本文選題：鈦材 + 2-甲基丙烯酰氧乙基磷酸膽堿(MPC)　； 參考：《西南交通大學(xué)》2015年碩士論文

【摘要】：鈦及其合金具有機械強度高、耐腐蝕、生物相容性好等特點,已經(jīng)廣泛的應(yīng)用于生物醫(yī)用材料領(lǐng)域。但鈦材作為制備植入器械和人工器官的生物醫(yī)用金屬材料,其抗凝血性能還有待進一步提高。2-甲基丙烯酰氧乙基磷酸膽堿(MPC)是一種兩親性的類磷脂分子,它由磷酸膽堿極性頭和甲基丙烯酸酯部分組成。其中磷酸膽堿基團(PC基團)是生物細胞外層膜的主要成分,PC基團同時帶有正、負兩種電荷,具有超強的親水性,有效阻止了蛋白質(zhì)的吸附,表現(xiàn)出良好的生物相容性；而乙烯基的存在,可以使MPC聚合成不同類型和功能的類磷脂聚合物,類磷脂聚合物具有仿生結(jié)構(gòu),可以滿足多種生物醫(yī)學(xué)的功能需求。本論文基于改善鈦材的血液相容性的目的,合成了兩種由MPC單體和TSMA單體聚合而成的ABA型三嵌段共聚物PMPC-PTSMA-PMP C。該共聚物分兩步合成,第一步利用MPC單體和鏈轉(zhuǎn)移劑合成含鏈轉(zhuǎn)移劑的MPC的均聚物PMPC,第二步是將單體TSMA與第一步合成的聚合物再次進行聚合,合成最終目標(biāo)ABA型三嵌段聚合物PMPC-PTSMA-PMPC。利用紅外光譜(FTIR)、核磁共振(H1NMR)、凝膠滲透色譜(GPC)等表征手段表征了聚合物的結(jié)構(gòu)及分子量。聚合物的檢測結(jié)果表明,第一步反應(yīng)中,通過控制鏈轉(zhuǎn)移劑和引發(fā)劑的比例,成功合成了三種PMPC聚合物,三種聚合物的分子量均超過了100KD,分別為192KD、188KD、147KD,并優(yōu)選出了其中聚合度較好的一種,進行下一步聚合。第二步反應(yīng)中,通過調(diào)控加入的第一步合成的大分子鏈轉(zhuǎn)移劑的量和TSMA單體的量,成功合成了兩種不同分子量的共聚物PMPC-PTSMA-PMPC,分子量分別為134KD和159KD。然后,通過共價接枝的方法將合成的三嵌段共聚物固定到活化之后的鈦表面。在此期間,嘗試使用質(zhì)子(CH3OH)和非質(zhì)子(DMF)兩種溶劑將聚合物固定,以期優(yōu)選出接枝量較大、較為均一的表面改性層。紅外光譜(FTIR)、水接觸角(WCA)和X射線光電子能譜(XPS)等表征分析結(jié)果證明,多功能層組裝成功；通過掃描電子顯微鏡(SEM)觀察改性層的形貌,結(jié)果顯示經(jīng)過CH30H溶劑固定的涂層聚合物含量較多,而DMF做溶劑時固定的聚合物量很少。初步的血液相容性試驗表明,改性后的表面能抑制血小板粘附和激活,對纖維蛋白原的粘附和激活也有一定的抑制作用。所以,在鈦表面構(gòu)建磷酸膽堿聚合物仿生改性涂層可以有效的改善鈦材的血液相容性。
[Abstract]:Titanium and its alloys have been widely used in biomedical materials due to their high mechanical strength, corrosion resistance and biocompatibility. However, the anticoagulant properties of titanium, as biomedical metal materials for the preparation of implants and artificial organs, need to be further improved. MPCs are amphiphilic phospholipid molecules. It consists of a polar head of choline phosphate and a portion of methacrylate. The PC group of choline phosphate group is the main component of the outer membrane of biological cells. The PC group has both positive and negative charges and has super hydrophilicity, which effectively prevents the adsorption of protein and shows good biocompatibility. The existence of vinyl can make MPC polymerize into phospholipid polymers of different types and functions. Phospholipid polymers have biomimetic structure and can meet the functional needs of many biomedicine. In order to improve the blood compatibility of titanium, two kinds of ABA triblock copolymers, PMPC-PTSMA-PMP C, which were polymerized by MPC monomer and TSMA monomer, were synthesized in this paper. The copolymer was synthesized in two steps. In the first step, the homopolymer PMPCs of MPC containing chain transfer agent were synthesized by using MPC monomer and chain transfer agent. In the second step, the monomer TSMA was polymerized again with the polymer synthesized in the first step, and the final target ABA triblock polymer PMPC-PTSMA-PMPCwas synthesized. The structure and molecular weight of the polymer were characterized by FTIR, NMR and GPC. The results showed that in the first step, three kinds of PMPC polymers were successfully synthesized by controlling the ratio of chain transfer agent and initiator. The molecular weights of the three kinds of polymers were all over 100 KD, respectively, and the one with better degree of polymerization was selected for further polymerization. In the second step, two copolymers, PMPC-PTSMA-PMPCs with different molecular weights, were successfully synthesized by adjusting the amount of macromolecular chain transfer agent and TSMA monomer. The molecular weights of the copolymers were 134KD and 159KD, respectively. The synthesized triblock copolymers were then immobilized onto the activated titanium surface by covalent grafting. During this period, two kinds of solvents, proton CH3OH) and non-protonated DMF, were used to immobilize the polymer in order to select a relatively uniform surface modification layer with large grafting amount. The results of FTIR, water contact angle (WCA) and X-ray photoelectron spectroscopy (XPS) show that the multifunctional layer was successfully assembled, and the morphology of the modified layer was observed by scanning electron microscope (SEM). The results show that the amount of polymer fixed by CH30H solvent is more than that by DMF solvent. Preliminary blood compatibility test showed that the modified surface could inhibit platelet adhesion and activation and fibrinogen adhesion and activation. Therefore, the biomimetic coating of choline phosphate polymer on titanium surface can effectively improve the blood compatibility of titanium.
【學(xué)位授予單位】：西南交通大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TB324

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本文編號：1780619