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

Abstract

The invention discloses a sustained-release sodium alginate/chitosan/zein composite material and a preparation method thereof. First, dissolve chitosan in deionized water; then dissolve zein, lipophilic functional substances and surfactants with ethanol solution to obtain a mixed solution of zein, and then use anti-solvent precipitation to prepare the zein base Microcapsule emulsion; add sodium alginate and hydrophilic substances into deionized water, and heat and stir in a water bath to obtain a mixed solution of sodium alginate, adjust the pH of the system, and add chitosan solution, zein microcapsules to it. The capsule emulsion and the divalent cation solution are aged to obtain a sustained-release sodium alginate/chitosan/zein composite material. The invention utilizes the antibacterial property of chitosan, the self-assembly property of zein and the gelatinization property of sodium alginate, and the prepared composite material has the properties of slow release and antibacterial.

Description

A slow-release sodium alginate/chitosan/zein composite material and its preparation preparation method

technical field

The invention belongs to the technical field of functional composite materials, in particular to a slow-release sodium alginate/chitosan/zein composite material and a preparation method thereof.

Background technique

my country consumes about 150 million tons of corn every year, of which about 840,000 tons of corn gluten meal are produced. Due to the high content of gliadin in corn gluten meal, its low water solubility and poor processing performance, the modification and utilization of zein (Zein) has high economic value and application significance. Zein is a polymer formed by agglomerating peptide chains with different molecular sizes, solubility and charge through disulfide bonds. It is a small and round particle with a diameter of 1-2 μm and an average molecular weight of 44 kDa. . As a recognized safe and valuable protein material, zein microcapsules can encapsulate a variety of lipophilic molecules for controlling the release of biologically active substances, and have a wide range of applications in food, medicine and chemical industries. research and application.

Chitosan, also known as deacetylated chitin, is obtained by deacetylation of chitin, which is widely present in nature. This natural polymer has been widely concerned for its excellent biocompatibility, blood compatibility, safety, and microbial degradability, and has made significant research progress in many fields such as food, chemical engineering, and biomedical engineering. Chitosan is easy to dissolve in weak acid solvents, and it is particularly worth noting that the dissolved solution contains amino groups (NH ²⁺ ), which inhibit bacteria by binding negative electrons. The antibacterial activity of chitosan makes it widely used in the fields of medicine, textile and food.

Sodium alginate is a by-product of the extraction of iodine and mannitol from kelp or Sargasso algae. Its molecule consists of β-D-mannuronic acid (β-D-mannuronic, M) and α-L-guluronic acid (α-L-guluronic, G) connected by (1→4) bonds, It is a natural polysaccharide with the stability, solubility, viscosity and safety required for pharmaceutical preparation excipients. Alginic acid has the characteristics of non-toxicity, odorless and high viscosity of aqueous solution, and can react with divalent metal cations rapidly to form a hydrogel by encapsulating water molecules in an ionic network structure. Therefore, with the help of sodium alginate, the aqueous solution of hydrophilic functional materials is converted into a hydrogel through physical cross-linking, which is expected to achieve sustained release.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a slow-release sodium alginate/chitosan/zein composite material and a preparation method thereof, which fully demonstrate the characteristics of three kinds of natural products, utilize the antibacterial properties of chitosan, The self-assembly properties of zein and the gelatinization properties of sodium alginate make the prepared composites have both antibacterial and sustained release functions.

In order to achieve the above object, technical scheme of the present invention is as follows:

A preparation method of slow-release sodium alginate/chitosan/zein composite material:

First, dissolve chitosan in deionized water; then dissolve zein, lipophilic functional substances and surfactants with ethanol solution to obtain a mixed solution of zein, and then use antisolvent precipitation to prepare zein base microcapsule emulsion; then, add sodium alginate and hydrophilic substances into deionized water, and heat and stir in a water bath to obtain a mixed solution of sodium alginate, adjust the pH of the system, and then add chitosan solution, The zein microcapsule emulsion and the divalent cation solution are aged to obtain a sustained-release sodium alginate/chitosan/zein composite material.

Specifically include the following steps, and the following parts are all parts by mass:

Step 1. Prepare sodium alginate solution:

Weigh 10.0-100.0 parts of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 0.2-4.0 parts of sodium alginate and add it to deionized water, then add it to 35-75 Stir in a water bath for 0.5-6 h to achieve complete dissolution, and obtain a sodium alginate solution;

Step 2, prepare chitosan solution:

Weigh 10.0-100.0 parts of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 1.0-10.0 parts of chitosan and 0.01-0.5 parts of hydrophilic functional substances, respectively. It is dissolved in deionized water, and then stirred for 2-6 h in a water bath at 35-75 °C to achieve complete dissolution to obtain a chitosan solution;

Step 3, prepare zein microcapsule emulsion:

Weigh 0.1-2.0 parts of zein into 10-100 parts of 85% ethanol aqueous solution, then add 0.1-1.5 parts of lipophilic functional substances and 0.1-1.5 parts of surfactant, and stir for 2 h. A mixed solution was obtained; then 200.0-700.0 parts of deionized water was added to the mixed system, and then the ethanol in the mixed system was removed by rotary evaporation, and the zein microcapsule emulsion was prepared by open stirring at room temperature for 2-6 h;

Step 4. Preparation of slow-release sodium alginate/chitosan/zein composite material:

Weigh 30.0-50.0 parts of the chitosan solution prepared in step 2 and 0.2-1.5 parts of the zein microcapsule emulsion prepared in step 3, respectively, and add them to 10 parts of the mixed solution of sodium alginate prepared in step 1. The pH of the system was adjusted with 0.1 mol/L NaOH and 0.1 mol/L HCl, and then an aqueous solution of divalent cations was used as a cross-linking agent and added to the sodium alginate solution. The ratio is 0.05-0.8:1, and after stirring at a medium speed for 0.5-2 h, the sustained-release sodium alginate/chitosan/zein composite material is prepared after standing at room temperature for overnight aging.

In step 2, the hydrophilic functional substance is one or more hydrophilic substances containing hydrophilic polar groups.

In step 3, the lipophilic functional substance is a mixture of one or more of alkane, oil or fat.

In step 3, the surfactant is a kind of nonionic surfactant or a mixture of multiple nonionic surfactants.

In step 4, the divalent cation is a divalent cation that can undergo ion exchange reaction with Na+ in sodium alginate.

A slow-release sodium alginate/chitosan/zein composite material prepared by the above preparation method.

Compared with the prior art, the beneficial effects of the present invention are:

(1) The invention combines anti-solvent precipitation, physical cross-linking and physical blending to prepare sustained-release sodium alginate/chitosan/zein composite material, the preparation conditions are simple, and the test method is easy to implement. Wide range of material sources, green and non-toxic, good biocompatibility and degradability;

(2) The slow-release sodium alginate/chitosan/zein composite material prepared by the present invention has the functions of inhibiting bacterial activity and controlling the release of functional substances, and has broad application prospects in the fields of biomedicine and food processing. .

Description of drawings

1 is a photo of the sustained-release sodium alginate/chitosan/zein composite material prepared in Example 3.

2 is a photo of the antibacterial of the sustained-release sodium alginate/chitosan/zein composite material prepared in Example 3.

FIG. 3 is a SEM image of the sustained-release sodium alginate/chitosan/zein composite material prepared in Example 3. FIG.

Detailed ways

The present invention will be described in further detail below with reference to specific examples, but the embodiments of the present invention include but are not limited to the scope represented by the following examples.

The invention mainly utilizes the good antibacterial activity and biocompatibility of chitosan, the unique solubility and good self-assembly of zein, the thermal irreversibility of sodium alginate-based hydrogel, mild reaction conditions and good drug absorption release and other properties, and finally a sustained-release sodium alginate/chitosan/zein composite material was prepared.

Example 1

Step 1. Prepare sodium alginate solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 0.2 parts by mass of sodium alginate and add it to deionized water, and then put it in a water bath at 35 °C. Stir for 6 h to achieve complete dissolution to obtain a sodium alginate solution.

Step 2, prepare chitosan solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 1.0 parts by mass of chitosan and 0.01 parts by mass of vanillin and dissolve them in deionized water. , and then stirred in a water bath at 35 °C for 6 h to achieve complete dissolution to obtain a chitosan solution.

Step 3, prepare zein microcapsule emulsion:

Weigh 2.0 parts by mass of zein and add it to 100.0 parts by mass of ethanol aqueous solution (85%, v/v), then add 0.1 parts by mass of Artemisia argyi essence and 0.1 parts by mass of Pluronic F127, and stir for 2 h. A mixed solution was obtained; then 200.0 parts by mass of deionized water was added to the mixed system, the ethanol in the mixed system was removed by rotary evaporation, and the zein microcapsule emulsion was obtained after open stirring at room temperature for 12 h.

Step 4. Preparation of slow-release sodium alginate/chitosan/zein composite material:

Weigh 40.0 parts by mass of chitosan solution and 1.0 parts by mass of zein microcapsule emulsion and add them to 10 parts by mass of sodium alginate mixed solution, then adjust with 0.1 mol/L NaOH and 0.1 mol/L HCl The pH of the system was then added to the sodium alginate solution with 0.1 mol/L CaCl ₂ aqueous solution as the cross-linking agent, according to the molar ratio of divalent calcium ions to sodium alginate carboxyl groups of 0.4, and stirred at medium speed for 0.5 h After 12 h at room temperature, the sustained-release sodium alginate/chitosan/zein composite material was prepared.

Example 2

Step 1. Prepare sodium alginate solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 0.5 parts by mass of sodium alginate and add it to deionized water, then place it in a water bath at 40 °C. Stir for 6 h to achieve complete dissolution to obtain a sodium alginate solution.

Step 2, prepare chitosan solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 2.0 parts by mass of chitosan and 0.05 parts by mass of strawberry essence and dissolve them in deionized water. , and then stirred for 6 h in a water bath at 40 °C to achieve complete dissolution, and a chitosan solution was obtained.

Step 3, prepare zein microcapsule emulsion:

Weigh 2.0 parts by mass of zein and add it to 100.0 parts by mass of ethanol aqueous solution (85%, v/v), then add 0.2 parts by mass of eugenol and 0.2 parts by mass of Tween-80, and stir for 2 h. A mixed solution was prepared; then 300.0 parts by mass of deionized water was added to the mixed system, ethanol in the mixed system was removed by rotary evaporation, and the zein microcapsule emulsion was prepared by open stirring at room temperature for 12 h.

Step 4. Preparation of slow-release sodium alginate/chitosan/zein composite material:

Weigh 40.0 parts by mass of chitosan solution and 1.0 parts by mass of zein microcapsule emulsion and add them to 10 parts by mass of sodium alginate mixed solution, then adjust with 0.1 mol/L NaOH and 0.1 mol/L HCl The pH of the system was then added to the sodium alginate solution with a 0.1 mol/L MgCl ₂ aqueous solution as the cross-linking agent, according to the ratio of the molar ratio of divalent magnesium ion to sodium alginate carboxyl group of 0.4, and after stirring at medium speed for 0.5 h , the sustained-release sodium alginate/chitosan/zein composite material was prepared after standing at room temperature for 12 h.

Example 3

Step 1. Prepare sodium alginate solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 1.0 parts by mass of sodium alginate and add it to deionized water, and then put it in a water bath at 45°C. Stir for 6 h to achieve complete dissolution to obtain a sodium alginate solution.

Step 2, prepare chitosan solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 3.0 parts by mass of chitosan and 0.1 parts by mass of vanillin and dissolve them in deionized water. , and then stirred for 6 h in a water bath at 45 °C to achieve complete dissolution, and a chitosan solution was obtained.

Step 3, prepare zein microcapsule emulsion:

Weigh 2.0 parts by mass of zein and add it to 100.0 parts by mass of ethanol aqueous solution (85%, v/v), then add 0.3 parts by mass of thymol and 0.3 parts by mass of Pluronic F127, and stir for 2 h. A mixed solution was obtained; then 400.0 parts by mass of deionized water was added to the mixed system, the ethanol in the mixed system was removed by rotary evaporation, and the zein microcapsule emulsion was obtained after open stirring at room temperature for 12 h.

Step 4. Preparation of slow-release sodium alginate/chitosan/zein composite material:

Weigh 40.0 parts by mass of chitosan solution and 1.0 parts by mass of zein microcapsule emulsion and add them to 10 parts by mass of sodium alginate mixed solution, then adjust with 0.1 mol/L NaOH and 0.1 mol/L HCl The pH of the system was then added to the sodium alginate solution with a 0.1 mol/L CaCl ₂ aqueous solution as a cross-linking agent according to the molar ratio of divalent calcium ions to sodium alginate carboxyl groups of 0.4, and after stirring at medium speed for 0.5 h , the sustained-release sodium alginate/chitosan/zein composite material was prepared after standing at room temperature for 12 h.

Example 4

Step 1. Prepare sodium alginate solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 1.5 parts by mass of sodium alginate and add it to deionized water, then place it in a water bath at 50 °C. Stir for 6 h to achieve complete dissolution to obtain a sodium alginate solution.

Step 2, prepare chitosan solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 4.0 parts by mass of chitosan and 0.15 parts by mass of rose essence and dissolve them in deionized water. , and then stirred for 6 h in a water bath at 50 °C to achieve complete dissolution to obtain a chitosan solution.

Step 3, prepare zein microcapsule emulsion:

Weigh 2.0 parts by mass of zein and add it to 100.0 parts by mass of ethanol aqueous solution (85%, v/v), then add 0.4 parts by mass of curcumin and 0.4 parts by mass of Tween 60, and stir for 2 h to prepare the solution. A mixed solution was obtained; then 500.0 parts by mass of deionized water was added to the mixed system, the ethanol in the mixed system was removed by rotary evaporation, and the zein microcapsule emulsion was obtained after open stirring at room temperature for 12 h.

Step 4. Preparation of slow-release sodium alginate/chitosan/zein composite material:

Weigh 40.0 parts by mass of chitosan solution and 1.0 parts by mass of zein microcapsule emulsion and add them to 10 parts by mass of sodium alginate mixed solution, then adjust with 0.1 mol/L NaOH and 0.1 mol/L HCl The pH of the system was then added to the sodium alginate solution with a 0.1 mol/L SrCl ₂ aqueous solution as a cross-linking agent according to the molar ratio of divalent strontium ions to sodium alginate carboxyl groups of 0.4, and after stirring at medium speed for 0.5 h , the sustained-release sodium alginate/chitosan/zein composite material was prepared after standing at room temperature for 12 h.

Example 5

Step 1. Prepare sodium alginate solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 2.0 parts by mass of sodium alginate and add it to deionized water, and then put it in a water bath at 55 °C. Stir for 6 h to achieve complete dissolution to obtain a sodium alginate solution.

Step 2, prepare chitosan solution:

Weigh 100.0 parts by mass of deionized water and adjust the pH with 0.1 mol/L NaOH and 0.1 mol/L HCl, then weigh 5.0 parts by mass of chitosan and 0.2 parts by mass of lemon essence and dissolve them in deionized water. , and then stirred for 6 h in a water bath at 55 °C to achieve complete dissolution, and a chitosan solution was obtained.

Step 3, prepare zein microcapsule emulsion:

Weigh 2.0 parts by mass of zein and add it to 100.0 parts by mass of ethanol aqueous solution (85%, v/v), then add 0.5 parts by mass of mugwort essence and 0.5 parts by mass of Tween 20, and stir for 2 h. A mixed solution was obtained; then 600.0 parts by mass of deionized water was added to the mixed system, the ethanol in the mixed system was removed by rotary evaporation, and the zein microcapsule emulsion was obtained after open stirring at room temperature for 12 h.

Step 4. Preparation of slow-release sodium alginate/chitosan/zein composite material:

Weigh 40.0 parts by mass of chitosan solution and 1.0 parts by mass of zein microcapsule emulsion and add them to 10 parts by mass of sodium alginate mixed solution, then adjust with 0.1 mol/L NaOH and 0.1 mol/L HCl The pH of the system was then added to the sodium alginate solution with a 0.1 mol/L MgCl ₂ aqueous solution as a cross-linking agent, according to the molar ratio of divalent magnesium ions to sodium alginate carboxyl groups of 0.4, and after stirring at medium speed for 0.5 h , the sustained-release sodium alginate/chitosan/zein composite material was prepared after standing at room temperature for 12 h.

1 is a photo of the sustained-release sodium alginate/chitosan/zein composite material prepared in Example 3. It can be seen from the observation that the composite material has a gel structure and has good absorbency and stability.

2 is a photo of the antibacterial of the filter paper after the slow-release sodium alginate/chitosan/zein composite material prepared in Example 3 was treated. It can be seen from the observation that the fabric has obvious inhibitory effect on Staphylococcus aureus after being immersed in the composite material.

FIG. 3 is a SEM image of the sustained-release sodium alginate/chitosan/zein composite material prepared in Example 3. FIG. Through observation, it can be seen that the dried composite material has obvious pore structure; at the same time, many spherical structures are evenly distributed in the material, which may be due to the combination of zein microcapsules with chitosan and sodium alginate and other substances to form Hydrogel-microcapsule composite structure. The results show that this scheme is effective.

The content of the present invention is not limited to those listed in the embodiments, and any equivalent transformations to the technical solutions of the present invention that are taken by those related in the art by reading the description of the present invention are covered by the claims of the present 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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