電化學(xué)法沉積水楊酸衍生物改善不銹鋼表面生物性能的研究
發(fā)布時(shí)間：2018-08-02 20:39
【摘要】：醫(yī)用316L不銹鋼材料由于其優(yōu)良的力學(xué)性能及化學(xué)穩(wěn)定性,在人工植入關(guān)節(jié),血管支架等介入器械制造中得到了廣泛應(yīng)用。然而,這些長(zhǎng)期植入人體內(nèi)與血液/體液接觸的介入器械,其自身抗凝血性能不足,且植入后腐蝕產(chǎn)物和病理反應(yīng)均會(huì)影響其使用功能的正常發(fā)揮。因此,改善不銹鋼表面的生物與血液相容性及耐腐蝕性一直是植入型不銹鋼材料的研究熱點(diǎn)。我們注意到,水楊酸具有類似苯酚的電氧化聚合的性質(zhì),利用水楊酸可反應(yīng)的羧基,分別合成了三種不同的水楊酸衍生物,探索采用電化學(xué)方法分別將其沉積到醫(yī)用316L不銹鋼表面的可行性,以提高不銹鋼植植入材料的耐腐蝕性,生物相容性、血液相容性及抗菌性等。主要工作如下:由于鮮見有關(guān)水楊酸衍生物在水溶液中電氧化聚合的研究報(bào)道,本文首先探索了水楊酸甲酯在堿性水溶液中電氧化聚合到316L不銹鋼表面的可行性。采用電化學(xué)循環(huán)伏安法將水楊酸甲酯沉積到316L不銹鋼表面。運(yùn)用紅外光譜法,研究了經(jīng)水楊酸甲酯改性前后不銹鋼表面的化學(xué)結(jié)構(gòu)成分的變化;利用Tafel曲線和電化學(xué)阻抗譜圖評(píng)估改性前后不銹鋼樣品的抗腐蝕性能等;使用SEM、水接觸角來表征不銹鋼表面形貌及親水性。結(jié)果表明,水楊酸甲酯可以通過電化學(xué)方法沉積到316L不銹鋼表面。采用電化學(xué)沉積方法將葡聚糖接枝到316L不銹鋼表面,以提高材料的血液相容性,同時(shí)提高不銹鋼的抗腐蝕性能。在二甲亞砜溶劑中,通過酯交換一步反應(yīng),將可以陽極電氧化聚合的水楊酸酯接枝到生物/血液相容性良好,但有機(jī)溶劑溶解性較差的葡聚糖上,得到產(chǎn)物葡聚糖-水楊酸酯(DEX-S)。采用核磁氫譜進(jìn)行結(jié)構(gòu)分析,計(jì)算改性產(chǎn)物的接枝率;使用電化學(xué)循環(huán)伏安法將DEX-S沉積到316L不銹鋼表面;運(yùn)用紅外光譜表征經(jīng)葡聚糖改性前后不銹鋼表面的化學(xué)結(jié)構(gòu)成分;利用Tafel曲線和電化學(xué)阻抗譜圖評(píng)估改性前后不銹鋼樣品的抗腐蝕性能;使用SEM、AFM和水接觸角來表征不銹鋼表面形貌及親水性;樣品的抗蛋白吸附能力通過石英晶體微天平定量測(cè)試;選用人血小板吸附及溶血性試驗(yàn)來評(píng)估改性前后不銹鋼樣品的血液相容性。采用電化學(xué)沉積方法將生物相容性優(yōu)異的PHEMA接枝到316L不銹鋼表面,提高材料的組織相容性,同時(shí)提高不銹鋼的抗腐蝕性能。先在乙酸乙酯溶劑中運(yùn)用沉淀聚合法制備出分子量相對(duì)均一的PHEMA-GMA共聚物,再通過環(huán)氧開環(huán)反應(yīng),將可以陽極電氧化聚合的水楊酸接枝到PHEMA-GMA共聚物上,運(yùn)用凝膠滲透色譜檢測(cè)聚合物反應(yīng)前后分子量大小及分布;PHEMA-GMA-S的接枝率使用紫外分光光度計(jì)來計(jì)算;使用電化學(xué)恒電位法將PHEMA-GMA-S沉積到316L不銹鋼表面;運(yùn)用紅外光譜表征經(jīng)PHEMA改性前后不銹鋼的表面化學(xué)結(jié)構(gòu)成分;利用Tafel曲線和電化學(xué)阻抗譜圖評(píng)估改性后不銹鋼樣品的抗腐蝕性能;使用SEM、水接觸角來表征不銹鋼表面形貌及親水性;樣品的抗蛋白吸附能力通過石英晶體微天平定量測(cè)試;選用人血小板吸附及溶血性試驗(yàn)來評(píng)估改性前后不銹鋼樣品的血液相容性。采用電化學(xué)沉積方法將β-環(huán)糊精接枝到不銹鋼表面,賦予其藥物負(fù)載和釋放功能,同時(shí)提高不銹鋼的抗腐蝕性能。在二甲亞砜溶劑中,通過酯交換一步反應(yīng),將水楊酸酯接枝到具有包合小分子能力的β-環(huán)糊精上,產(chǎn)物β-環(huán)糊精-水楊酸酯(β-CD-S)的結(jié)構(gòu)使用核磁氫譜表征;使用電化學(xué)循環(huán)伏安法將β-CD-S沉積到316L不銹鋼表面;運(yùn)用紅外光譜及X射線光電子能譜表征β-環(huán)糊精改性前后不銹鋼的表面化學(xué)結(jié)構(gòu)成分;利用Tafel曲線和電化學(xué)阻抗譜圖評(píng)估改性后不銹鋼樣品的抗腐蝕性能;使用SEM、AFM和水接觸角來表征不銹鋼表面形貌及親水性;氯霉素選作模型藥物,改性不銹鋼的藥物負(fù)載和釋放能力通過石英晶體微天平定量測(cè)試;選用大腸桿菌來評(píng)估改性及載藥前后不銹鋼樣品的抗菌效果。
[Abstract]:Because of its excellent mechanical and chemical stability, medical 316L stainless steel has been widely used in the manufacture of the interventional apparatus such as artificial implant joints and vascular stents. However, these intervening instruments which have long been implanted in the body with blood / body fluids have their own anticoagulant ability, and the corrosion products and pathological reactions are both after implantation. Therefore, the improvement of the biological and blood compatibility and corrosion resistance of the stainless steel surface has always been a hot topic in the research of implants. We have noticed that the salicylic acid has the properties of Electrooxidation polymerization similar to phenol, and three different kinds of water are synthesized by the carboxyl of salicylic acid, which can be reacted by salicylic acid. In order to improve the corrosion resistance, biocompatibility, blood compatibility and antibacterial properties of the stainless steel implant materials, the salicylic acid derivatives were prepared by electrochemical methods to deposit them on the surface of medical 316L stainless steel. The main work is as follows: there are few reports about the electrooxidation of salicylic acid derivatives in aqueous solution. The feasibility of electrooxidation and polymerization of Methylis salicylas on the surface of 316L stainless steel in alkaline aqueous solution was first explored in this paper. The electrochemical cyclic voltammetry was used to deposit Methylis salicylas on the surface of 316L stainless steel. The changes in the chemical composition of the surface of the stainless steel before and after the modification of Methylis salicylas were studied by means of infrared spectroscopy, and Ta was used. The corrosion resistance of stainless steel samples before and after modification was evaluated by FEL curve and electrochemical impedance spectroscopy. The surface morphology and hydrophilicity of stainless steel were characterized by SEM and water contact angle. The results showed that the Methylis salicylas could be deposited on the surface of 316L stainless steel by electrochemical method. The dextran was grafted to 316L stainless steel by electrodeposition. In order to improve the blood compatibility of the material and improve the corrosion resistance of the stainless steel, in the two methyl sulfoxide solvent, by transesterification, the salicylate can be grafted to the dextran with good biocompatibility and poor solubility in organic solvent, and the product of glucan - salicylate (D EX-S). The graft ratio of the modified products was calculated by the structure analysis of the nuclear magnetic hydrogen spectrum. The DEX-S was deposited on the surface of 316L stainless steel by electrochemical cyclic voltammetry, and the chemical composition of the surface of the stainless steel before and after the dextran modification was characterized by infrared spectroscopy; and the modified stainless steel samples were evaluated by the Tafel curve and the electrochemical impedance spectroscopy. The anti corrosion properties of the products were characterized by using SEM, AFM and water contact angles to characterize the surface morphology and hydrophilicity of stainless steel. The anti protein adsorption capacity of the samples was quantified by quartz crystal microbalance; the blood compatibility of the stainless steel samples before and after the modification was evaluated by human platelet adsorption and hemolytic test. The biological phase was used by electrochemical deposition. The excellent compatibility of PHEMA was grafted on the surface of 316L stainless steel to improve the microstructure compatibility and improve the corrosion resistance of stainless steel. A relatively homogeneous PHEMA-GMA copolymer was prepared by precipitation polymerization in ethyl acetate solvent, and then the anodic electropolymerization of salicylic acid was grafted by epoxy ring opening reaction. On PHEMA-GMA copolymer, the size and distribution of molecular weight before and after the reaction of polymer were detected by gel permeation chromatography, and the grafting ratio of PHEMA-GMA-S was calculated by UV spectrophotometer, and PHEMA-GMA-S was deposited on the surface of 316L stainless steel by electrochemical constant potential method, and the surface chemical junction of stainless steel before and after PHEMA modification was characterized by infrared spectroscopy. The corrosion resistance of the modified stainless steel samples was evaluated by Tafel curve and electrochemical impedance spectroscopy. The surface morphology and hydrophilicity of stainless steel were characterized by SEM and water contact angle. The anti protein adsorption capacity of the samples was quantified by quartz crystal microbalance; and the human platelet adsorption and hemolytic test were used to evaluate the modification before and after the modification. The blood compatibility of stainless steel samples was grafted onto the surface of stainless steel by electrochemical deposition. The drug load and release function were given, and the corrosion resistance of stainless steel was increased. In the two methyl sulfoxide solvent, the salicylate was grafted to the beta cyclodextrin with the ability to contain small molecules by transesterification. The structure of beta cyclodextrin - salicylate (beta -CD-S) was characterized by NMR spectroscopy, and beta -CD-S was deposited on the surface of 316L stainless steel by electrochemical cyclic voltammetry. The chemical composition of the surface of stainless steel before and after the modification of beta cyclodextrin was characterized by infrared spectroscopy and X ray photoelectron spectroscopy. The Tafel curve and electrochemical impedance spectroscopy were used. The corrosion resistance of the modified stainless steel samples was evaluated. The surface morphology and hydrophilicity of the stainless steel were characterized by SEM, AFM and water contact angles. Chloramphenicol was selected as a model drug. The drug load and release capacity of the modified stainless steel were measured by quartz crystal microbalance, and the stainless steel samples were evaluated before and after the modification and drug loading. Antibacterial effect.
【學(xué)位授予單位】：上海大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.4
本文編號(hào)：2160668
[Abstract]:Because of its excellent mechanical and chemical stability, medical 316L stainless steel has been widely used in the manufacture of the interventional apparatus such as artificial implant joints and vascular stents. However, these intervening instruments which have long been implanted in the body with blood / body fluids have their own anticoagulant ability, and the corrosion products and pathological reactions are both after implantation. Therefore, the improvement of the biological and blood compatibility and corrosion resistance of the stainless steel surface has always been a hot topic in the research of implants. We have noticed that the salicylic acid has the properties of Electrooxidation polymerization similar to phenol, and three different kinds of water are synthesized by the carboxyl of salicylic acid, which can be reacted by salicylic acid. In order to improve the corrosion resistance, biocompatibility, blood compatibility and antibacterial properties of the stainless steel implant materials, the salicylic acid derivatives were prepared by electrochemical methods to deposit them on the surface of medical 316L stainless steel. The main work is as follows: there are few reports about the electrooxidation of salicylic acid derivatives in aqueous solution. The feasibility of electrooxidation and polymerization of Methylis salicylas on the surface of 316L stainless steel in alkaline aqueous solution was first explored in this paper. The electrochemical cyclic voltammetry was used to deposit Methylis salicylas on the surface of 316L stainless steel. The changes in the chemical composition of the surface of the stainless steel before and after the modification of Methylis salicylas were studied by means of infrared spectroscopy, and Ta was used. The corrosion resistance of stainless steel samples before and after modification was evaluated by FEL curve and electrochemical impedance spectroscopy. The surface morphology and hydrophilicity of stainless steel were characterized by SEM and water contact angle. The results showed that the Methylis salicylas could be deposited on the surface of 316L stainless steel by electrochemical method. The dextran was grafted to 316L stainless steel by electrodeposition. In order to improve the blood compatibility of the material and improve the corrosion resistance of the stainless steel, in the two methyl sulfoxide solvent, by transesterification, the salicylate can be grafted to the dextran with good biocompatibility and poor solubility in organic solvent, and the product of glucan - salicylate (D EX-S). The graft ratio of the modified products was calculated by the structure analysis of the nuclear magnetic hydrogen spectrum. The DEX-S was deposited on the surface of 316L stainless steel by electrochemical cyclic voltammetry, and the chemical composition of the surface of the stainless steel before and after the dextran modification was characterized by infrared spectroscopy; and the modified stainless steel samples were evaluated by the Tafel curve and the electrochemical impedance spectroscopy. The anti corrosion properties of the products were characterized by using SEM, AFM and water contact angles to characterize the surface morphology and hydrophilicity of stainless steel. The anti protein adsorption capacity of the samples was quantified by quartz crystal microbalance; the blood compatibility of the stainless steel samples before and after the modification was evaluated by human platelet adsorption and hemolytic test. The biological phase was used by electrochemical deposition. The excellent compatibility of PHEMA was grafted on the surface of 316L stainless steel to improve the microstructure compatibility and improve the corrosion resistance of stainless steel. A relatively homogeneous PHEMA-GMA copolymer was prepared by precipitation polymerization in ethyl acetate solvent, and then the anodic electropolymerization of salicylic acid was grafted by epoxy ring opening reaction. On PHEMA-GMA copolymer, the size and distribution of molecular weight before and after the reaction of polymer were detected by gel permeation chromatography, and the grafting ratio of PHEMA-GMA-S was calculated by UV spectrophotometer, and PHEMA-GMA-S was deposited on the surface of 316L stainless steel by electrochemical constant potential method, and the surface chemical junction of stainless steel before and after PHEMA modification was characterized by infrared spectroscopy. The corrosion resistance of the modified stainless steel samples was evaluated by Tafel curve and electrochemical impedance spectroscopy. The surface morphology and hydrophilicity of stainless steel were characterized by SEM and water contact angle. The anti protein adsorption capacity of the samples was quantified by quartz crystal microbalance; and the human platelet adsorption and hemolytic test were used to evaluate the modification before and after the modification. The blood compatibility of stainless steel samples was grafted onto the surface of stainless steel by electrochemical deposition. The drug load and release function were given, and the corrosion resistance of stainless steel was increased. In the two methyl sulfoxide solvent, the salicylate was grafted to the beta cyclodextrin with the ability to contain small molecules by transesterification. The structure of beta cyclodextrin - salicylate (beta -CD-S) was characterized by NMR spectroscopy, and beta -CD-S was deposited on the surface of 316L stainless steel by electrochemical cyclic voltammetry. The chemical composition of the surface of stainless steel before and after the modification of beta cyclodextrin was characterized by infrared spectroscopy and X ray photoelectron spectroscopy. The Tafel curve and electrochemical impedance spectroscopy were used. The corrosion resistance of the modified stainless steel samples was evaluated. The surface morphology and hydrophilicity of the stainless steel were characterized by SEM, AFM and water contact angles. Chloramphenicol was selected as a model drug. The drug load and release capacity of the modified stainless steel were measured by quartz crystal microbalance, and the stainless steel samples were evaluated before and after the modification and drug loading. Antibacterial effect.
【學(xué)位授予單位】：上海大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.4
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 Mohammad Yusuf;Syed Aiman Hasan;Barket Ali;Shamsul Hayat;Qazi Fariduddin;Aqil Ahmad;;Effect of Salicylic Acid on Salinity-induced Changes in Brassica juncea[J];Journal of Integrative Plant Biology;2008年09期
2 孫艷,王鵬;水楊酸對(duì)黃瓜幼苗抗高溫脅迫能力的影響[J];西北植物學(xué)報(bào);2003年11期
，本文編號(hào)：2160668
本文鏈接：http://sikaile.net/kejilunwen/jiagonggongyi/2160668.html
最近更新
教材專著
