A composite functional starch composition and a method for preparing the same

Abstract

The application relates to the field of food / medicine auxiliary materials, and more particularly to a compound functional starch composition and a preparation method thereof. The compound functional starch composition is prepared from the following raw materials in mass parts: 65-100 parts of a compound starch matrix, 1-5 parts of a thickening agent, 3-6 parts of a water retention agent, 1-3 parts of a compatibility agent, 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. The finally obtained compound functional starch composition not only has excellent functionality, but also has good storage stability, compatibility stability and freeze-thaw stability; the compound functional starch composition can improve the loading efficiency and has good processing application performance, thereby greatly improving the functionality and functional stability of the compound functional starch composition, expanding the applicable range of the compound functional starch composition in the field of food / medicine auxiliary materials and having very excellent application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of food / pharmaceutical excipients, and more particularly to a composite functional starch composition and a preparation method thereof. BACKGROUND

[0002] Starch, as a natural macromolecular carbohydrate, has been widely used as a key excipient in 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 thickening agent, 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 of single source (such as corn starch, potato starch, cassava starch, etc.) are difficult to meet the functional requirements in diversified scenarios due to their inherent properties (such as gelatinization temperature, viscosity, shear resistance, retrogradation characteristics, etc.).

[0003] In recent years, researchers have improved the functionality of starch through physical modification, chemical modification or enzymatic modification, in order to improve its acid and alkali resistance, freeze-thaw stability, controlled release performance or intestinal targeting. For example, cross-linked starch can enhance the shear resistance and is suitable for the stabilization of acidic beverages; acetylated starch can improve the film-forming property and is used for embedding active pharmaceutical ingredients. However, chemically modified starches have complex processes, risks of reagent residues and regulatory restrictions, while physically modified starches have limited functional improvement and may be accompanied by increased processing energy consumption.

[0004] Although the prior art has tried to improve the performance by compounding different source starches with other polysaccharides, such compositions still have problems of insufficient compatibility, single functionality, poor storage stability and poor processing adaptability. In the pharmaceutical field, there are also problems of low loading rate, poor release precision and low sensory properties, which greatly affect the application effect and application prospect of such starch compositions. SUMMARY

[0005] Therefore, in order to effectively solve the above-mentioned existing problems, the present application provides a composite functional starch composition and a preparation method thereof. The finally prepared composite functional starch composition not only has excellent functionality, but also has good storage stability, compatibility stability and freeze-thaw stability. In addition, while improving the loading efficiency, the starch composition can also be endowed with good processing application performance, thereby greatly improving the functionality and functional stability of such starch composition, expanding its applicable range in the field of food / pharmaceutical excipients, and having very excellent application prospect.

[0006] As a preferred embodiment, the composite functional starch composition is prepared from the following raw materials in parts by mass: composite starch matrix 65-100 parts, thickening agent 1-5 parts, water-retaining agent 3-6 parts, compatibility agent 1-3 parts, antioxidant 0.1-0.3 parts, microcrystalline cellulose 3-5 parts, citric acid 1-3 parts, sodium trimetaphosphate 0.5-1.5 parts, functional anhydride 3-6.5 parts, and deionized water 180-250 parts.

[0007] As a preferred embodiment, the composite starch matrix is a combination of straight corn starch, waxy corn starch and resistant starch.

[0008] As a preferred embodiment, the mass ratio of the straight 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 straight 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 straight corn starch has a straight chain content of 55-75%.

[0011] As a preferred embodiment, the straight corn starch has a straight chain content of 65-70%.

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

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

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

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

[0016] As a preferred embodiment, the mass ratio of the composite 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 composite 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 combination of acetic anhydride and octenyl succinic anhydride.

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

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

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

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

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

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

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

[0026] As a preferred embodiment, the compatibilizing agent is a combination of lecithin and monoglyceride.

[0027] As a preferred embodiment, the mass ratio of the lecithin and the 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 comprises the following steps: S1: mixing the compound starch matrix in proportion, stirring uniformly, then passing through a 150-200 mesh sieve, then adding deionized water to make pulp, heating to 60-70°C in a sealed reaction kettle, keeping for 30-45 min, then rapidly cooling to 20-25°C, centrifugal dewatering to obtain mixed pulp; S2: mixing the mixed pulp 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 h, then supplementing deionized water again and adding functional anhydride and heating to 55-60°C for 3-5 h, and after the reaction is completed, centrifugal washing the product to neutral to remove unreacted raw materials, to obtain pretreated pulp; S3: mixing the pretreated pulp with the remaining raw materials, finally adding deionized water, homogenizing 3 times under a pressure of 50-100 MPa, controlling the particle size to D50≤10 μm, freeze-drying until the moisture content is ≤2%, and ensuring that the residual amount of raw materials is within the specified residual amount.

[0031] As a preferred embodiment, the mass ratio of the compound 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 compound starch matrix, and maintains good functionality and processability. First, the combination of amylose and amylopectin in the compound starch matrix can provide a good slow-release skeleton and viscosity site at the same time, and a continuous molecular chain network is constructed based on the skeleton and site during the formation of the composition, thereby enhancing the internal density of the composition system. The utilization of biological raw materials by the composition can be greatly improved together with the added resistant starch.

[0033] Secondly, through functional modification of the compound starch, the molecular structure can be further adjusted to realize the synergistic regulation of the molecular chain of the composition, thereby improving the three-dimensional stereoscopic property of the molecular chain network while limiting the molecular motion frequency of the starch chain, thereby enhancing the resistance and barrier property of the network system to shear force and acidic molecules in the related environment, and hindering the migration of water through more crosslinking points, greatly delaying the pasting speed and system cracking time of starch in the environment, thereby maintaining the excellent storage stability and functional effect of the starch composition.

[0034] Finally, the special chain segments and functional groups introduced after modification can greatly improve the barrier effect of the starch composition molecular chain system to moisture, and to a certain extent, the skeleton structure of the cross-linked system can assist the modified locally flexible groups to improve the resistance of the composition to molecular chain slip phenomenon, thereby ensuring a certain strength of the composition. And the overall porous structure formed after modification provides physical trapping sites to prevent functional material leakage, and various effects can greatly improve the functional adjustability of the starch composition in application.

[0035] The application has the following beneficial effects:

[0036] 1. The composite functional starch composition provided in the application not only has excellent functionality, but also maintains good storage stability, compatibility stability and freeze-thaw stability. In addition, while improving the loading efficiency, it can also endow the starch composition with good processing and application performance, thereby greatly improving the functionality and functional stability of such starch composition, expanding its application range in the field of food / pharmaceutical excipients, and having very excellent application prospect.

[0037] 2. The composite functional starch composition provided in the application, the combination of amylose and amylopectin in the compounded starch matrix can provide good slow-release skeleton and viscosity sites at the same time. During the formation of the composition, a continuous molecular chain network is constructed based on the skeleton and sites, thereby enhancing the internal density of the composition system. Together with the added resistant starch, it can greatly improve the utilization of biological raw materials by the composition.

[0038] 3. The composite functional starch composition provided in the application, through functional modification of the compounded starch, the molecular structure can be further adjusted to realize the synergistic regulation of the molecular chain of the composition, thereby improving the three-dimensional sterility of the molecular chain network while limiting the molecular motion frequency of the starch chain, thereby enhancing the resistance and barrier property of the network system to shear force and acidic molecules in the related environment, and hindering the migration of water through more cross-linking points, greatly delaying the pasting speed and system cracking time of starch in the environment, thereby maintaining the excellent storage stability and functional effect of the starch composition.

[0039] 4. The composite functional starch composition provided in the application, the special chain segments and functional groups introduced after modification can greatly improve the barrier effect of the starch composition molecular chain system to moisture, and to a certain extent, the skeleton structure of the cross-linked system can assist the modified locally flexible groups to improve the resistance of the composition to molecular chain slip phenomenon, thereby ensuring a certain strength of the composition. And the overall porous structure formed after modification provides physical trapping sites to prevent functional material leakage, and various effects can greatly improve the functional adjustability of the starch composition in application. DETAILED DESCRIPTION

[0040] The content in the summary of the application will be more intuitively displayed and explained in the specific embodiments of the detailed description. The following examples are only actual examples for illustrating and explaining the content of the technical solutions in the specification, and should not limit the scope of the claims of the application.

[0041] Example 1: The preparation raw materials of the composite functional starch composition are, by mass fraction: 80 parts of a compounded starch matrix, 3.2 parts of a thickening agent, 3.4 parts of a water retention agent, 1.6 parts of a compatibility agent, 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.

[0042] The compounded starch matrix is a composition of straight-chain corn starch, waxy corn starch, and resistant starch, with a mass ratio of 4.5:2.3:1.2.

[0043] The straight-chain corn starch has a straight-chain content of 70%, and is purchased from a corresponding specification product sold by Xi'an Darwen Biological Technology Co., Ltd. in China.

[0044] The waxy corn starch has a branched-chain content of 85%, and is purchased from a corresponding specification product sold by Henan Jusuo Biological Technology Co., Ltd. in China.

[0045] The resistant starch is green bean digestion-resistant starch, with a digestion resistance of 55%, and is purchased from a corresponding specification product sold by Shaanxi Soyang Biological Technology Co., Ltd. in China.

[0046] The functional anhydride is a composition of acetic anhydride and octenyl succinic anhydride, with a mass ratio of 2.1:1.4.

[0047] The thickening agent is xanthan gum; the water retention agent is inulin, purchased from Jiangsu Caowei Biological Technology Co., Ltd. in China; the compatibility agent is a composition of lecithin and monoglyceride, with a mass ratio of 3.5:1.8; and the antioxidant is tocopherol.

[0048] The preparation method of the composite functional starch composition specifically comprises the following steps: S1: mixing the compound starch matrix in proportion, stirring uniformly, and then passing through a 150-mesh sieve; then adding deionized water (50wt% of the total amount of deionized water) to make pulp, heating to 65℃ in a sealed reaction kettle, and keeping for 45 min; then rapidly cooling to 22℃, and centrifugal dewatering to obtain mixed slurry; S2: mixing the mixed slurry with a deionized water solution containing sodium trimetaphosphate and citric acid (10wt% of the total amount of deionized water), adjusting the pH value of the system to 8.5 with sodium hydroxide, and reacting at 45℃ for 2.5 h; then again supplementing deionized water (10wt% of the total amount of deionized water) and adding functional anhydride, and heating to 55℃ for 4 h; and after the reaction is completed, centrifugal washing the product to neutral to remove unreacted raw materials, to obtain pretreated slurry; S3: mixing the pretreated slurry with the remaining raw materials, and finally adding deionized water (30wt% of the total amount of deionized water), homogenizing 3 times under a pressure of 75 MPa, controlling the particle size to be D50≤10 μm, freeze-drying until the water content is ≤2%, and ensuring that the residual amount of raw materials is within the specified residual amount.

[0049] Example 2: The only difference between this example and Example 1 is that the preparation raw materials of the composite functional starch composition are, in mass parts: compound starch matrix 74 parts, thickening agent 4.1 parts, water-retaining agent 3.6 parts, compatibility agent 1.2 parts, antioxidant 0.3 parts, microcrystalline cellulose 3.8 parts, citric acid 1.5 parts, sodium trimetaphosphate 1 part, functional anhydride 3.8 parts, and deionized water 200 parts.

[0050] The compound starch matrix is a composition of straight-chain corn starch, waxy corn starch and resistant starch, with a mass ratio of 4:2:1.4.

[0051] Example 3: The only difference between this example and Example 1 is that the preparation raw materials of the composite functional starch composition are, in mass parts: compound starch matrix 80 parts, thickening agent 3.5 parts, water-retaining agent 4.5 parts, compatibility agent 2 parts, antioxidant 0.3 parts, microcrystalline cellulose 4.4 parts, citric acid 1.7 parts, sodium trimetaphosphate 1.2 parts, functional anhydride 5.2 parts, and deionized water 230 parts.

[0052] The compound starch matrix is a composition of straight-chain corn starch, waxy corn starch and resistant starch, with a mass ratio of 5:2.2:0.8.

[0053] Comparative Example 1

[0054] The only difference between this comparative example and Example 1 is that the compound starch matrix is a composition of straight-chain corn starch, waxy corn starch and resistant starch, with a mass ratio of 6:1:0.2.

[0055] Comparative Example 2

[0056] The comparative example and example 1 only exist in the following differences: the compound starch matrix is a combination of straight-chain corn starch, waxy corn starch and resistant starch, and the mass ratio of the three is 3:3:2.2.

[0057] Comparative example 3

[0058] The comparative example and example 1 only exist in the following differences: the compound starch matrix is 80 parts, the thickening agent is 3.2 parts, the water retaining agent is 3.4 parts, the compatibility agent is 1.6 parts, the antioxidant is 0.2 parts, the microcrystalline cellulose is 4.1 parts, the citric acid is 0.5 parts, the sodium trimetaphosphate is 0.2 parts, the functional anhydride is 5 parts, and the deionized water is 220 parts.

[0059] Comparative example 4

[0060] The comparative example and example 1 only exist in the following differences: the compound starch matrix is 80 parts, the thickening agent is 3.2 parts, the water retaining agent is 3.4 parts, the compatibility agent is 1.6 parts, the antioxidant is 0.2 parts, the microcrystalline cellulose is 4.1 parts, the citric acid is 1.8 parts, the sodium trimetaphosphate is 1.1 parts, the functional anhydride is 1.5 parts, and the deionized water is 220 parts.

[0061] Comparative example 5

[0062] The comparative example and example 1 only exist in the following differences: the functional anhydride is a combination of acetic anhydride and octenyl succinic anhydride, and the mass ratio of the two is 4:0.6.

[0063] Comparative example 6

[0064] The comparative example and example 1 only exist in the following differences: the functional anhydride is a combination of acetic anhydride and octenyl succinic anhydride, and the mass ratio of the two is 0.8:1.4.

[0065] Performance evaluation

[0066] 1. Freeze-thaw stability: (1) The starch composition prepared in the examples and comparative examples was dispersed in deionized water to ensure a solid content of 7.5%, heated and stirred at 90°C for 30 min to form a uniform gel; (2) The gel was frozen in a -20°C refrigerator for 24 hours to ensure complete freezing, and then the frozen sample was transferred to a 25°C constant temperature water bath, and stood for 6 hours until it completely returned to room temperature; (3) The above freezing-thawing process was repeated for a total of 5 cycles, and after the 5th thawing, the sample was centrifuged at 4000 rpm for 15 min to separate the gel from the separated water, the upper separated water was poured out, the remaining gel mass was weighed, and the water separation rate was calculated. The water separation rate%= (initial gel mass- gel mass after centrifugation) / initial gel mass x 100%, the test results were taken as the average of 10 tests, and recorded in Table 1.

[0067] 2. Storage stability: (1) The starch compositions prepared in the examples and comparative examples were dispersed in deionized water to ensure a solid content of 7.5%, heated and stirred at 90°C for 30 min to form a uniform gel; (2) The gel was placed in a constant temperature and humidity chamber at 60°C and 75% relative humidity, stored and observed every 2 h; (3) Until the sample showed system deterioration, system component stratification or system serious flocculation and aggregation, the storage time was recorded. The test results were the average of 10 tests, recorded in Table 1.

[0068] 3. Brittleness: The starch compositions prepared in the examples and comparative examples were tested by a brittleness tester (USP General <1216>). The test results were the average of 10 tests, recorded in Table 1.

[0069] Table 1 Performance evaluation results

[0070]

[0071] From the final performance test results of the examples and comparative examples, comparative examples 1-6 achieved worse performance results than the examples. The examples could further adjust the molecular structure due to better raw material ratio and better starch modification results, realize the synergistic regulation of the molecular chain of the composition, and at the same time limit the molecular motion frequency of the starch chain, thereby enhancing the resistance and barrier properties of the network system to shear force and acidic molecules in the related environment, and hindering the migration of water through more crosslinking points, greatly delaying the pasting speed and system cracking time of starch in the environment, thereby maintaining the excellent storage stability and functional effect of the starch composition, and thus showing better test results of comparative examples 1-6.

Claims

1. A complex functional starch composition, characterized by: The raw materials are prepared by mass parts: 65-100 parts of a compound starch matrix, 1-5 parts of a thickening agent, 3-6 parts of a water retention agent, 1-3 parts of a compatibility agent, 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; The compound starch matrix is a combination of straight-chain corn starch, waxy corn starch and resistant starch, with a mass ratio of (4-5):(2-2.5):(0.8-1.4); The straight-chain corn starch has a straight-chain content of 55-75%, and the waxy corn starch has a branched-chain content of 60-90%. The resistant starch is green bean digestion-resistant starch. 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). The functional anhydride is a combination of acetic anhydride and octenyl succinic anhydride, with a mass ratio of (1.5-2.5):(1-2). The compatibility agent is a combination of lecithin and monoglyceride, with a mass ratio of (3-4):(1.5-2). The preparation method of the compound functional starch composition specifically includes the following steps: S1: mixing the compound starch matrix in proportion, stirring uniformly, then passing through a 150-200 mesh sieve, then adding deionized water to make pulp, heating to 60-70°C in a sealed reaction kettle, keeping warm for 30-45 min, then quickly cooling to 20-25°C, centrifugal dewatering to obtain mixed pulp; S2: mixing the mixed pulp 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 h, then adding deionized water again and adding functional anhydride, heating to 55-60°C and reacting for 3-5 h, and then centrifugal washing the product to neutral to remove unreacted raw materials after the reaction is completed, to obtain pretreated pulp; S3: mixing the pretreated pulp with the remaining raw materials, and finally adding deionized water, homogenizing 3 times under a pressure of 50-100 MPa, controlling the particle size to D50≤10 μm, freeze-drying until the water content is ≤2%, and ensuring that the residual amount of raw materials is within the specified residual amount.

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

3. The composite functional starch composition according to claim 2, characterized in that: The thickening agent is at least one of xanthan gum, guar gum, carrageenan, gum arabic and gellan gum.

4. The composite functional starch composition according to claim 3, characterized in that: The water retention agent is at least one of inulin, konjac glucomannan and β-glucan.

5. The composite functional starch composition according to claim 4, characterized in that: The antioxidant is potassium sorbate or tocopherol.

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