电化学法沉积水杨酸衍生物改善不锈钢表面生物性能的研究
发布时间：2018-08-02 20:39
【摘要】：医用316L不锈钢材料由于其优良的力学性能及化学稳定性,在人工植入关节,血管支架等介入器械制造中得到了广泛应用。然而,这些长期植入人体内与血液/体液接触的介入器械,其自身抗凝血性能不足,且植入后腐蚀产物和病理反应均会影响其使用功能的正常发挥。因此,改善不锈钢表面的生物与血液相容性及耐腐蚀性一直是植入型不锈钢材料的研究热点。我们注意到,水杨酸具有类似苯酚的电氧化聚合的性质,利用水杨酸可反应的羧基,分别合成了三种不同的水杨酸衍生物,探索采用电化学方法分别将其沉积到医用316L不锈钢表面的可行性,以提高不锈钢植植入材料的耐腐蚀性,生物相容性、血液相容性及抗菌性等。主要工作如下:由于鲜见有关水杨酸衍生物在水溶液中电氧化聚合的研究报道,本文首先探索了水杨酸甲酯在碱性水溶液中电氧化聚合到316L不锈钢表面的可行性。采用电化学循环伏安法将水杨酸甲酯沉积到316L不锈钢表面。运用红外光谱法,研究了经水杨酸甲酯改性前后不锈钢表面的化学结构成分的变化;利用Tafel曲线和电化学阻抗谱图评估改性前后不锈钢样品的抗腐蚀性能等;使用SEM、水接触角来表征不锈钢表面形貌及亲水性。结果表明,水杨酸甲酯可以通过电化学方法沉积到316L不锈钢表面。采用电化学沉积方法将葡聚糖接枝到316L不锈钢表面,以提高材料的血液相容性,同时提高不锈钢的抗腐蚀性能。在二甲亚砜溶剂中,通过酯交换一步反应,将可以阳极电氧化聚合的水杨酸酯接枝到生物/血液相容性良好,但有机溶剂溶解性较差的葡聚糖上,得到产物葡聚糖-水杨酸酯(DEX-S)。采用核磁氢谱进行结构分析,计算改性产物的接枝率;使用电化学循环伏安法将DEX-S沉积到316L不锈钢表面;运用红外光谱表征经葡聚糖改性前后不锈钢表面的化学结构成分;利用Tafel曲线和电化学阻抗谱图评估改性前后不锈钢样品的抗腐蚀性能;使用SEM、AFM和水接触角来表征不锈钢表面形貌及亲水性;样品的抗蛋白吸附能力通过石英晶体微天平定量测试;选用人血小板吸附及溶血性试验来评估改性前后不锈钢样品的血液相容性。采用电化学沉积方法将生物相容性优异的PHEMA接枝到316L不锈钢表面,提高材料的组织相容性,同时提高不锈钢的抗腐蚀性能。先在乙酸乙酯溶剂中运用沉淀聚合法制备出分子量相对均一的PHEMA-GMA共聚物,再通过环氧开环反应,将可以阳极电氧化聚合的水杨酸接枝到PHEMA-GMA共聚物上,运用凝胶渗透色谱检测聚合物反应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计来计算;使用电化学恒电位法将PHEMA-GMA-S沉积到316L不锈钢表面;运用红外光谱表征经PHEMA改性前后不锈钢的表面化学结构成分;利用Tafel曲线和电化学阻抗谱图评估改性后不锈钢样品的抗腐蚀性能;使用SEM、水接触角来表征不锈钢表面形貌及亲水性;样品的抗蛋白吸附能力通过石英晶体微天平定量测试;选用人血小板吸附及溶血性试验来评估改性前后不锈钢样品的血液相容性。采用电化学沉积方法将β-环糊精接枝到不锈钢表面,赋予其药物负载和释放功能,同时提高不锈钢的抗腐蚀性能。在二甲亚砜溶剂中,通过酯交换一步反应,将水杨酸酯接枝到具有包合小分子能力的β-环糊精上,产物β-环糊精-水杨酸酯(β-CD-S)的结构使用核磁氢谱表征;使用电化学循环伏安法将β-CD-S沉积到316L不锈钢表面;运用红外光谱及X射线光电子能谱表征β-环糊精改性前后不锈钢的表面化学结构成分;利用Tafel曲线和电化学阻抗谱图评估改性后不锈钢样品的抗腐蚀性能;使用SEM、AFM和水接触角来表征不锈钢表面形貌及亲水性;氯霉素选作模型药物,改性不锈钢的药物负载和释放能力通过石英晶体微天平定量测试;选用大肠杆菌来评估改性及载药前后不锈钢样品的抗菌效果。
[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.
【学位授予单位】：上海大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TG174.4
本文编号：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.
【学位授予单位】：上海大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TG174.4
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相关期刊论文 前2条
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 孙艳,王鹏;水杨酸对黄瓜幼苗抗高温胁迫能力的影响[J];西北植物学报;2003年11期
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