Composite functional starch composition and preparation method thereofTechnical Field
The application relates to the field of food/drug auxiliary materials, in particular to a composite functional starch composition and a preparation method thereof.
Background
Starch, which is a natural high molecular carbohydrate, has been widely used as a key adjuvant in the food industry and pharmaceutical preparations for a long time because of its wide sources, low cost, high biocompatibility, and degradability. In the food field, starch is mainly used as a thickener, a gelatinizer, a stabilizer and a texture improver, and in the pharmaceutical field, starch is often used as a filler, a disintegrant or a slow-release carrier of tablets. However, native starches of a single origin (e.g., corn starch, potato starch, tapioca starch, etc.) are limited by their inherent properties (e.g., gelatinization temperature, viscosity, shear resistance, retrogradation characteristics, etc.), and it is difficult to meet the functional requirements in diverse scenarios.
In recent years, researchers perform functional modification on starch through means of physical modification, chemical modification or enzymatic modification and the like so as to improve acid and alkali resistance, freeze thawing stability, controlled release performance or intestinal targeting. For example, crosslinked starches can enhance shear resistance and are suitable for acidic beverage stabilization, and acetylated starches can improve film formation for embedding pharmaceutically active ingredients. However, chemically modified starch has problems of complex process, risk of reagent residue, regulatory restrictions, etc., and physically modified starch has limited functional enhancement range and may be accompanied by increased processing energy consumption.
Although attempts have been made in the prior art to synergistically improve performance by compounding starch of different sources with other polysaccharides, such compositions still suffer from insufficient compatibility, single functionalization, poor storage stability and poor processing suitability. And the problems of low loading rate, poor release precision and low organoleptic properties exist in the field of medicine, so that the application effect and application prospect of the starch composition are greatly influenced.
Disclosure of Invention
Therefore, in order to effectively solve the existing problems, the application provides the composite functional starch composition and the preparation method thereof, and the finally prepared composite functional starch composition not only has excellent functionality, but also can keep good storage stability, compatibility stability and freeze thawing stability, and can endow the starch composition with good processing application performance while improving the loading efficiency, thereby greatly improving the functionality and the functional stability of the starch composition, expanding the applicable range of the starch composition in the field of food/drug auxiliary materials, and having very excellent application prospect.
The composite functional starch composition comprises, by mass, 65-100 parts of a composite starch substrate, 1-5 parts of a thickening agent, 3-6 parts of a water retaining agent, 1-3 parts of a compatilizer, 0.1-0.3 part 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 functional anhydride and 180-250 parts of deionized water.
As a preferred embodiment, the compounded starch substrate is a combination of amylose, waxy corn starch and resistant starch.
As a preferred embodiment, the mass ratio of the amylose to the waxy corn to the resistant starch is (4-5): 2-2.5): 0.8-1.4.
As a preferred embodiment, the mass ratio of the amylose to the waxy corn to the resistant starch is (4.2-4.8): (2.2-2.4): (0.9-1.2).
As a preferred embodiment, the amylose content of the amylose is 55-75%.
In a preferred embodiment, the amylose content of the amylose is 65-70%.
As a preferred embodiment, the waxy corn starch has a branched chain content of 60-90%.
As a preferred embodiment, the waxy corn starch has a branched chain content of 75-85%.
As a preferred embodiment, the resistant starch is green bean digestion resistant starch.
As a preferred embodiment, the green bean digestion resistant starch has a digestion resistance of 50% or more.
As a preferred implementation mode, the mass ratio of the compound starch substrate to the citric acid to the sodium trimetaphosphate to the functional anhydride is (7-9): 1.5-2): 1-1.2): 3.5-5.5.
As a preferred implementation mode, the mass ratio of the compound starch substrate to the citric acid to the sodium trimetaphosphate to the functional anhydride is (7.5-8.5) (1.8-2) (1-1.1) (4-5).
As a preferred embodiment, the functional anhydride is a combination of acetic anhydride and octenyl succinic anhydride.
As a preferred implementation mode, the mass ratio of the acetic anhydride to the octenyl succinic anhydride is (1.5-2.5): 1-2.
As a preferred implementation mode, the mass ratio of the acetic anhydride to the octenyl succinic anhydride is (1.8-2.2): 1.4-1.6.
As a preferred embodiment, the thickener is at least one of xanthan gum, guar gum, carrageenan, gum arabic and gellan gum.
As a preferred embodiment, the thickener is xanthan gum.
As a preferred embodiment, the water-retaining agent is at least one of inulin, konjac glucomannan and β -glucan.
As a preferred embodiment, the water retaining agent is inulin or konjac glucomannan.
As a preferred embodiment, the water retaining agent is inulin.
As a preferred embodiment, the compatibilizing agent is a combination of lecithin and monoglycerides.
As a preferred embodiment, the mass ratio of the lecithin to the monoglyceride is (3-4): 1.5-2.
As a preferred embodiment, the antioxidant is potassium sorbate or tocopherol.
As a preferred embodiment, the antioxidant is tocopherol.
The preparation method of the composite functional starch composition specifically comprises the following steps of S1 mixing a composite starch substrate in proportion, sieving with a 150-200 mesh sieve after stirring uniformly, adding deionized water into pulping, heating to 60-70 ℃ in a closed reaction kettle, preserving heat for 30-45 min, rapidly cooling to 20-25 ℃ and centrifugally dewatering to obtain mixed slurry, S2 mixing the mixed slurry with deionized water solution containing sodium trimetaphosphate and citric acid, regulating the pH value of a system to 8-8.5 by sodium hydroxide, reacting for 2-3 h at 40-50 ℃, supplementing deionized water again, adding functional anhydride, heating to 55-60 ℃ for reacting for 3-5 h, centrifugally washing the product after the reaction is completed to neutrality, removing unreacted raw materials, and obtaining pretreated slurry, S3 mixing the pretreated slurry with the rest raw materials, finally adding deionized water, homogenizing under the pressure of 50-100 MPa for 3 times, controlling the particle size to be D50-10 mu m, freeze-drying until the moisture content is less than or equal to 2%, and ensuring that the rest raw materials remain below a specified amount.
As a preferred implementation mode, the mass ratio of the compound starch matrix to the deionized water in the step S1 is 1 (1-1.5).
The composite functional starch composition can effectively improve the storage stability, the compatibility stability and the freeze thawing stability of the starch composition through further modification combination of the composite starch matrix, and keeps good functionality and processability. Firstly, in a compound starch matrix, the combination of amylose and amylopectin can provide a good slow-release skeleton and a good viscosity site, a continuous molecular chain network is constructed on the basis of the skeleton and the site in the process of forming the composition, the internal density of a composition system is further enhanced, and the utilization rate of the composition to biological raw materials can be greatly improved under the combined action of the amylose and the amylopectin and the added resistant starch.
Secondly, through the functional modification of the compound starch, the molecular structure can be further adjusted, the molecular chain cooperative regulation and control of the composition is realized, the three-dimensional nature of a molecular chain network is further improved, and meanwhile, the molecular movement frequency of a starch chain is limited, so that the resistance and the barrier property of a network system to shearing force and acidic molecules are enhanced in a relevant environment, the migration of moisture is hindered through more crosslinking points, the gelatinization speed of the starch in the environment and the cracking time of the system are greatly delayed, and the excellent storage stability and the functional effect of the starch composition are maintained.
Finally, the special chain segment and the functional group introduced after modification can greatly improve the blocking effect of a molecular chain system of the starch composition on moisture, and the skeleton structure of the crosslinking system can assist in modifying the added locally-flexible group to a certain extent, so that the resistance of the composition to the phenomenon of molecular chain sliding is improved, and the certain strength of the composition is ensured. And the porous structure integrally formed after modification provides physical interception sites, prevents leakage of functional substances, and the like, and can greatly improve the functional adjustability of the starch composition in application.
The application has the beneficial effects that:
1. The composite functional starch composition provided by the application not only has excellent functionality, but also can keep good storage stability, compatibility stability and freeze thawing stability, and can endow the starch composition with good processing application performance while improving the loading efficiency, thereby greatly improving the functionality and the functional stability of the starch composition, expanding the applicable range of the starch composition in the field of food/drug auxiliary materials, and having very excellent application prospect.
2. In the composite functional starch composition provided by the application, in a composite starch matrix, the combination of amylose and amylopectin can simultaneously provide a good slow-release skeleton and a good viscosity site, and a continuous molecular chain network is constructed on the basis of the skeleton and the site in the process of forming the composition, so that the internal density of a composition system is enhanced, and the utilization rate of the composition to biological raw materials can be greatly improved under the combined action of the composite functional starch and the added resistant starch.
3. According to the composite functional starch composition provided by the application, the molecular structure can be further adjusted through functional modification of the composite starch, so that the molecular chain of the composition is synergistically regulated and controlled, the three-dimensional property of a molecular chain network is further improved, and meanwhile, the molecular movement frequency of the starch chain is limited, so that the resistance and the barrier property of a network system to shearing force and acidic molecules are enhanced in a relevant environment, the migration of moisture is hindered through more crosslinking points, the gelatinization speed of starch in the environment and the cracking time of the system are greatly delayed, and the excellent storage stability and the functional effect of the starch composition are maintained.
4. According to the composite functional starch composition provided by the application, the special chain segment and the functional group are introduced after modification, so that the blocking effect of a molecular chain system of the starch composition on moisture can be greatly improved, and the locally flexible group added in a modified manner can be assisted by a framework structure of a crosslinking system to a certain extent, so that the resistance of the composition to the phenomenon of molecular chain sliding is improved, and the certain strength of the composition is ensured. And the porous structure integrally formed after modification provides physical interception sites, prevents leakage of functional substances, and the like, and can greatly improve the functional adjustability of the starch composition in application.
Detailed Description
In the specific embodiments, the content in the application content of the application will be more intuitively shown and described by specific embodiments. And the following examples are merely practical examples for illustrating and explaining the technical aspects in the specification, and should not limit the scope of the claims to be protected by the present application.
The composite functional starch composition comprises, by mass, 80 parts of a composite starch substrate, 3.2 parts of a thickening agent, 3.4 parts of a water retaining agent, 1.6 parts of a compatilizer, 0.2 part of an antioxidant, 4.1 parts of microcrystalline cellulose, 1.8 parts of citric acid, 1.1 parts of sodium trimetaphosphate, 5 parts of functional anhydride and 220 parts of deionized water.
The compound starch matrix is a combination of amylose, waxy corn and resistant starch, and the mass ratio of the amylose to the waxy corn to the resistant starch is 4.5:2.3:1.2.
The amylose content was 70% and purchased from corresponding specification products sold by the company of the Siander Biotechnology, inc. of China.
Waxy corn starch has a branched chain content of 85% and is purchased from Henan Seto Biotechnology Inc. of China as a corresponding specification product.
The resistant starch is green bean digestion resistant starch, the digestion resistance is 55%, and the resistant starch is purchased from Shanxi Shuoyang biotechnology Co., ltd.
The functional anhydride is a composition of acetic anhydride and octenyl succinic anhydride, and the mass ratio of the acetic anhydride to the octenyl succinic anhydride is 2.1:1.4.
The thickener is xanthan gum, the water-retaining agent is inulin, the water-retaining agent is composition of lecithin and monoglyceride purchased from Jiangsu Miao national biotechnology Co., ltd, the mass ratio of the two is 3.5:1.8, and the antioxidant is tocopherol.
The preparation method of the composite functional starch composition specifically comprises the following steps of S1, mixing a compound starch matrix according to a proportion, sieving with a 150-mesh sieve after stirring uniformly, adding deionized water (50 wt% of the total amount of deionized water) into pulping, heating to 65 ℃ in a closed reaction kettle, preserving heat for 45min, rapidly cooling to 22 ℃, centrifugally dehydrating to obtain mixed slurry, S2, mixing the mixed slurry with deionized water solution (10 wt% of the total amount of deionized water) containing sodium trimetaphosphate and citric acid, regulating the pH value of a system to 8.5 by sodium hydroxide, reacting for 2.5 hours at 45 ℃, supplementing deionized water again (10 wt% of the total amount of deionized water) again, adding functional anhydride, heating to 55 ℃ for reacting for 4 hours, centrifugally washing the product after the reaction is completed to neutrality, and removing unreacted raw materials, and obtaining pretreated slurry, S3, mixing the pretreated slurry with the rest raw materials, finally adding deionized water (30 wt% of the total amount of deionized water), homogenizing for 3 times under the pressure of 75MPa, controlling the particle size to D50 to be less than or equal to 10 mu m, freeze-drying until the moisture content is less than or equal to 2%, and keeping the residual raw materials under the specified residual amount.
Example 2 the difference between the present example and example 1 is that the composite functional starch composition is prepared from 74 parts by mass of composite starch matrix, 4.1 parts by mass of thickener, 3.6 parts by mass of water retention agent, 1.2 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 3.8 parts by mass of microcrystalline cellulose, 1.5 parts by mass of citric acid, 1 part by mass of sodium trimetaphosphate, 3.8 parts by mass of functional anhydride and 200 parts by mass of deionized water.
The compound starch matrix is a combination of amylose, waxy corn and resistant starch, and the mass ratio of the amylose to the waxy corn to the resistant starch is 4:2:1.4.
Example 3 the difference between the present example and example 1 is that the composite functional starch composition is prepared from 80 parts of composite starch matrix, 3.5 parts of thickener, 4.5 parts of water retention agent, 2 parts of compatilizer, 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 by mass.
The compound starch matrix is a composition of amylose, waxy corn starch and resistant starch, and the mass ratio of the amylose to the waxy corn starch to the resistant starch is 5:2.2:0.8.
Comparative example 1
The difference between this comparative example and example 1 is only that the compounded starch substrate is a combination of amylose, waxy corn starch and resistant starch in a mass ratio of 6:1:0.2.
Comparative example 2
The difference between this comparative example and example 1 is that the compounded starch substrate is a combination of amylose, waxy corn starch and resistant starch in a mass ratio of 3:3:2.2.
Comparative example 3
The comparative example and example 1 only differ in 80 parts of compound starch matrix, 3.2 parts of thickener, 3.4 parts of water retention agent, 1.6 parts of compatilizer, 0.2 part of antioxidant, 4.1 parts of microcrystalline cellulose, 0.5 part of citric acid, 0.2 part of sodium trimetaphosphate, 5 parts of functional anhydride and 220 parts of deionized water.
Comparative example 4
The comparative example and example 1 only differ in 80 parts of compound starch matrix, 3.2 parts of thickener, 3.4 parts of water retention agent, 1.6 parts of compatilizer, 0.2 part of antioxidant, 4.1 parts of microcrystalline cellulose, 1.8 parts of citric acid, 1.1 parts of sodium trimetaphosphate, 1.5 parts of functional anhydride and 220 parts of deionized water.
Comparative example 5
This comparative example differs from example 1 only in that the functional anhydride is a combination of acetic anhydride and octenyl succinic anhydride in a mass ratio of 4:0.6.
Comparative example 6
This comparative example differs from example 1 only in that the functional anhydride is a combination of acetic anhydride and octenyl succinic anhydride in a mass ratio of 0.8:1.4.
Evaluation of Performance
1. Freezing and thawing stability (1) dispersing the starch compositions prepared in examples and comparative examples in deionized water to ensure the solid content to be 7.5%, heating and stirring at 90 ℃ for 30min to form uniform gel, (2) freezing in a refrigerator at 20 ℃ to 20 ℃ for 24 hours to ensure complete freezing of the gel, then transferring the frozen sample into a constant temperature water bath at 25 ℃, standing and thawing for 6 hours until the temperature is completely restored to room temperature, (3) repeating the freezing and thawing process for 5 times, centrifuging the sample at 4000 rpm min after thawing for 5 th time, separating the gel from the precipitated water, pouring out the upper layer of the precipitated water, weighing the mass of the residual gel, and calculating the water precipitation rate. Water extraction% = (initial gel mass-gel mass after centrifugation)/initial gel mass x 100%, and the average of 10 tests was taken as the test result and recorded in table 1.
2. Storage stability (1) the starch compositions prepared in examples and comparative examples were dispersed in deionized water to ensure a solid content of 7.5%, heated and stirred at 90℃for 30 minutes to form a uniform gel, (2) the gel was stored in a constant temperature and humidity cabinet at 60℃and 75% relative humidity and sample observation was carried out every 2 hours, and (3) the storage time was recorded until the samples were subject to system deterioration, system component delamination or severe flocculation agglomeration phenomena. The test results were averaged over 10 tests and are reported in Table 1.
3. Friability the starch compositions prepared in the examples and comparative examples were tested by a friability tester (USP general rule <1216 >). The test results were averaged over 10 tests and are reported in Table 1.
Table 1 results of performance evaluation
From the final performance test results of the examples and the comparative examples, the comparative examples 1 to 6 obtain poorer performance results than the examples, but in the examples, because of better raw material proportion and better starch modification results, molecular structures can be further adjusted to realize the cooperative regulation and control of molecular chains of the composition, so that the three-dimensional property of a molecular chain network is improved, and meanwhile, the molecular movement frequency of starch chains is limited, thereby enhancing the resistance and barrier property of a network system to shearing force and acidic molecules in a relevant environment, and preventing migration of moisture through more crosslinking points, greatly delaying the gelatinization speed of starch in the environment and the cracking time of the system, thereby maintaining the excellent storage stability and functional effect of the starch composition, and further reflecting the better test results of the comparative examples 1 to 6.