CN111905106A - Slow-release sodium alginate/chitosan/zein composite material and preparation method thereof - Google Patents

Slow-release sodium alginate/chitosan/zein composite material and preparation method thereof Download PDF

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CN111905106A
CN111905106A CN202010961346.3A CN202010961346A CN111905106A CN 111905106 A CN111905106 A CN 111905106A CN 202010961346 A CN202010961346 A CN 202010961346A CN 111905106 A CN111905106 A CN 111905106A
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sodium alginate
chitosan
zein
solution
parts
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徐群娜
白忠薛
李娇娇
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a slow-release sodium alginate/chitosan/zein composite material and a preparation method thereof. Firstly, dissolving chitosan in deionized water; dissolving zein, lipophilic functional substances and a surfactant in an ethanol solution to obtain a zein mixed solution, and preparing a zein-based microcapsule emulsion by using an anti-solvent precipitation method; adding sodium alginate and hydrophilic substances into deionized water, heating and stirring under the condition of water bath to obtain a sodium alginate mixed solution, adjusting the pH value of the system, adding a chitosan solution, a zein microcapsule emulsion and a divalent cation solution, and aging to obtain the slow-release sodium alginate/chitosan/zein composite material. The invention utilizes the antibacterial property of chitosan, the self-assembly property of zein and the gelation property of sodium alginate, and the prepared composite material has the characteristics of slow release, antibacterial property and the like.

Description

Slow-release sodium alginate/chitosan/zein composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of functional composite materials, and particularly relates to a slow-release sodium alginate/chitosan/zein composite material and a preparation method thereof.
Background
China consumes about 1.5 million tons of corn every year, and the produced corn protein powder is about 84 million tons. Due to the fact that the Zein powder is high in prolamin content, water solubility is low and processing performance is poor, and therefore the Zein powder has high economic value and application significance in modification and utilization of Zein (Zein). Zein is a polymer formed by conglomerating peptide chains with different molecular sizes, dissolving capacities and charges through disulfide bonds, is in the shape of small and round granules, has the diameter of 1-2 mu m, and has the average molecular weight of 44 kDa. As a class of well-recognized safe and valuable protein materials, zein microcapsules can encapsulate various lipophilic molecules for controlling the release of bioactive substances, and have wide research and application in various fields such as food, medicine, chemical industry and the like.
Chitosan (chitosan) is also called deacetylated chitinThe chitin is obtained by deacetylation of chitin (chitin) widely existing in nature. Such natural polymers have been widely noticed for their excellent biocompatibility, hemocompatibility, safety, biodegradability and the like, and have made great research progress in various fields such as food, chemical and biomedical engineering. Chitosan is easily dissolved in a weak acid solvent, and particularly, the dissolved solution contains amino (NH)2+) These amino groups inhibit bacteria by binding negative electrons. The chitosan has the function of inhibiting the activity of bacteria, so that the chitosan has wide application in the fields of medicine, textile, food and the like.
Sodium alginate (sodium alginate) is a by-product after extraction of iodine and mannitol from kelp or gulfweed of brown algae. The molecule is formed by connecting beta-D-mannuronic acid (beta-D-mannuronic, M) and alpha-L-guluronic acid (alpha-L-guluronic acid, G) according to a (1 → 4) bond, is a natural polysaccharide, and has the stability, solubility, viscosity and safety required by pharmaceutical preparation auxiliary materials. Alginic acid has the characteristics of no toxicity, no odor and high viscosity of an aqueous solution, and can quickly react with divalent metal cations to physically crosslink, so that water molecules are wrapped in an ion network structure to form hydrogel. Therefore, the sodium alginate is used for converting the hydrophilic functional material water solution into the hydrogel through physical crosslinking, and the slow release effect is expected to be realized.
Disclosure of Invention
The invention aims to provide a slow-release sodium alginate/chitosan/zein composite material and a preparation method thereof, which fully show the characteristics of three natural products, and utilize the antibacterial property of chitosan, the self-assembly property of zein, the gelation property of sodium alginate and other properties, so that the prepared composite material has the functions of antibiosis, slow release and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a slow-release sodium alginate/chitosan/zein composite material comprises the following steps:
firstly, dissolving chitosan in deionized water; dissolving zein, lipophilic functional substances and a surfactant in an ethanol solution to obtain a zein mixed solution, and preparing a zein-based microcapsule emulsion by using an anti-solvent precipitation method; then, adding sodium alginate and hydrophilic substances into deionized water, heating and stirring under the condition of water bath to obtain a sodium alginate mixed solution, adjusting the pH value of the system, then adding a chitosan solution, a zein microcapsule emulsion and a divalent cation solution into the mixed solution, and aging to obtain the slow-release sodium alginate/chitosan/zein composite material.
The method specifically comprises the following steps of:
step one, preparing a sodium alginate solution:
weighing 10.0-100.0 parts of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 0.2-4.0 parts of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 0.5-6 h under the condition of 35-75 ℃ water bath to completely dissolve the sodium alginate to obtain a sodium alginate solution;
step two, preparing a chitosan solution:
weighing 10.0-100.0 parts of deionized water, adjusting the pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then respectively weighing 1.0-10.0 parts of chitosan and 0.01-0.5 part of hydrophilic functional substance, dissolving the chitosan and the hydrophilic functional substance in the deionized water, and then stirring for 2-6 hours under the condition of 35-75 ℃ water bath to completely dissolve the chitosan and obtain a chitosan solution;
step three, preparing the zein microcapsule emulsion:
weighing 0.1-2.0 parts of zein, adding into 10-100 parts of 85% ethanol water solution, adding 0.1-1.5 parts of lipophilic functional substance and 0.1-1.5 parts of surfactant, and stirring for 2 h to obtain mixed solution; then adding 200.0-700.0 parts of deionized water into the mixed system, removing ethanol in the mixed system by rotary evaporation, and stirring the mixture for 2-6 hours in an open manner at room temperature to prepare zein microcapsule emulsion;
step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 30.0-50.0 parts of chitosan solution prepared in the second step and 0.2-1.5 parts of zein microcapsule emulsion prepared in the third step, adding the chitosan solution and the zein microcapsule emulsion into 10 parts of sodium alginate mixed solution prepared in the first step, adjusting the pH of a system by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then using water solution of divalent cations as a cross-linking agent, and adding the water solution of divalent cations into the sodium alginate solution, wherein the molar ratio of the divalent cations to sodium alginate carboxyl is 0.05-0.8: 1, stirring at medium speed for 0.5-2 h, standing at room temperature and aging overnight to obtain the slow-release sodium alginate/chitosan/zein composite material.
In the second step, the hydrophilic functional substance is one or more hydrophilic substances containing hydrophilic polar groups.
In the third step, the lipophilic functional substance is one or more of alkane, oil or fat.
In the third step, the surfactant is a nonionic surfactant or a mixture of a plurality of nonionic surfactants.
In the fourth step, the divalent cations are divalent cations capable of performing ion exchange reaction with Na + in the sodium alginate.
The slow-release sodium alginate/chitosan/zein composite material is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the slow-release sodium alginate/chitosan/zein composite material is prepared by combining the modes of anti-solvent precipitation, physical crosslinking and physical blending, the preparation condition is simple, the test method is easy to implement, and the three materials are wide in source, green, non-toxic, and good in biocompatibility and degradability;
(2) the slow-release sodium alginate/chitosan/zein composite material prepared by the method has the functions of inhibiting bacterial activity, controlling the release of functional substances and the like, and has wide application prospects in the fields of biological medicines, food processing and the like.
Drawings
Fig. 1 is a photograph of the sustained-release sodium alginate/chitosan/zein composite material prepared in example 3.
Fig. 2 is a bacteriostatic photo of the sustained-release sodium alginate/chitosan/zein composite material prepared in example 3.
Fig. 3 is an SEM image of the sustained-release sodium alginate/chitosan/zein composite material prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
The invention mainly utilizes the good antibacterial activity and biocompatibility of chitosan, the unique dissolubility and good self-assembly of zein, the thermal irreversibility of sodium alginate-based hydrogel, the mild and good drug absorption and release under the reaction condition and other properties to finally prepare the slow-release sodium alginate/chitosan/zein composite material.
Example 1
Step one, preparing a sodium alginate solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 0.2 parts by mass of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 6 hours at 35 ℃ in a water bath to completely dissolve the sodium alginate to obtain a sodium alginate solution.
Step two, preparing a chitosan solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then respectively weighing 1.0 part by mass of chitosan and 0.01 part by mass of vanillin, dissolving the chitosan and the vanillin in the deionized water, and then stirring for 6 hours under the condition of 35 ℃ water bath to completely dissolve the chitosan and obtain a chitosan solution.
Step three, preparing the zein microcapsule emulsion:
weighing 2.0 parts by mass of zein, adding the zein into 100.0 parts by mass of an ethanol aqueous solution (85%, v/v), adding 0.1 part by mass of folium artemisiae argyi essence and 0.1 part by mass of pluronic F127, and stirring for 2 hours to obtain a mixed solution; and then adding 200.0 parts by mass of deionized water into the mixed system, removing ethanol in the mixed system through rotary evaporation, and stirring the mixture for 12 hours in an open manner at room temperature to obtain the zein microcapsule emulsion.
Step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 40.0 parts by mass of chitosan solution and 1.0 part by mass of zein microcapsule emulsion, adding the chitosan solution and the zein microcapsule emulsion into 10 parts by mass of sodium alginate mixed solution, adjusting the pH of the system by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and then adding 0.1 mol/L CaCl2The water solution is a cross-linking agent, the divalent calcium ions and the sodium alginate carboxyl are added into the sodium alginate solution according to the molar ratio of 0.4, the mixture is stirred at medium speed for 0.5 h and then is kept stand and aged at room temperature for 12 h to prepare the slow-release sodium alginate/chitosan/zein composite material.
Example 2
Step one, preparing a sodium alginate solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 0.5 part by mass of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 6 hours at 40 ℃ in a water bath to completely dissolve the sodium alginate to obtain a sodium alginate solution.
Step two, preparing a chitosan solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then respectively weighing 2.0 parts by mass of chitosan and 0.05 parts by mass of strawberry essence, dissolving the chitosan and the strawberry essence in the deionized water, and stirring for 6 hours under the condition of water bath at 40 ℃ to completely dissolve the chitosan and obtain a chitosan solution.
Step three, preparing the zein microcapsule emulsion:
weighing 2.0 parts by mass of zein, adding the zein into 100.0 parts by mass of an ethanol aqueous solution (85%, v/v), adding 0.2 part by mass of eugenol and 0.2 part by mass of tween-80, and stirring for 2 hours to prepare a mixed solution; and then adding 300.0 parts by mass of deionized water into the mixed system, removing ethanol in the mixed system through rotary evaporation, and stirring the mixture for 12 hours at room temperature to prepare the zein microcapsule emulsion.
Step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 40.0 parts by mass of chitosan solution and 1.0 part by mass of zein microcapsule emulsion, adding the chitosan solution and the zein microcapsule emulsion into 10 parts by mass of sodium alginate mixed solution, adjusting the pH of the system by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and then using 0.1 mol/L MgCl2The water solution is a cross-linking agent, and is added into the sodium alginate solution according to the molar ratio of divalent magnesium ions to sodium alginate carboxyl of 0.4, the mixture is stirred at medium speed for 0.5 h and then is kept stand and aged at room temperature for 12 h to prepare the slow-release sodium alginate/chitosan/zein composite material.
Example 3
Step one, preparing a sodium alginate solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 1.0 part by mass of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 6 hours under the condition of water bath at 45 ℃ to completely dissolve the sodium alginate to obtain a sodium alginate solution.
Step two, preparing a chitosan solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weighing 3.0 parts by mass of chitosan and 0.1 part by mass of vanillin respectively, dissolving the chitosan and the vanillin in the deionized water, and stirring for 6 hours under the condition of water bath at 45 ℃ to completely dissolve the chitosan and obtain a chitosan solution.
Step three, preparing the zein microcapsule emulsion:
weighing 2.0 parts by mass of zein, adding the zein into 100.0 parts by mass of an ethanol aqueous solution (85%, v/v), adding 0.3 part by mass of thymol and 0.3 part by mass of pluronic F127, and stirring for 2 hours to obtain a mixed solution; and then adding 400.0 parts by mass of deionized water into the mixed system, removing ethanol in the mixed system through rotary evaporation, and stirring the mixture for 12 hours in an open manner at room temperature to obtain the zein microcapsule emulsion.
Step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 40.0 parts by mass of chitosanAdding the solution and 1.0 part by mass of zein microcapsule emulsion into 10 parts by mass of sodium alginate mixed solution, adjusting the pH of the system by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and adding 0.1 mol/L CaCl2The water solution is a cross-linking agent, and the divalent calcium ions and the sodium alginate carboxyl are added into the sodium alginate solution according to the molar ratio of 0.4, stirred at medium speed for 0.5 h and then kept stand and aged at room temperature for 12 h to prepare the slow-release sodium alginate/chitosan/zein composite material.
Example 4
Step one, preparing a sodium alginate solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 1.5 parts by mass of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 6 hours under the condition of 50 ℃ water bath to completely dissolve the sodium alginate to obtain a sodium alginate solution.
Step two, preparing a chitosan solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then respectively weighing 4.0 parts by mass of chitosan and 0.15 part by mass of rose essence, dissolving the chitosan and the rose essence in the deionized water, and stirring for 6 hours under the condition of water bath at 50 ℃ to completely dissolve the chitosan and obtain a chitosan solution.
Step three, preparing the zein microcapsule emulsion:
weighing 2.0 parts by mass of zein, adding the zein into 100.0 parts by mass of an ethanol aqueous solution (85%, v/v), adding 0.4 part by mass of curcumin and 0.4 part by mass of tween 60, and stirring for 2 hours to obtain a mixed solution; and then adding 500.0 parts by mass of deionized water into the mixed system, removing ethanol in the mixed system through rotary evaporation, and stirring the mixture for 12 hours in an open manner at room temperature to obtain the zein microcapsule emulsion.
Step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 40.0 parts by mass of chitosan solution and 1.0 part by mass of zein microcapsule emulsion, adding into 10 parts by mass of sodium alginate mixed solution, and adding into the mixed solution by 0.1 mol/L NThe system pH was adjusted with aOH and 0.1 mol/L HCl followed by 0.1 mol/L SrCl2The water solution is a cross-linking agent, and is added into the sodium alginate solution according to the molar ratio of the divalent strontium ions to the sodium alginate carboxyl of 0.4, the mixture is stirred at medium speed for 0.5 h and then is kept stand and aged at room temperature for 12 h to prepare the slow-release sodium alginate/chitosan/zein composite material.
Example 5
Step one, preparing a sodium alginate solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 2.0 parts by mass of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 6 hours at 55 ℃ in a water bath to completely dissolve the sodium alginate to obtain a sodium alginate solution.
Step two, preparing a chitosan solution:
weighing 100.0 parts by mass of deionized water, adjusting the pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then respectively weighing 5.0 parts by mass of chitosan and 0.2 part by mass of lemon essence, dissolving the chitosan and the lemon essence in the deionized water, and stirring for 6 hours under the condition of water bath at 55 ℃ to completely dissolve the chitosan and obtain a chitosan solution.
Step three, preparing the zein microcapsule emulsion:
weighing 2.0 parts by mass of zein, adding into 100.0 parts by mass of ethanol aqueous solution (85%, v/v), adding 0.5 part by mass of folium artemisiae argyi essence and 0.5 part by mass of tween-20, and stirring for 2 h to obtain a mixed solution; and then 600.0 parts by mass of deionized water is added into the mixed system, ethanol in the mixed system is removed through rotary evaporation, and the zein microcapsule emulsion is prepared after the zein microcapsule emulsion is stirred for 12 hours in an open manner at room temperature.
Step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 40.0 parts by mass of chitosan solution and 1.0 part by mass of zein microcapsule emulsion, adding the chitosan solution and the zein microcapsule emulsion into 10 parts by mass of sodium alginate mixed solution, adjusting the pH of the system by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and then using 0.1 mol/L MgCl2The aqueous solution is a cross-linking agent based on divalent magnesium ions and seaweedAdding the sodium alginate/chitosan/zein composite material into a sodium alginate solution according to the molar ratio of sodium carboxyl to sodium alginate/carboxyl of 0.4, stirring at a medium speed for 0.5 h, standing and aging at room temperature for 12 h to obtain the slow-release sodium alginate/chitosan/zein composite material.
Fig. 1 is a photograph of the sustained-release sodium alginate/chitosan/zein composite material prepared in example 3. The composite material is observed to be in a gel structure and has better absorbability, stability and the like.
FIG. 2 is a photograph of the filter paper treated with the sustained-release sodium alginate/chitosan/zein composite material prepared in example 3. It can be seen from the observation that the fabric has obvious inhibiting effect on staphylococcus aureus after being soaked in the composite material.
Fig. 3 is an SEM image of the sustained-release sodium alginate/chitosan/zein composite material prepared in example 3. The observation shows that the dried composite material has obvious pore structure; meanwhile, a plurality of spherical structures are uniformly distributed in the material, which may be the combination of the zein microcapsule and substances such as chitosan, sodium alginate and the like, so that a hydrogel-microcapsule composite structure is formed. The results demonstrate that this approach works.
The invention is not limited to the examples given, and any equivalent alterations to the technical solution of the invention which are made by those skilled in the art after reading the description of the invention are all covered by the claims of the invention.

Claims (7)

1. A preparation method of a slow-release sodium alginate/chitosan/zein composite material is characterized by comprising the following steps:
firstly, dissolving chitosan in deionized water; dissolving zein, lipophilic functional substances and a surfactant in an ethanol solution to obtain a zein mixed solution, and preparing a zein-based microcapsule emulsion by using an anti-solvent precipitation method; then, adding sodium alginate and hydrophilic substances into deionized water, heating and stirring under the condition of water bath to obtain a sodium alginate mixed solution, adjusting the pH value of the system, then adding a chitosan solution, a zein microcapsule emulsion and a divalent cation solution into the mixed solution, and aging to obtain the slow-release sodium alginate/chitosan/zein composite material.
2. The preparation method of the slow-release sodium alginate/chitosan/zein composite material according to claim 1, characterized in that:
the method specifically comprises the following steps of:
step one, preparing a sodium alginate solution:
weighing 10.0-100.0 parts of deionized water, adjusting the pH value with 0.1 mol/L NaOH and 0.1 mol/L HCl, weighing 0.2-4.0 parts of sodium alginate, adding the sodium alginate into the deionized water, and stirring for 0.5-6 h under the condition of 35-75 ℃ water bath to completely dissolve the sodium alginate to obtain a sodium alginate solution;
step two, preparing a chitosan solution:
weighing 10.0-100.0 parts of deionized water, adjusting the pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then respectively weighing 1.0-10.0 parts of chitosan and 0.01-0.5 part of hydrophilic functional substance, dissolving the chitosan and the hydrophilic functional substance in the deionized water, and then stirring for 2-6 hours under the condition of 35-75 ℃ water bath to completely dissolve the chitosan and obtain a chitosan solution;
step three, preparing the zein microcapsule emulsion:
weighing 0.1-2.0 parts of zein, adding into 10-100 parts of 85% ethanol water solution, adding 0.1-1.5 parts of lipophilic functional substance and 0.1-1.5 parts of surfactant, and stirring for 2 h to obtain mixed solution; then adding 200.0-700.0 parts of deionized water into the mixed system, removing ethanol in the mixed system by rotary evaporation, and stirring the mixture for 2-6 hours in an open manner at room temperature to prepare zein microcapsule emulsion;
step four, preparing the slow-release sodium alginate/chitosan/zein composite material:
respectively weighing 30.0-50.0 parts of chitosan solution prepared in the second step and 0.2-1.5 parts of zein microcapsule emulsion prepared in the third step, adding the chitosan solution and the zein microcapsule emulsion into 10 parts of sodium alginate mixed solution prepared in the first step, adjusting the pH of a system by using 0.1 mol/L NaOH and 0.1 mol/L HCl, then using water solution of divalent cations as a cross-linking agent, and adding the water solution of divalent cations into the sodium alginate solution, wherein the molar ratio of the divalent cations to sodium alginate carboxyl is 0.05-0.8: 1, stirring at medium speed for 0.5-2 h, standing at room temperature and aging overnight to obtain the slow-release sodium alginate/chitosan/zein composite material.
3. The preparation method of the slow-release sodium alginate/chitosan/zein composite material according to claim 2, characterized in that:
in the second step, the hydrophilic functional substance is one or more hydrophilic substances containing hydrophilic polar groups.
4. The preparation method of the slow-release sodium alginate/chitosan/zein composite material according to claim 3, characterized in that:
in the third step, the lipophilic functional substance is one or more of alkane, oil or fat.
5. The preparation method of the slow-release sodium alginate/chitosan/zein composite material according to claim 4, characterized in that:
in the third step, the surfactant is a nonionic surfactant or a mixture of a plurality of nonionic surfactants.
6. The preparation method of the slow-release sodium alginate/chitosan/zein composite material according to claim 5, characterized in that:
in the fourth step, the divalent cations are divalent cations capable of performing ion exchange reaction with Na + in the sodium alginate.
7. The preparation method of claims 1-6, wherein the preparation method is used for preparing a slow-release sodium alginate/chitosan/zein composite material.
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CN114098076A (en) * 2021-11-18 2022-03-01 江南大学 Preparation method of genipin-crosslinked quercetin-zein/pectin/chitosan nanoparticles
CN114392247A (en) * 2021-12-08 2022-04-26 大连民族大学 Preparation method of hydrophobic shell gel microcapsule with controllable shell thickness
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CN114892449A (en) * 2022-05-17 2022-08-12 浙江恒达新材料股份有限公司 Preparation method of fluorine-free antibacterial oilproof paper
CN114948903A (en) * 2022-06-06 2022-08-30 盐城工业职业技术学院 Preparation method of thymol-loaded zein-Arabic gum-chitosan hydrochloride composite nanoparticles
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