CN112048080A - Microcapsule-filled sodium alginate-based hydrogel and preparation method thereof - Google Patents

Microcapsule-filled sodium alginate-based hydrogel and preparation method thereof Download PDF

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CN112048080A
CN112048080A CN202010961334.0A CN202010961334A CN112048080A CN 112048080 A CN112048080 A CN 112048080A CN 202010961334 A CN202010961334 A CN 202010961334A CN 112048080 A CN112048080 A CN 112048080A
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sodium alginate
microcapsule
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zein
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CN112048080B (en
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徐群娜
白忠薛
彭楚奇
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Shaanxi University of Science and Technology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246Intercrosslinking of at least two polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/04Alginic acid; Derivatives thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00Characterised by the use of proteins; Derivatives thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
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Abstract

The invention discloses a microcapsule-filled sodium alginate-based hydrogel and a preparation method thereof, which comprises the steps of dissolving zein by using an ethanol solution to obtain a dissolved solution, adding a hydrophobic functional substance and a surfactant into the zein solution, and preparing a zein-based microcapsule emulsion by using an anti-solvent method; simultaneously, adding sodium alginate into water, heating and stirring under the condition of water bath to obtain sodium alginate solution, adjusting the pH of the system, and then sequentially adding zein-based microcapsule emulsion and CaCl into the system2Stirring the solution and agingAnd reacting for a period of time to obtain the microcapsule-filled sodium alginate-based hydrogel. The composite material prepared by the invention has the characteristics of hydrogel and microcapsule, has the advantages of good structural stability, capability of loading various hydrophobic functional substances, good controlled release property and the like, and has wide application prospect in the fields of biological medicine, food processing and the like.

Description

Microcapsule-filled sodium alginate-based hydrogel and preparation method thereof
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a microcapsule-filled sodium alginate-based hydrogel and a preparation method thereof.
Background
Hydrogels are a class of very hydrophilic three-dimensional network-structured gels that swell rapidly in water and in this swollen state can hold a large volume of water without dissolving. All water-soluble or hydrophilic polymers can form hydrogel through certain chemical crosslinking or physical crosslinking. These polymers can be classified into two major categories, natural and synthetic, depending on their origin. The natural hydrophilic polymer mainly comprises polypeptide (collagen, poly-L-lysine, poly-L-glutamic acid, etc.) and polysaccharide (cellulose, chitosan, sodium alginate, etc.). Wherein, the sodium alginate is a natural anionic polysaccharide extracted from brown algae, the molecule of the sodium alginate contains a large amount of-COO-which is protonated to form-COOH under the acidic condition, the repulsion between molecules is reduced and hydrogen bonds are formed, the hydrophilicity is reduced, and the molecular chain is contracted; under alkaline conditions, -COOH deprotonates to form-COO-, hydrophilicity increases, and the molecular chain stretches. Sodium alginate in the presence of Ca2+And Sr2+When cations exist, ion exchange can occur, hydrogel can be formed through crosslinking, and the sodium alginate hydrogel can be used as a carrier embedding functional substance by utilizing the strong water absorption of the gel. The gel can shrink and deform after being dried, and can absorb water to swell in a wet environment and restore to a spherical shape, so that the embedded object is released. However, due to the strong hydrophilicity of sodium alginate, a single sodium alginate hydrogel structure has some defects, such as low loading rate of hydrophobic functional substances, poor stability and the like, and the application of the sodium alginate-based hydrogel is limited to a certain extent.
Zein is the major storage protein in corn and is soluble in 60% -95% aqueous ethanol. Zein molecules contain a large number of nonpolar amino acids and lack acidic and basic amino acids, so zein has unique solubility, i.e., is insoluble in water and soluble in an alcohol-water solution. Zein has edible characteristics, good biocompatibility and biodegradability, and is approved to be used by the U.S. food and drug administration. Therefore, zein is widely used to develop new biomaterials, such as films, nano-bio composite scaffolds, nanofibers, and nanocapsules. Wherein the zein microcapsule can encapsulate various lipophilic molecules, such as curcumin, vitamin D, thymol, resveratrol, folium Artemisiae Argyi essence, etc., for controlling bioactive substance release.
Disclosure of Invention
The invention aims to provide a microcapsule-filled sodium alginate-based hydrogel and a preparation method thereof, wherein zein microcapsules are filled in the sodium alginate hydrogel, so that the stability of a hydrogel system is further improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing microcapsule-filled sodium alginate-based hydrogel comprises dissolving zein in ethanol solution to obtain a solution, adding lipophilic functional substance and surfactant into the zein solution, and preparing zein-based microcapsule emulsion by anti-solvent method; simultaneously, adding sodium alginate into water, heating and stirring under the condition of water bath to obtain sodium alginate solution, adjusting the pH of the system, and then sequentially adding zein-based microcapsule emulsion and CaCl into the system2And stirring the solution, and then aging for a period of time to obtain the microcapsule-filled sodium alginate-based hydrogel.
The method specifically comprises the following steps of:
step one, preparing a zein microcapsule:
weighing 0.05-0.2 part of zein, adding the zein into 5-15 parts of 85% ethanol water solution, adding 0.01-0.20 part of hydrophobic functional substance and 0.01-0.20 part of surfactant, and stirring for 0.5-2 h to prepare a mixed solution; adding the mixed solution into 20-70 parts of ultrapure water, emulsifying, and performing rotary evaporation to remove ethanol in the mixed system to obtain zein microcapsule emulsion;
step two, preparing a sodium alginate solution:
weighing 0.05-2.0 parts of sodium alginate, adding into 10-100 parts of pure water, and stirring for 1-6 h at 40-75 ℃ in a water bath until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
adding 0.1-2.0 parts of zein microcapsule emulsion prepared in the first step into 1.0 part of sodium alginate solution prepared in the second step, adjusting the pH of the system, and adding CaCl2And weighing calcium carbonate as a cross-linking agent, adding the calcium carbonate into a sodium alginate solution, wherein the molar ratio of calcium ions to sodium alginate carboxyl is 0.1-1.0, stirring at a low speed for 0.5 h, standing and aging at room temperature for 2-12 h, and thus obtaining the microcapsule-filled sodium alginate-based hydrogel.
In the first step, the hydrophobic functional substance is one or a mixture of alkanes, oil or fat.
In the first step, the surfactant is a mixture of one or more nonionic surfactants.
In the third step, the pH value of the system is adjusted to 3.0-10.0.
The microcapsule-filled sodium alginate-based hydrogel is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method is simple and easy to implement, and sodium alginate and zein are natural polymers, so that the preparation method has the advantages of safety, no toxicity, good biocompatibility, biodegradability and the like.
(2) The microcapsule-filled sodium alginate-based hydrogel prepared by the method has the characteristics of both hydrogel and microcapsule, and has the advantages of good structural stability, capability of loading various lipophilic substances, good controlled release property and the like.
Drawings
FIG. 1 is a photograph of a microcapsule-filled sodium alginate-based hydrogel obtained in example 2.
FIG. 2 is a release profile of the microcapsule-filled sodium alginate-based hydrogel prepared in example 2.
FIG. 3 is an SEM photograph of a microcapsule-filled sodium alginate-based hydrogel prepared in example 2.
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 utilizes the characteristics of thermal irreversibility, mild reaction condition, good stability, good drug absorption and release and the like of the sodium alginate-based hydrogel; meanwhile, the microcapsule-filled sodium alginate-based hydrogel is prepared by combining zein microcapsules with unique solubility, good controllable drug release and controllable size.
Example 1
Step one, preparing a zein-based microcapsule:
weighing 0.2 part by mass of zein, adding the zein into 10.0 parts by mass of 85% ethanol aqueous solution, adding 0.01 part by mass of thymol and 0.01 part by mass of lauryl alcohol polyoxyethylene ether, and stirring for 2 hours to prepare a mixed solution; and then adding 20 parts by mass of ultrapure water into the mixed system, and removing ethanol in the mixed system through rotary evaporation to obtain the zein-based microcapsule emulsion.
Step two, preparing a sodium alginate solution:
weighing 0.1 part by mass of sodium alginate, adding into 50 parts by mass of water, and stirring for 6 hours at 40 ℃ in a water bath condition until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
adding 0.1 mass part of zein microcapsule emulsion into 1.0 mass part of sodium alginate solution, adjusting the pH of the system to 6.5 by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and adding CaCl2The solution is a cross-linking agent, calcium carbonate is weighed according to the molar ratio of calcium ions to sodium alginate carboxyl of 0.1 and added into the sodium alginate solution, the mixture is stirred at a low speed for 0.5 h and then is kept stand and aged at room temperature for 6 h to prepare the microcapsule-filled sodium alginate-based hydrogel.
Example 2
Step one, preparing a zein-based microcapsule:
weighing 0.2 part by mass of zein, adding the zein into 10.0 parts by mass of 85% ethanol water solution, adding 0.05 part by mass of folium artemisiae argyi essence and 0.06 part by mass of pluronic F127, and stirring for 2 hours to prepare a mixed solution; and then adding 22 parts by mass of ultrapure water into the mixed system, and removing ethanol in the mixed system through rotary evaporation to obtain the zein-based microcapsule emulsion.
Step two, preparing a sodium alginate solution:
weighing 0.5 part by mass of sodium alginate, adding into 50 parts by mass of water, and stirring for 6 hours at 48 ℃ in a water bath until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
adding 0.5 mass part of zein microcapsule emulsion into 1.0 mass part of sodium alginate solution, adjusting the pH of the system to 6.5 by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and adding CaCl2The solution is a cross-linking agent, calcium carbonate is weighed according to the molar ratio of calcium ions to sodium alginate carboxyl of 0.3 and is added into the sodium alginate solution, the mixture is stirred at a low speed for 0.5 h and then is kept stand and aged at room temperature for 6 h to prepare the microcapsule-filled sodium alginate-based hydrogel.
Example 3
Step one, preparing a zein-based microcapsule:
weighing 0.2 part by mass of zein, adding the zein into 10.0 parts by mass of 85% ethanol water solution, adding 0.10 part by mass of eugenol and 0.10 part by mass of pluronic F127, and stirring for 2 hours to prepare a mixed solution; and then adding 25 parts by mass of ultrapure water into the mixed system, and removing ethanol in the mixed system through rotary evaporation to obtain the zein-based microcapsule emulsion.
Step two, preparing a sodium alginate solution:
weighing 1.0 part by mass of sodium alginate, adding into 50 parts by mass of water, and stirring for 6 hours at 56 ℃ in a water bath until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
adding 1.0 mass part of zein microcapsule emulsion into 1.0 mass part of sodium alginate solution, adjusting pH of the system to 6.5 with 0.1 mol/L NaOH and 0.1 mol/L HCl, and adding CaCl2The solution is a cross-linking agent, calcium carbonate is weighed according to the molar ratio of calcium ions to sodium alginate carboxyl of 0.5 and added into the sodium alginate solution, the mixture is stirred at a low speed for 0.5 h and then is kept stand and aged at room temperature for 6 h to prepare the microcapsule-filled sodium alginate-based hydrogel.
Example 4
Step one, preparing a zein-based microcapsule:
weighing 0.2 part by mass of zein, adding the zein into 10.0 parts by mass of 85% ethanol aqueous solution, adding 0.14 part by mass of vanillin and 0.15 part by mass of polyoxyethylene lauryl ether, and stirring for 2 hours to prepare a mixed solution; and then 27 parts by mass of ultrapure water is added into the mixed system, and the ethanol in the mixed system is removed by rotary evaporation to prepare the zein-based microcapsule emulsion.
Step two, preparing a sodium alginate solution:
weighing 1.5 parts by mass of sodium alginate, adding into 50 parts by mass of water, and stirring for 6 hours at 64 ℃ in a water bath until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
adding 1.5 parts by mass of zein microcapsule emulsion into 1.0 part by mass of sodium alginate solution, adjusting the pH of the system to 6.5 by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and adding CaCl2The solution is a cross-linking agent, calcium carbonate is weighed according to the molar ratio of calcium ions to sodium alginate carboxyl of 0.7 and added into the sodium alginate solution, the mixture is stirred at a low speed for 0.5 h and then is kept stand and aged at room temperature for 6 h to prepare the microcapsule-filled sodium alginate-based hydrogel.
Example 5
Step one, preparing a zein-based microcapsule:
weighing 0.2 part by mass of zein, adding the zein into 10.0 parts by mass of 85% ethanol aqueous solution, adding 0.20 part by mass of curcumin and 0.20 part by mass of polyoxyethylene ether, and stirring for 2 hours to prepare a mixed solution; and then adding 30 parts by mass of ultrapure water into the mixed system, and removing ethanol in the mixed system through rotary evaporation to obtain the zein-based microcapsule emulsion.
Step two, preparing a sodium alginate solution:
weighing 2.0 parts by mass of sodium alginate, adding into 50 parts by mass of water, and stirring for 6 hours at 75 ℃ in a water bath until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
adding 2.0 parts by mass of zein microcapsule emulsion into 1.0 part by mass of sodium alginate solution, adjusting the pH of the system to 6.5 by using 0.1 mol/L NaOH and 0.1 mol/L HCl, and adding CaCl2The solution is a cross-linking agent, calcium carbonate is weighed according to the molar ratio of calcium ions to sodium alginate carboxyl of 0.9 and added into the sodium alginate solution, the mixture is stirred at a low speed for 0.5 h and then is kept stand and aged at room temperature for 6 h to prepare the microcapsule-filled sodium alginate-based hydrogel.
FIG. 1 is a photograph of a microcapsule-filled sodium alginate-based hydrogel obtained in example 2. The obtained material was observed to be in the form of gel.
FIG. 2 is a release profile of the microcapsule-filled sodium alginate-based hydrogel prepared in example 2. It can be seen from the observation that when the prepared composite material is put into ethanol aqueous solution (50%, v/v), the cumulative release rate of the encapsulated substance in 120 h period is about 81%, and better controlled release is presented.
FIG. 3 is an SEM photograph of a microcapsule-filled sodium alginate-based hydrogel prepared in example 2. The observation shows that the prepared composite material has more pore structures, and a plurality of microsphere particles can be observed to be uniformly adsorbed on the surface and the inner gaps of the material. The result shows that the sodium alginate-based hydrogel and the zein microcapsule can be effectively combined by regulating and controlling the reaction conditions, and the scheme is proved to be effective.
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 (6)

1. A preparation method of microcapsule-filled sodium alginate-based hydrogel is characterized by comprising the following steps:
dissolving zein with an ethanol solution to obtain a dissolved solution, adding a lipophilic functional substance and a surfactant into the zein solution, and preparing a zein-based microcapsule emulsion by an anti-solvent method; simultaneously, adding sodium alginate into water, heating and stirring under the condition of water bath to obtain sodium alginate solution, adjusting the pH of the system, and then sequentially adding zein-based microcapsule emulsion and CaCl into the system2And stirring the solution, and then aging for a period of time to obtain the microcapsule-filled sodium alginate-based hydrogel.
2. The method for preparing the microcapsule-filled sodium alginate-based hydrogel according to claim 1, wherein the method comprises the following steps:
the method specifically comprises the following steps of:
step one, preparing a zein microcapsule:
weighing 0.05-0.2 part of zein, adding the zein into 5-15 parts of 85% ethanol water solution, adding 0.01-0.20 part of hydrophobic functional substance and 0.01-0.20 part of surfactant, and stirring for 0.5-2 h to prepare a mixed solution; adding the mixed solution into 20-70 parts of ultrapure water, emulsifying, and performing rotary evaporation to remove ethanol in the mixed system to obtain zein microcapsule emulsion;
step two, preparing a sodium alginate solution:
weighing 0.05-2.0 parts of sodium alginate, adding into 10-100 parts of pure water, and stirring for 1-6 h at 40-75 ℃ in a water bath until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
step three, preparing the microcapsule-filled sodium alginate-based hydrogel:
taking 0.1-2.0 parts ofAdding the zein microcapsule emulsion prepared in the first step into 1.0 part of the sodium alginate solution prepared in the second step, adjusting the pH of the system, and adding CaCl2And weighing calcium carbonate as a cross-linking agent, adding the calcium carbonate into a sodium alginate solution, wherein the molar ratio of calcium ions to sodium alginate carboxyl is 0.1-1.0, stirring at a low speed for 0.5 h, standing and aging at room temperature for 2-12 h, and thus obtaining the microcapsule-filled sodium alginate-based hydrogel.
3. The method for preparing the microcapsule-filled sodium alginate-based hydrogel according to claim 2, wherein the method comprises the following steps:
in the first step, the hydrophobic functional substance is one or a mixture of alkanes, oil or fat.
4. The method for preparing the microcapsule-filled sodium alginate-based hydrogel according to claim 3, wherein the method comprises the following steps:
in the first step, the surfactant is a nonionic surfactant or a mixture of a plurality of nonionic surfactants.
5. The method for preparing the microcapsule-filled sodium alginate-based hydrogel according to claim 3, wherein the method comprises the following steps:
in the third step, the pH value of the system is adjusted to 3.0-10.0.
6. A microcapsule-filled sodium alginate-based hydrogel obtained by the method of claims 1 to 5.
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CN112931699A (en) * 2021-03-29 2021-06-11 江苏省农业科学院 Rumen-bypass amino acid and preparation method thereof
CN113912868A (en) * 2021-10-18 2022-01-11 香港大学深圳医院 Hydrogel with temperature response characteristic and preparation method thereof
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
CN114409933A (en) * 2021-12-08 2022-04-29 大连民族大学 Preparation and application of novel hydrophobic shell-core structure gel particles

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111184870A (en) * 2019-10-23 2020-05-22 浙江海洋大学 Preparation method of astaxanthin transporter with gastric juice digestion resistance
CN112931699A (en) * 2021-03-29 2021-06-11 江苏省农业科学院 Rumen-bypass amino acid and preparation method thereof
CN112931699B (en) * 2021-03-29 2023-08-04 江苏省农业科学院 Rumen bypass amino acid and preparation method thereof
CN113912868A (en) * 2021-10-18 2022-01-11 香港大学深圳医院 Hydrogel with temperature response characteristic and preparation method thereof
CN113912868B (en) * 2021-10-18 2024-02-23 香港大学深圳医院 Hydrogel with temperature response characteristic and preparation method thereof
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
CN114409933A (en) * 2021-12-08 2022-04-29 大连民族大学 Preparation and application of novel hydrophobic shell-core structure gel particles

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