本篇論文共分為三章節。第一章為前言，主要在介紹亞硝酸還原酶以及其催化反應機制，包含了真實酵素與模擬的仿生化合物的行為。第二章是探討立體障礙與電子效應對於生化擬態CuI-nitro化合物的影響，研究結果發現立體障礙與電子效應有助於增加反應速率與產生之一氧化氮的量。第三章是在有機溶劑中，利用四個系統性的銅二價化合物在有L-抗壞血酸的條件下轉化亞硝酸鹽為一氧化氮。發現在銅二價的催化條件下，中性配位基相較於負電配位基有差不多的最初速率，立體障礙小的也會有較好的最初速率，並且配位基的存在可以提升亞硝酸轉變為一氧化氮的轉換率。配合理論計算的結果，此章節也提出催化過程中最有可能的反應機制。

The first chapter introduces copper cantaining nitrite reductase (Cu-NiRs) and its catalytic mechanism which include the real enzymes and bio-inspired model compounds. The second chapter discusses the steric effects and hindrance effects on CuI-nitro complexes. The results show that steric hindrance and electronic effects on ligand can increae the reaction rate and the NO(g) yield. In the third chapter, four copper(II) complexes were chossen to catalyze nitrite to nitric oxide gas. The results suggest that steric hindrance and negative charge on ligand will decrease the initial rate but auxiliary ligand can increase the NO(g) conversion yield.

學位論文審定書 i
謝誌 ii
摘要(中) iv
Abstract v
目錄 vi
圖目錄 viii
表目錄 x
流程圖目錄 xi
附錄 xii
第一章、緒論 1
1.1 亞硝酸還原酶的分類 1
1.2 含銅亞硝酸還原酶(Cu-NiRs)的蛋白質結構 2
1.3 含銅亞硝酸還原酶(Cu-NiRs)的反應機制演進 8
1.4 含銅亞硝酸還原酶之模型化合物鍵結模式與反應性介紹 15
1.5 含銅亞硝酸還原酶之反應中間體{CuNO}10的模型化合物 28
第二章、生物擬態的銅CuI-nitrite化合物之結構與亞硝酸還原反應性研究：N3配位基電子效應與立體障礙的考量 31
2.1 前言 31
2.2 CuI-nitro化合物的合成與鑑定 34
2.2.1 化合物 [Tpm3-tBuCuI(NO2)] (1) 和 [(Ph3P)2N][Tp3-tBuCuI(NO2)] (2) 的合成 34
2.2.2 化合物[Tpm3-tBuCuI(NO2)] (1) 和化合物 [(Ph3P)2N][Tp3-tBuCuI(NO2)] (2) 的固態結果與液態結構探討 34
2.3 結論 42
第三章、 電子效應以及立體障礙在循環催化亞硝酸根離子轉為一氧化氮的反應機制與效能探討 51
3.1 前言 51
3.2 化合物的合成與催化實驗的描述 55
3.3 催化實驗的結果探討 55
3.4 結論 69
第四章、實驗部分 71
4.1 試藥來源及前處理 71
4.2 儀器部分 72
4.3 實驗步驟 74
4.3.1 化合物[(Ph3P)2N][Tp3-tBuCuI(NO2)] (2)的合成 74
4.3.2 化合物Tpm3-tBuCu(O2CCH3)2] (3)的合成 74
4.3.3 化合物Tpm3-tBuCuII(NO3)2 (7)的合成 74
4.3.4 化合物Tp3-tBuCuIINO3 (8)的合成 75
第五章、參考文獻 76

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