CN108659168B - Double-bionic polymer and preparation method and application thereof - Google Patents
Double-bionic polymer and preparation method and application thereof Download PDFInfo
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- CN108659168B CN108659168B CN201810539671.3A CN201810539671A CN108659168B CN 108659168 B CN108659168 B CN 108659168B CN 201810539671 A CN201810539671 A CN 201810539671A CN 108659168 B CN108659168 B CN 108659168B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention belongs to the technical field of material surface science and biomedical high molecular materials, and particularly relates to a double-bionic polymer synthesized based on a pentafluorophenyl grafting reaction, and further discloses a preparation method and application thereof. The double-bionic polymer disclosed by the invention is prepared by carrying out free radical polymerization reaction on a vinyl monomer containing a phosphorylcholine group and a vinyl monomer containing a pentafluorophenyl group as raw materials to obtain a phosphorylcholine polymer containing the pentafluorophenyl group, and combining dopamine serving as an artificial mussel adhesive protein component with the phosphorylcholine polymer containing the pentafluorophenyl group, wherein the hydroxyl group of the ortho-diphenol has the adhesion function of the artificial mussel adhesive protein dopamine, so that the water-soluble polymer is endowed with excellent adhesion performance on the surface of a material, and the phosphorylcholine has the anti-fouling performance of an artificial outer cell membrane structure, so that good anti-biological pollution performance is obtained.
Description
Technical Field
The invention belongs to the technical field of material surface science and biomedical high molecular materials, and particularly relates to a double-bionic polymer synthesized based on a pentafluorophenyl grafting reaction, and further discloses a preparation method and application thereof.
Background
Biocompatibility refers to a concept of various biological, physical, chemical, etc. reactions generated after interaction between materials and organisms. Generally speaking, it is the degree of compatibility of the material with the human body after being implanted into the human body, that is, whether the material will cause toxic effects on human tissues. Generally, when the material is used in a living body, the material is easy to produce nonspecific protein adsorption, activate complement molecules and an immune system, and then cause blood coagulation, immunity and inflammation reactions, so that the performance of the material is remarkably reduced and even is ineffective, which is caused by poor biocompatibility of the material. Thus, biocompatibility studies have become a primary problem in the field of biomaterial research.
Because the surface of the material is a medium for contacting the material and the organism, the charge, hydrophilicity/hydrophobicity, chemical composition, morphology and the like of the surface of the material are all important factors influencing the interaction of the interface between the material and the organism and are also main factors determining whether the biocompatibility of the material is excellent. Therefore, improving the biocompatibility of the material surface is the key to solve this scientific problem. The modification by introducing the substance with good biocompatibility to the surface of the material is the simplest and most effective way to improve the interaction between the material and the organism and improve the biocompatibility of the material. Therefore, the biocompatibility modification of the material surface is a constant theme in the field of biomaterial research, and has important academic significance and huge application prospects.
It has been reported that the introduction of endothelial cells, albumin, heparin and/or polyethylene glycol with good blood compatibility into the surface of the material can significantly improve the biocompatibility, especially significantly improve the blood compatibility. However, the above-mentioned modified materials for improving the biocompatibility of the material surface have various problems, such as poor interaction between endothelial cells and the material surface, poor blood impact resistance, and easy exfoliation; and because albumin and active components in vivo compete for adsorption on the surface of the material, the content of albumin adsorbed on the surface of the material is reduced and even denatured; heparin is easy to hydrolyze, so that the activity of the heparin is obviously reduced, and complications such as bleeding and thrombocytopenia are induced; during vigorous respiration, polyethylene glycol is oxidized by superoxide anion and hydrogen peroxide, and the surface is also contaminated to various degrees. It can be seen that the properties of the existing modified materials for improving the surface biocompatibility of the materials are not ideal.
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.
The existing method for modifying the biocompatibility of the surface of the material mainly adopts physical coating, namely, modes of dip coating, spin coating, drip coating and the like, and is an ideal means for constructing a simulated outer cell membrane structure to obtain an excellent biocompatible surface due to the advantages of simple process, convenient operation and mild conditions. However, for phosphorylcholine modified materials, due to the strong hydrophilicity of the groups, phosphorylcholine polymer coatings physically coated on the surfaces of the materials are easy to dissolve, degrade and even fall off in complex physiological environments. Thus, it is desirable to incorporate crosslinkable or covalent bonding groups into the phosphorylcholine polymer to crosslink or covalently bond the polymer coating to the surface of the material via chemical reaction. This undoubtedly increases the difficulty of surface requirements for synthesis and application of such phosphorylcholine polymers, and makes the treatment process of the technology lengthy and complicated, so that research and development of a surface modification method with simple use and wide application range are urgently needed.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a double-bionic polymer to solve the problems that the coating is easy to dissolve, degrade and even fall off when the phosphorylcholine polymer is subjected to material surface biocompatibility modification in the prior art;
the second technical problem to be solved by the invention is to provide a preparation method of the double bionic polymer.
In order to solve the technical problems, the preparation method of the double-bionic polymer comprises the following steps:
(1) under the protection of inert gas, taking a vinyl monomer containing a phosphorylcholine group and a vinyl monomer containing a pentafluorophenyl group as raw materials, and carrying out free radical polymerization reaction under the action of an initiator to obtain a phosphorylcholine polymer containing the pentafluorophenyl group;
(2) dissolving the phosphorylcholine polymer containing pentafluorophenyl into a polar solvent to obtain a polymer solution; adding dopamine, and carrying out grafting reaction at 30-55 ℃ under the protection of inert gas; and (4) freezing and drying the obtained reactant to obtain the required double-bionic polymer.
In the step (1), the molar ratio of the vinyl monomer containing phosphorylcholine group to the vinyl monomer containing pentafluorophenyl group is 3:7-8: 2.
in the step (1):
the vinyl monomer containing phosphorylcholine groups comprises methacryloyloxyethyl phosphorylcholine;
the pentafluorophenyl containing vinyl monomer includes pentafluorophenyl methacrylate.
In the step (1), the temperature of the free radical polymerization reaction is controlled to be 60-80 ℃.
The step (1) further comprises a step of adding the reaction raw materials into an organic solvent for free radical polymerization, wherein the organic solvent is tetrahydrofuran and is added with a mixed solution of ethanol or methanol. The amount of the organic solvent is preferably such that sufficient dissolution of the reaction raw materials is achieved.
In the step (2), the molar amount of the dopamine is 10-120% of the molar amount of pentafluorophenyl group in the phosphorylcholine polymer containing pentafluorophenyl group.
In the step (2), the polar solvent includes water, methanol or ethanol. The amount of the polar solvent is preferably such that the reaction raw materials are sufficiently dissolved.
In the step (2), the temperature of the grafting reaction is controlled to be 30-55 ℃.
The step (1) and/or the step (2) further comprises a step of dialyzing the obtained reactant.
The invention also discloses the double-bionic polymer prepared by the method.
The invention also discloses the application of the double-bionic polymer in modification treatment of material surface biocompatibility.
The double-bionic polymer disclosed by the invention is prepared by carrying out free radical polymerization reaction on a vinyl monomer containing a phosphorylcholine group and a vinyl monomer containing a pentafluorophenyl group as raw materials to obtain a phosphorylcholine polymer containing the pentafluorophenyl group, and combining dopamine serving as an artificial mussel adhesive protein component with the phosphorylcholine polymer containing the pentafluorophenyl group, wherein the hydroxyl group of the ortho-diphenol has the adhesion function of the artificial mussel adhesive protein dopamine, so that the water-soluble polymer is endowed with excellent adhesion performance on the surface of a material, and the phosphorylcholine has the anti-fouling performance of an artificial outer cell membrane structure, so that good anti-biological pollution performance is obtained.
The dopamine group in the double-bionic polymer has various noncovalent bond effects such as pi-pi accumulation and the like, is easy to oxidize and polymerize to form adhesive Polydopamine (PDA), and can generate a water-resistant strong adhesive effect with various substrates including metal, glass and plastic. In addition, dopamine coatings can be grafted with biologically functional molecules by michael addition or schiff base reaction. The mussel adhesion-imitating surface modification method can make up the limitation that the prior physical coating needs to be subjected to complex chemical treatment to obtain a stable coating, and simplifies the condition and process of material surface modification. In addition, the preparation method of the invention utilizes the reaction of pentafluorophenyl group and amino group to graft dopamine on phosphorylcholine polymer containing pentafluorophenyl group, which can omit the protection process of phenolic hydroxyl group, solves the problem that phenolic hydroxyl group protection is necessary when the monomers are polymerized because phenolic hydroxyl group in dopamine monomer is polymerization inhibitor of free radical polymerization, and solves the difficult problem of existing dopamine polymer synthesis; in addition, in the double-bionic polymer prepared by the method, the grafting rate of the dopamine is controllable and reaches up to 65%, and compared with the grafting rate of the dopamine which is only 4% in the common method in the prior art, the coating adhesion of the double-bionic polymer prepared by the method is further enhanced and the double-bionic polymer is not easy to fall off.
The bionic polymer containing phosphorylcholine serving as an extracellular membrane component and dopamine serving as a mussel adhesive protein component is used for modifying the surface of the material, a dopamine side group in the polymer can be adhered to the surfaces of various materials including polytetrafluoroethylene from an aqueous solution, and the phosphorylcholine side group automatically forms an extracellular membrane-simulated structure on the surface of a coating, so that the biocompatibility of the substrate material is obviously improved. The double-bionic polymer prepared by the method has wide application prospect in the fields of in-vivo implantation materials, tissue engineering, drug sustained release, biosensors and the like.
The preparation method of the double-bionic derivative has the advantages of wide material source, simple preparation method, mild conditions and controllable grafting rate, solves the problem of difficult product purification in the prior art, and provides a new way for obtaining the double-bionic polymer.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a graph showing the dynamic contact angles of a chitosan membrane and a modified chitosan membrane of the present invention, in which the left side column in each group is an advancing angle value and the right side column is a receding angle value;
FIG. 2 is the surface fine energy spectrum of the chitosan film and the modified chitosan film of the present invention.
Detailed Description
The preparation of the bionical polymer described in the following examples of the invention is carried out based on a pentafluorophenyl based grafting reaction, and the specific synthetic route is as follows:
example 1
The preparation method of the double biomimetic polymer comprises the following steps:
(1) accurately weighing 8mmol 2-methacryloyloxyethyl phosphorylcholine and 2mmol pentafluorophenyl methacrylate, dissolving and mixing with mixed solvent of ethanol and tetrahydrofuran (volume ratio of 4: 1), dissolving 0.1mmol azobisisobutyronitrile with tetrahydrofuran to obtain initiator solution, and adding N-methyl ethyl phosphorylcholine2Protecting, adding a monomer mixed solution into a three-necked bottle under the condition of stirring at 70 ℃, preheating for 30min, adding the initiator solution, continuing to react for 24h, concentrating the reaction solution after the reaction is finished, and dialyzing by using a dialysis bag with the intercepted molecular weight of 6000-ion 8000D; finally, freeze-drying the dialyzed sample at-50 ℃ to obtain a phosphorylcholine polymer containing pentafluorophenyl; the nuclear magnetic test result shows that the molar content of the pentafluorophenyl in the polymer is about 17%;
using 400MHz NMR spectrometer with D2O is the hydrogen nuclear magnetism of the solvent test polymer. No peak was observed at 5 to 7ppm, indicating that no residual monomer was present in the resulting copolymer, and the polymer was successfully synthesized at 3.28ppm as-N+(CH3)3The characteristic peak, the polymer composition is calculated by taking the peak of methylene and side chain methyl on the main chain at 0.9-2.2ppm, and the polymer composition is basically consistent with the charge ratio;
(2) 0.5g of the pentafluorophenyl group-containing phosphorylcholine polymer produced in step (1) above was dissolved in 20mL of methanol to give a polymer solution, which was then purified under N2Protecting, namely stirring at the temperature of 30 ℃,adding the polymer solution into a three-necked bottle, preheating for 30min, adding 0.15g of dopamine, and carrying out heat preservation stirring reaction for 12 h; after the reaction is finished, concentrating the reaction solution, dialyzing the concentrated reaction solution in hydrochloric acid aqueous solution with the pH value of 3-4 by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and freeze-drying the dialyzed sample at-50 ℃ to obtain the double-bionic polymer. Through detection and calculation, the grafting rate of dopamine in the polymer obtained in the embodiment is 11%.
Example 2
The preparation method of the double biomimetic polymer comprises the following steps:
(1) weighing 2 mmol-methacryloyloxyethyl phosphorylcholine and 3mmol pentafluorophenyl methacrylate, dissolving and mixing with mixed solvent of methanol and tetrahydrofuran (volume ratio of 4: 1), dissolving 0.1mmol azodiisobutyronitrile with tetrahydrofuran to obtain initiator solution, and adding N-methyl pyrrolidone solution2Protecting, adding a monomer mixed solution into a three-necked bottle under the condition of stirring at 60 ℃, preheating for 30min, adding an initiator solution, continuing to react for 24h, concentrating the reaction solution after the reaction is finished, and dialyzing by using a dialysis bag with the intercepted molecular weight of 6000-ion 8000D; finally, freeze-drying the dialyzed sample at-50 ℃ to obtain a phosphorylcholine polymer containing pentafluorophenyl; the nuclear magnetic test result shows that the molar content of the pentafluorophenyl in the polymer is about 26%;
(2) 0.5g of the phosphorylcholine polymer containing a pentafluorophenyl group obtained in the step (1) above was dissolved in 20mL of ethanol to obtain a polymer solution, and the polymer solution was purified by N2Protecting, adding the polymer solution into a three-necked bottle under the stirring condition of 35 ℃, preheating for 30min, adding 0.2g of dopamine, preserving heat, stirring and reacting for 14 h; after the reaction is finished, concentrating the reaction solution, dialyzing the concentrated reaction solution in hydrochloric acid aqueous solution with the pH value of 3-4 by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and freeze-drying the dialyzed sample at-50 ℃ to obtain the double-bionic polymer. Through detection and calculation, the grafting rate of dopamine in the polymer obtained in the embodiment is 19%.
Example 3
The preparation method of the double biomimetic polymer comprises the following steps:
(1) accurately weighing 6mmol of 2-methacryloyloxyethyl phosphorylcholine and 4mmol of pentafluorophenyl methacrylate, dissolving and mixing uniformly (volume ratio is 4: 1) by using a mixed solvent of ethanol and tetrahydrofuran, dissolving 0.1mmol of azobisisobutyronitrile by using tetrahydrofuran to obtain an initiator solution, and adding the initiator solution into the initiator solution in N2Protecting, adding a monomer mixed solution into a three-necked bottle under the condition of stirring at 80 ℃, preheating for 30min, adding an initiator solution, continuing to react for 24h, concentrating the reaction solution after the reaction is finished, and dialyzing by using a dialysis bag with the intercepted molecular weight of 6000-ion 8000D; finally, freeze-drying the dialyzed sample at-50 ℃ to obtain a phosphorylcholine polymer containing pentafluorophenyl; the results of nuclear magnetic tests show that the molar content of the pentafluorophenyl group in the polymer is about 38%;
(2) 0.5g of the phosphorylcholine polymer containing a pentafluorophenyl group obtained in the above-mentioned step (1) was dissolved in 20mL of distilled water to obtain a polymer solution in N2Protecting, adding the polymer solution into a three-necked bottle under the stirring condition of 40 ℃, preheating for 30min, adding 0.4g of dopamine, preserving heat, stirring and reacting for 16 h; after the reaction is finished, concentrating the reaction solution, dialyzing the concentrated reaction solution in hydrochloric acid aqueous solution with the pH value of 3-4 by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and freeze-drying the dialyzed sample at-50 ℃ to obtain the double-bionic polymer. Through detection and calculation, the grafting rate of dopamine in the polymer obtained in the embodiment is 31%.
Example 4
The preparation method of the double biomimetic polymer comprises the following steps:
(1) weighing 5mmol of 2-methacryloyloxyethyl phosphorylcholine and 5mmol of pentafluorophenyl methacrylate, dissolving and mixing the materials uniformly (volume ratio is 4: 1) by using a mixed solvent of methanol and tetrahydrofuran, dissolving 0.1mmol of azobisisobutyronitrile by using tetrahydrofuran to obtain an initiator solution, and dissolving the initiator solution in N2Protecting, adding a monomer mixed solution into a three-necked bottle under the stirring condition of 65 ℃, preheating for 30min, adding an initiator solution, continuing to react for 24h, concentrating the reaction solution after the reaction is finished, and dialyzing by using a dialysis bag with the intercepted molecular weight of 6000-ion 8000D; finally, will permeateFreeze-drying the separated sample at-50 ℃ to obtain a phosphorylcholine polymer containing pentafluorophenyl; the nuclear magnetic test result shows that the molar content of the pentafluorophenyl in the polymer is about 47%;
(2) 0.5g of the phosphorylcholine polymer containing a pentafluorophenyl group obtained in the step (1) was dissolved in 20mL of methanol to obtain a polymer solution, and the polymer solution was purified by the reaction with N2And (3) protecting, adding the polymer solution into a three-necked bottle under the stirring condition of 45 ℃, preheating for 30min, adding 0.2g of dopamine, preserving heat, stirring and reacting for 18 h. After the reaction is finished, concentrating the reaction solution, dialyzing the concentrated reaction solution in hydrochloric acid aqueous solution with the pH value of 3-4 by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and freeze-drying the dialyzed sample at-50 ℃ to obtain the double-bionic polymer. Through detection and calculation, the grafting rate of dopamine in the polymer obtained in the embodiment is 40%.
Example 5
The preparation method of the double biomimetic polymer comprises the following steps:
(1) weighing 4mmol of 2-methacryloyloxyethyl phosphorylcholine and 6mmol of pentafluorophenyl methacrylate, dissolving and mixing the materials uniformly (volume ratio is 4: 1) by using a mixed solvent of methanol and tetrahydrofuran, dissolving 0.1mmol of azobisisobutyronitrile by using tetrahydrofuran to obtain an initiator solution, and dissolving the initiator solution in N2Protecting, adding a monomer mixed solution into a three-necked bottle under the condition of stirring at 75 ℃, preheating for 30min, adding an initiator solution, continuing to react for 24h, concentrating the reaction solution after the reaction is finished, and dialyzing by using a dialysis bag with the intercepted molecular weight of 6000-ion 8000D; finally, freeze-drying the dialyzed sample at-50 ℃ to obtain a phosphorylcholine polymer containing pentafluorophenyl; the results of nuclear magnetic tests show that the molar content of the pentafluorophenyl group in the polymer is about 57%;
(2) 0.5g of the phosphorylcholine polymer containing a pentafluorophenyl group in step (1) was dissolved in 20mL of ethanol to give a polymer solution in N2Protecting, adding the polymer solution into a three-necked bottle under the stirring condition of 50 ℃, preheating for 30min, adding 0.5g of dopamine, preserving heat, stirring and reacting for 20 h. After the reaction, the reaction solution was concentrated and dialyzed against a molecular weight cut-off of 6000-Dialyzing the concentrated reaction solution in hydrochloric acid water solution with pH value of 3-4, and freeze-drying the dialyzed sample at-50 deg.C to obtain the double-bionic polymer. Through detection and calculation, the grafting rate of dopamine in the polymer obtained in the embodiment is 49%.
Example 6
The preparation method of the double biomimetic polymer comprises the following steps:
(1) weighing 3mmol of 2-methacryloyloxyethyl phosphorylcholine and 7mmol of pentafluorophenyl methacrylate, dissolving and mixing the materials uniformly (volume ratio is 4: 1) by using a mixed solvent of methanol and tetrahydrofuran, dissolving 0.1mmol of azobisisobutyronitrile by using tetrahydrofuran to obtain an initiator solution, and dissolving the initiator solution in N2Protecting, adding a monomer mixed solution into a three-necked bottle under the condition of stirring at 70 ℃, preheating for 30min, adding an initiator solution, continuing to react for 24h, concentrating the reaction solution after the reaction is finished, and dialyzing by using a dialysis bag with the intercepted molecular weight of 6000-ion 8000D; finally, freeze-drying the dialyzed sample at-50 ℃ to obtain a phosphorylcholine polymer containing pentafluorophenyl; the results of nuclear magnetic tests show that the molar content of the pentafluorophenyl group in the polymer is about 71%;
(2) 0.5g of the phosphorylcholine polymer containing a pentafluorophenyl group in step (1) was dissolved in 20mL of distilled water to give a polymer solution in N2And (3) protecting, adding the polymer solution into a three-necked bottle under the stirring condition of 55 ℃, preheating for 30min, adding 0.7g of dopamine, and carrying out heat preservation stirring reaction for 24 h. After the reaction is finished, concentrating the reaction solution, dialyzing the concentrated reaction solution in hydrochloric acid aqueous solution with the pH value of 3-4 by using a dialysis bag with the molecular weight cutoff of 6000-8000D, and freeze-drying the dialyzed sample at-50 ℃ to obtain the double-bionic polymer. Through detection and calculation, the grafting rate of dopamine in the polymer obtained in the embodiment is 65%.
The bionic polymer can be used for modifying the biocompatibility of the surface of a material, and is specifically applied to the preparation of the adhesive bionic coating with the structure of the outer cell membrane by dissolving the prepared bionic polymer in a polar solvent, dripping the obtained bionic polymer on the surface of a material membrane to be modified, airing the obtained product, treating the product in an aqueous solution with the pH value of 8.0-9.0 at the temperature of 30-80 ℃, and fixing phosphorylcholine groups on the surface of a chitosan membrane by means of the anchoring effect of nucleophilic substitution reaction between pentafluorophenyl groups in phosphorylcholine polymer and amino groups on the surface of the chitosan membrane and the adhesion of dopamine.
As shown in fig. 1, the chitosan membrane treated with the coating of the present embodiment has a decreased advancing angle and a decreased receding angle compared with the chitosan membrane not treated with the coating, because the phosphorylcholine polymer with good hydrophilicity is anchored by the reaction of pentafluorophenyl group with the amino group on the surface of chitosan and the adhesion of dopamine to fix phosphorylcholine group on the surface of chitosan membrane, so as to obtain a surface with a structure simulating the outer membrane of cell, such that the hydrophilicity is significantly increased, and the advancing angle and the receding angle are significantly decreased.
As shown in fig. 2, compared with the chitosan membrane without coating, the chitosan membrane with coating treatment of this example has characteristic absorption peaks of N and P on phosphorylcholine groups on the surface of the chitosan membrane with modification treatment, which indicates that phosphorylcholine groups with good hydrophilicity are fixed on the surface of the chitosan membrane. The phosphorylcholine group is adhered and fixed on the surface of the chitosan membrane through the reaction anchoring of pentafluorophenyl and the amino on the surface of the chitosan and the adhesion of dopamine, so that the hydrophilicity of the phosphorylcholine group is obviously improved, and N and P characteristic absorption peaks on the phosphorylcholine group appear. Therefore, the method provided by the invention can effectively improve the biocompatibility of the surface of the chitosan material.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The preparation method of the double bionic polymer is characterized by comprising the following steps:
(1) under the protection of inert gas, taking a vinyl monomer containing a phosphorylcholine group and a vinyl monomer containing a pentafluorophenyl group as raw materials, and carrying out free radical polymerization reaction under the action of an initiator to obtain a phosphorylcholine polymer containing the pentafluorophenyl group;
(2) dissolving the phosphorylcholine polymer containing pentafluorophenyl into a polar solvent to obtain a polymer solution; under the protection of inert gas, adding dopamine to carry out grafting reaction; freeze-drying the obtained reactant to obtain the required double-bionic polymer;
in the step (1), the molar ratio of the vinyl monomer containing the phosphorylcholine group to the vinyl monomer containing the pentafluorophenyl group is 3:7-8: 2;
in the step (2), the molar amount of the dopamine is 10-120% of the molar amount of pentafluorophenyl group in the phosphorylcholine polymer containing pentafluorophenyl group.
2. The method for preparing a biomimetic polymer according to claim 1, wherein in the step (1): the vinyl monomer containing phosphorylcholine groups comprises methacryloyloxyethyl phosphorylcholine; the pentafluorophenyl containing vinyl monomer includes pentafluorophenyl methacrylate.
3. The method for preparing a biomimetic polymer according to claim 1 or 2, wherein in the step (1), the temperature of the radical polymerization reaction is controlled to be 60-80 ℃.
4. The method for preparing the biomimetic polymer according to claim 1 or 2, wherein the step (1) further comprises a step of adding the reaction raw material into an organic solvent to perform a radical polymerization reaction, wherein the organic solvent is tetrahydrofuran and a mixed solution of ethanol or methanol is added.
5. The method for preparing a biomimetic polymer according to claim 1 or 2, wherein in the step (2), the polar solvent comprises water, methanol or ethanol.
6. The method for preparing a biomimetic polymer according to claim 1 or 2, wherein in the step (2), the temperature of the grafting reaction is controlled to be 30-55 ℃.
7. A bionical polymer produced by the method of any one of claims 1-6.
8. Use of the biomimetic polymer of claim 7 for performing a material surface biocompatibility modification treatment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881126A (en) * | 2014-04-06 | 2014-06-25 | 西安科技大学 | Method for improving blood compatibility of material |
| CN104744635A (en) * | 2015-04-17 | 2015-07-01 | 西安科技大学 | Preparation method of di-bionic polymer |
| CN106380990A (en) * | 2016-08-27 | 2017-02-08 | 西安科技大学 | Preparation method of aldehyde-containing phosphorylcholine polymer and dopamine cross-linked coating |
| CN106750450A (en) * | 2016-11-07 | 2017-05-31 | 西安科技大学 | Preparation method containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating |
| CN106832382A (en) * | 2016-11-07 | 2017-06-13 | 西安科技大学 | A kind of synthesis of double bionical dopamine Phosphorylcholine materials and its painting method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881126A (en) * | 2014-04-06 | 2014-06-25 | 西安科技大学 | Method for improving blood compatibility of material |
| CN104744635A (en) * | 2015-04-17 | 2015-07-01 | 西安科技大学 | Preparation method of di-bionic polymer |
| CN106380990A (en) * | 2016-08-27 | 2017-02-08 | 西安科技大学 | Preparation method of aldehyde-containing phosphorylcholine polymer and dopamine cross-linked coating |
| CN106750450A (en) * | 2016-11-07 | 2017-05-31 | 西安科技大学 | Preparation method containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating |
| CN106832382A (en) * | 2016-11-07 | 2017-06-13 | 西安科技大学 | A kind of synthesis of double bionical dopamine Phosphorylcholine materials and its painting method |
Non-Patent Citations (4)
| Title |
|---|
| Layer-by-layer deposition of antifouling coatings on stainless steel via catechol-amine reaction;Li Qun Xu，等;《RSC Advances》;20140717;第4卷(第61期);第32335-32344页 * |
| Overcoming the Insolubility of Molybdenum Disulfide Nanoparticles through a High Degree of Sidewall Functionalization Using Polymeric Chelating Ligands;Muhammad Nawaz Tahir，等;《Angew. Chem. Int. Ed》;20061231;第45卷(第29期);第4809-4815页 * |
| Poly(dopamine acrylamide)-co-poly(propargyl acrylamide)-modified titanium surfaces for ‘click’ functionalization;Li Qun Xu，等;《Polym. Chem.》;20120130;第3卷(第4期);第920-927页 * |
| 含儿茶酚的聚氨酯基仿生高分子的设计、合成及性能研究;孙培育;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20170215(第2期);第30-31页A部分、图1-44 * |
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