臺灣博碩士論文加值系統

　　　 摘要
本篇論文研究合成含有naphthoic ester的非水溶性紫質ZnENP，CuENP。含有naphthoic acid的非水溶性紫質ZnHNP，CuHNP以及cis-VOHNP和trans-VOHNP。並研究其光譜及電化學性質。
循環伏特安培法掃描ZnTMP，VOTMP和CuTMP發現在氧化部分有兩對可逆氧化還原對，光譜電化學偵測ZnENP和CuENP在第二個電子氧化反應時有一部份會形成isoporphyrin。而ZnHNP，cis-VOHNP，trans-VOHNP，CuHNP在第一個電子氧化，會形成isoporphyrin 。因為酸基相較於酯基為較強的親核基，所以再滴一個電子氧化中就會產生isoporphyrin。而ENP是第一個以較弱的酯基為親核基而能夠打在紫質中meso-碳上的
VOHNP有兩種異構物，分別為cis-form和trans-form。VOTMP，trans-VOHNP和cis-VOHNP以6種單基配位基和4種雙基配位基進行光譜滴定。其中pyridine和乙二胺(ethylenediamine)對trans-VOHNP有很軸配位基選擇性，其他配位基則無。trans-VOHNP無法與pyridine形成錯合鍵結，光譜上沒有明顯的變化；對乙二胺而言，乙二胺對trans-VOHNP的配位形成常數為VOTMP和cis-VOHNP的數倍。

Abstract
We reported synthesis of nonaqueous porphyrins about ZnENP, CuENP with naphthoic ester and ZnHNP, cis-VOHNP and trans-VOHNP with naphthoic acid. The electrochemical properties of porphyrin have been studied by cyclic voltammetry (CV) and spectroelectrochemistry.
There are two reversible redox couples in the CV of ZnTMP and ZnENP at oxidation potential. Observation by UV-vis-near IR spectroelectrochemistry indicated that ZnENP was first oxidation to cation radical ,ZnENP+· and that the second oxidation renders rapid intramolecular chemical reaction to form isoporphyrin. ZnHNP was first oxidation renders rapid intramolecular chemical reaction to form isoporphyrin. The electrochemical properties of CuENP is similar to ZnENP. The electrochemical properties of CuHNP, cis-VOHNP and trans-VOHNP are similar to ZnHNP.
VOHNP has two isomers in the forms of cis-form and trans-form. VOTMP, cis-VOHNP and trans-VOHNP are titrated with 6 kinds of monodentate ligands and 4 kinds of bidentate ligands under UV-vis spectra detection. There is axial ligand selectivity when trans-VOHNP is titrated with pyridine and ethylenediamine. In the case of pyridine, it can not be ligated with trans-VOHNP and there is no change on UV-Vis spectra. In the case of ethylenediamine, the formation constant of trans-VOHNP is three order larger than those of VOTMP and cis-VOHNP.

目錄
摘要……………………………………………………………………….I
目錄……………………………………………………………………..III
圖表目錄………………………………………………………………...V
第一章簡介………………………………………………….………… 1
1.1生物體中的紫質和釩紫質………………………………………….1
1.2釩紫質軸配位形成常數和光譜研究……………………………….5
1.3Isoporphyrin的研究……………………………………………… 11
第二章實驗……………………………………………………….…...20
2.1合成………………………………………………………………….20
2.2 ZnTMP，ZnENP，ZnHNP的滴定光譜…………………….………52
2.3 VOTMP，cis-VOHNP，trans-VOHNP的滴定光譜……………….53
2.4 鋅，釩，銅紫質的電化學和光譜電化學分析………………….…55
第三章結果與討論……………………………………………………56
3.1 H2ENP，H2HNP的合成研究………………………………………56
3.2 ZnTMP，ZnENP，ZnHNP化合物研究……………….……………59
3.3 ZnTMP，ZnENP，ZnHNP滴定光譜……….……………………….63
3.4 cis-VOHNP和trans-VOHNP化合物位向研究……………………68
3.5 VOTMP，cis-VOHNP，trans-VOHNP滴定光譜………………….73
3.6 鋅，釩，銅紫質的電化學和光譜電化學的研究………………… 105
結論……………………………………………………………………127
附錄……………………………………………………………………128
參考文獻………………………………………………………………130

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