本文選題：磷銨-聚氨酯納米微球 + 表面改性��； 參考：《南京師范大學》2012年碩士論文

【摘要】：作為植入或介入人體內的血液接觸醫(yī)用高分子材料,其必須具有良好的血液相容性、組織相容性和力學性能。其中,目前該類生物材料最為突出的問題是其進入人體會引起血栓形成等,這嚴重制約新型血液相容性生物材料開發(fā)的瓶頸。因而,具有良好血液相容性的生物高分子材料的研制已成為生物醫(yī)學工程的前沿課題和關鍵所在。 聚氨酯(PU)是一種含有氨基甲酸基團的高聚物,被廣泛應用于工業(yè)生產以及日常生活中。聚氨酯具有相對較好的生物相容性、機械性能和一定的血液相容性,因而被作為重要的血液接觸材料,應用于血管移植物、人工導管、人工心臟等方面。但是,同其他生物醫(yī)用聚合物材料一樣,聚氨酯在體內使用后也存在明顯的誘導血栓形成等血液相容性的問題。因此,該類材料在應用于血液接觸材料時,必須對其進行抗凝血改性,提高其血液相容性。 如何提高聚氨酯基人工合成心、血管替代材料的血液相容性是生物醫(yī)用材料領域中一個非常重要但尚未圓滿解決的關鍵問題。為了改善作為心、血管替代材料的聚氨酯材料的血液相容性,研究人員一直采用表面改性等方法對其進行改性。南京大學沈健課題組率先使用磷銨、羧胺、磺胺等兩性離子對PU等聚合物材料進行表面改性,并取得了極其明顯的抗凝血效果。 本論文在本課題組研究的基礎上,用共沉淀法將磷銨兩性離子表面修飾聚氨酯納米微球(PUI-NPs)對醫(yī)用聚氨酯進行表面改性,并對其表面結構進行有效的表征,并對其血液相容性、細胞相容性及機械性能進行研究。 通過掃描電子顯微鏡(SEM)觀察可知,和未改性PU相比,改性的PU材料表面均勻分布了大量微小突起,且在PU表面分布較為均勻,說明共沉淀法已成功的將PUI-NPs納米微球引入PU膜的表面。XPS測試,在PU/PU-NPs的表面可以觀測到在133.6eV處有P2p峰。這進一步說明,PUI-NPs納米微球已經成功接枝到PU的表面。ATR-FTIR的測試發(fā)現,改性的PU在3460cm-1處的吸收峰,這個吸收峰可認為是由PUI-NPs表面殘留的N-H基團引起的,該結果也進一步證明了PUI-NPs已經被成功引入空白PU膜的表面。同時,靜態(tài)接觸角試驗表明,改性過程能略微提高了PU表面的親水性,說明PUI-NPs的表面改性改善了PU的親水性。 我們主要對材料的血液相容性進行了深入研究。溶血實驗結果表明,經PUI-NPs納米微球改性過PU的溶血率小于5%,試驗結果符合國際標準。復鈣化凝血時間實驗表明,相較于未改性的PU,材料的復鈣時間有明顯的延長,說明聚氨酯納米復合材料血液相容性得到提高。血小板粘附實驗結果證明,經磷銨兩性離子表面修飾聚氨酯納米微球改性過的聚氨酯材料的抗血小板粘附能力有了較大的提高。同時,動態(tài)凝血試驗結果表明,改性材料抗凝血性能稍微比原材料提高一些。 細胞毒性實驗結果表明,相比較于未改性PU的毒性,改性過的PU在與活細胞作用24h和72h后,顯示出更低的細胞毒性,完全符合生物材料的醫(yī)用標準。同時,內皮細胞生長實驗表明,內皮細胞能更好的在改性過的PU表面粘附生長,且不發(fā)生組織增生等問題。 之后,我們還對復合材料機械性能進行了研究。力學性能拉伸實驗和SEM觀測斷裂面結果證明,經共沉淀法改性后的聚氨酯,在提高PU膜抗凝血性能的同時,并不會對PU膜的機械性能產生不利影響,其機械仍可得以保持。同時,流變測試結果表明,PUI-NPs納米微球與PU之間可以同時形成共價鍵和氫鍵相互作用,且可以進一步形成一定的交聯,且交聯結構在各個溫度下均能穩(wěn)定存在。因此證明共沉淀法制備的PU/PUI-NPs復合材料PUI-NPs納米微球與PU之間的界面作用較強,且在不同溫度下均可穩(wěn)定存在。 在上述工作的基礎上,我們制備出了一種新型的具有優(yōu)良抗凝血性功能和良好力學性能的聚氨酯／納米復合材料,期望能在生物醫(yī)學工程方面得到廣泛的應用。
[Abstract]:As a medical polymer implanted or intervened in the human body, it must have good blood compatibility, histocompatibility and mechanical properties. Among them, the most prominent problem of this kind of biomaterial is that its entry into the human body will cause thrombosis and so on, which seriously restricts the development of new blood compatible biomaterials. Therefore, the development of biopolymer with good blood compatibility has become a frontier topic and key point in biomedical engineering.
Polyurethane (PU) is a kind of polymer containing carbamate group, which is widely used in industrial production and daily life. Polyurethane has relatively good biocompatibility, mechanical properties and certain blood compatibility. Therefore, it is used as an important blood contact material and should be used in vascular graft, artificial catheter, artificial heart and so on. However, as with other biomedical polymer materials, after the use of polyurethane in the body, there is a significant problem of inducing blood compatibility, such as thrombus formation. Therefore, this kind of material must be used in blood contact material, it must be modified to improve its blood compatibility.
How to improve the blood compatibility of the polyurethane based synthetic heart and the blood vessel substitute material is a very important problem in the biomedical materials field. In order to improve the blood compatibility of the polyurethane material as the heart and the replacement material of the blood vessel, the researchers have been using the surface modification methods to modify it. The Shen Jian team of Nanjing University took the lead in the surface modification of PU and other polymer materials such as ammonium phosphate, carboxyamine, sulfonamides and other amphoteric ions, and achieved very obvious anticoagulant effect.
On the basis of this research group, the surface modified polyurethane nano microspheres (PUI-NPs) were modified by coprecipitation method, and the surface structure of the polyurethane was characterized effectively, and the blood compatibility, cell compatibility and mechanical properties were studied.
Through the scanning electron microscope (SEM) observation, it is found that the surface of the modified PU material is evenly distributed in a large number of small protrusions compared with the unmodified PU, and the distribution of the PU surface is more uniform. It shows that the co precipitation method has successfully introduced the PUI-NPs nanospheres into the.XPS test of the PU film, and the P2p peak can be observed at 133.6eV at the surface of PU/PU-NPs. This further illustrates that the PUI-NPs nanospheres have been successfully grafted on the surface of the surface of the PU and found that the absorption peak of the modified PU at 3460cm-1 is considered to be caused by the N-H group remaining on the PUI-NPs surface, which further proves that PUI-NPs has been successfully introduced to the surface of the blank PU membrane. At the same time, the static connection is still connected. The results showed that the hydrophilicity of PU surface was slightly increased by the modification process, indicating that the surface modification of PUI-NPs improved the hydrophilicity of PU.
The blood compatibility of the material was studied in depth. The results of hemolysis test showed that the hemolysis rate of PUI-NPs nanospheres modified by PU was less than 5%, and the experimental results accorded with the international standard. The blood compatibility of the material was improved. The platelet adhesion test results showed that the anti platelet adhesion ability of the polyurethane modified by the amphoteric surface modified polyurethane nanospheres was greatly improved. Meanwhile, the dynamic coagulation test showed that the anticoagulant properties of the modified materials were slightly higher than those of the raw materials.
The cytotoxicity test showed that compared with the toxicity of unmodified PU, the modified PU showed lower cytotoxicity and fully conformed to the medical standards of biomaterials after the action of 24h and 72h with living cells. Meanwhile, endothelial cell growth experiments showed that endothelial cells could be better adhered to the modified PU surface and did not occur in tissue. Hyperplasia and other problems.
After that, the mechanical properties of the composites were also studied. The tensile test of mechanical properties and the results of the SEM observation fracture surface showed that the polyurethane modified by coprecipitation could not have a negative effect on the mechanical properties of the PU film while improving the anticoagulant properties of the PU film, and the mechanical properties of the polyurethane could still be maintained. It is shown that the interaction between covalent and hydrogen bonds between PUI-NPs nanospheres and PU can be formed at the same time, and a certain cross-linking can be formed, and the cross-linking structure can be stable at various temperatures. Therefore, it is proved that the interface between PUI-NPs nanospheres of PU/PUI-NPs composite prepared by co precipitation method is stronger and is different from that of PU. It can be stable at temperature.
On the basis of the above work, a new type of polyurethane / nano composite with excellent anticoagulant function and good mechanical properties is prepared. It is expected to be widely used in biomedical engineering.
【學位授予單位】：南京師范大學
【學位級別】：碩士
【學位授予年份】：2012
【分類號】：R318.08

【參考文獻】

相關期刊論文 前10條

1 趙國梁,魯險鋒,王曉春;聚酯纖維抗凝血性能研究進展[J];北京服裝學院學報;2004年02期

2 袁琳;馬悠琴;周峰;陳紅;;聚氨酯/碳納米管復合材料的制備及其對血小板黏附的抑制作用[J];材料導報;2009年18期

3 項昭保;霍丹群;候長軍;;全身肝素化聚醚砜抗凝血生物材料的研究[J];材料科學與工藝;2007年06期

4 許海燕,孔樺,楊子彬;聚氨酯/碳納米纖維復合材料的結構和抗凝血性能[J];材料研究學報;2003年02期

5 裴仁軍,崔小強,楊秀榮,汪爾康;表面等離子體子共振技術實時研究蛋白質在修飾表面的靜電吸附行為[J];高等學�；瘜W學報;2001年07期

6 計劍,季任天,邱永興,陳寶林,封麟先;聚氧乙烯功能基復合修飾聚氨酯的合成及其血液相容性研究 (Ⅰ)──聚氨酯-接枝-十八烷基聚氧乙烯[J];高等學�；瘜W學報;1999年05期

7 張克勝,孫君坦,何炳林;新型低密度脂蛋白吸附劑的合成及吸附性能研究[J];高分子學報;1999年06期

8 艾飛,袁幼菱,吳一多,周靜,沈健,林思聰;血液相容材料的合成研究Ⅷ.磺銨兩性離子單體在聚醚氨酯表面的臭氧活化接枝[J];高分子學報;2002年04期

9 羅祥林,何斌,李賽,鐘銀屏;表面紫外光接枝潤滑改性醫(yī)用聚氨酯材料[J];高分子材料科學與工程;2000年02期

10 許海燕,孔樺,楊子彬;抗凝血高分子材料的研究進展及其在心血管外科中的應用[J];高分子材料科學與工程;2001年05期

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