CN106380990B - The preparation method of phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating - Google Patents
The preparation method of phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, including：First, the phosphoryl choline polymer containing aldehyde radical is prepared；2nd, dopamine and phosphoryl choline polymer containing aldehyde radical are dissolved in polar solvent and obtain mixed solution, the mixed solution is then coated on material surface to be modified, is dried；3rd, the material to be modified after drying is placed in alkaline aqueous solution, heats 2h~12h under the conditions of 40 DEG C~90 DEG C, obtains the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.The preparation method of the present invention is simple and convenient to operate, the crosslinking adhesion bionic coating surface with imitating cell outer-layer membrane structure to obtain stable provides a kind of new approach, the coating of preparation will be in blood purification, it is material implanted, the fields such as organizational project, medicament slow release and biology sensor have broad application prospects.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to one kind contains aldehyde
The phosphoryl choline polymer of base and the preparation method of dopamine cross-linked coating.
Background technology
Chitosan has the advantages that degradability, antibiotic property, nontoxic, non-stimulated, pH responses (Carbohydrate
Polymers 2010,79:724-730), it has been widely used in the fields such as biomedicine.More and more researchs show：
Chitosan-phospholipid complex material can be used for blood purification.Amino in chitosan molecule contributes to a variety of toxin in blood
Absorption, can be used for blood Absorbent (Chemical Journal of Chinese Universities 2002,23:75-77；Journal of
Microencapsulation 1993,10:475-486).Chitosan film has high dialysance, selectivity and intensity, can be with
As haemodialysis material (Journal of Applied Polymer Science 1992,46:255-261；263-269).
Although Chitosan-phospholipid complex has many advantages as blood purification material, there is also protein absorption, blood is small
Plate sticks, the problems such as ultimately resulting in blood coagulation, form thrombus, so the blood compatibility for improving Chitosan-phospholipid complex material is compeled
In the eyebrows and eyelashes (Applied Surface Science 2005,241:485-492；Biomaterials 2002,23:2561-
2568；Biomaterials 2003,24:3213-3220).
Phosphorylcholine (phosphorylcholine, PC) is the terminal hydrophyllic group for forming cell membrane elementary cell lecithin, is
Outer layer functional group in extracellular tunic, simultaneous with positive and negative xenogenesis electric charge, ability and hydrophily with stronger combination water
Can, the surface of this structure and composition will not only be adsorbed with physiological environment interaction and depositing proteins, will not trigger
Platelet activation, cause the adverse reactions such as blood coagulation, has good biocompatibility.Research in recent years shows, using phosphinylidyne
Choline group and its polymer have imitating cell outer-layer membrane structure in material surface structure, can significantly improve the blood phase of material
Capacitive.
In recent years, using approach (the Carbohydrate Polymers 2007,70 of grafting Phosphorylcholine small molecule: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,Polymer edition2002,13:501-510；
Colloids and Surfaces B:Biointerfaces 2009,71:268-274) modification of chitosan so that chitosan
Blood compatibility significantly improves.But these modes are not often high in the density of the Phosphorylcholine group of material surface, limit
It is modified the application in field and further improving for blood compatibility in bio-medical material.
For this reason, by the methacrylic acid containing Phosphorylcholine group-methylacryoyloxyethyl Phosphorylcholine binary copolymerization
Thing (PMA) polyanion, carries out layer upon layer electrostatic self assembly with chitosan (polycation), obtains with imitating cell outer-layer film knot
Coating surface (the Colloids and Surfaces B of structure:Biointerfaces 2011,85:48-55).Protein adsorbs
With platelet adhesion reaction test result indicates that：The blood compatibility of modified rear surface is obviously improved.In view of this modification side
The all the advantages of method, will provide technical support to lift the blood compatibility of bio-medical material.However, with physical absorption side
Formula is incorporated in the polymer with simulated cellulosa membrane structure coating of transplanting device surface, inevitably occurs in complex environment in vivo molten
Solve, come off.For this reason, Lewis and Xu build equality (Biomaterials 2001,22:99-111；Biomaterials 2004,
25:3099-3108；European Polymer Journal 2004,40:291-298) respectively to containing trimethoxy silicon substrate
The polymer coating of group and Phosphorylcholine group is studied.The result shows that trimethoxy on polymer molecular chain in coating
Silicon group meets water and can hydrolyze, be crosslinked, and also covalent bond can be formed with the active group of substrate surface, so that Phosphorylcholine class
The stability of polymer coating is significantly improved.It can be seen from the above that crosslinking between polymer and its with substrate surface functional group
Reaction, be to improve Phosphorylcholine to birds of the same feather flock together the key factor of compound coating stability.However, the polymer in the synthesis process may be used
Crosslinked group facile hydrolysis, crosslinking so that its building-up process condition is excessively harsh, is difficult to preserve, and causes its application range to be limited.
The content of the invention
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, there is provided a kind of containing aldehyde radical
The preparation method of phosphoryl choline polymer and dopamine cross-linked coating.This method by the phosphoryl choline polymer containing aldehyde radical with it is more
Bar amine is dissolved in polar solvent, coated in modified material surface is needed, is dried and is placed at the heated in water solution of pH8.5
Reason, hands over dopamine while amino and chitosan film surface amino groups are reacted with aldehyde radical in phosphoryl choline polymer in dopamine
Connection, by the schiff base reaction of aldehyde radical in phosphoryl choline polymer and chitosan film surface amino groups and the adhesion of dopamine by phosphorus
Phatidylcholine group is fixed on chitosan film surface, you can prepares the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of Phosphorylcholine polymerization containing aldehyde radical
The preparation method of thing and dopamine cross-linked coating, it is characterised in that comprise the following steps：
Step 1: under nitrogen protection, by the vinyl monomer containing aldehyde radical and the vinyl monomer containing Phosphorylcholine
Raolical polymerizable is carried out under the action of initiator, obtains the phosphoryl choline polymer containing aldehyde radical；
Obtained Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in polar solvent
Mixed solution, is then coated on material surface to be modified by the mixed solution, dries；
Step 3: the material to be modified after being dried in step 2 is placed in the alkaline aqueous solution that pH value is 8~9,40
DEG C~90 DEG C under the conditions of heat 2h~12h, obtain having the crosslinking adhesion bionic coating of imitating cell outer-layer membrane structure.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
Vinyl monomer containing aldehyde radical described in step 1 is methacrolein, and the vinyl monomer containing Phosphorylcholine is 2-
Methylacryoyloxyethyl Phosphorylcholine.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
The mole of vinyl monomer containing Phosphorylcholine described in step 1 is the vinyl monomer containing aldehyde radical and contains phosphinylidyne
The 70%~95% of the vinyl monomer integral molar quantity of choline.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
The solvent of Raolical polymerizable described in step 1 is methanol and tetrahydrofuran according to (3~5):1 volume ratio mixing mixes
Bonding solvent.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
Initiator described in step 1 is azodiisobutyronitrile.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
The concentration of dopamine is 0.1mg/mL~0.5mg/mL in mixed solution described in step 2, the phosphoryl choline polymer containing aldehyde radical
Concentration be 0.2mg/mL~5mg/mL.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
Polar solvent described in step 2 is methanol or ethanol.
The preparation method of the above-mentioned phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that
Material to be modified described in step 2 is chitosan.
The present invention has the following advantages compared with prior art：
1st, the phosphoryl choline polymer containing aldehyde radical and dopamine are dissolved in polar solvent by the present invention, are changed coated in needs
Property material surface, dry be placed on pH8.5 heated in water solution processing, make amino and chitosan film surface ammonia in dopamine
Dopamine is crosslinked while base is reacted with aldehyde radical in phosphoryl choline polymer, by aldehyde radical in phosphoryl choline polymer and chitosan
Phosphorylcholine group is fixed on chitosan film surface by the schiff base reaction of film surface amino and the adhesion of dopamine, you can system
The standby crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
2nd, preparation method of the invention is simple and convenient to operate, to obtain the stable friendship with imitating cell outer-layer membrane structure
Connection adhesion bionic coating surface provides a kind of new approach.
3rd, coating prepared by the present invention will be passed in blood purification, material implanted, organizational project, medicament slow release and biology
The fields such as sensor have broad application prospects.
With reference to the accompanying drawings and examples, technical scheme is described in further detail.
Brief description of the drawings
Fig. 1 is the receding angle of coating and the block diagram of advancing angle that chitosan material is prepared with the embodiment of the present invention 1.
Fig. 2 is the surface fine energy spectrum diagram for the coating that chitosan material is prepared with the embodiment of the present invention 1.
Embodiment
Embodiment 1
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 4:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, are dialysed with the bag filter that molecular cut off is 7000 after reaction,
Then it is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.25mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is 1mg/
ML, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 8.5 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions) in, heat 5h under the conditions of 60 DEG C, obtain having the crosslinking of imitating cell outer-layer membrane structure to adhere to bionical painting
Layer.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
As shown in Figure 1, the crosslinking manufactured in the present embodiment with imitating cell outer-layer membrane structure adheres to bionic coating (i.e. in figure
Shown modification of chitosan) compared with chitosan material, the adhesion bionic coating of the crosslinking with imitating cell outer-layer membrane structure of preparation
Advancing angle and receding angle decrease, this is because the phosphoryl choline polymer of good hydrophilic property passes through aldehyde radical and chitosan table
The reaction of amino in face and dopamine, Phosphorylcholine group is adhered fixed on the surface of chitosan, and obtaining has imitative cell
The surface of outer layer membrane structure so that its hydrophily significantly improves, and advancing angle and receding angle substantially reduce.In addition, dopamine is deposited
The hydrophily of modification of chitosan is being added, advancing angle and receding angle all reduce.This explanation dopamine adds chitosan film table
The content of face Phosphorylcholine group.
As shown in Fig. 2, the crosslinking manufactured in the present embodiment with imitating cell outer-layer membrane structure adheres to bionic coating (i.e. in figure
Shown modification of chitosan) compared with the chitosan material without coating treatment, there is phosphinylidyne on the chitosan film surface of modified processing
N and P characteristic absorption peaks on choline group, the Phosphorylcholine group of this explanation good hydrophilic property are fixed on chitosan film surface.It is more
Dopamine is crosslinked while amino and chitosan film surface amino groups are reacted with aldehyde radical in phosphoryl choline polymer in bar amine, by phosphorus
The schiff base reaction of aldehyde radical and chitosan film surface amino groups and the adhesion of dopamine are by Phosphorylcholine base in phatidylcholine polymer
Briquetting is scheduled on chitosan film surface, can prepare the surface with imitating cell outer-layer membrane structure so that its hydrophily significantly improves, and goes out
N and P characteristic absorption peaks on existing Phosphorylcholine group.
Embodiment 2
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 14mmol 2- methylacryoyloxyethyls Phosphorylcholines and 6mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 5:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, dialyse, be then freeze-dried at -50 DEG C, obtained after reaction
Phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.5mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is 2mg/
ML, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 8.5 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions), heat 12h under the conditions of 40 DEG C, obtain having the crosslinking of imitating cell outer-layer membrane structure to adhere to bionical painting
Layer.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
Embodiment 3
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 19mmol 2- methylacryoyloxyethyls Phosphorylcholines and 1mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 3:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, dialyse, be then freeze-dried at -50 DEG C, obtained after reaction
Phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.4mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is 5mg/
ML, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 8 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions), heat 2h under the conditions of 90 DEG C, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
Embodiment 4
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 15mmol 2- methylacryoyloxyethyls Phosphorylcholines and 5mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 4:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, dialyse, be then freeze-dried at -50 DEG C, obtained after reaction
Phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.3mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is 4mg/
ML, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 9 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions), heat 4h under the conditions of 80 DEG C, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
Embodiment 5
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 17mmol 2- methylacryoyloxyethyls Phosphorylcholines and 3mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 3:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, dialyse, be then freeze-dried at -50 DEG C, obtained after reaction
Phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.2mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is 3mg/
ML, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 8.5 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions), heat 6h under the conditions of 70 DEG C, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
Embodiment 6
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 18mmol 2- methylacryoyloxyethyls Phosphorylcholines and 2mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 3:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, dialyse, be then freeze-dried at -50 DEG C, obtained after reaction
Phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.1mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is 1mg/
ML, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 8.5 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions), heat 8h under the conditions of 60 DEG C, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
Embodiment 7
The phosphoryl choline polymer containing aldehyde radical of the present embodiment and the preparation method of dopamine cross-linked coating, including it is following
Step：
Step 1: 14mmol 2- methylacryoyloxyethyls Phosphorylcholines and 6mmol methacrolein are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methanol and tetrahydrofuran are according to 5:The mixed solvent of 1 volume ratio mixing is as anti-
Solvent is answered, under nitrogen protection, 70 DEG C of polymerisation 24h, dialyse, be then freeze-dried at -50 DEG C, obtained after reaction
Phosphoryl choline polymer containing aldehyde radical；
Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in methanol
Solution, the concentration of dopamine is 0.15mg/mL in the mixed solution, and the concentration of the phosphoryl choline polymer containing aldehyde radical is
0.2mg/mL, then dries the mixed solution drop coating on chitosan surface；
Step 3: by the chitosan after being dried in step 2 be placed in pH value be 8.5 alkaline aqueous solution (NaOH aqueous solutions or
KOH aqueous solutions), heat 10h under the conditions of 50 DEG C, obtain having the crosslinking of imitating cell outer-layer membrane structure to adhere to bionical painting
Layer.
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic that solvent tests polymer manufactured in the present embodiment.5~
Appearance is had no at 7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, at 3.28ppm
For-N+(CH3)3Characteristic peak, calculates polymer composition at 0.9~2.2ppm, as a result for methylene on main chain and the peak of pendant methyl
It has been shown that, polymer composition are basically identical with rate of charge.
Before prepared by measurement embodiment 1 to embodiment 7 has the crosslinking adhesion bionic coating of imitating cell outer-layer membrane structure
Into angle and receding angle, as a result see the table below：
The advancing angle and receding angle for the coating that 1 embodiment 1 of table is prepared to embodiment 7
| Material | Advancing angle (°) | Receding angle (°) |
| Undressed chitosan | 84±3 | 11±1 |
| Embodiment 1 | 45±2 | 7±1 |
| Embodiment 2 | 44±3 | 6±1 |
| Embodiment 3 | 46±3 | 7±1 |
| Embodiment 4 | 45±3 | 6±1 |
| Embodiment 5 | 44±2 | 7±1 |
| Embodiment 6 | 47±2 | 7±1 |
| Embodiment 7 | 45±3 | 6±1 |
As can be seen from Table 1, the adhesion of the crosslinking with imitating cell outer-layer membrane structure that the present invention is prepared on chitosan surface
The advancing angle and receding angle of bionic coating decrease, this is because the phosphoryl choline polymer of good hydrophilic property by aldehyde radical with
The reaction of amino in chitosan surface and dopamine, Phosphorylcholine group is adhered fixed on the surface of chitosan, is had
There is the surface of imitating cell outer-layer membrane structure so that its hydrophily significantly improves, and advancing angle and receding angle substantially reduce.It is in addition, more
The presence of bar amine adds the hydrophily of modification of chitosan, and advancing angle and receding angle all reduce.This explanation dopamine adds shell
The content of glycan film surface Phosphorylcholine group.
The above, is only presently preferred embodiments of the present invention, and any restrictions are not done to the present invention, every according to invention skill
Any simple modification, change and the equivalent structure change that art substantially makees above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (8)
- A kind of 1. preparation method of phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating, it is characterised in that including Following steps：Step 1: under nitrogen protection, the vinyl monomer containing aldehyde radical and the vinyl monomer containing Phosphorylcholine are being drawn Raolical polymerizable is carried out under the action of hair agent, obtains the phosphoryl choline polymer containing aldehyde radical；Mixed Step 2: the phosphoryl choline polymer containing aldehyde radical described in dopamine and step 1 is dissolved in polar solvent Solution, is then coated on material surface to be modified by the mixed solution, dries；Step 3: the material to be modified after being dried in step 2 be placed in pH value be 8~9 alkaline aqueous solution in, 40 DEG C~ Heat 2h~12h under the conditions of 90 DEG C, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
- 2. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, the vinyl monomer containing aldehyde radical described in step 1 is methacrolein, the second containing Phosphorylcholine Alkenyl monomer is 2- methylacryoyloxyethyl Phosphorylcholines.
- 3. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, the mole of the vinyl monomer containing Phosphorylcholine described in step 1 is the vinyl monomer containing aldehyde radical With 70%~95% of the vinyl monomer integral molar quantity containing Phosphorylcholine.
- 4. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, the solvent of Raolical polymerizable described in step 1 is methanol and tetrahydrofuran according to (3~5):1 volume Than the mixed solvent of mixing.
- 5. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, initiator described in step 1 is azodiisobutyronitrile.
- 6. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, the concentration of dopamine is 0.1mg/mL~0.5mg/mL in mixed solution described in step 2, the phosphorus containing aldehyde radical The concentration of phatidylcholine polymer is 0.2mg/mL~5mg/mL.
- 7. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, polar solvent described in step 2 is methanol or ethanol.
- 8. the preparation method of the phosphoryl choline polymer according to claim 1 containing aldehyde radical and dopamine cross-linked coating, It is characterized in that, material to be modified described in step 2 is chitosan.
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| CN108794794B (en) * | 2018-05-30 | 2021-02-26 | 西安文理学院 | Method for modifying surface biocompatibility of material and bionic coating prepared by method |
| CN108659168B (en) * | 2018-05-30 | 2020-12-11 | 西安文理学院 | Double-bionic polymer and preparation method and application thereof |
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| CN103275269A (en) * | 2013-06-22 | 2013-09-04 | 西安科技大学 | Phosphoryl choline polymer containing aldehyde group and preparation method and application thereof |
| CN105670022A (en) * | 2016-02-25 | 2016-06-15 | 西安科技大学 | Preparation method of phosphorylcholine bionic coating |
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| CN101531740A (en) * | 2009-01-12 | 2009-09-16 | 西北大学 | Method for forming simulated cell outer layer membrane structure on surface of cross-linked chitosan |
| CN103275269A (en) * | 2013-06-22 | 2013-09-04 | 西安科技大学 | Phosphoryl choline polymer containing aldehyde group and preparation method and application thereof |
| CN105670022A (en) * | 2016-02-25 | 2016-06-15 | 西安科技大学 | Preparation method of phosphorylcholine bionic coating |
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