CN108715644B - Preparation method of aldehyde group and aminophosphorylcholine polymer bionic adhesion coating - Google Patents

Preparation method of aldehyde group and aminophosphorylcholine polymer bionic adhesion coating Download PDF

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CN108715644B
CN108715644B CN201810615338.6A CN201810615338A CN108715644B CN 108715644 B CN108715644 B CN 108715644B CN 201810615338 A CN201810615338 A CN 201810615338A CN 108715644 B CN108715644 B CN 108715644B
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phosphorylcholine
vinyl monomer
coating
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polymer
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CN108715644A (en
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宫铭
杨容
霍煜
何晶晶
林港
杨振昊宇
董刚浩
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Xian University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/34—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an aldehydo radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Abstract

The invention relates to a preparation method of an aldehyde group and aminophosphorylcholine polymer bionic adhesion coating. Vinyl monomers containing phosphorylcholine hydrophilic groups and vinyl monomers containing aldehyde groups are polymerized through simple solution free radicals to synthesize the phosphorylcholine polymer containing aldehyde groups. And (2) carrying out free radical polymerization on the vinyl monomer containing the phosphorylcholine hydrophilic group and the vinyl monomer containing the amino group to synthesize the phosphorylcholine polymer containing the amino group. Dissolving two phosphorylcholine polymers and dopamine in a polar solvent, coating the solution on the surface of a chitosan membrane, drying the chitosan membrane, and then heating the chitosan membrane in a Tris-HCl solution to prepare the bionic adhesive coating with the structure of the simulated cell outer membrane. The method is simple to prepare and convenient to operate, and provides a new way for obtaining the bionic adhesive coating with excellent blood compatibility.

Description

Preparation method of aldehyde group and aminophosphorylcholine polymer bionic adhesion coating
Technical Field
The invention belongs to the technical field of material surface science and biomedical high polymer materials, and particularly relates to a method for preparing a coating adhered with a simulated cell outer membrane structure.
Background
Chitosan has the advantages of degradability, antibacterial property, no toxicity, no irritation, pH responsiveness and the like (Carbohydrate Polymers 2010,79: 724-. More and more studies have shown that: the chitosan and the derivative material thereof can be used for blood purification. The amino groups on the chitosan molecule contribute to the adsorption of various toxins in blood, and can be used as a blood perfusion material (advanced chemical science 2002,23: 75-77; Journal of Microencapsis 1993,10: 475-. The chitosan membrane has high dialysis rate, selectivity and strength, and can be used as a hemodialysis material (Journal of Applied Polymer Science 1992,46: 255-. Although chitosan and its derivatives have many advantages as blood purification materials, there are problems of protein adsorption, platelet adhesion, final coagulation, thrombus formation, etc., so it is very important to improve the blood compatibility of chitosan and its derivatives (Applied Surface Science 2005,241: 485-.
Phosphorylcholine (PC) is a hydrophilic end group of lecithin which is a basic unit of a cell membrane, is an outer layer functional group in an outer layer membrane of a cell, has positive and negative heterogeneous charges, has strong water binding capacity and hydrophilic performance, does not adsorb and deposit protein due to the interaction of the structure and the surface of the composition with a physiological environment, does not cause platelet activation, causes adverse reactions such as blood coagulation and the like, and has good biocompatibility. Researches in recent years show that the phosphorylcholine group and the polymer thereof are adopted to construct a structure with an imitated extracellular membrane on the surface of the material, so that the blood compatibility of the material can be obviously improved.
In recent years, the chitosan is modified by a way of grafting phosphorylcholine small molecules (Carbohydrate Polymers 2007, 70: 82-88; Biomacromolecules 2007,8: 3169-3176; Biomacromolecules 2006,7: 3151-3156; Journal of Applied Polymer Science 2003,88: 489-493; Polymer International 2003,52: 81-85; Journal of biomaterials Science 2002,13: 501-510; Colloids and Surfaces B: Biointerfaces 2009,71:268-274), so that the blood compatibility of the chitosan is remarkably improved. However, the density of phosphorylcholine groups on the surface of the material is not high, so that the application of the material in the field of modification of biomedical materials and the further improvement of blood compatibility are limited.
Therefore, methacrylic acid-methacryloyloxyethyl phosphorylcholine binary copolymer (PMA) polyanion containing phosphorylcholine groups and chitosan (polycation) are subjected to layer-by-layer electrostatic self-assembly to obtain a coating surface with a simulated cell outer membrane structure (Colloids and Surfaces B: Biointerfaces 2011,85: 48-55). The experimental results of protein adsorption and platelet adhesion show that: the blood compatibility of the modified surface is obviously improved. In view of the advantages of the modification method, technical support is necessarily provided for improving the blood compatibility of the biomedical materials. However, the polymer coating with the structure of the simulated extracellular membrane, which is bonded on the surface of the transplanting device in a physical adsorption mode, is inevitably dissolved and shed in a complex environment in vivo. For this purpose, Lewis and Xuedian et al (Biomaterials 2001,22: 99-111; Biomaterials 2004,25: 3099-. The result shows that trimethoxy silicon group on the polymer molecular chain in the coating can be hydrolyzed and crosslinked when meeting water, and can also form covalent bond with active group on the surface of the substrate, thereby obviously improving the stability of the phosphorylcholine polymer coating. Therefore, the cross-linking between the polymers and the reaction of the polymers and the functional groups on the surface of the substrate are key factors for improving the stability of the phosphorylcholine polymer coating.
However, the crosslinkable group of the polymer is easy to hydrolyze and crosslink in the synthetic process, so that the synthetic process conditions are too harsh and difficult to store, and the application range of the polymer is limited. Yao et al studied coating on titanium alloy surfaces by grafting mussel-attached dopamine onto a phosphorylcholine polymer containing carboxyl groups by reacting the amino groups with the carboxyl groups, but the dopamine content was only 4% and the polymer adhesion was low. Therefore, Gong et al synthesizes a phosphorylcholine polymer with high dopamine content and controllable dopamine content by using an active ester monomer approach, and uses the phosphorylcholine polymer for surface modification of various materials such as polypropylene, polytetrafluoroethylene and the like. Dang et al used eight-arm PEG containing dopamine and phosphorylcholine polymers for surface coating modification of various materials. The bionic adhesion method can increase the stability of the coating to a certain extent, but the adhesion force of the bionic mussel adhesion coating is not strong, and the stability needs to be improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a bionic adhesive coating of aldehyde group and aminophosphorylcholine polymer aiming at the defects of the prior art. Vinyl monomers containing phosphorylcholine hydrophilic groups and vinyl monomers containing aldehyde groups are polymerized through simple solution free radicals to synthesize the phosphorylcholine polymer containing aldehyde groups. Vinyl monomers containing phosphorylcholine groups and vinyl monomers containing amino groups are polymerized through simple solution free radicals to synthesize phosphorylcholine polymers containing amino groups. And then dissolving two phosphorylcholine polymers and dopamine in a polar solvent, coating the solution on the surface of a chitosan membrane, drying the chitosan membrane, and then placing the chitosan membrane in a Tris-HCl solution for heating treatment to prepare the bionic adhesive coating with the structure of the simulated cell outer layer membrane. The preparation method of the coating with the simulated extracellular membrane structure is simple and convenient to operate, and provides a new way for obtaining a stable coating surface with the simulated extracellular membrane structure.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of an aldehyde group and aminophosphorylcholine polymer bionic adhesion coating comprises the following steps:
under the protection of nitrogen, carrying out free radical solution polymerization reaction on a vinyl monomer containing aldehyde groups and a vinyl monomer containing phosphorylcholine under the action of an initiator to synthesize a phosphorylcholine polymer containing aldehyde groups;
under the protection of nitrogen, carrying out free radical solution polymerization reaction on a vinyl monomer containing amino and a vinyl monomer containing phosphorylcholine under the action of an initiator to synthesize a phosphorylcholine polymer containing aldehyde groups;
and step three, dissolving the two phosphorylcholine polymers and dopamine by using a polar solvent, coating the solution on the surface of a chitosan membrane, drying the chitosan membrane, and then placing the chitosan membrane in a Tris-HCl solution for heating treatment to prepare the bionic adhesive coating with the structure of the simulated cell outer layer membrane.
The mol ratio of the vinyl monomer containing the phosphorylcholine hydrophilic group to the vinyl monomer containing the aldehyde group is (9.5:0.5) - (6: 4).
The mol ratio of the vinyl monomer containing the phosphorylcholine hydrophilic group to the vinyl monomer containing the amino group is about (9.5:0.5) - (6: 4).
The vinyl monomer containing the phosphorylcholine hydrophilic group is methacryloyloxyethyl phosphorylcholine, the vinyl monomer containing aldehyde group is methacrolein, and the vinyl monomer containing amino group is 2-aminoethyl methacrylate hydrochloride.
In the first step, the solvent is a mixed solvent of methanol and tetrahydrofuran, the initiator is azobisisobutyronitrile, the reaction temperature is 65-80 ℃, the reaction time is 20-26 h, dialysis is carried out by using a dialysis bag with the molecular weight cutoff of 7000, and freeze drying is carried out at-50 ℃.
In the second step, the solvent for synthesizing the phosphorylcholine polymer containing the amino is distilled water, the initiator is potassium persulfate, the reaction temperature is 65-80 ℃, the reaction time is 20-26 hours, dialysis is carried out by using a dialysis bag with the molecular weight cutoff of 7000, and freeze drying is carried out at-50 ℃.
In the third step, two phosphorylcholine polymers containing aldehyde groups and amino groups are prepared into a solution with the concentration of 1-8 mg/mL, the mass ratio of the two phosphorylcholine polymers containing aldehyde groups and amino groups is (9.5:0.5) - (6:4), and dopamine accounts for 1-8% of the total mass of the two phosphorylcholine polymers.
In the third step, the volume of drop coating on the surface of the chitosan film is 10-45 mu L/cm2Vacuum drying at 30 deg.C for 24 hr.
The polar solvent is methanol or ethanol.
The coating is placed in a Tris-HCl solution with the pH value of 8-9, and is heated at the temperature of 40-75 ℃ for 17-24 hours.
Compared with the prior art, the invention has the following advantages:
the invention synthesizes phosphorylcholine polymer containing aldehyde group by simple solution free radical polymerization of vinyl monomer containing phosphorylcholine hydrophilic group and vinyl monomer containing aldehyde group. Vinyl monomers containing phosphorylcholine groups and vinyl monomers containing amino groups are polymerized through simple solution free radicals to synthesize phosphorylcholine polymers containing amino groups. Then dissolving two phosphorylcholine polymers and dopamine in a polar solvent, coating the mixture on the surface of a chitosan membrane, drying the mixture, then placing the mixture in a Tris-HCl solution for heating treatment, so that when aldehyde groups in the phosphorylcholine polymers containing aldehyde groups react with amino groups on the surface of the chitosan membrane to anchor a substrate, the aldehyde groups also react with the amino groups in the phosphorylcholine polymers containing amino groups for crosslinking, and when the dopamine adheres to and reacts with the amino groups on the surface of the chitosan membrane to anchor the substrate, the aldehyde groups and the amino groups in the phosphorylcholine polymers containing amino groups and aldehyde groups also react for crosslinking, thereby obviously improving the stability of the coating and the density of the phosphorylcholine groups on the surface, and obtaining the bionic adhesive coating with the structure of the simulated outer cell membrane. The preparation method of the coating with the simulated extracellular membrane structure is simple and convenient to operate, and provides a new way for obtaining a stable coating surface with the simulated extracellular membrane structure. The coating with the simulated cell outer layer membrane structure has wide application prospect in the fields of blood purification, in-vivo implanted materials, tissue engineering, drug slow release, biosensors and the like.
Drawings
FIG. 1 is a dynamic contact angle of a chitosan membrane and a modified chitosan membrane of the present invention.
FIG. 2 is the element fine energy spectrum of the chitosan film and the modified chitosan film of the present invention.
Detailed Description
The invention relates to a preparation method of an aldehyde and aminophosphorylcholine polymer bionic adhesion coating, which comprises the following steps:
under the protection of nitrogen, carrying out free radical solution polymerization reaction on a vinyl monomer (methacrolein) containing aldehyde groups and a vinyl monomer (methacryloyloxyethyl phosphorylcholine) containing phosphorylcholine under the action of an initiator to synthesize a phosphorylcholine polymer containing aldehyde groups; the mol ratio of the vinyl monomer containing the phosphorylcholine hydrophilic group to the vinyl monomer containing the aldehyde group is (9.5:0.5) - (6: 4). The solvent is a mixed solvent of methanol and tetrahydrofuran, the initiator is azobisisobutyronitrile, the reaction temperature is 65-80 ℃, the reaction time is 20-26 h, dialysis is carried out by using a dialysis bag with the molecular weight cutoff of 7000, and freeze drying is carried out at-50 ℃.
Under the protection of nitrogen, carrying out free radical solution polymerization reaction on a vinyl monomer (2-aminoethyl methacrylate hydrochloride) containing amino and a vinyl monomer (methacryloyloxyethyl phosphorylcholine) containing phosphorylcholine under the action of an initiator to synthesize a phosphorylcholine polymer containing aldehyde groups; the molar ratio of the vinyl monomer containing the phosphorylcholine hydrophilic group to the vinyl monomer containing the amino group is about (9.5:0.5) to (6: 4). The solvent for synthesizing the phosphorylcholine polymer containing amino is distilled water, the initiator is potassium persulfate, the reaction temperature is 65-80 ℃, the reaction time is 20-26 h, dialysis is carried out by using a dialysis bag with the molecular weight cutoff of 7000, and freeze drying is carried out at-50 ℃.
Dissolving two phosphorylcholine polymers and dopamine by using a polar solvent (methanol or ethanol), coating the solution on the surface of a chitosan membrane, and dripping the solution on the surface of the chitosan membrane by the volume of 10-45 mu L/cm2Vacuum drying at 30 deg.C for 24 hr. And drying, placing in a Tris-HCl solution, heating, placing the coating in a Tris-HCl solution at the pH value of 8-9, and treating at the temperature of 40-75 ℃ for 17-24 h. Namely, the bionic adhesive coating with the structure of imitating the outer membrane of the cell is prepared. The two phosphorylcholine polymers containing aldehyde groups and amino groups are prepared into a solution with the concentration of 1-8 mg/mL, the mass ratio of the two phosphorylcholine polymers containing aldehyde groups to the amino groups is (9.5:0.5) - (6:4), and dopamine accounts for 1-8% of the total mass of the two phosphorylcholine polymers.
The best implementation scheme of the invention is as follows: synthesizing phosphorylcholine polymer containing aldehyde groups by adopting solution free radical polymerization of a methacryloyloxyethyl phosphorylcholine monomer containing phosphorylcholine hydrophilic groups and a methacrolein monomer containing aldehyde groups according to the molar ratio of 8: 2. Meanwhile, synthesizing a phosphorylcholine polymer containing amino by adopting solution free radical polymerization of a methacryloyloxyethyl phosphorylcholine monomer containing a phosphorylcholine hydrophilic group and a 2-aminoethyl methacrylate hydrochloride monomer according to the molar ratio of 8: 2. Then, two phosphorylcholine polymers containing aldehyde groups and amino groups are taken according to the mass ratio of 7:3, and about 3% of the dosage of dopamine is taken, dissolved in a methanol solvent and uniformly mixed, and then the solution is dripped on the surface of the chitosan membrane, and vacuum drying is carried out for 24h at the temperature of 30 ℃. Drying, placing in Tris-HCl solution with pH 8.5, and processing at 50 deg.C for 22h to obtain bionic adhesive coating with simulated cell outer membrane structure.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Example 1
Weighing 16mmol of 2-methacryloyloxyethyl phosphorylcholine and 4mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 70 ℃ for 24 hours under the protection of nitrogen, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 16mmol of 2-methacryloyloxyethyl phosphorylcholine and 4mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into a 4mg/mL methanol solution at a mass ratio of 7: 3. Then adding dopamine to make its concentration about 0.12mg/mL and mixing uniformly. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 30 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. Then, the chitosan membrane is placed in a Tris-HCl solution with the pH value of 8.5 and treated at 50 ℃ for 22h, so that when aldehyde groups in the phosphorylcholine polymer containing aldehyde groups react with amino groups on the surface of the chitosan membrane to anchor the substrate, the chitosan membrane also reacts with the amino groups in the phosphorylcholine polymer containing amino groups to crosslink, and when dopamine adheres to the chitosan membrane and reacts with the amino groups on the surface of the chitosan membrane to anchor the substrate, the dopamine also reacts with the amino groups and the aldehyde groups in the two phosphorylcholine polymers containing amino groups and aldehyde groups to crosslink, thereby remarkably improving the stability of the coating and the density of the phosphorylcholine groups on the surface, namely the coating stability and theThe bionic adhesive coating with the structure of imitating the outer membrane of the cell can be obtained.
As shown in fig. 1, in the chitosan membrane treated with the coating of the present embodiment, compared with the chitosan membrane not treated with the coating, both the advancing angle and the receding angle of the chitosan treated with the coating are reduced, because the phosphorylcholine polymer with good hydrophilicity fixes phosphorylcholine groups on the surface of the chitosan membrane through the reaction of aldehyde groups with amino groups on the surface of the chitosan and amino groups in the phosphorylcholine polymer containing amino groups and the adhesion and anchoring action of dopamine, so as to obtain a surface with a structure simulating an outer membrane of a cell, such that the hydrophilicity of the surface is significantly improved, and the advancing angle and the receding angle are significantly reduced. In addition, the presence of dopamine increases the hydrophilicity of the modified chitosan membrane, and both the advancing angle and the receding angle decrease. This shows that dopamine increases the density of phosphorylcholine groups on the surface of the chitosan membrane, so that the advancing angle and the retreating angle are reduced after modification.
As shown in FIG. 2, in the chitosan membrane treated with coating of this example, compared with the chitosan membrane without coating, the chitosan membrane treated with modification has N on phosphorylcholine group on the surface+And a characteristic absorption peak of P, which indicates that phosphorylcholine groups with good hydrophilicity are fixed on the surface of the chitosan membrane. The surface with the structure of the simulated cell outer layer membrane can be prepared by fixing the phosphorylcholine group on the surface of the chitosan membrane by means of anchoring of the reaction of the aldehyde group in the phosphorylcholine polymer and the amino group on the chitosan membrane surface and reaction adhesion of the reaction of the aldehyde group in the phosphorylcholine polymer and the amino group on the chitosan membrane surface and the dopamine so as to obviously improve the hydrophilicity of the surface, and N on the phosphorylcholine group appears+And a P characteristic absorption peak.
Example 2
Weighing 19mmol of 2-methacryloyloxyethyl phosphorylcholine and 1mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 70 ℃ for 24 hours under the protection of nitrogen, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 12mmol of 2-methacryloyloxyethyl phosphorylcholine and 8mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into an ethanol solution of 8mg/mL in a mass ratio of 9.5: 0.5. Then adding dopamine to make the concentration of dopamine about 0.08mg/mL and mixing uniformly. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 10 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8.5 at 40 ℃ for 24 hours to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 3
Weighing 18mmol of 2-methacryloyloxyethyl phosphorylcholine and 2mmol of methacrolein, carrying out polymerization reaction for 24h at 70 ℃ under the protection of nitrogen by taking 0.1mmol of azobisisobutyronitrile as an initiator and methanol and tetrahydrofuran in a volume ratio of 4:1, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 13mmol of 2-methacryloyloxyethyl phosphorylcholine and 7mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into a methanol solution of 7mg/mL in a mass ratio of 9: 1. Then adding dopamine to make the concentration of dopamine about 0.14mg/mL and mixing uniformly.Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 15 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8.5 at 45 ℃ for 23 hours to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 4
Weighing 17mmol of 2-methacryloyloxyethyl phosphorylcholine and 3mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 70 ℃ for 24 hours under the protection of nitrogen, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 14mmol of 2-methacryloyloxyethyl phosphorylcholine and 6mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the embodiment are prepared into 6mg/mL ethanol solution according to the mass ratio of 8: 2. Then adding dopamine to make the concentration of dopamine about 0.24mg/mL and mixing uniformly. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 20 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8.5 at the temperature of 55 ℃ for 21h to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 5
Weighing 15mmol of 2-methacryloyloxyethyl phosphorylcholine and 5mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 70 ℃ for 24 hours under the protection of nitrogen, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 15mmol of 2-methacryloyloxyethyl phosphorylcholine and 5mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into a methanol solution of 5mg/mL in a mass ratio of 6: 4. Then, dopamine was added to a concentration of about 0.25mg/mL and mixed well. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 25 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8.5 at the temperature of 60 ℃ for 20 hours to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 6
Weighing 14mmol of 2-methacryloyloxyethyl phosphorylcholine and 6mmol of methacrolein, carrying out polymerization reaction for 24h at 70 ℃ under the protection of nitrogen by taking 0.1mmol of azobisisobutyronitrile as an initiator and methanol and tetrahydrofuran in a volume ratio of 4:1, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 17mmol of 2-methacryloyloxyethyl phosphorylcholine and 3mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the embodiment are prepared into an ethanol solution of 3mg/mL according to the mass ratio of 6.5: 3.5. Then, dopamine was added to a concentration of about 0.18mg/mL and mixed well. Then the two phosphoryl gallbladders are put into the reactorThe mixed solution of alkali polymer and dopamine is coated on the surface of chitosan membrane in a dropping volume of 35 muL/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8.5 at 65 ℃ for 19h to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 7
Weighing 13mmol of 2-methacryloyloxyethyl phosphorylcholine and 7mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 70 ℃ for 24 hours under the protection of nitrogen, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 18mmol of 2-methacryloyloxyethyl phosphorylcholine and 2mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into a methanol solution of 2mg/mL in a mass ratio of 7.5: 2.5. Then adding dopamine to make the concentration of dopamine about 0.14mg/mL and mixing uniformly. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 40 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, the bionic adhesive coating with the simulated extracellular membrane structure can be prepared by processing the bionic adhesive coating in a Tris-HCl solution with the pH value of 8.5 at 70 ℃ for 18 h.
Example 8
Weighing 12mmol of 2-methacryloyloxyethyl phosphorylcholine and 8mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 70 ℃ for 24 hours under the protection of nitrogen, concentrating reaction liquid after the reaction is finished, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing aldehyde groups.
Weighing 19mmol of 2-methacryloyloxyethyl phosphorylcholine and 1mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 12h at 70 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into an ethanol solution of 1mg/mL in a mass ratio of 8.5: 1.5. Then adding dopamine to make the concentration of dopamine about 0.08mg/mL and mixing uniformly. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 45 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8.5 at 75 ℃ for 17 hours to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 9
Weighing 10mmol of 2-methacryloyloxyethyl phosphorylcholine and 1mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 65 ℃ for 20h under the protection of nitrogen, concentrating the reaction solution after the reaction is finished, dialyzing the reaction solution by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing epoxy.
Weighing 10mmol of 2-methacryloyloxyethyl phosphorylcholine and 1mmol of 2-aminoethyl methacrylate hydrochloride, taking 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, carrying out polymerization reaction for 20h at 65 ℃ under the protection of nitrogen, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the example were prepared into a methanol solution of 8mg/mL in a mass ratio of 9.5: 0.5. Then, dopamine was added to a concentration of about 0.5mg/mL and mixed well. Then mixing the two phosphorylcholine polymers and dopamineThe mixed solution is dripped on the surface of the chitosan membrane, and the dripping volume is 10 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with the pH value of 8 for 17 hours at the temperature of 75 ℃ to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
Example 10
Weighing 6mmol of 2-methacryloyloxyethyl phosphorylcholine and 4mmol of methacrolein, taking 0.1mmol of azobisisobutyronitrile as an initiator, taking methanol and tetrahydrofuran in a volume ratio of 4:1 as solvents, carrying out polymerization reaction at 80 ℃ for 20h under the protection of nitrogen, concentrating the reaction solution after the reaction is finished, dialyzing the reaction solution by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing epoxy.
Weighing 6mmol of 2-methacryloyloxyethyl phosphorylcholine and 4mmol of 2-aminoethyl methacrylate hydrochloride, carrying out polymerization reaction for 20h at 80 ℃ under the protection of nitrogen by using 0.1mmol of potassium persulfate as an initiator and distilled water as a solvent, dialyzing after the reaction is finished, and then carrying out freeze drying at-50 ℃ to obtain the phosphorylcholine polymer containing amino.
The phosphorylcholine polymer containing aldehyde groups and the phosphorylcholine polymer containing amino groups prepared in the embodiment are prepared into an ethanol solution of 2.5mg/mL according to the mass ratio of 6: 4. Then, dopamine was added to a concentration of about 0.2mg/mL and mixed well. Then the mixed solution of the two phosphorylcholine polymers and dopamine is dripped on the surface of the chitosan membrane, and the dripping volume is 27 mu L/cm2A/side. And then dried in vacuum at 30 ℃ for 24 h. And then, treating the mixture in Tris-HCl solution with pH of 9 at 40 ℃ for 17 hours to prepare the bionic adhesive coating with the structure of the simulated extracellular membrane.
In a word, the invention is a preparation method of the aldehyde group and aminophosphorylcholine polymer bionic adhesion coating. The mixed solution of the phosphorylcholine polymer containing aldehyde group, the phosphorylcholine polymer containing amino group and dopamine is coated on the surface of a material, so that the bionic adhesion coating with a simulated outer cell membrane structure and excellent blood compatibility is prepared. The invention synthesizes phosphorylcholine polymer containing aldehyde group by simple solution free radical polymerization of vinyl monomer containing phosphorylcholine hydrophilic group and vinyl monomer containing aldehyde group. And (2) carrying out free radical polymerization on the vinyl monomer containing the phosphorylcholine hydrophilic group and the vinyl monomer containing the amino group to synthesize the phosphorylcholine polymer containing the amino group. Dissolving two phosphorylcholine polymers and dopamine in a polar solvent, coating the solution on the surface of a chitosan membrane, drying the chitosan membrane, and then heating the chitosan membrane in a Tris-HCl solution to prepare the bionic adhesive coating with the structure of the simulated cell outer membrane. The method is simple to prepare and convenient to operate, and provides a new way for obtaining the bionic adhesive coating with excellent blood compatibility. The modified material with the simulated cell outer membrane structure has wide application prospect in the fields of blood purification, in-vivo implantation materials, tissue engineering, drug slow release, biosensors and the like.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (4)

1. A preparation method of an aldehyde group and aminophosphorylcholine polymer bionic adhesion coating is characterized by comprising the following steps:
under the protection of nitrogen, carrying out free radical solution polymerization reaction on a vinyl monomer containing aldehyde groups and a vinyl monomer containing phosphorylcholine under the action of an initiator to synthesize a phosphorylcholine polymer containing aldehyde groups;
the mol ratio of the vinyl monomer containing the phosphorylcholine hydrophilic group to the vinyl monomer containing the aldehyde group is (9.5:0.5) - (6: 4);
the solvent is a mixed solvent of methanol and tetrahydrofuran, the initiator is azobisisobutyronitrile, the reaction temperature is 65-80 ℃, the reaction time is 20-26 h,
under the protection of nitrogen, carrying out free radical solution polymerization reaction on a vinyl monomer containing amino and a vinyl monomer containing phosphorylcholine under the action of an initiator to synthesize a phosphorylcholine polymer containing amino;
the solvent for synthesizing the phosphorylcholine polymer containing amino is distilled water, the initiator is potassium persulfate, the reaction temperature is 65-80 ℃, and the reaction time is 20-26 h;
the mol ratio of the vinyl monomer containing the phosphorylcholine hydrophilic group to the vinyl monomer containing the amino group is (9.5:0.5) - (6: 4);
dissolving two phosphorylcholine polymers and dopamine by using a polar solvent, coating the solution on the surface of a chitosan membrane, drying the chitosan membrane, and then placing the chitosan membrane in a Tris-HCl solution for heating treatment to prepare a bionic adhesive coating with a structure imitating an outer cell membrane;
in the third step, the polar solvent is methanol or ethanol;
two phosphorylcholine polymers containing aldehyde groups and amino groups are prepared into a solution with the concentration of 1-8 mg/mL, the mass ratio of the two phosphorylcholine polymers containing aldehyde groups and amino groups is (9.5:0.5) - (6:4), and dopamine accounts for 1-8% of the total mass of the two phosphorylcholine polymers;
the coating is placed in a Tris-HCl solution with the pH = 8-9, and is heated at the temperature of 40-75 ℃ for 17-24 hours; the vinyl monomer containing the phosphorylcholine hydrophilic group is methacryloyloxyethyl phosphorylcholine, the vinyl monomer containing aldehyde group is methacrolein, and the vinyl monomer containing amino group is 2-aminoethyl methacrylate hydrochloride.
2. The method for preparing the bionic adhesive coating of the aldehyde and the aminophosphocholine polymer as claimed in claim 1, wherein in the first step, dialysis is performed with a dialysis bag with a molecular weight cut-off of 7000, and freeze drying is performed at-50 ℃.
3. The method for preparing the bionic adhesive coating of the aldehyde group and the aminophosphocholine polymer as claimed in claim 1, wherein in the second step, dialysis is performed by using a dialysis bag with a molecular weight cut-off of 7000, and freeze drying is performed at-50 ℃.
4. An aldehyde and amino group according to claim 1The preparation method of the phosphorylcholine polymer bionic adhesion coating is characterized in that in the third step, the volume of the coating drop-coated on the surface of the chitosan membrane is 10-45 mu L/cm2Vacuum drying at 30 deg.C for 24 hr.
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