CN107652394A - 抗生物粘附材料及其制备方法和表面涂覆有该抗生物粘附材料的金属器械 - Google Patents
抗生物粘附材料及其制备方法和表面涂覆有该抗生物粘附材料的金属器械 Download PDFInfo
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- CN107652394A CN107652394A CN201710928693.4A CN201710928693A CN107652394A CN 107652394 A CN107652394 A CN 107652394A CN 201710928693 A CN201710928693 A CN 201710928693A CN 107652394 A CN107652394 A CN 107652394A
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- monomer
- phosphonic acids
- antibiont
- adhesion material
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 96
- 229920001577 copolymer Polymers 0.000 claims abstract description 51
- -1 phosphonate ester Chemical class 0.000 claims abstract description 46
- 229920001519 homopolymer Polymers 0.000 claims abstract description 33
- 150000003009 phosphonic acids Chemical class 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical group N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical group CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical group Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 24
- 229920000642 polymer Polymers 0.000 abstract description 17
- 102000018697 Membrane Proteins Human genes 0.000 abstract description 6
- 108010052285 Membrane Proteins Proteins 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 241001044369 Amphion Species 0.000 description 19
- 239000000956 alloy Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000007769 metal material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010067268 Post procedural infection Diseases 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000702 anti-platelet effect Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000028993 immune response Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers 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
- C08F130/02—Homopolymers 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F220/10—Esters
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- Animal Behavior & Ethology (AREA)
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Abstract
本发明提供一种抗生物粘附材料,为两性离子单体与膦酸或膦酸酯单体共聚形成的共聚物。本发明另一方面提供该抗生物粘附材料的制备方法,将两性离子单体与膦酸或膦酸酯单体直接混合共聚,或先制备两种单体中一种单体的均聚物,然后以制得的均聚物作为大分子引发剂或链转移剂,以两种单体中另一种单体作为聚合单体,制备两性离子单体与膦酸或膦酸酯单体的共聚物。本发明还提供一种抗生物粘附的金属器械,该金属器械表面设置有上述抗生物粘附材料的涂层。本发明的抗生物粘附材料稳定性高,通过简单的涂层工艺即可在金属表面形成稳定的聚合物涂层;经抗生物粘附材料表面改性的金属表面蛋白质的非特异性吸附显著降低,抗生物粘附性能显著提高。
Description
技术领域
本发明属于生物医用材料领域,具体涉及一种用于抗生物粘附材料及其制备方法和表面涂覆有该抗生物粘附材料的金属器械。
技术背景
金属材料因具有高的机械强度、可加工性和一定的生物相容性等诸多优点而被广泛应用于生物医用领域。然而,金属材料固有的生物惰性以及缺乏有效抗生物粘附性能(抗炎症、抗菌、抗凝血等)容易导致免疫反应,引起术后感染并形成血栓,大大地降低了用金属材料制备植入型器械的生物安全性能。因此,在植入型金属器械表面构建高效的抗生物粘附涂层一直是金属器械改性的热点与难点。
表面改性是一种有效改善或提高材料性能的途径。它可在保持基材物理机械性能的同时赋予材料新的功能。在过去的二十多年中,采用两性离子材料来提高各类生物医用金属材料的抗生物粘附性能引起了广泛的关注。通过将带有特定引发基团的硅烷偶联剂固定在金属表面,两性离子单体能够可控地在金属表面发生聚合,从而在金属表面可控地构建功能性两性离子聚合物涂层,提高基材的抗生物粘附性能(Acta Biomater.,2016,40,78;ACSAppl.Mater.Inter.,2017,9,47)。然而,有研究报道硅烷偶联剂与金属的结合水解稳定性欠佳,因此,在生理环境下的使用有较大的限制。
多巴胺及其衍生物是近年来受到广泛关注的一类高效粘合材料。通过在弱碱性条件下的聚合,多巴胺几乎能在所有材料表面形成稳定的多巴胺聚合物(Science,2007,318,426)。但是这一特性通常仅用于金属表面的固定的基于多巴胺的引发剂或者引发体系的制备,构建两性离子聚合物还需要后续较为繁琐的聚合反应。
发明内容
本发明的目的是提供一种稳定的抗生物粘附材料。
本发明的另一目的是提供上述抗生物粘附材料的制备方法和表面涂覆有上述抗生物粘附材料的抗生物粘附金属器械。
技术方案:本发明提供一种抗生物粘附材料,该抗生物粘附材料为两性离子单体与膦酸或膦酸酯单体共聚形成的共聚物。
两性离子单体为磷铵、羧铵或磺铵两性离子单体,磷铵、羧铵或磺铵两性离子单体结构式分别如下:
磷铵:
磺铵:
羧铵:
n=1~8 m=1~12
R:
膦酸或膦酸酯单体为结构式如下所示的不饱和膦酸或膦酸酯单体:
R1=H或OCH3或OCH2CH3
上述共聚物由物质的量之比为99∶1~1∶99的两性离子单体和膦酸或膦酸酯单体共聚形成,共聚物分子量为5000~1000000,分子量分散系数为1.1~10.0。
两性离子单体与膦酸或膦酸酯单体形成共聚物的共聚方法为无规自由基共聚、原子转移自由基聚合或可逆加成断裂链转移自由基聚合。
本发明另一方面提供上述抗生物粘附材料的制备方法,该制备方法包括方法A和方法B中任意一种方法:
方法A:将两性离子单体与膦酸或膦酸酯单体混合并溶解,在引发剂和催化剂存在下进行共聚反应,得到两性离子单体与膦酸或膦酸酯单体的共聚物;
方法B:制备包含两性离子单体和膦酸或膦酸酯单体的两种单体中一种单体的均聚物,然后以均聚物作为大分子引发剂或链转移剂,以两种单体中另一种单体作为聚合单体,得到两性离子单体与膦酸或膦酸酯单体的共聚物。
方法A和方法B都是在惰性气氛中进行的,惰性气氛为氮气或氩气气氛。
方法A中,共聚反应使用的溶剂为水、磷酸盐缓冲液(PBS)、三氟乙醇或二甲亚砜,引发剂为过硫酸盐或过氧化氢,催化剂为亚铁盐、亚硫酸盐或四甲基乙二胺,反应温度为20~90℃,反应时间为1~48h,两性离子单体与膦酸或膦酸酯单体的物质的量之比为99∶1~1∶99。
方法B中,制备均聚物和共聚物的反应中使用的溶剂为水、磷酸盐缓冲液或三氟乙醇,反应温度为20~90℃,反应时间为1~48h;制备均聚物和共聚物的反应中使用了引发剂和催化剂或链转移剂;制备均聚物和共聚物的反应中使用的催化剂为溴化亚铜/联二吡啶复合催化剂或氯化亚铜/联二吡啶复合催化剂;制备均聚物的反应中使用的引发剂为2-溴异丁酸乙酯或偶氮二异丁腈,制备均聚物的反应中使用的链转移剂为2-氰基-2-丙基苯并二硫或甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯。
本发明另一方面提供一种抗生物粘附的金属器械,该金属器械表面设置有包含上述抗生物粘附材料的涂层。
金属器械为钛、钛合金、不锈钢或镁合金器械;该抗生物粘附的金属器械的制备方法包括以下步骤:
1)配制所述抗生物粘附材料的溶液,使该溶液中所述抗生物粘附材料的浓度为0.5~200mg/mL;
2)将经过等离子体清洗的金属器械在步骤1)配制的所述抗生物粘附材料的溶液中浸泡1min~24h,取出后在20~200℃反应1~48h。
步骤2)之后,将经步骤2)处理的金属器械索氏提取24~72h,以清洗金属器械表面杂质。
有益效果:本发明通过简单的方法制得抗生物粘附材料,该抗生物粘附材料稳定性高、生物相容性好、抗生物粘附性好,通过简单的涂层工艺即可在金属表面形成稳定的聚合物涂层,可用于金属器械表面改性的抗生物粘附共聚物涂层,还可用于制备金属基生物相容性材料及其器械,适用于各种医用金属材料,在生物医疗领域有广阔的市场应用前景。经两性离子/膦酸(酯)聚合物涂层改性的金属表面蛋白质的非特异性吸附显著降低,抗生物粘附性能(低蛋白质吸附,高抗血小板粘附、高抗细胞粘附、高抗细菌粘附)显著提高。
附图说明
图1抗生物粘附材料核磁共振图谱;
图2两种不同摩尔比的抗生物粘附材料GPC曲线(重均分子量Mw及分子量分散系数PDI);
图3抗生物粘附材料改性前后钛合金表面XPS图谱;
图4抗生物粘附材料改性前后金属表面蛋白吸附对比图;
图5抗生物粘附材料改性前后金属表面血小板粘附SEM对比照片;
图6抗生物粘附材料改性前后金属表面细胞粘附对比图。
图7抗生物粘附材料改性前后金属表面大肠杆菌粘附对比图;
具体实施方式
实施例1
(1)抗生物粘附材料的制备方法为:
在氩气保护下,将(0.75mmol)磺胺两性离子单体(n=2,m=3,R:甲基丙烯酸酯型)与(6.75mmol)膦酸单体(n=1,R1:H,R2:甲基丙烯酸酯型)以摩尔比1∶9的比例溶解于水中,再将过硫酸钾(APS)(0.5mmol)、四甲基乙二胺(TEMED)(11.25μL)加入反应体系,经均匀混合后于室温下反应24h,产物经甲醇沉降后得到白色聚合物,将聚合物于室温下真空干燥,制备得到两性离子/膦酸共聚物,其分子量为9.9万,分子量分散系数为2.7。
磺铵:
膦酸:
(2)抗生物粘附的钛合金材料制备方法为:
将步骤(1)制得的共聚物溶于无菌PBS中配制成50mg/mL共聚物PBS溶液,再将经等离子处理后的钛合金在新配制的共聚物PBS溶液中浸渍12h。取出钛合金材料并于室温下真空干燥48小时。将经真空干燥过后的钛合金在水中索氏提取24h,并真空干燥,即得抗生物粘附的钛合金材料。
实施例2
(1)抗生物粘附材料的制备方法为:
在氮气保护下,将(1mmol)磷铵两性离子单体(n=3,m=4,R:丙烯酸酯型)溶解于甲醇(10mL)中,再将2-溴异丁酸乙酯(0.2mmol)、溴化亚铜(0.2mmol)/联二吡啶(0.4mmol)加入反应体系,经均匀混合后于37℃下反应12h,经乙醚沉降后的白色聚合物于室温下真空干燥,即得两性离子均聚物。向制得的两性离子均聚物中加入39mmol膦酸单体,以膦酸单体(n=3,R1:H,R2:苯乙烯型)为聚合单体,以两性离子均聚物为大分子引发剂(膦酸单体与制备均聚物使用的磷铵两性离子单体的摩尔比为97.5∶2.5),经与两性离子均聚物制备同样的聚合条件(单体浓度以及催化剂类型和浓度),在37℃下反应12h,制备得到两性离子/膦酸共聚物。
磷铵:
膦酸:
(2)抗生物粘附的钛合金材料制备方法为:
将步骤(1)制得的共聚物溶于甲醇中配制成100mg/mL共聚物甲醇溶液,再将经等离子处理后的钛合金在新配制的共聚物甲醇溶液溶液中浸渍30min。取出钛合金材料并于80℃下真空干燥24小时。将经真空干燥过后的钛合金在水中索氏提取36h,并真空干燥,即得抗生物粘附的钛合金材料。
实施例3
(1)抗生物粘附材料的制备方法为:
在氩气保护下,将羧铵两性离子单体(n=3,m=5,R:甲基丙烯酰胺酯型)溶解于三氟乙醇中,再将偶氮二异丁腈、2-氰基-2-丙基苯并二硫加入反应体系(各物质的摩尔比为羧铵两性离子单体∶偶氮二异丁腈∶2-氰基-2-丙基苯并二硫=50∶1∶1),经均匀混合后于60℃下反应24h,经乙醚沉降后的白色聚合物于室温下真空干燥,即得两性离子均聚物。向制得的两性离子均聚物中加入膦酸酯单体,以膦酸酯单体(n=4,R1:OCH2CH3,R2:乙烯基型)为聚合单体,以两性离子均聚物为大分子链转移剂(膦酸酯单体与制备均聚物使用的羧铵两性离子单体的摩尔比为1∶1),经与两性离子均聚物制备同样的聚合条件(单体浓度以及催化剂类型和浓度),在60℃下反应24h,制备得到两性离子/膦酸酯共聚物。
羧铵:
膦酸酯:
(2)抗生物粘附的钛合金材料制备方法为:
将步骤(1)制得的共聚物溶于三氟乙醇中配制成10mg/mL共聚物溶液,再将经等离子处理后的钛金属在新配制的共聚物甲醇溶液中浸渍10min。取出钛金属材料并于120℃下真空干燥24小时。将经真空干燥过后的钛金属在水中索氏提取48h,并真空干燥,即得抗生物粘附的钛金属材料。
实施例4
(1)抗生物粘附材料的制备方法为:
在氮气保护下,将(4.5mmol)羧铵两性离子单体(n=6,m=3,R:乙烯基型)与(0.3mmol)膦酸单体(n=6,R1:H,R2:丙烯酸酯型)以摩尔比15∶1的比例溶解于7.5mL PBS中,再将过硫酸钾(APS)0.5mmol、四甲基乙二胺(TEMED)11.25μL加入反应体系,经均匀混合后于50℃下反应24h,经甲醇沉降后的白色聚合物于室温下真空干燥,制备得到两性离子/膦酸共聚物,共聚物分子量为13.7万,分子量分散系数为3.4。
羧铵:
膦酸:
(2)抗生物粘附的钛合金材料制备方法为:
将步骤(1)制得的共聚物溶于无菌PBS中配制成5mg/mL共聚物水溶液,再将经等离子处理后的镁合金在新配制的共聚物水溶液中浸渍1h。取出镁合金材料并于室温下真空干燥12小时。将经真空干燥过后的镁合金在水中索氏提取72h,并真空干燥,即得抗生物粘附的镁合金材料。
实施例5
(1)抗生物粘附材料的制备方法为:
在氮气保护下,将膦酸酯单体(n=1,R1:OCH2CH3,R2:甲基丙烯酰胺酯型)溶解于三氟乙醇中,再将2-溴异丁酸乙酯、氯化亚铜/联二吡啶加入反应体系(各物质的摩尔比为膦酸酯单体∶2-溴异丁酸乙酯∶氯化亚铜∶联二吡啶=50∶1∶1∶2),经均匀混合后于室温下反应24h,经乙醚沉降后的白色聚合物于室温下真空干燥,即得膦酸酯均聚物。向制得的膦酸酯均聚物中加入磺铵两性离子单体,以磺铵两性离子单体(n=5,m=2,R:甲基丙烯酸酯型)为聚合单体,以膦酸酯均聚物为大分子链转移剂(磺铵两性离子单体与制备膦酸酯均聚物使用的膦酸酯单体的摩尔比为1∶1),经均匀混合后于37℃下反应12h,制备得到两性离子/膦酸酯共聚物。
磺铵:
膦酸酯:
(2)抗生物粘附的钛合金材料制备方法为:
将共聚物溶于二甲亚砜中配制成1mg/mL共聚物溶液,再将经等离子处理后的不锈钢在新配制的共聚物溶液中浸渍30min。取出不锈钢材料并于80℃下真空干燥24小时。将经真空干燥过后的不锈钢在水中索氏提取36h,并真空干燥,即得抗生物粘附的不锈钢材料。
实施例6
(1)抗生物粘附材料的制备方法为:
在氩气保护下,将膦酸酯单体(n=4,R1:OCH3,R2:丙烯酰胺酯型)溶解于甲醇中,再将偶氮二异丁腈、甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯(各物质的摩尔比为膦酸酯单体∶偶氮二异丁腈∶甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯=50∶1∶1)加入反应体系,经均匀混合后于室温下反应36h,经乙醚沉降后的白色聚合物于室温下真空干燥,即得膦酸酯均聚物。向制得的膦酸酯均聚物中加入羧铵两性离子单体,以羧铵两性离子(n=4,m=6,R:苯乙烯)为聚合单体,以膦酸酯均聚物为大分子链转移剂(羧铵两性离子单体与制备膦酸酯均聚物使用的膦酸酯单体的摩尔比为1∶1),经均匀混合后于37℃下反应12h,制备得到两性离子/膦酸酯共聚物。
羧铵:
膦酸酯:
(2)抗生物粘附的钛合金材料制备方法为:
将共聚物溶于甲醇中配制成20mg/mL共聚物溶液,再将经等离子处理后的钛合金在新配制的共聚物甲醇溶液中浸渍10min。取出钛合金材料并于120℃下真空干燥24小时。将经真空干燥过后的钛合金在水中索氏提取48h,并真空干燥,即得抗生物粘附的钛合金材料。
实施例7
(1)抗生物粘附材料的制备方法为:
在氩气保护下,将(7.125mmol)磺铵两性离子单体(n=2,m=3,R:甲基丙烯酸酯型)与(0.375mmol)膦酸单体(n=1,R1:H,R2:甲基丙烯酸酯型)以摩尔比95∶5的比例溶解于水中,再将过硫酸钾(APS)0.5mmol、四甲基乙二胺(TEMED)11.25μL加入反应体系,经均匀混合后于室温下反应24h,产物经甲醇沉降后得到白色聚合物,将聚合物于室温下真空干燥,制备得到两性离子/膦酸共聚物,共聚物分子量为23.7万,分子量分散系数为2.4。
磺铵:
膦酸:
(2)抗生物粘附的钛合金材料制备方法为:
将步骤(1)制得的共聚物溶于无菌PBS中配制成50mg/mL共聚物PBS溶液,再将经等离子处理后的钛合金在新配制的共聚物PBS溶液中浸渍12h。取出钛合金材料并于室温下真空干燥48小时。将经真空干燥过后的钛合金在水中索氏提取24h,并真空干燥,即得抗生物粘附的钛合金材料。
结构、性能表征
图1为抗生物粘附材料的核磁共振图谱,pSBMA-co-pMMPA代表磺铵两性离子单体与膦酸单体反应生成的共聚物,pDEMMP-b-pSBMA代表磷酸酯单体与磺胺两性离子的均聚物反应生成的共聚物,核磁图谱可看出各特征峰明显,且聚合物不含杂质;图2为抗生物粘附材料凝胶渗透色谱(GPC)曲线(重均分子量Mw及分子量分散系数PDI);图3为抗生物粘附材料改性前后钛合金表面的XPS图谱,其中TC4代表抗生物粘附材料改性前的钛合金,TC4-pSBMA-co-pMMPA代表抗生物粘附材料改性后的钛合金,由图3可看抗生物粘附材料成功涂覆到了合金表面。从图1到图3可以看出,本发明成功制备了各种两性离子/膦酸(酯)聚合物,并通过简单的工艺成功将聚合物接枝到金属基材表面。
图4为经抗生物粘附材料改性前后金属表面蛋白吸附量对比图,由图4看出抗生物粘附材料改性后的金属表面蛋白吸附量明显低于未改性的金属表面蛋白吸附量;图5为经抗生物粘附材料改性前后金属表面血小板粘附SEM对比照片,由图5可以看出抗生物粘附材料改性后的金属表面血小板的粘附数量明显减少;图6为经抗生物粘附材料改性前后金属表面细胞粘附对比图,由图6可以看出表面改性后细胞的粘附数量明显减少;图7为经抗生物粘附材料改性前后金属表面大肠杆菌粘附对比图,由图7可以看出,抗生物粘附材料改性后的大肠杆菌的粘附数量明显减少。从图3到图7可以看出:经抗生物粘附材料改性的金属表面显著降低蛋白质的非特异性的吸附,而且几乎不再粘附血小板、大肠杆菌和细胞,得到抗生物粘附性能显著提升的金属表面。
Claims (10)
1.一种抗生物粘附材料,其特征在于,该抗生物粘附材料为两性离子单体与膦酸或膦酸酯单体共聚形成的共聚物。
2.根据权利要求1所述的抗生物粘附材料,其特征在于,所述两性离子单体为磷铵、羧铵或磺铵两性离子单体,所述磷铵、羧铵或磺铵两性离子单体结构式分别如下所示:
磷铵:
磺铵:
羧铵:
R:
3.根据权利要求1所述的抗生物粘附材料,其特征在于,所述膦酸或膦酸酯单体为不饱和膦酸或膦酸酯单体,所述膦酸或膦酸酯单体结构式如下所示:
R1=H或OCH3或OCH2CH3
4.根据权利要求1所述的抗生物粘附材料,其特征在于,所述共聚物由物质的量之比为99∶1~1∶99的两性离子单体和膦酸或膦酸酯单体共聚形成,所述共聚物分子量为5000~1000000,分子量分散系数为1.1~10.0。
5.权利要求1~4中任意一项所述的抗生物粘附材料的制备方法,其特征在于,该制备方法包括方法A和方法B中任意一种方法:
方法A:将两性离子单体与膦酸或膦酸酯单体混合并溶解,在引发剂和催化剂存在下进行共聚反应,得到两性离子单体与膦酸或膦酸酯单体的共聚物;
方法B:制备包含两性离子单体和膦酸或膦酸酯单体的两种单体中一种单体的均聚物,然后以所述均聚物作为大分子引发剂或链转移剂,以所述两种单体中另一种单体作为聚合单体,制备两性离子单体与膦酸或膦酸酯单体的共聚物。
6.根据权利要求5所述的制备方法,其特征在于,方法A和方法B都是在惰性气氛中进行的。
7.根据权利要求5所述的制备方法,其特征在于,方法A中,共聚反应使用的溶剂为水、磷酸盐缓冲液、三氟乙醇或二甲亚砜,引发剂为过硫酸盐或过氧化氢,催化剂为亚铁盐、亚硫酸盐或四甲基乙二胺,反应温度为20~90℃,反应时间为1~48h。
8.根据权利要求5所述的制备方法,其特征在于,方法B中,制备所述均聚物和所述共聚物的反应中使用的溶剂为水、磷酸盐缓冲液或三氟乙醇,反应温度为20~90℃,反应时间为1~48h;制备均聚物和共聚物的反应中使用了引发剂和催化剂或链转移剂;制备所述均聚物和所述共聚物的反应中使用的催化剂为溴化亚铜/联二吡啶或氯化亚铜/联二吡啶;制备所述均聚物的反应中使用的引发剂为2-溴异丁酸乙酯或偶氮二异丁腈,制备所述均聚物的反应中使用的链转移剂为2-氰基-2-丙基苯并二硫或甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯。
9.一种抗生物粘附的金属器械,其特征在于,该金属器械表面设置有包含权利要求1~4中任意一项所述的抗生物粘附材料的涂层。
10.根据权利要求9所述的抗生物粘附的金属器械,其特征在于,所述金属器械为钛、钛合金、不锈钢或镁合金器械;所述抗生物粘附的金属器械的制备方法包括以下步骤:
1)配制所述抗生物粘附材料的溶液,使该溶液中所述抗生物粘附材料的浓度为0.5~200mg/mL;
2)将经过等离子体清洗的金属器械在步骤1)配制的所述抗生物粘附材料的溶液中浸泡1min~24h,取出后在20~200℃反应1~48h。
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