CN115181314B - Method for carrying out surface modification on polyether-ether-ketone based on main chain grafting method - Google Patents
Method for carrying out surface modification on polyether-ether-ketone based on main chain grafting method Download PDFInfo
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- CN115181314B CN115181314B CN202210894722.0A CN202210894722A CN115181314B CN 115181314 B CN115181314 B CN 115181314B CN 202210894722 A CN202210894722 A CN 202210894722A CN 115181314 B CN115181314 B CN 115181314B
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- ether
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- polyether
- surface modification
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 163
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000012986 modification Methods 0.000 title claims abstract description 30
- 230000004048 modification Effects 0.000 title claims abstract description 30
- 229920001690 polydopamine Polymers 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 43
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000661 sodium alginate Substances 0.000 claims abstract description 33
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 33
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 33
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 21
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 229960003638 dopamine Drugs 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 29
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 24
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 18
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 12
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 12
- 239000000872 buffer Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 iron ions Chemical class 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000007943 implant Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 abstract 2
- 239000011575 calcium Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000004071 biological effect Effects 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 238000004113 cell culture Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- DVLFYONBTKHTER-UHFFFAOYSA-N 3-(N-morpholino)propanesulfonic acid Chemical compound OS(=O)(=O)CCCN1CCOCC1 DVLFYONBTKHTER-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910001427 strontium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08J7/12—Chemical modification
-
- 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
- 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
- C08J7/056—Forming hydrophilic coatings
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of surface modification of high polymer materials, and particularly discloses a method for carrying out surface modification on polyether-ether-ketone based on a main chain grafting method, which comprises the following steps: s10, depositing dopamine on the surface of the polyether-ether-ketone to obtain the polyether-ether-ketone with the polydopamine coating; step S20, grafting sodium alginate on the surface of the polyether-ether-ketone with the polydopamine coating by adopting a main chain grafting method to obtain grafted modified polyether-ether-ketone; and S30, chemically crosslinking metal ions on the surface of the grafted modified polyether-ether-ketone to obtain the surface modified polyether-ether-ketone. The method for carrying out surface modification on the polyether-ether-ketone based on the main chain grafting method can effectively improve the bioactivity of the polyether-ether-ketone surface; in addition, the method is simple and convenient to operate, and is beneficial to improving the preparation efficiency; in addition, the method is based on a wet chemical method, can carry out surface modification on PEEK with complex-shape structures, and meets the surface treatment requirements of PEEK implants with complex-shape structures.
Description
Technical Field
The invention relates to the technical field of surface modification of high polymer materials, in particular to a method for carrying out surface modification on polyether-ether-ketone based on a main chain grafting method.
Background
Polyether-ether-ketone (PEEK) materials have good biochemical characteristics and radiation penetrability, so that the PEEK materials have wide application in the biomedical field, but the PEEK materials are low in biological activity, so that the biological activity after being implanted into a human body is poor, and the application of the PEEK materials in clinic is limited to a certain extent.
Disclosure of Invention
The invention mainly aims to provide a method for carrying out surface modification on polyether-ether-ketone based on a main chain grafting method, and aims to solve the problem of low bioactivity of PEEK materials.
In order to achieve the above purpose, the invention provides a method for carrying out surface modification on polyether-ether-ketone based on a main chain grafting method, which comprises the following steps:
S10, depositing dopamine on the surface of the polyether-ether-ketone to obtain the polyether-ether-ketone with the polydopamine coating;
Step S20, grafting sodium alginate on the surface of the polyether-ether-ketone with the polydopamine coating by adopting a main chain grafting method to obtain grafted modified polyether-ether-ketone;
and S30, chemically crosslinking metal ions on the surface of the grafted modified polyether-ether-ketone to obtain the surface modified polyether-ether-ketone.
Optionally, the step S10 includes:
and S11, adding polyether-ether-ketone and dopamine hydrochloride into the buffer solution, stirring, separating out solid matters, cleaning, and drying to obtain the polyether-ether-ketone with the polydopamine coating.
Optionally, in the step S11, dopamine hydrochloride is added to a concentration of 1-10 mg/mL.
Optionally, in the step S11, the pH of the buffer solution is 8.5-10.0.
Optionally, the step S20 includes:
S21, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into a sodium alginate solution, stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, washing and drying to obtain the grafted modified polyether-ether-ketone.
Optionally, in the step S21, the concentration of the sodium alginate solution is 0.01-10 mol/L.
Optionally, in the step S21, the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1: (1-10).
Optionally, in the step S21, the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1: (0.5-7).
Optionally, the step S30 includes:
and S31, adding the grafted modified polyether-ether-ketone into a metal ion solution, stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone.
Optionally, in the step S31, the metal ion solution includes one of copper ions, strontium ions, calcium ions, magnesium ions, zinc ions, and iron ions.
According to the method for carrying out surface modification on the polyether-ether-ketone based on the main chain grafting method, firstly, the polydopamine coating is deposited on the surface of the polyether-ether-ketone, the polydopamine coating can improve the surface hydrophilicity and biocompatibility of the polyether-ether-ketone, and promote the adhesion and diffusion of various cells, so that the bioactivity of the surface of the polyether-ether-ketone is improved, then, the main chain grafting method is adopted to graft sodium alginate on the polydopamine coating, the bioactivity of the surface of the polyether-ether-ketone is further improved by utilizing good adhesion and biocompatibility of the sodium alginate, and then, metal ions with good bioactivity are chemically crosslinked on the surface of the grafted modified polyether-ether-ketone, so that the bioactivity of the surface of the polyether-ether-ketone is further improved, and the bioactivity of the surface of the polyether-ether-ketone is effectively improved by three-step treatment; in addition, the method is simple and convenient to operate, and is beneficial to improving the preparation efficiency; in addition, the method is based on a wet chemical method, can carry out surface modification on PEEK with complex-shape structures, and meets the surface treatment requirements of PEEK implants with complex-shape structures.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an embodiment of a method for surface modification of PEEK based on backbone grafting according to the present invention;
FIG. 2 is a schematic flow chart of another embodiment of a method for surface modification of polyetheretherketone based on backbone grafting according to the present invention;
FIG. 3 is a scanning electron microscope image of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) of example 1 of the present invention;
FIG. 4 shows surface contact angle measurements of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) according to example 1 of the present invention;
FIG. 5 is an X-ray photoelectron spectroscopy (XPS) chart of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) of example 1 of the present invention;
FIG. 6 shows the results of cell activity tests during MC3T3-E1 cell culture of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) according to example 1 of the present invention;
FIG. 7 shows the fluorescence of cells during MC3T3-E1 cell culture of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) of example 1 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention.
The specific conditions were not specified in the examples, and the examples were conducted under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for carrying out surface modification on polyether-ether-ketone based on a main chain grafting method, referring to fig. 1, the method for carrying out surface modification on polyether-ether-ketone based on the main chain grafting method comprises the following steps:
and S10, depositing dopamine on the surface of the polyether-ether-ketone to obtain the polyether-ether-ketone with the polydopamine coating.
The polydopamine coating is deposited on the surface of the polyether-ether-ketone, so that the surface hydrophilicity and biocompatibility of the polyether-ether-ketone can be improved, adhesion and diffusion of various cells can be promoted, and the bioactivity of the surface of the polyether-ether-ketone can be improved.
Specifically, referring to fig. 2, the step S10 includes:
And S11, adding polyether-ether-ketone and dopamine hydrochloride into the buffer solution, stirring, separating out solid matters, cleaning, and drying to obtain the polyether-ether-ketone with the polydopamine coating. Wherein, adding dopamine hydrochloride to the concentration of 1-10 mg/mL; the pH value of the buffer solution is 8.5-10.0, and an alkaline reaction environment is formed by limiting the pH value of the buffer solution in the above range, so that the deposition of dopamine on the surface of polyether-ether-ketone is realized by utilizing the self-polymerization characteristic of dopamine and the alkaline polymerization process, and the deposition effect of the obtained polydopamine coating is better.
Further, in the step S11, the buffer is one of Tris buffer, phosphate (PBS) buffer, 3-morpholinopropane sulfonic acid (MOPS) buffer, 4-hydroxyethylpiperazine ethanesulfonic acid (HEPES) buffer, and Triethanolamine (TEA) buffer; in step S11, before the polyether-ether-ketone is added, the polyether-ether-ketone may be subjected to a cleaning treatment and a drying treatment, wherein the cleaning treatment uses distilled water and absolute ethyl alcohol as reagents, and the drying treatment temperature is 25-100 ℃.
And S20, grafting sodium alginate on the surface of the polyether-ether-ketone with the polydopamine coating by adopting a main chain grafting method to obtain the grafted modified polyether-ether-ketone.
And the main chain grafting method is adopted to graft sodium alginate on the polydopamine coating, and the biological activity of the surface of the polyether-ether-ketone is further improved by utilizing good adhesiveness and biocompatibility of the sodium alginate.
Specifically, referring to fig. 2, the step S20 includes:
S21, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into a sodium alginate solution, stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, washing and drying to obtain the grafted modified polyether-ether-ketone. Wherein the concentration of the sodium alginate solution is 0.01-10 mol/L; the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1: (1-10); the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1: (0.5-7). It is understood that the above conditions may be satisfied simultaneously or only one of them may be satisfied, and as a preferred embodiment of the present invention, the above conditions are satisfied simultaneously, so that the bioactivity of the prepared graft modified polyether ether ketone is better.
And S30, chemically crosslinking metal ions on the surface of the grafted modified polyether-ether-ketone to obtain the surface modified polyether-ether-ketone.
The metal ions with good biological activity are chemically crosslinked on the surface of the grafted modified polyether-ether-ketone, so that the biological activity is further improved.
Referring to fig. 2, the step S30 specifically includes:
And S31, adding the grafted modified polyether-ether-ketone into a metal ion solution, stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone. The method comprises the steps of adding grafted modified polyether-ether-ketone into a solution containing metal ions with good bioactivity, initiating the cross-linking of alginic acid on the surface of the grafted modified polyether-ether-ketone and the metal ions, and finally forming an alginate hydrogel coating with a space network structure on the surface of PEEK to obtain the surface modified polyether-ether-ketone. Wherein, in the metal ion solution, the metal ion is one of copper ion, strontium ion, calcium ion, magnesium ion, zinc ion and iron ion, and under the metal ion, the cross-linking effect with alginic acid is better, so that the surface modification effect of the surface modified polyether-ether-ketone is better and the biological activity is better. Of course, the present invention is not limited to the specific type of the metal ion solution, and may be one of a calcium chloride solution, a copper chloride solution, a zinc oxide solution, a calcium chlorate solution, a calcium hydrogen phosphate solution, a calcium sulfate solution, an iron chloride solution, an iron sulfate solution, a magnesium chloride solution, a2, 2-dimethylpropyl magnesium chloride solution, and a strontium carbonate solution.
According to the method for carrying out surface modification on the polyether-ether-ketone based on the main chain grafting method, firstly, the polydopamine coating is deposited on the surface of the polyether-ether-ketone, the polydopamine coating can improve the surface hydrophilicity and biocompatibility of the polyether-ether-ketone, and promote the adhesion and diffusion of various cells, so that the bioactivity of the surface of the polyether-ether-ketone is improved, then, the main chain grafting method is adopted to graft sodium alginate on the polydopamine coating, the bioactivity of the surface of the polyether-ether-ketone is further improved by utilizing good adhesion and biocompatibility of the sodium alginate, and then, metal ions with good bioactivity are chemically crosslinked on the surface of the grafted modified polyether-ether-ketone, so that the bioactivity of the surface of the polyether-ether-ketone is further improved, and the bioactivity of the surface of the polyether-ether-ketone is effectively improved by three-step treatment; in addition, the method is simple and convenient to operate, and is beneficial to improving the preparation efficiency; in addition, the method is based on a wet chemical method, can carry out surface modification on PEEK with complex-shape structures, and meets the surface treatment requirements of PEEK implants with complex-shape structures.
An example of the method for surface modification of polyetheretherketone based on the backbone grafting method according to the present invention is given below:
(1) Adding polyether-ether-ketone and dopamine hydrochloride (to the concentration of 1-10 mg/mL) into a buffer solution (pH value is 8.5-10.0), stirring, separating out solid matters, washing and drying to obtain the polyether-ether-ketone with the polydopamine coating.
(2) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into sodium alginate solution (the concentration is 0.01-10 mol/L), stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, cleaning, and drying to obtain grafted modified polyether-ether-ketone, wherein the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1: (1-10), the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide being 1: (0.5-7).
(3) Adding the grafted modified polyether-ether-ketone into a metal ion solution, stirring, separating out a solid, cleaning, and drying to obtain the surface modified polyether-ether-ketone, wherein the metal ion solution is a calcium chloride solution, an ferric chloride solution, a copper chloride solution, a zinc chloride solution or a magnesium chloride solution.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
(1) Adding polyether-ether-ketone and dopamine hydrochloride (to the concentration of 2 mg/mL) into a buffer solution (pH value is 8.5), stirring, separating out solid matters, cleaning and drying to obtain the polyether-ether-ketone with the polydopamine coating.
(2) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into sodium alginate solution (the concentration is 0.02 mol/L), stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, cleaning, and drying to obtain grafted modified polyether-ether-ketone, wherein the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:2.3, the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1:0.8.
(3) And adding the grafted modified polyether-ether-ketone into a calcium chloride solution (the concentration is 0.1 mol/L), stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone.
Example 2
(1) Adding polyether-ether-ketone and dopamine hydrochloride (to the concentration of 4 mg/mL) into a buffer solution (pH value is 8.5), stirring, separating out solid matters, cleaning and drying to obtain the polyether-ether-ketone with the polydopamine coating.
(2) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into sodium alginate solution (the concentration is 0.05 mol/L), stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, cleaning, and drying to obtain grafted modified polyether-ether-ketone, wherein the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:1.5, the molar amount ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1:6.7.
(3) And adding the grafted modified polyether-ether-ketone into a magnesium chloride solution (the concentration is 0.2 mol/L), stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone.
Example 3
(1) Adding polyether-ether-ketone and dopamine hydrochloride (until the concentration is 10 mg/mL) into a buffer solution (pH value is 9), stirring, separating out solid matters, washing and drying to obtain the polyether-ether-ketone with the polydopamine coating.
(2) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into a sodium alginate solution (the concentration is 1 mol/L), stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, cleaning, and drying to obtain grafted modified polyether-ether-ketone, wherein the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:10, the molar amount ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1:3.
(3) And adding the grafted modified polyether-ether-ketone into ferric chloride solution (with the concentration of 0.2 mol/L), stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone.
Example 4
(1) Adding polyether-ether-ketone and dopamine hydrochloride (until the concentration is 5 mg/mL) into a buffer solution (pH value is 10.0), stirring, separating out solid matters, cleaning and drying to obtain the polyether-ether-ketone with the polydopamine coating.
(2) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into a sodium alginate solution (the concentration is 5 mol/L), stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, cleaning, and drying to obtain grafted modified polyether-ether-ketone, wherein the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:5, the molar amount ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1:7.
(3) And adding the grafted modified polyether-ether-ketone into a copper chloride solution (the concentration is 0.1 mol/L), stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone.
Example 5
(1) Adding polyether-ether-ketone and dopamine hydrochloride (to the concentration of 1 mg/mL) into a buffer solution (pH value is 9.5), stirring, separating out solid matters, cleaning and drying to obtain the polyether-ether-ketone with the polydopamine coating.
(2) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into a sodium alginate solution (the concentration is 10 mol/L), stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, cleaning, and drying to obtain grafted modified polyether-ether-ketone, wherein the molar ratio of the sodium alginate to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:1, the molar amount ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1:0.5.
(3) And adding the grafted modified polyether-ether-ketone into zinc chloride solution (with the concentration of 0.2 mol/L), stirring, separating out solid matters, cleaning and drying to obtain the surface modified polyether-ether-ketone.
Taking the surface modified polyether ether ketone prepared in example 1 as an example, the polyether ether ketone with the polydopamine coating obtained in step (1) in example 1 is PEEK-PDA, the grafted modified polyether ether ketone obtained in step (2) in example 1 is PEEK-PDA-Alg, and the surface modified polyether ether ketone obtained in step (3) in example 1 is PEEK-PDA-Alg (Ca 2+).
Scanning electron microscope scanning is carried out on PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) respectively, and a scanning electron microscope diagram is shown in figure 3. As can be seen from the figure, the PEEK sample surface has significant indentations and holes; the surface of the grafted material can obviously show that the polydopamine coating and the sodium alginate coating are adhered to the surface of the sample.
The surface contact angles of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) were measured, respectively, and the measurement results are shown in FIG. 4. From the figure, it can be seen that the contact angle of the surface of the unmodified PEEK is about 82 degrees, and the contact angle of the PEEK surface is reduced to (76.43 degrees) after the poly-dopamine coating is grafted on the PEEK surface; the contact angle after grafting sodium alginate is reduced to (71.31 °); the contact angle of the complex metal ion decreases to (62.33 °); the measurement result of the contact angle shows that the surface wettability of the PEEK material is changed from hydrophobic to hydrophilic.
The results of the X-ray photoelectron spectroscopy (XPS) test of PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+) are shown in FIG. 5, wherein FIG. 5 (a) is a C1s high resolution result chart, FIG. 5 (b) is an O1s high resolution result chart, FIG. 5 (C) is an N1s high resolution result chart, and FIG. 5 (d) is a Ca2p high resolution result chart. As can be seen from the high resolution map of fig. 5 (b) O1s, the surface of PEEK is modified before and after grafting, and the original double peak of PEEK is changed into a hill-inclusion peak, which indicates that the chemical bonding related to O may be changed before and after grafting; (c) The graph (d) further demonstrates that the coating adheres to the material surface.
MC3T3-E1 cell culture experiments are respectively carried out by PEEK, PEEK-PDA, PEEK-PDA-Alg and PEEK-PDA-Alg (Ca 2+), cell activity after 1 day and 5 days of culture is detected by using an Alarm Blue kit in the culture process, and the detection results are shown in FIG. 6; the fluorescence results of the cells after 3 days of culture are shown in FIG. 7. The results show that with increasing incubation time, the cell activity of the material surface after grafting coating increased, but there was no significant difference between groups; this may be due to degradation or shedding of the coating surface after prolonged incubation, resulting in no significant difference in cell activity values.
In conclusion, compared with unmodified PEEK, the wettability, the microcosmic appearance, the surface chemical composition and the cell compatibility of the PEEK-PDA-Alg (Ca 2+) surface are improved, and the method for carrying out surface modification on the PEEK based on the main chain grafting method can effectively improve the bioactivity of the PEEK surface.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for carrying out surface modification on polyether-ether-ketone based on a main chain grafting method is characterized by comprising the following steps:
S10, depositing dopamine on the surface of the polyether-ether-ketone to obtain the polyether-ether-ketone with the polydopamine coating;
Step S20, grafting sodium alginate on the surface of the polyether-ether-ketone with the polydopamine coating by adopting a main chain grafting method to obtain grafted modified polyether-ether-ketone;
Step S30, chemically crosslinking metal ions on the surface of the grafted modified polyether-ether-ketone to obtain surface modified polyether-ether-ketone;
The step S10 is as follows: adding polyether-ether-ketone and dopamine hydrochloride into a buffer solution, stirring, separating out solid matters, cleaning, and drying to obtain polyether-ether-ketone with a polydopamine coating;
the step S30 includes:
s31, adding the grafted modified polyether-ether-ketone into a metal ion solution, stirring, separating out solid matters, cleaning and drying to obtain surface modified polyether-ether-ketone; the metal ion solution includes one of copper ions, calcium ions, magnesium ions, zinc ions, and iron ions.
2. The method for surface modification of polyetheretherketone by backbone grafting according to claim 1, wherein in step S10, dopamine hydrochloride is added to a concentration of 1-10 mg/mL.
3. The method for surface modification of polyetheretherketone by backbone grafting according to claim 1, wherein in step S10, the pH of the buffer is 8.5-10.0.
4. The method for surface modification of polyetheretherketone based on backbone grafting according to claim 1, wherein the step S20 comprises:
S21, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into a sodium alginate solution, stirring, adding the polyether-ether-ketone with the polydopamine coating, continuously stirring, separating out solid matters, washing and drying to obtain the grafted modified polyether-ether-ketone.
5. The method for surface modification of polyether-ether-ketone by backbone grafting according to claim 4, wherein the concentration of the sodium alginate solution in the step S21 is 0.01-10 mol/L.
6. The method for surface modification of polyetheretherketone based on backbone grafting according to claim 4, wherein in step S21, the molar amount ratio of sodium alginate to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1: (1-10).
7. The method for surface modification of polyetheretherketone based on backbone grafting according to claim 4, wherein in step S21, the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to the N-hydroxysuccinimide is 1: (0.5-7).
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