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研究生: 蔡東洲
論文名稱: 天然胺基酸支鏈對電子移轉速率的影響
指導教授: 張一知
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 85
語文別: 中文
論文頁數: 84
中文關鍵詞: 胺基酸
英文關鍵詞: amino acid
論文種類: 學術論文
相關次數: 點閱:154下載:0
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  • 本研究合成出二系列的胺基酸金屬衍生物(1)D-gly-A、D-ile-A、D-phe-A以及(2)D-gly-A、D''-gly-A。D表示Ru(bpy)2phenNH22+;D'表示Ru(tmbpy)2phenNH22+-;D''表示Ru(tmbpy)2phenNH22-;A表示dinitrophenyl 。利用元素分析、質譜圖、紫外光-可見光吸叫光譜、螢光磷光光譜等…方法,完成錯合物各種性質的探討。各錯合物的電子轉移速率常數,可用螢光磷光光譜及Time-Resulted luminescence decay的方式測得。D-gly-A、D-phe-A、D-ile-A、的電子轉移常數KET分別為2.2×107、3.2×107、3.7×107S-1。對於不同電子提供者的金屬錯合物D'-gly-A、D''-gly-A,其電子轉移常數KET超出我們儀器所能偵測的範圍,只能做大概估計,約為>5.1×107以及>5.56×107S-1。
    由此可知,此種D-amino acid-A的電子轉移方法是利用Q-tunneling。

    Electron donor-acceptor complexes that are bridged by single amino acid have been prepared.Ru(bpy)2phenNH22+ has been used as electron donor and dinitrophenyl as electron acceptor. Ruthenium complexes with methyl substitution on bipyridine have been made to evaluate the driving force dependency of the electron transfer rate.
    Excitation into the MLCT band of the ruthenium complex induces electron transfer from phenanthroline radical to dinitrophenyl moiety through the amino acid bridge.The rates for glycine-, phenylalanine-, and isoluecine-bridged complexes are 2.1×107, 3.1×107 and 3.6×107s-1 respectively, The trends in the rates are consistent with the electron donating ability of the side chain for each amino acid. These results indicate that hole tunneling through □-bonds is a good model for electron transfer in metalloproteins.
    Electron transfer rates in Ru(dmbpy)2phenNH-and Ru(tmbpy)2phenNH-complexes are much too fast to measure at current time.The lower limit of the rate is 5 ×107s-1.

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