研究生: |
王秋錦 |
---|---|
論文名稱: |
含銅蛋白質活性中心之擬態化合物-含氮硫三牙基之一價和二價銅錯合物之合成、結構及反應性探討 |
指導教授: |
李位仁
Lee, Way-Zen 蘇展政 Su, Chan-Cheng |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2008 |
畢業學年度: | 96 |
語文別: | 中文 |
論文頁數: | 90 |
中文關鍵詞: | 藍銅蛋白 、胜肽甘胺酸 羥化氧化酶 |
論文種類: | 學術論文 |
相關次數: | 點閱:209 下載:0 |
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為了模擬藍銅蛋白以及胜肽甘胺酸-羥化氧化酶(Peptidylglycine -hydroxylating monooxygenase,簡稱PHM)的活性中心,我們合成出一個含氮硫之三牙配位基(BMPS),並成功地合成出一系列具有BMPS二價和一價銅錯合物:[Cu(BMPS)(CH3CN)2](ClO4)2 (1)、[Cu(BMPS)2]- (ClO4)2 (2)、[Cu(BMPS)(CH3CN)](ClO4)2 (3) 和 [Cu(BMPS)2](OTf)2 (4)。將錯合物1與硫醇鈉鹽反應希望合成出模擬氧化態的藍銅蛋白活性中心。於- 40 ºC低溫下將硫醇鈉鹽加入錯合物1,隨著溫度回到室溫溶液由原本深藍色變至棕色沉澱,可知反應所得之二價銅錯合物在室溫下不穩定。因此我們嘗試模擬還原態的藍銅蛋白活性中心,將錯合物4分別與[(CH3)3SiC6H4S]-以及[C6H5C(O)NHC6H5S]-反應,其產物由核磁共振氫譜推測,有[Cu(BMPS)((CH3)3SiC6H4S)]和[Cu (BMPS) (C6H5C(O) NHC6- H5 S)]的生成。將雙核結構的錯合物4與PPh3、CNC(CH3)3、CO等小分子反應可形成一系列單核錯合物:[Cu(BMPS)PPh3](OTf) (5), [Cu(BMPS)(CNC(CH3)3)](OTf) (6),而 [Cu(BMPS)(CO)](OTf) 分子的生成由IR光譜鑑定,顯示錯合物4具有良好的反應性。若將氧氣與錯合物4在乙腈下反應,以紫外-可見光光譜偵測該溶液在400 nm附近並無發現任何的電荷轉移峰,故得知沒有形成Cu(II)-superoxo錯合物。
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