Preparation method of mussel-imitated underwater high-viscosity hydrogel
阅读说明：本技术 一种仿贻贝的水下高粘性水凝胶的制备方法 (Preparation method of mussel-imitated underwater high-viscosity hydrogel ) 是由 张天柱 付一夫 陆祖宏 何春鹏 于 2019-10-31 设计创作，主要内容包括：本发明公开了一种仿贻贝的水下高粘性水凝胶的制备方法,包括以下步骤：(1)将壳聚糖溶解于乙酸中,制成壳聚糖乙酸溶液；(2)向步骤(1)制得的溶液中加入3,4-二羟基苯乙酸、EDC、NHS,调节pH后反应一段时间；(3)将步骤(2)得到的溶液在pH=5的水中透析,取截留液冷冻干燥；(4)将步骤(3)得到的样品制备成溶液；(5)将葡聚糖溶于水,加入氧化剂,避光反应一段时间后加入乙二醇终止反应；(6)将步骤(5)得到的溶液在水中透析,取截留液冷冻干燥；(7)将步骤(6)得到样品制备成溶液；(8)将步骤(4)和步骤(7)得到的溶液混合,制得水凝胶。本发明提供的制备方法,制备的水凝胶可用作水下粘合剂。(The invention discloses a preparation method of mussel-imitated underwater high-viscosity hydrogel, which comprises the following steps: (1) dissolving chitosan in acetic acid to prepare a chitosan acetic acid solution; (2) adding 3, 4-dihydroxy phenylacetic acid, EDC and NHS into the solution prepared in the step (1), adjusting the pH value and reacting for a period of time; (3) dialyzing the solution obtained in the step (2) in water with pH =5, and taking the trapped fluid for freeze drying; (4) preparing the sample obtained in the step (3) into a solution; (5) dissolving glucan in water, adding an oxidant, reacting for a period of time in a dark place, and adding ethylene glycol to terminate the reaction; (6) dialyzing the solution obtained in the step (5) in water, and taking trapped fluid for freeze drying; (7) preparing the sample obtained in the step (6) into a solution; (8) and (4) mixing the solutions obtained in the step (4) and the step (7) to prepare the hydrogel. According to the preparation method provided by the invention, the prepared hydrogel can be used as an underwater adhesive.)
1. A preparation method of mussel-imitated underwater high-viscosity hydrogel is characterized by comprising the following steps:
1) dissolving chitosan in acetic acid to prepare a chitosan acetic acid solution;
2) adding 3, 4-dihydroxy phenylacetic acid, 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide into the solution prepared in the step 1), and adjusting the pH value to react;
3) putting the solution obtained in the step 2) into a dialysis belt, dialyzing in water with pH of 5, taking trapped fluid, and freeze-drying to obtain chitosan containing catechol grafts;
4) adding water into the chitosan containing catechol grafts obtained in the step 3) to prepare a chitosan solution containing catechol grafts;
5) dissolving dextran in water to obtain dextran water solution;
6) adding an oxidant into the solution prepared in the step 5), carrying out a light-resistant reaction, adding ethylene glycol, and terminating the reaction;
7) putting the solution obtained in the step 6) into a dialysis belt, dialyzing in water, taking trapped fluid, and freeze-drying to obtain oxidized dextran;
8) adding water into the oxidized glucan obtained in the step 7) to prepare an oxidized glucan solution;
9) mixing the catechol-grafted chitosan solution prepared in the step 4) with the oxidized glucan solution prepared in the step 8) to prepare the hydrogel.
2. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: the volume fraction of the acetic acid solution in the step 1) is 2%; the mass of the chitosan in the step 1) is 2% of the volume of the acetic acid solution.
3. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: the mass of the 3, 4-dihydroxyphenylacetic acid in the step 2) is equal to the mass of the chitosan, the mass of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is equal to the mass of the chitosan, and the mass of the N-hydroxysuccinimide is equal to the mass of the chitosan.
4. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: in the step 2), the pH value is adjusted to 5, and the reaction is carried out for 10 hours.
5. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: the molecular cut-off of the dialysis band in the step 3) and the step 7) is 3500-14000 KDa.
6. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: in the step 6), the oxidant is sodium periodate, the reaction time is 4-12 hours in a dark place, and the dosage of the ethylene glycol is 1-2 mL.
7. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: the mass of the oxidant in the step 6) is 60% -100% of the mass of the glucan substance in the step 5).
8. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: the dialysis time in water in the step 3) and the step 7) is 2-3 days, and the freeze-drying time is 24-48 hours.
9. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: the mass of the chitosan containing catechol grafts in the step 4) is 2-2.5% of the volume of water, and the mass of the oxidized glucan in the step 8) is 5-10% of the volume of water.
10. The method for preparing a mussel-like underwater highly adhesive hydrogel according to claim 1, wherein: in the step 9), the volume ratio of the chitosan solution containing catechol grafts to the oxidized glucan solution is 1: 1.
Technical Field
The invention relates to the field of hydrogel preparation, in particular to a preparation method of mussel-imitated underwater high-viscosity hydrogel.
Background
With the application and development of medical hydrogel, the development of moisture-resistant adhesives is a hot spot of recent research. Mussels exhibit strong wet adhesion resistance despite the constant waves on the coast, where mussel adhesive proteins play a key role in this wet adhesion. Inspired by the abundance of catechol groups in mussel adhesive proteins, the wet adhesion of hydrogels was increased by grafting catechol groups. The polysaccharide-based hydrogel has good biocompatibility and can be widely applied to various biomedical environments.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a preparation method of mussel-imitated underwater high-viscosity hydrogel, which aims to solve the problems of adhesion in a wet environment, poor biocompatibility and the like.
The technical scheme is as follows: in order to solve the problems, the invention provides a preparation method of a mussel-imitated underwater high-viscosity hydrogel, which comprises the following steps:
1) dissolving chitosan in acetic acid to prepare a chitosan acetic acid solution;
2) adding 3, 4-dihydroxy phenylacetic acid, 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide into the solution prepared in the step 1), and adjusting the pH value to react;
3) putting the solution obtained in the step 2) into a dialysis belt, dialyzing in water with pH of 5, taking trapped fluid, and freeze-drying to obtain chitosan containing catechol grafts;
4) adding water into the chitosan containing catechol grafts obtained in the step 3) to prepare a chitosan solution containing catechol grafts;
5) dissolving dextran in water to obtain dextran water solution;
6) adding an oxidant into the solution prepared in the step 5), carrying out a light-resistant reaction, adding ethylene glycol, and terminating the reaction;
7) putting the solution obtained in the step 6) into a dialysis belt, dialyzing in water, taking trapped fluid, and freeze-drying to obtain oxidized dextran;
8) adding water into the oxidized glucan obtained in the step 7) to prepare an oxidized glucan solution;
9) mixing the catechol-grafted chitosan solution prepared in the step 4) with the oxidized glucan solution prepared in the step 8) to prepare the hydrogel.
Preferably, the volume fraction of the acetic acid solution in the step 1) is 2%; the mass of the chitosan in the step 1) is 2% of the volume of the acetic acid solution.
Preferably, in the step 2), the mass of the 3, 4-dihydroxyphenylacetic acid is equal to the mass of the chitosan, the mass of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is equal to the mass of the chitosan, and the mass of the N-hydroxysuccinimide is equal to the mass of the chitosan.
Preferably, the pH is adjusted to 5 in the step 2), and the reaction is carried out for 10 hours.
Preferably, the molecular cut-off of the dialysis band in the step 3) and the step 7) is 3500-14000 KDa.
Preferably, the oxidizing agent in the step 6) is sodium periodate, the reaction time is 4 to 12 hours in a dark place, and the dosage of the ethylene glycol is 1mL to 2 mL.
Preferably, the mass of the oxidant in the step 6) is 60% -100% of the amount of the glucan material in the step 5).
Preferably, the dialysis time in water in the step 3) and the step 7) is 2-3 days, and the freeze-drying time is 24-48 hours.
Preferably, the mass of the chitosan containing catechol grafts in the step 4) is 2-2.5% of the volume of water, and the mass of the oxidized glucan in the step 8) is 5-10% of the volume of water.
Preferably, in the step 9), the volume ratio of the chitosan solution containing catechol grafts to the oxidized dextran solution is 1: 1.
Has the advantages that: compared with the prior art, the hydrogel prepared by the method has the advantages of simple preparation method, obvious underwater adhesion effect and good biocompatibility, and can be widely applied to various fields. Based on Schiff base reaction of amino and aldehyde groups, catechol groups are grafted to chitosan chains, and then the gel is prepared by reaction with oxidized dextran. The glucan and the chitosan are common mucopolysaccharide, have good biocompatibility and can be applied to biomedical materials; meanwhile, the grafting of the catechol group can greatly improve the adhesion effect of the hydrogel under water, and is a new idea for increasing the adhesion under water.
Drawings
FIG. 1 is a graph of infrared data for a mussel-like underwater highly viscous polysaccharide hydrogel obtained in example 1;
FIG. 2 is a graph showing the wet adhesion properties of the hydrogels obtained in examples 1 to 3.
Detailed Description
The present invention is further illustrated by the following specific examples.