CN111363172A - Preparation method of self-healing zwitterionic hydrogel - Google Patents

Preparation method of self-healing zwitterionic hydrogel Download PDF

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CN111363172A
CN111363172A CN202010262156.2A CN202010262156A CN111363172A CN 111363172 A CN111363172 A CN 111363172A CN 202010262156 A CN202010262156 A CN 202010262156A CN 111363172 A CN111363172 A CN 111363172A
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hydrogel
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彭新艳
刘云鸿
刘云晖
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    • 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
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • C08G73/024Polyamines containing oxygen in the form of ether bonds in the main chain
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • C08G73/0246Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/0253Polyamines containing sulfur in the main chain
    • CCHEMISTRY; METALLURGY
    • 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
    • C08J2379/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02Polyamines

Abstract

The invention discloses a preparation method of self-healing zwitterionic hydrogel. According to the invention, the N, N '-carbonyl diimidazole, N' -thiocarbonyl diimidazole and reactants of a zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine and the like are reacted to prepare the hydrogel material containing a zwitterionic group, a urea group and/or a thiourea group, and the hydrogel material has a good self-repairing function. The self-healing zwitterionic hydrogel has the advantages of simple preparation method, low preparation cost and good biocompatibility of the prepared hydrogel.

Description

Preparation method of self-healing zwitterionic hydrogel
Technical Field
The invention relates to the field of hydrogel preparation, in particular to a preparation method of self-healing zwitterionic hydrogel.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The hydrogel material has important potential application value in the field of flexible electronics, wearable equipment, wound healing and cartilage repair. For example, the molecular chain segment of the zwitterionic hydrogel material has positive and negative charges, so that the zwitterionic hydrogel material can be combined with water molecules through ionic solvation, a large number of water molecules can be bound, the water molecules are retained in the material structure, and a good wet environment can be maintained; meanwhile, a hydration layer formed on the surface of the zwitterionic polymer material has strong nonspecific protein adsorption resistance and biocompatibility, so that protein adhesion can be effectively resisted, foreign body rejection and bacterial adhesion can be resisted, and good biocompatibility is shown.
However, the existing zwitterionic hydrogel still has some problems, such as easy breakage in deformation, unrecoverable damage and short service life; on the other hand, most of the zwitterionic hydrogels adopt acrylic monomers or acrylamide monomers containing zwitterionic functional groups as polymerization monomers, ester bonds or amide bonds of the monomers are easy to hydrolyze under alkaline conditions, so that the zwitterionic hydrogels are not alkali-resistant and damaged, and the application of the zwitterionic hydrogels is limited. Development of hydrogels having self-healing function and resistance to degradation has become a new research direction. However, the hydrogel having self-repairing properties has some problems that it is difficult to ignore, such as poor self-repairing properties, a preparation method that is not simple enough, and a relatively high preparation cost.
Disclosure of Invention
The invention aims to: provides a preparation method of self-healing zwitterionic hydrogel. The zwitterionic hydrogel has a good self-repairing healing function, the preparation method is simple and convenient, the preparation cost is low, and the prepared hydrogel has good biocompatibility and a good alkali-resistant function.
The object of the invention is achieved by:
a preparation method of self-healing zwitterionic hydrogel comprises the following steps:
(A) mixing a diimidazole compound, a zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine, a thickening agent and water to obtain a hydrogel pre-reaction liquid;
the number average molecular weight of the amino-terminated polyethylene glycol is 200-5000 g/mol;
the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole;
the thickening agent is at least one of hydroxyethyl cellulose, sodium carboxymethylcellulose, laponite, lithium magnesium silicate, magnesium aluminum silicate and polyacrylamide;
the zwitterionic polyamine compound is at least one of the substances shown in the following structural formula:
Figure 100002_DEST_PATH_IMAGE002
Figure 100002_DEST_PATH_IMAGE004
the polyamine is at least one of the substances shown in the following structural formula:
Figure 100002_DEST_PATH_IMAGE006
Figure 100002_DEST_PATH_IMAGE008
Figure 100002_DEST_PATH_IMAGE010
wherein m is 1-200; n is 0 to 5; t is 1-5; k is 1-16;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 2-48 h at 20-60 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Further, in the step (a), the mass ratio of the zwitterionic polyamine compound, the diimidazole compound, the amino-terminated polyethylene glycol, the polyamine, the thickener and the water is 1: (0.01-10): (0-100): (0-10): (0-10): (1-1000).
The amphoteric ion hydrogel has a self-repairing function, and the preparation method comprises the following steps:
the reaction conditions of reactants such as N, N' -thiocarbonyl diimidazole, zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine and the like are controlled, and a thiourea-containing group can be introduced into the system as shown in the following;
Figure DEST_PATH_IMAGE012
wherein:
Figure DEST_PATH_IMAGE014
represents a zwitterionic polyamine compound, an amino-terminated polyethylene glycol, a polyamine, etc.
The reaction conditions of reactants such as N, N' -carbonyl diimidazole, zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine and the like are controlled, and a thiourea-containing group can be introduced into the system as shown in the following;
Figure DEST_PATH_IMAGE016
wherein:
Figure DEST_PATH_IMAGE014A
represents a zwitterionic polyamine compound, an amino-terminated polyethylene glycol, a polyamine, etc.
The reaction conditions of reactants of N, N '-carbonyl diimidazole, N' -thiocarbonyl diimidazole, a zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine and the like are controlled, and urea-containing groups and thiourea groups can be introduced into a system at the same time, as shown in the specification;
Figure DEST_PATH_IMAGE018
wherein:
Figure DEST_PATH_IMAGE014AA
represents a zwitterionic polyamine compound, an amino-terminated polyethylene glycol, a polyamine, etc.
The preparation method comprises the steps of mixing reactants such as a diimidazole compound, a zwitterionic polyamine compound, amino-terminated polyethylene glycol and polyamine for reaction to obtain a thiourea group and urea group-containing hydrogel material, introducing hydrogen bond groups such as thiourea group and urea group into a hydrogel polymer chain segment, and realizing self-repair of the material by means of breakage and recombination of hydrogen bonds in molecules or between molecules, so that the zwitterionic hydrogel material has a good self-repairing function. The principle of hydrogen bond action inside the zwitterionic hydrogel material containing hydrogen bond groups such as thiourea group and urea group is as follows:
Figure DEST_PATH_IMAGE020
Figure DEST_PATH_IMAGE022
Figure DEST_PATH_IMAGE024
meanwhile, the zwitterion structure in the chemical structure of the prepared zwitterion hydrogel contains a positive ion group and a negative ion group, and the self-repairing capability of the hydrogel material is further enhanced by the charge acting force between zwitterions, such as electrostatic action, so that the hydrogel material is endowed with a better self-repairing function.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the N, N '-carbonyl diimidazole, N' -thiocarbonyl diimidazole and reactants of a zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine and the like are reacted to prepare the hydrogel material containing a zwitterionic group, a urea group and/or a thiourea group, and the hydrogel material has a good self-repairing function.
2. The self-healing zwitterionic hydrogel has the advantages of simple preparation method and low preparation cost, and the prepared hydrogel has good biocompatibility and better alkali resistance.
Drawings
Fig. 1 is a self-healing process diagram of the self-healing zwitterionic hydrogel of example 1 of the present invention.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
(A) Mixing 20g of N, N' -thiocarbonyldiimidazole, 10g of a zwitterionic polyamine compound, 40g of amino-terminated polyethylene glycol (average molecular weight 800 g/mol), 10g of 1, 2-bis (2-aminoethoxy) ethane, 2g of hydroxyethyl cellulose and 3000g of water to obtain a hydrogel pre-reaction liquid;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 28h at 30 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Wherein the structural formula of the zwitterionic polyamine compound is as follows:
Figure DEST_PATH_IMAGE025
the resulting self-healing zwitterionic hydrogel material was disconnected and re-contacted as shown in figure 1, and the hydrogel material healed within 2 minutes and allowed to stretch. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The prepared zwitter-ion hydrogel material is soaked in an alkaline solution with the pH value of 14 for 48 hours, and the degradation of the hydrogel material is not found; the treated hydrogel material is extracted and leached by water, and still can detect the zwitter-ionic group. It can be seen that the hydrogel material maintains good alkali resistance.
The biocompatibility of the hydrogel prepared in the examples is evaluated through protein adsorption, cytotoxicity, antibacterial adhesion and the like. And (3) evaluating the protein adsorption resistance of the prepared zwitter-ion hydrogel material by adopting a static protein adsorption experiment, selecting bovine serum albumin (BSA, 5mg/ml), and calculating the adsorption quantity per unit area of the sample and the protein adsorption resistance. As a result, it was found that the hydrogel of the present invention had a protein adsorption amount of 0.02. mu.g/mm2Significantly lower than the adsorption capacity of the glass control (1.2. mu.g/mm)2). According to the requirements of ISO 10993-52009 on cytotoxicity, the hydrogel is evaluated by the CCK-8 method in vitro, and the hydrogel disclosed by the invention is of a toxicity grade of 1 and has no cytotoxicity. In-vitro bacterial adhesion evaluation was performed to evaluate the anti-bacterial adhesion ability of the prepared zwitterionic hydrogel material, and the hydrogel material was cultured in bacterial suspension for 4 hours using Escherichia coli and Staphylococcus aureus as test bacteria, and as a result, it was found that the amount of bacterial adhesion on the surface of the hydrogel of this example was extremely large compared to that of the blank glass sampleAnd the number of bacteria is reduced to 1% of that on the surface of the blank glass reference sample, and therefore, the hydrogel material of the embodiment has a better antibacterial adhesion function.
Example 2
(A) 50g of N, N' -thiocarbonyldiimidazole, 10g of a zwitterionic polyamine compound, 100g of amino-terminated polyethylene glycol (average molecular weight 1000 g/mol), 30g of triethylene glycol bis (2-aminoethyl) ether, 5g of polyacrylamide and 9000g of water were mixed to obtain a hydrogel pre-reaction solution;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 18h at 40 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Wherein the structural formula of the zwitterionic polyamine compound is as follows:
Figure DEST_PATH_IMAGE025A
the obtained self-healing zwitterionic hydrogel material is disconnected and contacted again, and the hydrogel material can heal and repair within 4 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The prepared zwitter-ion hydrogel material is soaked in an alkaline solution with the pH value of 14 for 48 hours, and the degradation of the hydrogel material is not found; the treated hydrogel material is extracted and leached by water, and still can detect the zwitter-ionic group. It can be seen that the hydrogel material maintains good alkali resistance.
The biocompatibility of the hydrogel prepared in the examples is evaluated through protein adsorption, cytotoxicity, antibacterial adhesion and the like. And (3) evaluating the protein adsorption resistance of the prepared zwitter-ion hydrogel material by adopting a static protein adsorption experiment, selecting bovine serum albumin (BSA, 5mg/ml), and calculating the adsorption quantity per unit area of the sample and the protein adsorption resistance. As a result, it was found that the hydrogel of the present invention had a protein adsorption amount of 0.03. mu.g/mm2Significantly lower than the adsorption capacity of the glass control (1.2. mu.g/mm)2). The invention is based on the requirements of ISO 10993-52009 on cytotoxicityThe hydrogel was evaluated for cytotoxicity in vitro using the CCK-8 method. As a result, the hydrogel of this example was found to have a toxicity rating of 1 and no cytotoxicity. The antibacterial adhesion ability of the prepared zwitterionic hydrogel material was evaluated by in vitro bacterial adhesion. When the hydrogel material was cultured in a bacterial suspension for 4 hours using Escherichia coli and Staphylococcus aureus as test bacteria, it was found that the amount of adhered bacteria on the surface of the hydrogel of this example was extremely small compared to that of the blank glass sample, and the amount of bacteria was reduced to 1% of that on the surface of the blank glass sample. It can be seen that the hydrogel material of this example exhibits a better anti-bacterial adhesion function.
Example 3
(A) Mixing 10g of N, N' -thiocarbonyldiimidazole, 10g of a zwitterionic polyamine compound, 1g of amino-terminated polyethylene glycol (average molecular weight 2000 g/mol), 1g of ethylene glycol mono (2-aminoethyl) ether, 0.6g of lithium magnesium silicate and 1000g of water to obtain a hydrogel pre-reaction solution;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 12h at 30 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Wherein the structural formula of the zwitterionic polyamine compound is as follows:
Figure DEST_PATH_IMAGE025AA
the obtained self-healing zwitterionic hydrogel material is disconnected and contacted again, and the hydrogel material can heal and repair within 7 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The prepared zwitter-ion hydrogel material is soaked in an alkaline solution with the pH value of 14 for 48 hours, and the degradation of the hydrogel material is not found; the treated hydrogel material is extracted and leached by water, and still can detect the zwitter-ionic group. It can be seen that the hydrogel material maintains good alkali resistance.
Evaluation of hydrogel prepared in examples by protein adsorption, cytotoxicity and anti-bacterial adhesionBiocompatibility. And evaluating the protein adsorption resistance of the prepared zwitter-ion hydrogel material by adopting a static protein adsorption experiment. Bovine serum albumin (BSA, 5mg/ml) is selected, and the adsorption quantity per unit area and the anti-protein adsorption capacity of the sample are calculated. As a result, it was found that the hydrogel of the present invention had a protein adsorption amount of 0.1. mu.g/mm2Significantly lower than the adsorption capacity of the glass control (1.2. mu.g/mm)2). The hydrogel was evaluated for cytotoxicity in vitro according to ISO 10993-52009 using CCK-8. As a result, the hydrogel of this example was found to have a toxicity rating of 1 and no cytotoxicity. The antibacterial adhesion ability of the prepared zwitterionic hydrogel material was evaluated by in vitro bacterial adhesion. When the hydrogel material was cultured in a bacterial suspension for 4 hours using Escherichia coli and Staphylococcus aureus as test bacteria, it was found that the amount of adhered bacteria on the surface of the hydrogel of this example was extremely small and the number of bacteria was reduced to 2% of the number of bacteria on the surface of the blank glass control sample, as compared with the blank glass sample. It can be seen that the hydrogel material of this example exhibits a better anti-bacterial adhesion function.
Example 4
(A) Mixing 20g of N, N' -carbonyldiimidazole, 10g of a zwitterionic polyamine compound, 50g of amino-terminated polyethylene glycol (average molecular weight 800 g/mol), 10g of ethylenediamine, 1g of laponite and 2000g of water to obtain a hydrogel pre-reaction solution;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 38 hours at 40 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Wherein the structural formula of the zwitterionic polyamine compound is as follows:
Figure DEST_PATH_IMAGE025AAA
the obtained self-healing zwitterionic hydrogel material is disconnected and contacted again, and the hydrogel material can heal and repair within 30 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The prepared zwitter-ion hydrogel material is soaked in an alkaline solution with the pH value of 14 for 48 hours, and the degradation of the hydrogel material is not found; the treated hydrogel material is extracted and leached by water, and still can detect the zwitter-ionic group. It can be seen that the hydrogel material maintains good alkali resistance.
The biocompatibility of the hydrogel prepared in the examples is evaluated through protein adsorption, cytotoxicity, antibacterial adhesion and the like. And evaluating the protein adsorption resistance of the prepared zwitter-ion hydrogel material by adopting a static protein adsorption experiment. Bovine serum albumin (BSA, 5mg/ml) is selected, and the adsorption quantity per unit area and the anti-protein adsorption capacity of the sample are calculated. As a result, it was found that the hydrogel of the present invention had a protein adsorption amount of 0.03. mu.g/mm2Significantly lower than the adsorption capacity of the glass control (1.2. mu.g/mm)2). The hydrogel was evaluated for cytotoxicity in vitro according to ISO 10993-52009 using CCK-8. As a result, the hydrogel of this example was found to have a toxicity rating of 1 and no cytotoxicity. The antibacterial adhesion ability of the prepared zwitterionic hydrogel material was evaluated by in vitro bacterial adhesion. When the hydrogel material was cultured in a bacterial suspension for 4 hours using Escherichia coli and Staphylococcus aureus as test bacteria, it was found that the amount of adhered bacteria on the surface of the hydrogel of this example was extremely small and the number of bacteria was reduced to 2% of the number of bacteria on the surface of the blank glass control sample, as compared with the blank glass sample. It can be seen that the hydrogel material of this example exhibits a better anti-bacterial adhesion function.
Example 5
(A) Mixing 100g of N, N' -carbonyldiimidazole, 10g of a zwitterionic polyamine compound, 1000g of amino-terminated polyethylene glycol (average molecular weight of 5000 g/mol), 100g of hexamethylenediamine, 100g of sodium carboxymethylcellulose and 10000g of water to obtain a hydrogel pre-reaction solution;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 2h at 60 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Wherein the structural formula of the zwitterionic polyamine compound is as follows:
Figure DEST_PATH_IMAGE026
the obtained self-healing zwitterionic hydrogel material is disconnected and contacted again, and the hydrogel material can heal and repair within 11 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The prepared zwitter-ion hydrogel material is soaked in an alkaline solution with the pH value of 14 for 48 hours, and the degradation of the hydrogel material is not found; the treated hydrogel material is extracted and leached by water, and still can detect the zwitter-ionic group. It can be seen that the hydrogel material maintains good alkali resistance.
The biocompatibility of the hydrogel prepared in the examples is evaluated through protein adsorption, cytotoxicity, antibacterial adhesion and the like. And evaluating the protein adsorption resistance of the prepared zwitter-ion hydrogel material by adopting a static protein adsorption experiment. Bovine serum albumin (BSA, 5mg/ml) is selected, and the adsorption quantity per unit area and the anti-protein adsorption capacity of the sample are calculated. As a result, it was found that the hydrogel of the present invention had a protein adsorption amount of 0.04. mu.g/mm2Significantly lower than the adsorption capacity of the glass control (1.2. mu.g/mm)2). The hydrogel was evaluated for cytotoxicity in vitro according to ISO 10993-52009 using CCK-8. As a result, the hydrogel of this example was found to have a toxicity rating of 1 and no cytotoxicity. The antibacterial adhesion ability of the prepared zwitterionic hydrogel material was evaluated by in vitro bacterial adhesion. When the hydrogel material was cultured in a bacterial suspension for 4 hours using Escherichia coli and Staphylococcus aureus as test bacteria, it was found that the amount of adhered bacteria on the surface of the hydrogel of this example was extremely small and the number of bacteria was reduced to 2% of the number of bacteria on the surface of the blank glass control sample, as compared with the blank glass sample. It can be seen that the hydrogel material of this example exhibits a better anti-bacterial adhesion function.
Example 6
(A) Mixing 0.1g of N, N' -carbonyldiimidazole, 10g of zwitterionic polyamine compound and 500g of water to obtain a hydrogel pre-reaction liquid;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 48 hours at the temperature of 20 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
Wherein the structural formula of the zwitterionic polyamine compound is as follows:
Figure DEST_PATH_IMAGE026A
the obtained self-healing zwitterionic hydrogel material is disconnected and contacted again, and the hydrogel material can heal and repair within 2 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The prepared zwitter-ion hydrogel material is soaked in an alkaline solution with the pH value of 14 for 48 hours, and the degradation of the hydrogel material is not found; the treated hydrogel material is extracted and leached by water, and still can detect the zwitter-ionic group. It can be seen that the hydrogel material maintains good alkali resistance.
The biocompatibility of the hydrogel prepared in the examples is evaluated through protein adsorption, cytotoxicity, antibacterial adhesion and the like. The protein adsorption resistance of the prepared zwitter-ion hydrogel material is evaluated by adopting a static protein adsorption experiment, bovine serum albumin (BSA, 5mg/ml) is selected, the adsorption capacity per unit area and the protein adsorption resistance of a sample are calculated, and the result shows that the protein adsorption capacity of the hydrogel is 0.01 mu g/mm2Significantly lower than the adsorption capacity of the glass control (1.2. mu.g/mm)2). The hydrogel was evaluated for cytotoxicity in vitro according to ISO 10993-52009 using CCK-8. As a result, the hydrogel of this example was found to have a toxicity rating of 1 and no cytotoxicity. The antibacterial adhesion ability of the prepared zwitterionic hydrogel material was evaluated by in vitro bacterial adhesion. As a result of culturing the hydrogel material in a bacterial suspension for 4 hours using Escherichia coli and Staphylococcus aureus as test bacteria, it was found that the hydrogel surface of this example had a very small amount of adhered bacteria and a reduced amount of bacteria as compared with the blank glass sampleAs little as 0.4% of the bacteria on the surface of the blank glass control. It can be seen that the hydrogel material of this example exhibits a better anti-bacterial adhesion function.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (2)

1. A preparation method of self-healing zwitterionic hydrogel is characterized by comprising the following steps:
(A) mixing a diimidazole compound, a zwitterionic polyamine compound, amino-terminated polyethylene glycol, polyamine, a thickening agent and water to obtain a hydrogel pre-reaction liquid;
the number average molecular weight of the amino-terminated polyethylene glycol is 200-5000 g/mol;
the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole;
the thickening agent is at least one of hydroxyethyl cellulose, sodium carboxymethylcellulose, laponite, lithium magnesium silicate, magnesium aluminum silicate and polyacrylamide;
the zwitterionic polyamine compound is at least one of the substances shown in the following structural formula:
Figure DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE004
the polyamine is at least one of the substances shown in the following structural formula:
Figure DEST_PATH_IMAGE006
Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE010
wherein m is 1-200; n is 0 to 5; t is 1-5; k is 1-16;
(B) pouring the hydrogel pre-reaction liquid into a mold, reacting for 2-48 h at 20-60 ℃, and purifying to obtain the self-healing zwitterionic hydrogel.
2. A method for preparing a self-healing zwitterionic hydrogel according to claim 1, wherein:
in the step (A), the mass ratio of the zwitterionic polyamine compound, the diimidazole compound, the amino-terminated polyethylene glycol, the polyamine, the thickener and the water is 1: (0.01-10): (0-100): (0-10): (0-10): (1-1000).
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114671977A (en) * 2022-02-18 2022-06-28 中国科学院宁波材料技术与工程研究所 Zwitterionic polymer hydrogel and preparation method and application thereof
CN114671977B (en) * 2022-02-18 2023-10-31 中国科学院宁波材料技术与工程研究所 Zwitterionic polymer hydrogel and preparation method and application thereof

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