CN110845744A - Antibacterial self-repairing hydrogel and preparation method thereof - Google Patents

Antibacterial self-repairing hydrogel and preparation method thereof Download PDF

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CN110845744A
CN110845744A CN201911197589.8A CN201911197589A CN110845744A CN 110845744 A CN110845744 A CN 110845744A CN 201911197589 A CN201911197589 A CN 201911197589A CN 110845744 A CN110845744 A CN 110845744A
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amino acid
choline
ionic liquid
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贺晓凌
孙晓倩
宋浩德
王帅
贺婷婷
魏东盛
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Tianjin Polytechnic University
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    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract

The invention relates to an antibacterial self-repairing hydrogel and a preparation method thereof. The gel is endowed with a self-repairing function through a physical crosslinking method based on hydrophobic effect: the gel is endowed with antibacterial property and conductivity by introducing choline-amino acid ionic liquids (VILs): the tensile property and the toughness of the Bacterial Cellulose (BC) are enhanced by the bacterial cellulose with good biocompatibility. The preparation of the gel comprises the following steps: (1) synthesizing choline-amino acid ionic liquid; (2) preparing vinyl choline-amino acid ionic liquid monomers (VILs); (3) purifying and hydrolyzing bacterial cellulose; (4) and forming the self-repairing gel of the choline-amino acid ionic liquid. The gel provided by the invention has high self-healing efficiency, good antibacterial property, mechanical property, conductivity and biocompatibility, and is suitable for the fields of biology, medical treatment and tissue engineering.

Description

Antibacterial self-repairing hydrogel and preparation method thereof
Technical Field
The invention relates to the technical fields of high polymer materials, biomedicine and tissue engineering, in particular to hydrogel with antibacterial property and self-repairing property and a preparation method thereof.
Background
Hydrogels have been widely used in the biomedical field because their polymer network is filled with a large amount of water, giving the entire material the properties of a fluid, very similar to body tissues filled with a large amount of aqueous fluids. However, in the use process of the existing medical gel material, micro-nano cracks are easily generated, which can hinder the diffusion and permeation of drug molecules, thereby causing the interruption of treatment. As a novel biomedical intelligent material, the self-repairing hydrogel has important significance in solving the damage repairing problem of the flexible biological material and realizing the intellectualization and high efficiency of the biological material.
Self-repairing materials generally have two modes of external self-repairing and internal self-repairing. Extrinsic self-repair systems include capsule self-repair and vessel self-repair, both of which are achieved by releasing a repair agent. The internal self-repairing is realized through reversible interaction between materials, and self-repairing functions including physical action and chemical action can be realized without any external stimulation and energy. Physical effects such as hydrophobic effects, electrostatic effects, hydrogen bonding effects, host-guest interactions, metal coordination effects, etc., and chemical effects including Diels-Alder reactions, imine bonds, acylhydrazone bonds, etc. For example, Wang and the like use lithium montmorillonite and dendritic macromolecule to prepare organic/inorganic composite self-repairing hydrogel based on electrostatic interaction; phadke et al prepared self-healing hydrogels based on hydrogen bonding by polymerization of acryloyl-6-aminocaproic acid. Although the synthetic polymer hydrogels show good self-repairing performance, the synthetic polymer hydrogels have the defects of poor biocompatibility, high toxicity and the like, and the application range of the synthetic polymer hydrogels is severely limited.
Bacterial Cellulose (BC) is natural cellulose produced by microorganisms mainly using bacteria, has the advantages of superfine nanofiber network structure, crystallinity, oxygen permeability, biocompatibility, high water absorption rate, high porosity, excellent mechanical property, biodegradability and the like, and is widely applied to the fields of food industry, paper industry, biomedicine and the like at present. The demand of the current generation for BC products with superior performance is more and more obvious so as to meet the demands of different fields. The BC has an arrangement mode of nano fibers and a large number of hydroxyl active sites are provided on BC molecules, so that the BC can be used as a matrix to carry out a composite reaction to develop a novel BC composite material. In the biomedical field, the functional nano coagulant, the conductive polymer, the graphene oxide nano film and the biopolymer can be combined with bacterial cellulose, so that the functional nano coagulant has wide application in the manufacturing and processing of biosensors, acoustic diaphragms and supercapacitors. As a natural polymer material with a plurality of excellent properties, the bacterial cellulose still has huge research and development space in the future.
Although the bacterial cellulose has a plurality of excellent performances, the bacterial cellulose has no self-repairing function and no antibacterial function, and the bacterial cellulose-based functional material is developed by introducing functional components, so that the application potential of the bacterial cellulose-based functional material can be fully exploited. The polyionic liquid is an ionic liquid polymer which is generated by polymerizing an ionic liquid monomer and has anionic and cationic groups on a repeating unit, and has the excellent performances of the ionic liquid and the polymer. When the microorganism contacts the surface of the cationic polymer, the cationic unit adsorbs to the bacteria and penetrates the cell membrane, resulting in cell death, showing high antibacterial activity. The choline-amino acid ionic liquid prepared by combining choline and amino acid not only has higher antibacterial property, but also has low cytotoxicity and good biocompatibility. According to the invention, a hydrophobic self-repairing system and an ionic liquid with an antibacterial function are introduced into a BC network structure, so that the self-repairing biomedical gel with the antibacterial function is provided.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide self-repairing gel based on hydrophobic effect and a preparation method thereof.
The invention is realized by the following technical scheme:
(1) synthesis of choline-amino acid ionic liquid: adding amino acid into deionized water until the amino acid is dissolved, placing the mixture into an ice water bath, uniformly mixing choline and deionized water, slowly dripping the mixture into an amino acid solution at a speed of 2-3 drops/second, wherein the mol ratio of the choline to the amino acid is 1: 1-1: 1.05, placing the mixture in the ice water bath for 36-48 hours, performing rotary evaporation on the mixture by using a rotary evaporator at a temperature of 55-65 ℃ and at a speed of 110-140 r/min after the reaction is finished, and obtaining concentrated choline-amino acid ionic liquid which is stored for later use.
The amino acid is any one of isoleucine, phenylalanine, proline, glycine and serine.
The molar ratio of the amino acid to the deionized water in the amino acid water solution is 1: 25-1: 30.
The mol ratio of the choline to the deionized water in the choline water solution is 1: 25-1: 30.
(2) Preparation of vinyl choline-amino acid ionic liquid monomers (VILs): uniformly dissolving acrylic acid (AAc), EDC and N-hydroxysuccinimide in deionized water, reacting for 2-3 h, adding corresponding choline-amino acid ionic liquid, then reacting, adding EDC every 5-6 h for 5 times, after the EDC is added, carrying out secondary rotary evaporation on the reaction liquid under the same condition by using a rotary evaporator to obtain concentrated VILs, and storing for later use.
The AAc, the EDC, the N-hydroxysuccinimide and the choline-amino acid ionic liquid are respectively prepared from the following components in percentage by mass: 7 to 6 percent, 16 to 19 percent, 1.5 to 2.3 percent, 11 to 27 percent and the balance of deionized water.
(3) Preparing and purifying Bacterial Cellulose (BC): and statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane with distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1% -2%, heating the BC membrane in a water bath kettle at 75-85 ℃ for 50min to remove the residual mixed bacteria in the BC membrane until the BC membrane is milky, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use.
(4) Hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting BC into small pieces, and adding 55-60 wt% of H into BC under vigorous stirring at 20-30 deg.C2SO4Carrying out acid hydrolysis on the solution for 36-48 h, centrifuging the obtained solution for 5-8 min at 2300-2700 r/min, washing with deionized water, repeating the operation until the pH value reaches 7, and obtaining BC slurry with the content of 7-8%。
(5) Forming the self-repairing gel of the choline-amino acid ionic liquid: dissolving NaCl and SDS in 9.5-10 mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 100-120 uL of hydrophobic monomer octadecyl methacrylate (C18) in a NaCl-SDS system, stirring for 1h to make the solution transparent, then adding BC, VILs and acrylamide (AAm) after C18 is dissolved, magnetically stirring for 1-2 h to mix uniformly, fully mixing the BC, VILs and AAm, finally adding 0.1-0.2 mL of APS and 25-50 uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mold, and obtaining the choline-amino acid ionic liquid self-healing gel.
The mass fractions of the components are NaCl: 1.0% -2.0%, SDS: 5.5% -6.5%, BC: 0.2% -0.3%, VILs: 1.2% -5.5%, AAm: 8.0 to 8.5 percent.
Compared with the prior art, the invention has the following advantages:
(1) vinyl choline-amino acid ionic liquids (VILs) and Bacterial Cellulose (BC) are introduced to endow the self-repairing hydrogel with good antibacterial performance, conductive performance and mechanical performance.
(2) The pure natural raw materials have antibacterial property and biocompatibility, and can be used in the fields of biomedicine and tissue engineering.
(3) By utilizing the dynamic and reversible hydrophobic effect, the self-healing can be realized without external effect, and the healing efficiency is high.
(4) The preparation process has mild reaction conditions, simple operation method and short reaction period.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. The following embodiments are merely illustrative of the present invention and do not limit the scope of the invention, and those skilled in the art who have the benefit of this disclosure will appreciate that many insubstantial changes, modifications, substitutions, combinations, and simplifications are possible within the scope of the invention.
Example 1:
(1) synthesis of choline-isoleucine ionic liquid: uniformly mixing isoleucine and deionized water according to a molar ratio of 1: 30, slowly dropwise adding choline and deionized water into an amino acid solution after uniformly mixing choline and deionized water according to a molar ratio of 1: 30, wherein the molar ratio of choline to amino acid is 1: 1.05, placing the mixture in an ice water bath for 48 hours, performing rotary evaporation on the mixture by using a rotary evaporator at the temperature of 55 ℃ and the temperature of 110r/min after the reaction is finished, thus obtaining concentrated choline-amino acid ionic liquid, and storing the concentrated choline-amino acid ionic liquid for later use.
(2) Preparation of vinyl choline-isoleucine ionic liquid monomer: respectively taking the mass fractions of AAc, EDC and N-hydroxysuccinimide as follows: 7 percent, 19 percent and 2.3 percent are uniformly dissolved in deionized water, the mixture is reacted for 2 hours, choline-isoleucine ionic liquid with the mass fraction of 11 percent is added, EDC is added every 6 hours for 5 times, after the EDC is added, the reaction solution is subjected to secondary rotary evaporation by a rotary evaporator under the same condition to obtain concentrated VILs, and the concentrated VILs are stored for later use.
(3) Preparing and purifying Bacterial Cellulose (BC): statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1%, heating the BC membrane in a water bath kettle at the temperature of 75 ℃ for 50min to remove the residual mixed bacteria in the BC membrane until the BC membrane is milky white, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use.
(4) Hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting the BC into small pieces, and placing the BC in 55 wt% H at 30 deg.C under vigorous stirring2SO4And performing acid hydrolysis on the solution for 36h, centrifuging the obtained solution for 5min at 2700r/min, washing the solution by using deionized water, and repeating the operation until the pH value reaches 7 to obtain BC slurry with the content of 7-8%.
(5) Forming the self-healing gel of the choline-isoleucine ionic liquid: dissolving NaCl and SDS (wherein the concentration of the NaCl is 1wt percent and the concentration of the SDS is 5.5wt percent) in 10mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 120uL of hydrophobic monomer C18 in a NaCl-SDS system, stirring for 1h to make the solution transparent, then adding BC, VILs and AAm (wherein the mass percentages of the BC, the VILs and the AAm are respectively 0.2 percent, 5.5 percent and 8.5 percent) after C18 is dissolved, stirring for 1h by magnetic force to fully and uniformly mix the BC, the VILs and the AAm, finally adding 0.2mL of APS and 25uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mould, and obtaining the choline-isoleucine ionic liquid self-healing gel.
Example 2:
(1) and (3) synthesizing a choline-phenylalanine ionic liquid: uniformly mixing phenylalanine and deionized water according to a molar ratio of 1: 30, slowly dropwise adding choline and deionized water into an amino acid solution after uniformly mixing the choline and the deionized water according to a molar ratio of 1: 30, wherein the molar ratio of the choline to the amino acid is 1: 1, placing the mixture in an ice water bath for 48 hours, performing rotary evaporation on the mixture by using a rotary evaporator at 65 ℃ and 140r/min after the reaction is finished, thus obtaining concentrated choline-amino acid ionic liquid, and storing the concentrated choline-amino acid ionic liquid for later use.
(2) Preparing a vinyl choline-phenylalanine ionic liquid monomer: respectively taking the mass fractions of AAc, EDC and N-hydroxysuccinimide as follows: 6 percent, 16 percent and 1.5 percent are uniformly dissolved in deionized water, the mixture is reacted for 1 hour, choline-isoleucine ionic liquid with the mass fraction of 11 percent is added, EDC is added every 5 hours for 5 times, after the EDC is added, the reaction solution is subjected to secondary rotary evaporation by a rotary evaporator under the same condition to obtain concentrated VILs, and the concentrated VILs are stored for later use.
(3) Preparing and purifying Bacterial Cellulose (BC): statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 2%, heating the BC membrane in a water bath kettle at 85 ℃ for 50min to remove the residual mixed bacteria in the BC membrane until the BC membrane is milky white, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use.
(4) Hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting BC into small pieces, adding BC 60 wt% H under vigorous stirring at 30 deg.C2SO4And (3) carrying out acid hydrolysis on the solution for 36h, centrifuging the obtained solution for 8min at 2300r/min, washing the solution by using deionized water, and repeating the operation until the pH value reaches 7 to obtain BC slurry with the content of 7-8%.
(5) Forming the self-healing gel of the choline-phenylalanine ionic liquid: dissolving NaCl and SDS (wherein the concentration of the NaCl is 2wt percent and the concentration of the SDS is 6.5wt percent) in 10mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 100uL of hydrophobic monomer C18 in a NaCl-SDS system, stirring for 1h to make the solution transparent, then adding BC, VILs and AAm (wherein the mass percentages of the BC, the VILs and the AAm are respectively 0.2 percent, 1.2 percent and 8.0 percent) after C18 is dissolved, stirring for 1h by magnetic force to fully and uniformly mix the BC, the VILs and the AAm, finally adding 0.1mL of APS and 25uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mould, and obtaining the choline-phenylalanine ionic liquid self-healing gel.
Example 3:
(1) synthesis of choline-serine ionic liquid: uniformly mixing serine and deionized water according to a molar ratio of 1: 25, slowly dropwise adding choline and deionized water into an amino acid solution after uniformly mixing the choline and the deionized water according to a molar ratio of 1: 25, wherein the molar ratio of the choline to the amino acid is 1: 1.03, placing the mixture in an ice water bath for 48 hours, performing rotary evaporation on the mixture by using a rotary evaporator at 60 ℃ and 130r/min after the reaction is finished, thus obtaining concentrated choline-amino acid ionic liquid, and storing the concentrated choline-amino acid ionic liquid for later use.
(2) Preparation of vinyl choline-serine ionic liquid monomer: respectively taking the mass fractions of AAc, EDC and N-hydroxysuccinimide as follows: 6 percent, 18 percent and 1.9 percent are uniformly dissolved in deionized water, the mixture is reacted for 2 hours, choline-serine ionic liquid with the mass fraction of 20 percent is added, EDC is added every 5 hours for 5 times, after the EDC is added, the reaction solution is subjected to secondary rotary evaporation by a rotary evaporator under the same condition to obtain concentrated VILs, and the concentrated VILs are stored for later use.
(3) Preparing and purifying Bacterial Cellulose (BC): performing static culture on BC by adopting a culture medium, repeatedly washing a cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1.5%, heating the BC membrane in a water bath kettle at 80 ℃ for 50min to remove residual mixed bacteria in the BC membrane until the BC membrane is creamy white, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use.
(4) Hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting the BC into small pieces, and placing the BC in 55 wt% H at 30 deg.C under vigorous stirring2SO4Hydrolyzing the solution for 48h, centrifuging the obtained solution for 6min at 2500r/min, washing with deionized water, repeating the above steps until pH reaches 7,BC slurry with the content of 7-8% is obtained.
(5) Forming the self-healing gel of the choline-serine ionic liquid: dissolving NaCl and SDS (wherein the concentration of the NaCl is 1.5 wt% and the concentration of the SDS is 6.0 wt%) in 9.5mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 110uL of hydrophobic monomer C18 in a NaCl-SDS system, stirring for 2h to make the solution transparent, then adding BC, VILs and AAm (wherein the mass percentages of the BC, the VILs and the AAm are respectively 0.3%, 3.0% and 8.5%) after C18 is dissolved, magnetically stirring for 1h to fully and uniformly mix the BC, the VILs and the AAm, finally adding 0.2mL of APS and 50uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mold, and obtaining the choline-serine ionic liquid self-healing gel.
Example 4:
(1) synthesizing choline-glycine ionic liquid: uniformly mixing glycine and deionized water according to a molar ratio of 1: 25, slowly dropwise adding choline and deionized water into an amino acid solution after uniformly mixing the choline and the deionized water according to a molar ratio of 1: 25, wherein the molar ratio of the choline to the amino acid is 1: 1.05, placing the mixture in an ice water bath for 40 hours, performing rotary evaporation on the mixture by using a rotary evaporator at 60 ℃ and 130r/min after the reaction is finished, thus obtaining concentrated choline-amino acid ionic liquid, and storing the concentrated choline-amino acid ionic liquid for later use.
(2) Preparation of vinyl choline-glycine ionic liquid monomer: respectively taking the mass fractions of AAc, EDC and N-hydroxysuccinimide as follows: 6 percent, 19 percent and 2.3 percent are uniformly dissolved in deionized water, the mixture is reacted for 2 hours, choline-serine ionic liquid with the mass fraction of 25 percent is added, EDC is added every 5 hours for 5 times, after the EDC is added, the reaction solution is subjected to secondary rotary evaporation by a rotary evaporator under the same condition to obtain concentrated VILs, and the concentrated VILs are stored for later use.
(3) Preparing and purifying Bacterial Cellulose (BC): statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1.5%, heating the BC membrane in a water bath kettle at the temperature of 75 ℃ for 50min to remove residual mixed bacteria in the BC membrane until the BC membrane is milky, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use.
(4) Bacterial cellulose (A)BC): freeze drying BC, cutting the BC into small pieces, and placing the BC in 55 wt% H at 30 deg.C under vigorous stirring2SO4And (3) carrying out acid hydrolysis on the solution for 36h, centrifuging the obtained solution for 8min at 2300r/min, washing the solution by using deionized water, and repeating the operation until the pH value reaches 7 to obtain BC slurry with the content of 7-8%.
(5) Forming the self-healing gel of the choline-glycine ionic liquid: dissolving NaCl and SDS (wherein the concentration of the NaCl is 1.5wt percent and the concentration of the SDS is 6.5wt percent) in 10mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 110uL of hydrophobic monomer C18 in a NaCl-SDS system, stirring for 2h to make the solution transparent, then adding BC, VILs and AAm (wherein the mass percentages of the BC, the VILs and the AAm are respectively 0.25 percent, 4.0 percent and 8.1 percent) after C18 is dissolved, stirring for 1h by magnetic force to fully and uniformly mix the BC, the VILs and the AAm, finally adding 0.15mL of APS and 25uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mould, and obtaining the choline-glycine ionic liquid self-healing gel.
Example 5:
(1) and (3) synthesizing a choline-proline ionic liquid: uniformly mixing proline and deionized water in a molar ratio of 1: 25, slowly dropwise adding choline and deionized water in an amino acid solution after uniformly mixing choline and deionized water in a molar ratio of 1: 25, placing the mixture in an ice water bath for 42 hours, performing rotary evaporation on the mixture by using a rotary evaporator at 55 ℃ and 115r/min after the reaction is finished, and obtaining concentrated choline-amino acid ionic liquid which is stored for later use.
(2) Preparation of vinyl choline-proline ionic liquid monomer: respectively taking the mass fractions of AAc, EDC and N-hydroxysuccinimide as follows: 7 percent, 18 percent and 2 percent are uniformly dissolved in deionized water, the mixture is reacted for 3 hours, choline-serine ionic liquid with the mass fraction of 20 percent is added, EDC is added every 5 hours for 5 times, after the EDC is added, the reaction solution is subjected to secondary rotary evaporation by a rotary evaporator under the same condition to obtain concentrated VILs, and the concentrated VILs are stored for later use.
(3) Preparing and purifying Bacterial Cellulose (BC): statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1%, heating the BC membrane in a water bath kettle at the temperature of 75 ℃ for 50min to remove the residual mixed bacteria in the BC membrane until the BC membrane is milky white, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use.
(4) Hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting the BC into small pieces, and placing the BC in 55 wt% H at 30 deg.C under vigorous stirring2SO4And (3) carrying out acid hydrolysis on the solution for 40h, centrifuging the obtained solution for 6min at a speed of 2600r/min, washing the solution with deionized water, and repeating the operation until the pH reaches 7 to obtain BC slurry with the content of 7-8%.
(5) Forming the self-healing gel of the choline-proline ionic liquid: dissolving NaCl and SDS (wherein the concentration of the NaCl is 2.0 wt% and the concentration of the SDS is 6.0 wt%) in 10mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 120uL of hydrophobic monomer C18 in a NaCl-SDS system, stirring for 2h to make the solution transparent, then adding BC, VILs and AAm (wherein the mass percentages of the BC, the VILs and the AAm are respectively 0.25%, 5.3% and 8.5%) after C18 is dissolved, stirring for 1h magnetically to make the BC, the VILs and the AAm mixed uniformly, finally adding 0.1mL of APS and 25uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mold, and obtaining the choline-proline ionic liquid self-healing gel.

Claims (6)

1. An antibacterial self-repairing hydrogel and a preparation method thereof are characterized by having good self-repairing function, antibacterial property, conductivity, mechanical property and biocompatibility, and the gel can be prepared by the following method:
(1) synthesis of choline-amino acid ionic liquid: adding amino acid into deionized water until the amino acid is dissolved, placing the mixture into an ice water bath, uniformly mixing choline and the deionized water, slowly dripping the mixture into an amino acid solution at a speed of 2-3 drops/second, wherein the mol ratio of the choline to the amino acid is 1: 1-1: 1.05, placing the mixture in the ice water bath for 36-48 hours, performing rotary evaporation on the mixture by using a rotary evaporator at a temperature of 55-65 ℃ and at a speed of 110-140 r/min after the reaction is finished, and storing the concentrated choline-amino acid ionic liquid for later use;
(2) preparation of vinyl choline-amino acid ionic liquid monomers (VILs): uniformly dissolving acrylic acid (AAc), EDC and N-hydroxysuccinimide in deionized water, reacting for 2-3 h, adding corresponding choline-amino acid ionic liquid, then reacting, adding EDC every 5-6 h for 5 times, after the EDC is added, performing secondary rotary evaporation on the reaction liquid under the same condition by using a rotary evaporator to obtain concentrated VILs, and storing for later use;
(3) preparing and purifying Bacterial Cellulose (BC): statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1% -2%, heating the BC membrane for 50min at 75-85 ℃ in a water bath kettle to remove residual mixed bacteria in the BC membrane until the BC membrane is creamy white, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use;
(4) hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting BC into small pieces, and adding 55-60 wt% of H into BC under vigorous stirring at 20-30 deg.C2SO4Carrying out acid hydrolysis on the solution for 36-48 h, centrifuging the obtained solution for 5-8 min at a speed of 2300-2700 r/min, washing with deionized water, and repeating the operation until the pH value reaches 7 to obtain BC slurry with the content of 7-8%;
(5) forming the self-repairing gel of the choline-amino acid ionic liquid: dissolving NaCl and SDS in 9.5-10 mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 100-120 uL of hydrophobic monomer octadecyl methacrylate (C18) in a NaCI-SDS system, stirring for 1h to make the solution transparent, then adding BC, VILs and acrylamide (AAm) after C18 is dissolved, magnetically stirring for 1-2 h to mix uniformly, fully mixing the BC, VILs and AAm, finally adding 0.1-0.2 mL of APS and 25-50 uL of TEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mold, and obtaining the choline-amino acid ionic liquid self-healing gel.
2. The antibacterial self-repairing hydrogel of claim 1, wherein the preparation method comprises the following steps:
(1) synthesis of choline-amino acid ionic liquid: adding amino acid into deionized water until the amino acid is dissolved, placing the mixture into an ice water bath, uniformly mixing choline and the deionized water, slowly dripping the mixture into an amino acid solution at a speed of 2-3 drops/second, wherein the mol ratio of the choline to the amino acid is 1: 1-1: 1.05, placing the mixture in the ice water bath for 36-48 hours, performing rotary evaporation on the mixture by using a rotary evaporator at a temperature of 55-65 ℃ and at a speed of 110-140 r/min after the reaction is finished, and storing the concentrated choline-amino acid ionic liquid for later use;
(2) preparation of vinyl choline-amino acid ionic liquid monomers (VILs): uniformly dissolving acrylic acid (AAc), EDC and N-hydroxysuccinimide in deionized water, reacting for 2-3 h, adding corresponding choline-amino acid ionic liquid, then reacting, adding EDC every 5-6 h for 5 times, after the EDC is added, performing secondary rotary evaporation on the reaction liquid under the same condition by using a rotary evaporator to obtain concentrated VILs, and storing for later use;
(3) preparing and purifying Bacterial Cellulose (BC): statically culturing BC by adopting a culture medium, repeatedly washing the cultured BC membrane by using distilled water, putting the BC membrane into a NaOH solution with the mass fraction of 1% -2%, heating the BC membrane for 50min at 75-85 ℃ in a water bath kettle to remove residual mixed bacteria in the BC membrane until the BC membrane is creamy white, taking out the BC membrane, and storing the BC membrane in a refrigerator for later use;
(4) hydrolysis of Bacterial Cellulose (BC): freeze drying BC, cutting BC into small pieces, and adding 55-60 wt% of H into BC under vigorous stirring at 20-30 deg.C2SO4Carrying out acid hydrolysis on the solution for 36-48 h, centrifuging the obtained solution for 5-8 min at a speed of 2300-2700 r/min, washing with deionized water, and repeating the operation until the pH value reaches 7 to obtain BC slurry with the content of 7-8%;
(5) forming the self-repairing gel of the choline-amino acid ionic liquid: dissolving NaCl and SDS in 9.5-10 mL of distilled water at 35 ℃ to obtain a transparent solution, dissolving 100-120 uL of hydrophobic monomer octadecyl methacrylate (C18) in a NaCl-SDS system, stirring for 1h to make the solution transparent, then adding BC, VILs and acrylamide (AAm) after C18 is dissolved, magnetically stirring for 1-2 h to mix uniformly, fully mixing the BC, the VILs and the AAm, finally adding 0.1-0.2 mLAPS and 25-50 uLTEMED into the reaction solution, stirring for 2h, pouring the reaction solution into a prepared mold, and obtaining the choline-amino acid ionic liquid self-healing gel.
3. The method for preparing the antibacterial self-repairing hydrogel according to claim 2, wherein the amino acid in the step (1) is any one of isoleucine, phenylalanine, proline, glycine and serine.
4. The preparation method of the antibacterial self-repairing hydrogel according to claim 2, characterized in that the molar ratio of choline to amino acid in the step (1) is 1: 1-1: 1.05, and the molar ratio of amino acid to deionized water is 1: 25-1: 30; the mol ratio of the choline to the deionized water is 1: 25-1: 30.
5. The preparation method of the antibacterial self-repairing hydrogel according to claim 2, characterized in that the mass percentages of the components in the step (2) are as follows: AAc: 7% -6%, EDC: 16% -19%, N-hydroxysuccinimide: 2.3-1.5% and 11-27% of ionic liquid.
6. The preparation method of the antibacterial self-repairing hydrogel according to claim 2, characterized in that the mass fractions of the components in the step (5) are as follows: NaCl: 1.0% -2.0%, SDS: 5.5% -6.5%, BC: 0.2% -0.3%, VILs: 1.2% -5.5%, AAm: 8.0 to 8.5 percent.
CN201911197589.8A 2019-11-29 2019-11-29 Antibacterial self-repairing hydrogel and preparation method thereof Pending CN110845744A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113058444A (en) * 2021-04-25 2021-07-02 山东理工大学 Polyion liquid/EVA composite antibacterial film and preparation and application methods thereof
CN116333565A (en) * 2023-03-02 2023-06-27 四川大学 Method for preparing three-component antibacterial coating by choline amino acid ionic liquid

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113058444A (en) * 2021-04-25 2021-07-02 山东理工大学 Polyion liquid/EVA composite antibacterial film and preparation and application methods thereof
CN116333565A (en) * 2023-03-02 2023-06-27 四川大学 Method for preparing three-component antibacterial coating by choline amino acid ionic liquid
CN116333565B (en) * 2023-03-02 2024-05-17 四川大学 Method for preparing three-component antibacterial coating by choline amino acid ionic liquid

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