Composite functional starch composition and preparation method thereof

Abstract

The invention relates to the field of food / medicine auxiliary materials, in particular to a compound functional starch composition and a preparation method thereof. The compound functional starch composition is prepared from the following raw materials in parts by mass: 65 to 100 parts of compound starch matrix, 1 to 5 parts of thickening agent, 3 to 6 parts of water-retaining agent, 1 to 3 parts of compatilizer, 0.1 to 0.3 part of antioxidant, 3 to 5 parts of microcrystalline cellulose, 1 to 3 parts of citric acid, 0.5 to 1.5 parts of sodium trimetaphosphate, 3 to 6.5 parts of functional anhydride and 180 to 250 parts of deionized water. The finally prepared composite functional starch composition not only has excellent functionality, but also can maintain good storage stability, compatibility stability and freeze-thaw stability, and can endow the starch composition with good processing application performance while improving the loading efficiency of the composite functional starch composition. Therefore, the functionality and the functional stability of the starch composition are greatly improved, the application range of the starch composition in the field of food / medicine auxiliary materials is expanded, and the starch composition has a very excellent application prospect.

Description

Technical Field

[0001] This application relates to the field of food / drug excipients, and more specifically, it refers to a composite functional starch composition and its preparation method. Background Art

[0002] As a natural polymer carbohydrate, starch has been widely used as a key excipient in the food industry and pharmaceutical preparations for a long time due to its wide source, low cost, high biocompatibility, and degradability. In the food field, starch is mainly used as a thickener, gelling agent, stabilizer, and texture modifier; in the pharmaceutical field, starch is often used as a filler, disintegrant, or sustained-release carrier for tablets. However, natural starches from a single source (such as corn starch, potato starch, cassava starch, etc.) are limited by their inherent properties (such as gelatinization temperature, viscosity, shear resistance, retrogradation characteristics, etc.) and are difficult to meet the functional requirements in diverse scenarios.

[0003] In recent years, researchers have functionalized starch through physical modification, chemical modification, or enzymatic modification to improve its acid-base resistance, freeze-thaw stability, controlled-release performance, or intestinal targeting. For example, cross-linked starch can enhance shear resistance and is suitable for stabilizing acidic beverages; acetylated starch can improve film-forming properties and is used for encapsulating drug active ingredients. However, chemically modified starches have problems such as complex processes, risks of reagent residues, and regulatory restrictions, while the functional improvement of physically modified starches is limited, and it may be accompanied by an increase in processing energy consumption.

[0004] Although the prior art has tried to synergistically improve the performance by compounding starches from different sources with other polysaccharides, this kind of composition still has problems such as insufficient compatibility, single functionality, poor storage stability, and poor processing adaptability. And in the pharmaceutical field, there are also problems such as low loading rate, poor release precision, and low sensory properties, which greatly affect the application effect and application prospects of such starch compositions. Summary of the Invention

[0005] Therefore, in order to effectively solve the above existing problems, this application provides a composite functional starch composition and its preparation method. The finally prepared composite functional starch composition can not only have excellent functionality but also maintain good storage stability, compatibility stability, and freeze-thaw stability. And while improving its loading efficiency, it can endow the starch composition with good processing and application properties, thus greatly improving the functionality and functional stability of such starch compositions, expanding their applicable range in the field of food / drug excipients, and having very excellent application prospects.

[0006] As a preferred embodiment, the raw materials for preparing the composite functional starch composition, by mass, are: 65 - 100 parts of a compound starch matrix, 1 - 5 parts of a thickener, 3 - 6 parts of a water retention agent, 1 - 3 parts of a compatibilizer, 0.1 - 0.3 parts of an antioxidant, 3 - 5 parts of microcrystalline cellulose, 1 - 3 parts of citric acid, 0.5 - 1.5 parts of sodium trimetaphosphate, 3 - 6.5 parts of a functional anhydride, and 180 - 250 parts of deionized water.

[0007] As a preferred embodiment, the compound starch matrix is a composition of linear corn starch, waxy corn starch, and resistant starch.

[0008] As a preferred embodiment, the mass ratio of the linear corn starch, waxy corn starch, and resistant starch is (4 - 5):(2 - 2.5):(0.8 - 1.4).

[0009] As a preferred embodiment, the mass ratio of the linear corn starch, waxy corn starch, and resistant starch is (4.2 - 4.8):(2.2 - 2.4):(0.9 - 1.2).

[0010] As a preferred embodiment, the linear content of the linear corn starch is 55 - 75%.

[0011] As a preferred embodiment, the linear content of the linear corn starch is 65 - 70%.

[0012] As a preferred embodiment, the branched-chain content of the waxy corn starch is 60 - 90%.

[0013] As a preferred embodiment, the branched-chain content of the waxy corn starch is 75 - 85%.

[0014] As a preferred embodiment, the resistant starch is green bean resistant starch.

[0015] As a preferred embodiment, the resistant digestion of the green bean resistant starch is ≥50%.

[0016] As a preferred embodiment, the mass ratio of the compound starch matrix, citric acid, sodium trimetaphosphate, and functional anhydride is (7 - 9):(1.5 - 2):(1 - 1.2):(3.5 - 5.5).

[0017] As a preferred embodiment, the mass ratio of the compound starch matrix, citric acid, sodium trimetaphosphate, and functional anhydride is (7.5 - 8.5):(1.8 - 2):(1 - 1.1):(4 - 5).

[0018] As a preferred embodiment, the functional anhydride is a composition of acetic anhydride and octenyl succinic anhydride.

[0019] As a preferred embodiment, the mass ratio of acetic anhydride to octenyl succinic anhydride is (1.5 - 2.5):(1 - 2).

[0020] As a preferred embodiment, the mass ratio of acetic anhydride to octenyl succinic anhydride is (1.8 - 2.2):(1.4 - 1.6).

[0021] As a preferred embodiment, the thickener is at least one of xanthan gum, guar gum, carrageenan, arabic gum and gellan gum.

[0022] As a preferred embodiment, the thickener is xanthan gum.

[0023] As a preferred embodiment, the water retention agent is at least one of inulin, konjac glucomannan and β-glucan.

[0024] As a preferred embodiment, the water retention agent is inulin or konjac glucomannan.

[0025] As a preferred embodiment, the water retention agent is inulin.

[0026] As a preferred embodiment, the compatibilizer is a composition of lecithin and monoglyceride.

[0027] As a preferred embodiment, the mass ratio of lecithin to monoglyceride is (3 - 4):(1.5 - 2).

[0028] As a preferred embodiment, the antioxidant is potassium sorbate or tocopherol.

[0029] As a preferred embodiment, the antioxidant is tocopherol.

[0030] As a preferred embodiment, the preparation method of the composite functional starch composition specifically includes the following steps: S1: mixing the composite starch matrix in proportion, stirring evenly and passing through a 150-200 mesh sieve, then adding deionized water to make pulp, heating to 60-70°C in a closed reactor, keeping warm for 30-45 minutes, then quickly cooling to 20-25°C, and centrifuging to dehydrate to obtain a mixed slurry; S2: mixing the mixed slurry with a deionized water solution containing sodium trimetaphosphate and citric acid, adjusting the pH value of the system to 8-8.5 with sodium hydroxide, reacting at 40-50°C for 2-3 hours, then replenishing deionized water again and adding functional acid anhydride and heating to 55-60°C for reaction for 3-5 hours, and after the reaction is completed, centrifuging and washing the product to neutral to remove unreacted raw materials to obtain a pretreated slurry; S3: mixing the pretreated slurry with the remaining raw materials, and finally adding deionized water, and heating at 50-100 Homogenize 3 times under MPa pressure, control the particle size to D50≤10μm, freeze-dry until the moisture content is ≤2%, and ensure that the raw material residues are below the specified residual amount.

[0031] As a preferred embodiment, the mass ratio of the composite starch matrix to deionized water in S1 is 1:(1-1.5).

[0032] The composite functional starch composition can effectively improve the storage stability, compatibility stability and freeze-thaw stability of the starch composition through further modification and combination of the composite starch matrix, and maintain good functionality and processability. First, in the composite starch matrix, the combination of amylose and amylopectin can simultaneously provide a good sustained-release skeleton and adhesive sites. In the process of forming the composition, a continuous molecular chain network is constructed based on the skeleton and sites, thereby enhancing the internal density of the composite system, and the combined effect with the added resistant starch can greatly improve the utilization of the composition for biological raw materials.

[0033] Secondly, through the functional modification of the compound starch, the molecular structure can be further adjusted to achieve coordinated regulation of the molecular chains of the composition, thereby improving the three-dimensionality of the molecular chain network while limiting the molecular movement frequency of the starch chain, thereby enhancing the network system's resistance and barrier properties to shear force and acidic molecules in the relevant environment, and hindering the migration of water through more cross-linking points, greatly delaying the gelatinization rate of starch in the environment and the cracking time of the system, thereby maintaining the excellent storage stability and functional effects of the starch composition.

[0034] Finally, the special chain segments and functional groups introduced after modification can significantly improve the water barrier effect of the starch composition molecular chain system, and can assist the locally softening groups added by modification to a certain extent in the framework structure of the crosslinking system, thereby improving the resistance of the composition to the molecular chain slip phenomenon, and thus ensuring a certain strength of the composition. Moreover, the overall porous structure formed after its modification provides physical retention sites to prevent the leakage of functional substances, and various effects such as this can significantly improve the functional adjustability of the starch composition in applications.

[0035] Advantages of this application: 1. A composite functional starch composition provided in this application can not only have excellent functionality, but also maintain good storage stability, compatibility stability, and freeze-thaw stability. While improving its loading efficiency, it can endow the starch composition with good processing and application properties, thereby significantly improving the functionality and functional stability of such starch compositions, expanding its applicable range in the field of food / drug excipients, and having a very excellent application prospect.

[0036] 2. A composite functional starch composition provided in this application. In the compound starch matrix, the combination of amylose and amylopectin can simultaneously provide a good sustained-release framework and sticky sites, and construct a continuous molecular chain network based on the framework and sites during the formation of the composition, thereby enhancing the internal density of the composition system. Acting together with the added resistant starch can significantly improve the utilization rate of the composition for biological raw materials.

[0037] 3. A composite functional starch composition provided in this application. Through the functional modification of the compound starch, the molecular structure can be further adjusted to achieve the coordinated regulation of the molecular chains of the composition. While improving the three-dimensional stereoscopicity of the molecular chain network, it restricts the molecular movement frequency of the starch chain, thereby enhancing the resistance and barrier properties of the network system to shear force and acidic molecules in the relevant environment, and hindering the migration of water through more crosslinking sites, significantly delaying the gelatinization rate of starch in the environment and the system cracking time, and thus maintaining the excellent storage stability and functional effects of the starch composition.

[0038] 4. A composite functional starch composition provided in this application. The special chain segments and functional groups introduced after modification can significantly improve the water barrier effect of the starch composition molecular chain system, and can assist the locally softening groups added by modification to a certain extent in the framework structure of the crosslinking system, thereby improving the resistance of the composition to the molecular chain slip phenomenon, and thus ensuring a certain strength of the composition. Moreover, the overall porous structure formed after its modification provides physical retention sites to prevent the leakage of functional substances, and various effects such as this can significantly improve the functional adjustability of the starch composition in applications. Detailed implementation mode

[0039] In the specific implementation manners, specific implementation cases will be used to more intuitively display and explain the content in the invention content of the present application. And the following embodiments are only actual examples for explaining and interpreting the content of the technical solutions in the specification, and should not limit the scope of the claims to be protected by the present application.

[0040] Example 1: A composite functional starch composition, by mass, the raw materials for preparation are: 80 parts of a compound starch matrix, 3.2 parts of a thickener, 3.4 parts of a water retention agent, 1.6 parts of a compatibilizer, 0.2 parts of an antioxidant, 4.1 parts of microcrystalline cellulose, 1.8 parts of citric acid, 1.1 parts of sodium trimetaphosphate, 5 parts of a functional anhydride, and 220 parts of deionized water.

[0041] The compound starch matrix is a composition of linear corn starch, waxy corn starch and resistant starch, and the mass ratio of the three is 4.5:2.3:1.2.

[0042] The linear content of the linear corn starch is 70%, and it is purchased from the corresponding specification products sold by Xi'an Darwen Biotechnology Co., Ltd., China.

[0043] The branched-chain content of the waxy corn starch is 85%, and it is purchased from the corresponding specification products sold by Jushuo Biotechnology Co., Ltd., Henan, China.

[0044] The resistant starch is green pea resistant starch with a resistant digestion of 55%, and it is purchased from the corresponding specification products sold by Shuoyang Biotechnology Co., Ltd., Shaanxi, China.

[0045] The functional anhydride is a composition of acetic anhydride and octenyl succinic anhydride, and the mass ratio of the two is 2.1:1.4.

[0046] The thickener is xanthan gum; the water retention agent is inulin, purchased from Caiwei Biotechnology Co., Ltd., Jiangsu, China; the compatibilizer is a composition of lecithin and monoglyceride, and the mass ratio of the two is 3.5:1.8; the antioxidant is tocopherol.

[0047] The preparation method of the composite functional starch composition specifically includes the following steps: S1: Mix the compound starch matrix in proportion, stir evenly, and then pass through a 150-mesh sieve. Then, add deionized water (50 wt% of the total amount of deionized water) to make pulp, heat it to 65 °C in a closed reaction kettle, keep it warm for 45 min, and then quickly cool it to 22 °C, and centrifuge and dehydrate to obtain a mixed slurry; S2: Mix the mixed slurry with a deionized water solution containing sodium trimetaphosphate and citric acid (10 wt% of the total amount of deionized water), adjust the pH value of the system to 8.5 with sodium hydroxide, react at 45 °C for 2.5 h, then supplement deionized water again (10 wt% of the total amount of deionized water), add functional anhydride and heat it to 55 °C to react for 4 h, and after the reaction is completed, centrifuge and wash the product to neutral to remove unreacted raw materials to obtain a pretreated slurry; S3: Mix the pretreated slurry with the remaining raw materials, finally add deionized water (30 wt% of the total amount of deionized water), homogenize 3 times under a pressure of 75 MPa, control the particle size to D50 ≤ 10 μm, freeze-dry until the moisture content ≤ 2%, and ensure that the raw material residues are all below the specified residue amounts, then it is obtained.

[0048] Example 2: The difference between this example and Example 1 is only as follows: For the composite functional starch composition, in parts by mass, the preparation raw materials are: 74 parts of compound starch matrix, 4.1 parts of thickener, 3.6 parts of water retention agent, 1.2 parts of compatibilizer, 0.3 part of antioxidant, 3.8 parts of microcrystalline cellulose, 1.5 parts of citric acid, 1 part of sodium trimetaphosphate, 3.8 parts of functional anhydride, and 200 parts of deionized water.

[0049] The compound starch matrix is a composition of linear corn starch, waxy corn starch and resistant starch, and the mass ratio of the three is 4:2:1.4.

[0050] Example 3: The difference between this example and Example 1 is only as follows: For the composite functional starch composition, in parts by mass, the preparation raw materials are: 80 parts of compound starch matrix, 3.5 parts of thickener, 4.5 parts of water retention agent, 2 parts of compatibilizer, 0.3 part of antioxidant, 4.4 parts of microcrystalline cellulose, 1.7 parts of citric acid, 1.2 parts of sodium trimetaphosphate, 5.2 parts of functional anhydride, and 230 parts of deionized water.

[0051] The compound starch matrix is a composition of linear corn starch, waxy corn starch and resistant starch, and the mass ratio of the three is 5:2.2:0.8.

[0052] Comparative Example 1 The difference between this comparative example and Example 1 is only as follows: The compound starch matrix is a composition of linear corn starch, waxy corn starch and resistant starch, and the mass ratio of the three is 6:1:0.2.

[0053] Comparative Example 2 This comparative example is only different from Example 1 in the following aspects: the compound starch matrix is a composition of linear corn starch, waxy corn starch, and resistant starch, and the mass ratio of the three is 3:3:2.2.

[0054] Comparative Example 3 This comparative example is only different from Example 1 in the following aspects: 80 parts of the compound starch matrix, 3.2 parts of the thickener, 3.4 parts of the water retention agent, 1.6 parts of the compatibilizer, 0.2 parts of the antioxidant, 4.1 parts of microcrystalline cellulose, 0.5 parts of citric acid, 0.2 parts of sodium trimetaphosphate, 5 parts of the functional anhydride, and 220 parts of deionized water.

[0055] Comparative Example 4 This comparative example is only different from Example 1 in the following aspects: 80 parts of the compound starch matrix, 3.2 parts of the thickener, 3.4 parts of the water retention agent, 1.6 parts of the compatibilizer, 0.2 parts of the antioxidant, 4.1 parts of microcrystalline cellulose, 1.8 parts of citric acid, 1.1 parts of sodium trimetaphosphate, 1.5 parts of the functional anhydride, and 220 parts of deionized water.

[0056] Comparative Example 5 This comparative example is only different from Example 1 in the following aspects: the functional anhydride is a composition of acetic anhydride and octenyl succinic anhydride, and the mass ratio of the two is 4:0.6.

[0057] Comparative Example 6 This comparative example is only different from Example 1 in the following aspects: the functional anhydride is a composition of acetic anhydride and octenyl succinic anhydride, and the mass ratio of the two is 0.8:1.4.

[0058] Performance Evaluation 1. Freeze-thaw stability: (1) Disperse the starch compositions prepared in the examples and comparative examples in deionized water to ensure a solid content of 7.5%, heat and stir at 90 °C for 30 min to form a uniform gel; (2) Freeze in a -20 °C refrigerator for 24 hours to ensure that the gel is completely frozen, then transfer the frozen sample to a 25 °C constant temperature water bath and let it stand and thaw for 6 hours until it completely returns to room temperature; (3) Repeat the above freezing-thawing process for a total of 5 cycles. After the 5th thawing, centrifuge the sample at 4000 rpm for 15 min to separate the gel and the separated water, pour out the upper separated water, weigh the remaining gel mass, and calculate the water separation rate. The water separation rate % = (initial gel mass - gel mass after centrifugation) / initial gel mass × 100%. The test results are the average of 10 tests and are recorded in Table 1.

[0059] 2. Storage stability: (1) Disperse the starch compositions prepared in the examples and comparative examples in deionized water to ensure a solid content of 7.5%, heat and stir at 90 °C for 30 min to form a uniform gel; (2) Place the gel in a constant temperature and humidity chamber at 60 °C and 75% relative humidity, store and observe the samples every 2 h; (3) Record the storage time until system deterioration, system component stratification or severe flocculation and agglomeration of the system components occur in the samples. The test results are the average of 10 tests and are recorded in Table 1.

[0060] 3. Friability: Test the starch compositions prepared in the examples and comparative examples using a friabilimeter (USP General Chapter <1216>). The test results are the average of 10 tests and are recorded in Table 1.

[0061] Table 1 Performance evaluation results

[0062] From the final performance test results of the examples and comparative examples, Comparative Examples 1-6 obtained worse performance results compared to the examples. The examples, due to better raw material ratios and better starch modification results, can further adjust the molecular structure, achieve coordinated regulation of the molecular chains of the composition, and then improve the three-dimensionality of the molecular chain network while restricting the molecular motion frequency of the starch chains. As a result, the resistance and barrier properties of the network system to shear force and acidic molecules are enhanced in the relevant environment, and the migration of water is hindered by more cross-linking sites, significantly delaying the gelatinization rate of starch in the environment and the system cracking time, thus maintaining the excellent storage stability and functional effects of the starch composition, and further demonstrating better test results for Comparative Examples 1-6.

Claims

1. A composite functional starch composition, characterized in that: The raw materials for preparation are as follows: 65-100 parts of compound starch base, 1-5 parts of thickener, 3-6 parts of water retaining agent, 1-3 parts of compatibilizer, 0.1-0.3 parts of antioxidant, 3-5 parts of microcrystalline cellulose, 1-3 parts of citric acid, 0.5-1.5 parts of sodium trimetaphosphate, 3-6.5 parts of functional acid anhydride, and 180-250 parts of deionized water. The composite starch matrix is ​​a composition of linear corn starch, waxy corn starch and resistant starch; The mass ratio of the straight chain corn starch, waxy corn starch and resistant starch is (4-5): (2-2.5): (0.8-1.4); The linear content of the straight-chain corn starch is 55-75%; the branched content of the waxy corn starch is 60-90%; The resistant starch is green bean resistant to digestion starch.

2. The composite functional starch composition according to claim 1, characterized in that: The digestibility of the green bean resistant starch is ≥50%.

3. The composite functional starch composition according to claim 2, characterized in that: The mass ratio of the composite starch matrix, citric acid, sodium trimetaphosphate and functional acid anhydride is (7-9): (1.5-2): (1-1.2): (3.5-5.5).

4. The composite functional starch composition according to claim 3, characterized in that: The functional acid anhydride is a composition of acetic anhydride and octenyl succinic anhydride.

5. The composite functional starch composition according to claim 4, characterized in that: The mass ratio of the acetic anhydride to octenyl succinic anhydride is (1.5-2.5):(1-2).

6. The composite functional starch composition according to claim 5, characterized in that: The thickener is at least one of xanthan gum, guar gum, carrageenan, gum arabic and gellan gum.

7. The composite functional starch composition according to claim 6, characterized in that: The water retaining agent is at least one of inulin, konjac glucomannan and beta-glucan.

8. The composite functional starch composition according to claim 7, characterized in that: The compatibilizer is a composition of lecithin and monoglyceride; the mass ratio of the lecithin and monoglyceride is (3-4): (1.5-2).

9. The composite functional starch composition according to claim 8, characterized in that: The antioxidant is potassium sorbate or tocopherol.

10. A method for preparing the composite functional starch composition according to any one of claims 1 to 9, characterized in that: The specific steps include: S1: Mix the compound starch matrix according to proportion, stir evenly and pass through a 150-200 mesh sieve, then add deionized water to make pulp, heat to 60-70°C in a closed reactor, keep warm for 30-45 minutes, then quickly cool to 20-25°C, and centrifuge to dehydrate to obtain a mixed slurry; S2: Mix the mixed slurry with a deionized water solution containing sodium trimetaphosphate and citric acid, adjust the pH value of the system to 8-8.5 with sodium hydroxide, react at 40-50°C for 2-3 hours, then add deionized water again and add functional acid anhydride and heat to 55-60°C for 3-5 hours, and after the reaction is completed, centrifuge and wash the product to neutral to remove unreacted raw materials to obtain a pretreated slurry; S3: Mix the pretreated slurry with the remaining raw materials, and finally add deionized water, homogenize 3 times at a pressure of 50-100 MPa, control the particle size to D50≤10 μm, freeze-dry until the moisture content is ≤2%, and ensure that the raw material residues are below the specified residual amount.

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