研究生: |
黃麗蓉 |
---|---|
論文名稱: |
[Re(phen(phSO3)2)(CO)3(im)]-之光化學及光物理性質研究 |
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: | 126 |
中文關鍵詞: | 錯合物 |
英文關鍵詞: | complex |
論文種類: | 學術論文 |
相關次數: | 點閱:152 下載:0 |
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[Re(phen(phSO3)2)(CO)3(im)]-錯合物已由本實驗室自備出,此錯合物之π→π*吸收位於289nm,metal-to-ligand harge-tansfer(MLCT)的吸收位於374nm,3MLCT發光位於590nm,在水溶液中的lifetime為180ns,氧化電位為+1.23V vs SCE,還原電位為-1.31V vs SCE,由淬息反應得到E00 = 2.37eV。
[Re(phen(phSO3)2)(CO)3(L')]-和[Re(phen(CO)3(L')]+(L'為imidazole、1,3-diimidazole-yl-propane、和1,4-diimidazole-yl-butane)與AcMp8的反應,發現最大吸收峰會由396nm位移至404nm,binding constant為104M-1,金屬確寶以一端的imidazole接在heme上的鐵,為六配位的電子組態。金屬之間的電了轉移非常快,無法測其lifetime,由發光光譜確寶可以觀察到金屬之激發態會由於電子傳遞到AcMp8而被淬息。[Re(phen(phSO3)2)(CO)3(im)]-和[Re(phen(CO)3(im)]+因立體障礙太大而無法反應。
將cytochrome c與[Re(phen(phSO3H)2)(CO)3(triflate)]的反應中發現金屬可能具有將蛋白質切成碎片的能力,約以20個胺基酸為單位,可以進一步探討其作為photoprotease的可能。
[Re(phen(phSO3)2)(CO)3(im)]-complex have been prepared.The absorption spectrum of the complex exhibits π→π*transition at the 298 nm and the metal-to-ligand charge-transfer (MLCT) at the 374 nm.The broad emission profile centered at 590 nm is consist of a 3MLCT excited-state.The lifetime of this state is 180 ns.The reduction and oxidation potentials of this complex are-1.31 and +1.23V vs SCE respectively.Systematic quenching reaction results 2.37 eV for the 3MLCT excited state potential.
[Re(LL)(CO)3(L')]-complexes, (LL:phenathroline (phen),bathophenathroline disulfonic acid (phen(phSO3)2); L':imidazole, 1,3-diimidazole-yl-propane (3C(im)2),1,4-diimidazole-yl-butane (4C(im)2),binding relatively tighy with iron in AcMP8 through imidazole bridge.The binding constant is on the order of 104M-1.Upon binding ,the iron changes to low spin state and results the soret band of AcMP8 shifts from 396 nm to 404nm.
[Re(phen(phSO3H)2)(CO)3(triflate)] exhibits hydrolysis ability while bound to cytochrome c.This potential protease usage will be for the investigated.