar chain molecules form hydrogen bonds with water or starch chains, or entangle with amylopectin chains, thereby interfering with or promoting the crystallization of amylose and amylopectin, thereby regulating the starch retrogradation properties.

[0005] The first object of the present invention is to provide a method for regulating starch retrogradation, wherein the method comprises adding linear sugar chains with medium or high polymerization degrees to starch to regulate its retrogradation properties.

[0006] In one embodiment of the present invention, the method is to disperse linear sugar chains with medium and high polymerization degrees into water, add starch, mix well, heat for gelatinization, and cool for storage.

[0007] In one embodiment of the present invention, regulating starch retrogradation includes promoting or inhibiting starch retrogradation.

[0008] In one embodiment of the present invention, the medium-to-high degree of polymerization linear sugar chain is maltooligosaccharide or glucan with a DP of 6-35.

[0009] In one embodiment of the present invention, the medium-to-high degree of polymerization linear sugar chain is maltohexaose, maltoheptaose, maltooctaose, or glucan with an average degree of polymerization of 9, 21, or 34.

[0010] In one embodiment of the present invention, the method comprises adding one or more linear sugar chains simultaneously.

[0011] In one embodiment of the present invention, the addition amount of the linear sugar chains with medium to high polymerization degree is 2%-10% (w / w).

[0012] In one embodiment of the present invention, the amount of water added is 0.5-1.5 mL for every 100 mg of sugar chain and starch.

[0013] In one embodiment of the present invention, the starch is specifically corn starch, potato starch, tapioca starch, sweet potato starch, pea starch, wheat starch, rice starch, mung bean starch, red bean starch, lotus seed starch or chestnut starch.

[0014] In one embodiment of the present invention, the method of adding sugar chains to starch includes adding sugar chains before starch gelatinization or adding sugar chains during starch gelatinization.

[0015] In one embodiment of the present invention, in the method, the temperature during starch gelatinization is controlled at 90-100° C., and the heating time is 30-90 min.

[0016] In one embodiment of the present invention, the stirring speed during starch gelatinization in the method is 300-1000 r / min.

[0017] In one embodiment of the present invention, the storage condition in the method is 1-10° C. for 3-7 days.

[0018] In one embodiment of the present invention, the method comprises dispersing glucan with an average degree of polymerization of 34 into water, adding wheat starch, mixing evenly, stirring and heating for gelatinization, and storing at 4°C for 3 days; the amount of glucan added is 2% (w / w); the stirring and heating gelatinization conditions are a temperature of 95°C, a rotation speed of 500 r / min, and constant temperature heating for 60 minutes.

[0019] In one embodiment of the present invention, the method is to disperse maltoheptaose in water, add wheat starch, mix evenly, stir and heat for gelatinization, and store at 4°C for 7 days; the amount of maltoheptaose added is 2% (w / w); the stirring and heating gelatinization conditions are a temperature of 95°C, a rotation speed of 500r / min, and constant temperature heating for 60min.

[0020] The second object of the present invention is to provide a method for promoting starch retrogradation.

[0021] In one embodiment of the present invention, the method comprises dispersing glucan having an average degree of polymerization of 21-34 in water, adding starch, mixing uniformly, stirring, heating, and gelatinization, and storing at 1-10°C for 2-5 days. The glucan is added in an amount of 2-5% (w / w); and the stirring and heating gelatinization conditions are a temperature of 90-100°C, a rotation speed of 300-1000 rpm, and constant temperature heating for 30-90 minutes.

[0022] The third object of the present invention is to provide a modified starch prepared by the above method.

[0023] The fourth object of the present invention is to provide an application of the modified starch in the preparation of starch foods.

[0024] In one embodiment of the present invention, the starchy food includes steamed buns, bread and rice noodles.

[0025] The fifth object of the present invention is to provide an application of the above-mentioned method for regulating starch retrogradation in regulating starch retrogradation.

[0026] Beneficial effects:

[0027] The method of the present invention mixes linear sugar chains with medium and high degrees of polymerization (DP) with starch. The sugar chain molecules form hydrogen bonds with water molecules and starch chains, or entangle with amylopectin chains, interfering with or promoting starch crystallization at the molecular level, thereby regulating starch retrogradation. Sugar chains with varying DP all exhibited a certain regulatory effect on starch retrogradation. The one with the best inhibition of retrogradation, when supplemented with 2% maltoheptaose, reduced retrogradation by 48.2% after 7 days. The one with the best promotion of retrogradation, when supplemented with glucan with an average DP of 34, increased retrogradation by 61.3% after 3 days. The long-chain sugar molecules guide the amylose molecules into helical formation, significantly promoting starch retrogradation. DETAILED DESCRIPTION

[0028] The following describes preferred embodiments of the present application, and it should be understood that the embodiments are for better explaining the present application and are not used to limit the present application.

[0029] The materials involved in the following examples are as follows:

[0030] Wheat starch was purchased from Hangzhou Prostar Starch Co., Ltd.; malt hexaose, malt heptaose and malt octaose were purchased from Carbosynth Limited, UK; glucan with average degree of polymerization of 9, 21 and 34 were purchased from Shanghai Aldrin Reagent (Shanghai) Co., Ltd.

[0031] The determination method of the retrogradation properties of the starches involved in the following examples is as follows:

[0032] The retrogradation properties of the starches were characterized by the retrogradation enthalpy of the starches, and the determination method was to determine the retrogradation properties of all samples under ultra-pure nitrogen using a differential scanning calorimeter (DSC). 2-4 mg of the starch sample and 2 times of deionized water (w / w) were mixed in an aluminum pan, and then sealed. The sealed aluminum pan was equilibrated at room temperature for 12 h. Then the aluminum pan with the sample was heated from 30℃ to 100℃ at a speed of 10℃ / min, and an empty aluminum pan was used as a control. The Muse working software was used to calculate the enthalpy value (ΔH) according to the DSC curve.

[0033] Example 1:

[0034] 30 mg and 75 mg of malt hexaose were respectively dispersed into 15 mL of ultra-pure water, 1470 mg or 1425 mg of wheat starch was added (i.e. the addition amount of malt hexaose was 2% / 5%), mixed uniformly and placed in a magnetic stirrer, the temperature was set to 95℃ and the rotation speed was set to 500 r / min. Constant temperature heating for 60 min to gelatinize. After cooling, it was evenly divided into two parts, which were respectively stored at 4℃ for 3 d and 7 d, and then dried and ground through a 100 mesh sieve.

[0035] Example 2:

[0036] 30 mg and 75 mg of malt heptaose were respectively dispersed into 15 mL of ultra-pure water, 1470 mg or 1425 mg of wheat starch was added (i.e. the addition amount of malt heptaose was 2% / 5%), mixed uniformly and placed in a magnetic stirrer, the temperature was set to 95℃ and the rotation speed was set to 500 r / min. Constant temperature heating for 60 min to gelatinize. After cooling, it was evenly divided into two parts, which were respectively stored at 4℃ for 3 d and 7 d, and then dried and ground through a 100 mesh sieve.

[0037] Example 3:

[0038] Disperse 30 mg and 75 mg of maltooctaose, respectively, in 15 mL of ultrapure water. Add 1470 mg or 1425 mg of wheat starch (i.e., 2% or 5% maltooctaose). Mix thoroughly and place in a magnetic stirrer set to 95°C and 500 rpm. Heat for 60 minutes to gelatinize. After cooling, divide the mixture into two equal portions, store at 4°C for 3 and 7 days, respectively, dry, grind, and pass through a 100-mesh sieve.

[0039] Example 4:

[0040] Disperse 30 mg and 75 mg of glucan with an average degree of polymerization of 9 in 15 mL of ultrapure water, then add 1470 mg or 1425 mg of wheat starch (i.e., 2% and 5% of glucan with an average degree of polymerization of 9, respectively). Mix thoroughly and place in a magnetic stirrer set to 95°C and 500 rpm. Heat at this constant temperature for 60 minutes to achieve gelatinization. After cooling, divide the mixture into two equal portions, store at 4°C for 3 and 7 days, respectively, dry, grind, and pass through a 100-mesh sieve.

[0041] Example 5:

[0042] Disperse 30 mg and 75 mg of glucan with an average degree of polymerization of 21 in 15 mL of ultrapure water, add 1470 mg or 1425 mg of wheat starch (i.e., 2% and 5% of glucan with an average degree of polymerization of 21, respectively). Mix thoroughly and place in a magnetic stirrer set to 95°C and 500 rpm. Heat at this constant temperature for 60 minutes to gelatinize. After cooling, divide the mixture into two equal portions, store at 4°C for 3 and 7 days, respectively, dry, grind, and pass through a 100-mesh sieve.

[0043] Example 6:

[0044] Disperse 30 mg and 75 mg of glucan with an average degree of polymerization of 34, respectively, in 15 mL of ultrapure water. Add 1470 mg or 1425 mg of wheat starch (i.e., 2% and 5% of glucan with an average degree of polymerization of 34). Mix thoroughly and place in a magnetic stirrer set to 95°C and 500 rpm. Heat at this constant temperature for 60 minutes to gelatinize. After cooling, divide the mixture into two equal portions, store at 4°C for 3 and 7 days, respectively, dry, grind, and pass through a 100-mesh sieve.

[0045] Comparative Example 1:

[0046] Dissolve 1500 mg of wheat starch in 15 mL of ultrapure water, mix thoroughly, and place in a magnetic stirrer at 95°C and 500 rpm. Heat for 60 minutes to gelatinize. Cool, store at 4°C for 3 days, dry, and grind through a 100-mesh sieve.

[0047] Comparative Example 2:

[0048] Dissolve 1500 mg of wheat starch in 15 mL of ultrapure water, mix thoroughly, and place in a magnetic stirrer at 95°C and 500 rpm. Heat for 60 minutes to gelatinize. Cool, store at 4°C for 7 days, dry, and grind through a 100-mesh sieve.

[0049] The retrogradation enthalpy of the modified starch was measured according to the method for measuring the retrogradation properties of starch. The results are shown in Tables 1 and 2.

[0050] Table 1 Regeneration enthalpy of different modified starch samples after short-term storage (3 days)

[0051]

[0052]

[0053] Table 2 Retrogradation enthalpy of different modified starch samples after long-term storage (7 days)

[0054]

[0055] From the data analysis of Table 1 and Table 2, it can be seen that all examples have a regulating effect on wheat starch retrogradation. Among them, Example 6 has the most significant promoting effect, increasing the retrogradation enthalpy by 61.3%, and Example 2 has the most significant inhibitory effect, reducing the retrogradation enthalpy by 48.2%.

[0056] Linear sugar chains with different degrees of polymerization exhibit varying regulatory effects. The retrogradation enthalpies of samples in Examples 1 and 2 exhibit the following pattern: 2% increases the 3-day retrogradation enthalpy, while 2% decreases the 7-day retrogradation enthalpy; 5% decreases the 3-day retrogradation enthalpy, while 5% decreases the 7-day retrogradation enthalpy. Samples in Examples 3, 4, and 5 exhibit an increase in the 3-day retrogradation enthalpy and a decrease in the 7-day retrogradation enthalpy. This is because when the degree of polymerization of the sugar chains is between 6 and 20, the sugar molecules act as solutes, increasing their regional concentration and promoting short-term retrogradation of starch. They also form hydrogen bonds with starch molecules, thereby delaying long-term retrogradation. Sample 6 shows an increase in the 3-day retrogradation enthalpy, a slight increase in the 7-day retrogradation enthalpy at 2%, and a decrease at 5%. At higher degrees of polymerization, the long-chain sugar molecules act as the backbone, guiding the amylose molecules into helical formation, promoting short-term retrogradation. However, this hinders the binding of branched chains, inhibiting long-term retrogradation.

[0057] Therefore, adding 2% maltoheptaose reduced the retrogradation effect by 48.2% after 7 days, while adding glucan with an average degree of polymerization of 34 increased the retrogradation effect by 61.3% after 3 days. The long-chain sugar molecules guided the amylose molecules to form helices, which significantly promoted starch retrogradation. These results show that treatment with different medium- and high-degree-of-polymerization linear sugar chains can significantly regulate starch retrogradation.

[0058] Although the present invention has been disclosed as above with the preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be

[0059] The definition in the claims shall prevail.

Claims

1. A method for regulating starch retrogradation, characterized in that: The method comprises adding linear sugar chains with medium or high polymerization degrees to starch, mixing the mixture evenly, and then heating and gelatinizing the mixture to regulate the retrogradation properties of the starch; regulating starch retrogradation includes promoting or inhibiting starch retrogradation; and the linear sugar chains with medium or high polymerization degrees are maltooligosaccharides or glucans with a DP between 6 and 35.

2. The method according to claim 1, characterized in that The method comprises adding one or both linear sugar chains at the same time, and the added ratio of the sugar chains is 2%-10% (w / w).

3. The method according to claim 1, characterized in that The starch is specifically corn starch, potato starch, tapioca starch, sweet potato starch, pea starch, wheat starch, rice starch, mung bean starch, red bean starch, lotus seed starch or chestnut starch.

4. The method according to claim 1, wherein Adding sugar chains to starch includes adding sugar chains before starch gelatinization and adding sugar chains during starch gelatinization.

5. The method according to claim 1, wherein During starch gelatinization, the temperature is controlled at 90-100°C and the heating time is 30-90 minutes.

6. A method for promoting starch retrogradation, characterized in that: The method comprises the following steps: dispersing glucan with an average degree of polymerization of 21-34 into water, adding starch, mixing, stirring, heating and gelatinization, and storing at 1-10°C for 2-5 days; the amount of glucan added is 2-5% (w / w); and the stirring, heating and gelatinization conditions are 90-100°C and constant temperature heating for 30-90 minutes.

7. A modified starch prepared by the method according to any one of claims 1 to 6.

8. Use of the modified starch according to claim 7 in the preparation of starchy foods, characterized in that: The starchy foods include steamed buns, bread and rice noodles.

9. Use of the method according to any one of claims 1 to 6 in regulating starch retrogradation.

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