一氧化氮還原酶 (Nitric oxide reductases, NORs) 在微生物中扮演調節一氧化氮濃度的重要角色，將NO進行兩個電子還原成N2O，以降低生物體內毒性。對於酵素運作的反應機構，過去文獻中大多是推測兩個NO進行耦合，生成金屬橋接亞硝酸鹽中間產物(Hyponitrite−bound intermediate)的機制。其中，實驗室也以DNIC作為模板，使用配位基1,3-bis(dimethylamino)propan-2-olate (Bdmap) 合成出{Fe(NO)2}9−{Fe(NO)2}10 [Fe(NO)2(𝜇-Bdmap)Fe(NO)2 (THF)] (2) ，與等當量NO 反應，使得N-N 鍵coupling，成功合成出trans−hyponitrite 四核DNIC {[Fe(NO)2]2(μ-bdmap)}2 (κ4-N2O2)，並用Hbdmap進行質子化反應後觀察到N2O的生成，共軛鹼配位形成[Fe(NO)2(bdmap)]2 (1)。
本文一開始先合成出化合物2，使其與氧氣反應，探討其活化小分子的反應性。接著，使用甲醇、苯酚、對硝基苯酚三種含氧酸再次將{[Fe(NO)2]2(μ-bdmap)}2 (κ4-N2O2)進行質子化反應，同時也使用化合物 2進行質子化反應，誘使 [N2O2]2- → N2O之轉換，成功合成出化合物 3−5 [Fe(NO)2(𝜇-bdmap)(𝜇-OR)Fe(NO)2] (OR = -OMe (3), -OPh (4), OPhNO2 (5))，證明質子化反應後的產物，模擬NOR反應的過程。
進一步將化合物 3−5使用EPR、SQUID及XAS等儀器鑑定結構，發現三者電子結構特殊，而過去實驗室發表的文獻中，對於以氧橋接雙核DNICs的例子也較為稀少，尤其化合物 3−5為兩個不同配位基同時以氧橋接雙鐵之新型DNICs，發現輔基(coligand)不同使結構扭曲，進而影響電子結構性質的差異是值得探討的地方。

In order to ease nitrosative stress, nitric oxide reductases (NORs) evolved in pathogens play an essential role in NO-detoxifying process which occurs via 2-electron reduction of two NO molecules to N2O. About the mechanism of NO reduction generating N2O, hyponitrite moiety is proposed as a common intermediate in biomimetic model studies. In the previous study, we have shown how the electronically localized {Fe(NO)2}9−{Fe(NO)2}10 [(NO)2Fe(μ-bdmap)Fe(NO)2(THF)](2) (bdmap = 1,3-bis(dimethylamino)-2-propanolate) induces a reductive coupling of NO to form trans-hyponitrite-bound tetranuclear DNIC [(NO)2Fe(μ-bdmap)Fe(NO)2]2 (κ4-N2O2), which then converts to N2O and [Fe(NO)2(bdmap)]2 (1) upon Hdmap added.
In this study, complex 2 was adopted to investigate small molecule activation of O2. Furthermore, complex 2 and hyponitrite-bound complex was protonated to release N2O by using methanol, phenol, 4-nitrophenol. Crystal structures of complexes 3−5 [Fe(NO)2(𝜇-bdmap)(𝜇-OR)Fe(NO)2] (OR = -OMe (3), -OPh (4), OPhNO2 (5)) were isolated to prove the products and procedures of [N2O2]2--to-N2O conversion.
There are only few crystal structures of O-bridged dDNICs reported. The electronic structures of complexes 3−5 are all characterized by EPR, XAS, SQUID. These different O-bridged dDNICs may inform how electron structures can be affected by structural distortion with different coligands.

摘要 I
ABSTRACT II
目錄 III
FIGURE LIST VI
SCHEME LIST IX
TABLE LIST XI
第一章 緒論 1
1-1 一氧化氮(nitric oxide,NO) 1
1-2 雙亞硝基鐵錯合物 ( Dinitrosyl iron complexes, DNICs ) 5
1-3 雙亞硝基鐵錯合物對小分子的反應性 9
1-4 一氧化氮還原酶 (Nitric oxide reductase, NOR) 13
1-4-1 Heme−containing Nitric Oxide reductase的介紹 14
1-4-2 Non-heme NO reductases的介紹 17
1-5 連二次亞硝酸鹽金屬錯合物 (Hyponitrite-bound metal complexes) 20
1-6 實驗研究方向 30
第二章 實驗部分 31
2-1 一般實驗 31
2-2 儀器 31
2-3 藥品 33
2-4 化合物之合成及鑑定 34
2-4-1 化合物[Fe(NO)2(Bdmap)]2(1)的合成 34
2-4-2 化合物[Fe(NO)2(𝜇-bdmap)Fe(NO)2(THF)](2)的合成 35
2-5 化合物之反應性 35
2-5-1 化合物[Fe(NO)2(𝜇-bdmap)Fe(NO)2(THF)](2)與Methanol (MeOH)反應 35
2-5-2 化合物[Fe(NO)2(𝜇-bdmap)Fe(NO)2(THF)](2)與苯酚(Phenol)反應 36
2-5-3 化合物[Fe2(NO)2(𝜇-Bdmap)(THF)](2)與4-nitrophenol反應 37
2-5-4 化合物[Fe(NO)2(𝜇-bdmap)Fe(NO)2(THF)](2)與O2反應 37
2-6 電化學特性測試 38
2-7 X−ray吸收光譜測量 (X−ray Absorption Spectroscopy Measurements) 39
2-8 晶體結構解析 (Crystallography) 39
2-8-1 化合物[Fe(NO)2(𝜇−bdmap)(𝜇−OMe)Fe(NO)2] (3)晶體參數 40
2-8-2 化合物[Fe(NO)2(𝜇−bdmap)(𝜇−OPh)Fe(NO)2] (4)晶體參數 41
2-8-3 化合物[Fe(NO)2(𝜇−bdmap)(𝜇−OPhNO2)Fe(NO)2] (5) 晶體參數 42
第三章 結果與討論 43
3-1 起始物的合成與鑑定 43
3-1-1 化合物[Fe(NO)2(Bdmap)]2 (1)的合成與光譜分析 43
3-1-2 化合物[Fe(NO)2(𝜇-Bdmap)Fe(NO)2 (THF)] (2)的合成與光譜分析 45
3-2 化合物[Fe(NO)2(𝜇-Bdmap)Fe(NO)2(THF)] (2) 反應性 47
3-3 化合物[Fe(NO)2(𝜇-Bdmap)Fe(NO)2(THF)] (2) 質子化反應 50
3-3-1 化合物 2 與甲醇(Methanol, MeOH) 反應 50
3-3-2 化合物 2 與苯酚(Phenol) 反應 53
3-3-3 化合物 2 與對硝基苯酚(4-nitrophenol) 反應 56
3-4 化合物3−5 之電化學性質 61
3-5 化合物3−5 電子結構比較 66
3-5-1 X−ray吸收光譜分析 (XAS, X−ray Absorption Spectroscopy) 66
3-5-2 電子順磁共振光譜(EPR)及超導量子干涉(SQUID)分析 68
第四章 結論 76
參考文獻 78

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