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研究生: 余俊彥
Yu, Jyun-Yan
論文名稱: 利用不同溶劑製備含磷酸乙醇胺官能基的雙電性自組裝單分子層之表面性質、血小板吸附以及電化學特性之研究
Surface characterization, platelet adhesion and electrochemical analysis by different solvents for zwitterionic self-assembled monolayers with phosphorylethanolamine terminal group
指導教授: 林睿哲
Lin, Jui-Che
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2010
畢業學年度: 98
語文別: 中文
論文頁數: 102
中文關鍵詞: 自組裝單分子層雙電性分子仿生溶劑效應表面性質化學分析電子光譜儀血液相容性
外文關鍵詞: self-assembled monolayers (SAMs), biomimetic, zwitterionic molecules, solvent effect, surface characterization, ESCA, platelet adhesion
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  •   生醫材料在現今醫學應用很廣泛,但其生物相容性是個須克服的問題,因此將材料表面改質以增加生物相容性是個很重要的議題。表面改質技術中,自組裝單分子層提供了一個很好的方式,可形成緻密的排列並且末端官能基也可自由搭配以達所需的性質。本研究利用自組裝單分子層以仿生的概念將細胞膜內富含的磷脂質中的磷酸化乙醇胺官能基製成鏈長為11 碳的硫醇(11-mercaptoundecanylphosphoryl ethanolamine, HS-(CH2)11-PO4H-CH2CH2-NH3+),將此硫醇以不同溶劑及不同濃度製備自組裝單分子層,利用表面分析儀器、電化學分析及血小板吸附的方式探討以此材料製成的自組裝單分子層,以了解不同溶劑及濃度對自組裝單分子層結構的的排列性質及血液相容性。
      由接觸角測試的結果顯示,與未改質的金基材相比,含磷酸乙醇胺之自組裝單分子層較為親水,其中又以去離子水製備的0.1mM硫醇溶液為最佳;由化學分析電子光譜儀的結果推測,SAMs 表面因末端巨大官能基產生的立體障礙及電荷效應使得排列較差,此現象可解釋與部分接觸角偏高的現象;由S2p 光譜可看出每種條件製備的SAMs 其末端皆有未鍵結硫的產生;也可由N1s 看出有NH2 的產生。由CV 分析結果得知所形成的氧化還原峰不明顯,代表硫醇分子緊密排列在基材表面,且覆蓋很好;由EIS 分析結果所得的阻抗質皆很大,代表硫醇分子緊密排列或是材料表面帶電性的影響使得阻抗變大。
      由血小板吸附的測試中得知,血小板在部分試片上有極度活化、聚集的情形,以血液相容性看來,含磷酸乙醇胺官能基的硫醇製備出的SAMs 血液相容性較未改質的金試片好,其中以0.1mM 去離子水製備的SAMs 血液相容性為最佳。

    Biomedical materials have been widely used for medical environments, but its biocompatibility remains concerned. The modification of surface property to improve biocompatibility, therefore, has become crucial. Self-assembled monolayers (SAMs) technologies have been shown as avenues to achieve surface modification, since SAMs can be formed densely-packed while the functional group can also be tuned in accordance with different needs. This study utilizes biomimetics to synthesize 11-mercaptoundecanylphosphoryl ethanolamine (HS-(CH2)11-PO4H-CH2CH2-NH3+), one of the phospholipids abundant in cell membrane. The SAMs with different solvent and concentration are examined by surface analysis, electrochemical analysis, and platelet adhesion method, so as to understand its surface characterization and blood compatibility.
    The contact angle measurements indicated that the SAMs formed by phosphorylethanolamine functional group thiol are more hydrophilic than the SAMs formed by bare gold, especially 0.1mM deionic water is used. The structural disorder of SAMs in the electrochemical analysis suggests the charge effect and steric hindrance caused by large functional group and; it is the reason why the contact angels are higher. The ESCA data demonstrates clearly the unbound thiol in S2p spectra, and NH2 peak in N1s spectra. The CV data shows unapparent oxidized-redox peak, which denotes that PE SAMs are formed closed-packed and fully covered, meanwhile, the huge impedance caused by PE SAMs closed-packed or charged surface also appears in the EIS analysis. Furthermore, the platelet adhesion exhibits platelet activation and aggregation in some samples. On the other hand, the SAMs with phosphorylethanolamine functional group performed better than the sample of gold in terms of blood compatibility, and the SAMs have the best performance when prepared by 0.1mM deionic water.

    摘要 I Abstract III 致謝 V 圖目錄 X 表目錄 XIV 第一章 前言 1 第二章 文獻回顧 2 2.1 自組裝單分子層(Self-Assembled Monolayers, SAMs) 2 2.1.2 SAMs的組成 6 2.1.3 SAMs的種類及分類 8 2.2 基材的選擇與影響 13 2.3 溶劑對自組裝單分子層之影響 14 2.4 凝血機制探討 16 2.4.1 血液的組成 16 2.4.2 凝血機制探討 21 2.5 帶電性表面對血液相容性的影響 23 2.5.1 帶負電性官能基表面對血液相容性的影響 24 2.5.2 帶雙電性官能基表面對血液相容性的影響 25 2.6 動機與研究目的 26 第三章 儀器原理及應用 28 3.1 儀器簡介 28 3.2 物理氣相蒸鍍(Physical Vapor Deposition, PVD)之原理 30 3.3 靜態接觸角(Static contact angle measurement)及動態接觸角(Dynamic contact angle measurement) 31 3.4 化學分析電子光譜儀(Electron Spectroscopy for Chemical Analysis, ESCA) 34 3.5 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 36 3.6 循環伏安法(Cyclic voltammetry, CV) 37 3.7 電化學阻抗分析儀(Electrochemical impedance spectroscopy, EIS) 39 第四章 實驗方法 41 4.1 實驗藥品 41 4.2 實驗方法 47 4.2.1 實驗步驟 47 4.2.1.1 11-Undecylenylphosphoric Acid (EPA)之合成方法 48 4.2.1.2 11-Undecylenylphosphoryl ethanolamine (EPNH3)之合成方法 48 4.2.1.3 11-Thioaceto-undecylphosphony ethanolamine (AcSPNH3)之合成方法 48 4.2.1.4 11-Mercaptoundecanylphosphoryl ethanolamine (PESH)之合成方法 49 4.2.2 金基材之製備 49 4.2.3 自組裝單分子層之製備 49 4.2.4 接觸角測試 50 4.2.5 血小板吸附之步驟 50 4.2.6 循環伏安法(Cyclic voltammetry, CV )及電化學阻抗頻譜量測法(Electrochemical impedance spectroscopy, EIS) 54 第五章 結果與討論 55 5.1 合成之結果 56 5.1.1 11-Undecylenylphosphoric Acid (EPA) 56 5.1.2 11-Undecylenylphosphoryl ethanolamine (EPNH3) 58 5.1.3 11-Thioaceto-undecylphosphony ethanolamine (AcSPNH3) 60 5.1.4 11-mercaptoundecanylphosphonyl ethanolamine (PESH) 62 5.2 接觸角測試 63 5.3 化學分析電子光譜儀測試 66 5.4 電化學分析 77 5.4.1 循環伏安法 77 5.4.2 電化學頻譜阻抗分析儀 81 5.5 血小板吸附 87 第六章 結論 96 參考文獻 98

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