淡江大學機構典藏:Item 987654321/74534
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    题名: 光可調控溫度敏感型聚氮異丙基丙烯醯胺高分子的製備及其細胞相容性
    其它题名: Preparation and cellular compatibility of optical-controlled thermo-responsive poly (N-isopropyl acrylamide)
    作者: 張耿銘;Zhang, Geng-Ming
    贡献者: 淡江大學化學工程與材料工程學系碩士班
    董崇民;Don, Trong-ming
    关键词: 聚氮異丙基丙烯醯胺;奈米金桿;PNIPAAm;Gold Nanorod
    日期: 2011
    上传时间: 2011-12-28 18:50:03 (UTC+8)
    摘要: 本研究主要是利用帶酸基之偶氮型起始劑4,4''-偶氮双(4-氰基戊酸)(4,4′-azobis(4-cyanovaleric acid), ACPA)起始聚合氮異丙基丙烯醯胺單體(N-isopropyl acrylamide, NIPAAm)，以形成末端具有酸基之聚氮異丙基丙烯醯胺(PNIPAAm-COOH)；經過70 oC反應12小時後，可得到分子量為6180的PNIPAAm-COOH。接著利用1-(3-二甲氨基丙基)-3-乙基碳二亞胺鹽酸鹽((N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride)與2-巰基乙胺鹽酸鹽(cysteamine hydrochloride)進行修飾，成為一硫醇封端聚氮-異丙基丙烯醯胺(PNIPAAm-SH)，硫醇封端基含量為28.32 μmole/g polymer，取代度為11.4%。另外利用種晶生成法合成出長37.23(±0.91) nm和寬11.15(±0.29) nm，長寬比值(aspect ratio, AR)為3.34，且形狀均一之奈米金桿(GNR)。最後將不同莫耳數的PNIPAAm-SH加入奈米金桿溶液中進行接枝反應以形成PNIPAAm接枝奈米金桿(PNIPAAm-GNR)。實驗結果發現以2.5 μmol之PNIPAAm-SH與4.64 nM的奈米金桿在30 oC進行接枝反應所形成之PNIPAAm接枝奈米金桿會有較佳之穩定性，經過5日後，最大吸收波長依然可維持在811 nm，吸光度一樣維持不變。並藉由STEM證實硫元素確實鍵結在奈米金桿表面，而在TEM影像顯示奈米金桿受到高分子鏈層層之保護。將此PNIPAAm-GNR溶液進行紅外光雷射引導(808 nm)及細胞培養等測試。測試結果顯示，LSCT在各階段(PNIPAAm-COOH、PNIPAAm-SH、PNIPAAm-GNR)皆無太大之改變，都在35 oC左右。PNIPAAm-AuR溶液經過近紅外光(808 nm, 500 mW)照射15分鐘後，由於奈米金桿的表面電漿共振效應(surface plasmon effect)，溫度可從27 oC上昇至45 oC，此溫度上昇進而引發PNIPAAm的相變化；同時此溫度敏感性行為在經過5次循環，仍具有可逆變化。PNIPAAm-GNR複合材料此複合材料不但具有光熱轉換之效應，且具可逆性，並且明顯改善原奈米金桿之生物毒性，細胞存活率從原先之1.07 %提升至89.0 %。
    In this study, 4,4''-azobis(4-cyanovaleric acid) (ACPA) was used to initiate polymerization of N-isopropyl acrylamide (NIPAAm) monomer in ethanol at 70oC to form carboxyl-terminated poly(N-isopropyl acrylamide) telechelic polymer (PNIPAAm-COOH). Subsequently, N-(3-dimethylaminopropyl)-N''-ethylcarbo- diimide hydrochloride and 2-mercapto-ethylamine hydrochloride (cysteamine hydrochloride) were chosen to modify the PNIPAAm-COOH to prepare thiol-end-capped poly(N-isopropyl acrylamide) (PNIPAAm-SH) , SH-functionalized content of 28.32 μmole/g polymer, instead of 11.4 %. In addition, nano-sized gold rod (GNR) was synthesized via the well-known seed-mediated method. The synthesized GNR was very uniform and had a dimension of 37.23(±0.91) nm in length and 11.15(±0.29) nm in width, thus having an aspect ratio (AR) of 3.34. Finally, PNIPAAm-SH with different amounts was added to the GNR solution to produce PNIPAAm-g-GNR composite. It was found the PNIPAAm-g-GNR solution prepared by grafting 2.5 μmol PNIPAAm-SH onto 4.64 nM of GNR solution at 30 oC had a superior stability. STEM results confirmed that the thiol group bonded onto the surface of gold nanorod, and the TEM image showed that the gold nanorod was protected by multi-layers of PNIPAAm chains. The PNIPAAm-g-GNR solution was tested for the near-IR irradiation-induced thermo-responsibility and cell compatibility. The results showed that all PNIPAAm-COOH, PNIPAAm-SH and PNIPAAm-g-GNR had the same LSCT at about 35 oC. Because of the surface plasmon effect of gold nanorod, the irradiation of near-IR at 808 nm for 15 minutes could induce the temperature rise from 27 oC to 45 oC. The thermo-responsibility was also reversible during five test cycles. Moreover, the PNIPAAm protection layer could decrease the cytotoxicity of the gold nanorod. The Cell Viability of 1.07 % from the previous increase to 89.0 %.
    显示于类别:[化學工程與材料工程學系暨研究所] 學位論文

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