以3,5-dihydroxybenzyl alcohol為monomer之dendron，利用Hawker以及Fre´chet所發表的合成法”convergent methodology”可合成出[G-1]-Br (3)、[G-2]-Br (5) ( [G-1]-Br 為第一代、[G-2]-Br為第二代之poly(benzyl ether) dendron，其focal point為Br原子)，將化合物3或5分別和[K-18-crown-6-ether]2[Fe2S2(NO)4] (6)在THF下反應會生成dinuclear [{Fe(NO)2}9-{Fe(NO)2}9] DNIC ( dinitrosyl iron complex ) [Fe(SR)(NO)2]2 ( R = [G-2] (7) or [G-1]) (10) )。將化合物7和10進一步與不同化合物反應得到的化合物 [Fe(S-[G-2])(Im)(NO)2]-(8a), [Fe(S-[G-2])(SPh)(NO)2]-(8b), [Fe2(μ-S-[G-2])(μ-S)(NO)4]- (9) 與 anti-[Fe(μ-S-[G-1])(NO)2]2-(11)，以IR、UV-Vis、EPR光譜及X-ray單晶繞射解析，得知化合物11為具有delocalized mixed-valence core 的anionic [{Fe(NO)2}9-{Fe(NO)2}10] Roussin’s red ester，與實驗室所發表的結果相符。接著更以胺基酸為配位基合成出水溶性較佳的化合物[Fe(μ-SCys)(NO)2]2(12), [Fe(μ-SCysMe)(NO)2]2(13), [Fe(SCysMe)2(NO)2] (14)，以IR、UV-Vis光譜鑑定，化合物12在水中與L-Cysteine反應可以得到與化合物14同為13-line hyperfine splitting spectra之[H3O+][Fe(SCys)2(NO)2]，但是化合物14在水中則會轉換成化合物13，由EPR silent的光譜及UV-Vis吸收光譜得到證實。

[G-1]-Br (3) and [G-2]-Br (5) ([G-x]-Br stands for x generation dendron with Br at the focal point) can be synthesized from the monomer, 3,5-dihydroxybenzyl alcohol by Hawker and Fre´chet’s ”convergent methodology”. Reaction of compound 3 ( or compound 5 ) and [K-18-crown-6-ether]2[Fe2S2(NO)4] (6) in a 2:1 molar ratio in THF yielded the dinuclear [{Fe(NO)2}9-{Fe(NO)2}9] dinitrosyl iron complex (DNIC) [Fe(SR)(NO)2]2 (R= [G-2] (7) or [G-1] (10) ). Reaction of compound 7 and NaIm (or NaSPh, [PPN][NO2] ) led to the production of [Fe(S-[G-2])(Im)(NO)2]- (8a) (or [Fe(S-[G-2])(SPh)(NO)2]- (8b), [Fe2(μ-S-[G-2])(μ-S)(NO)4]- (9) ). Reaction of compound 10 and NaNSi2(CH3)6 led to the production of anti-[Fe(μ-S-[G-1])(NO)2]2- (11). Complex 8,9 and 11 were characterized by IR、UV-vis、EPR and X-ray diffraction. Complex 11 is best decribed as the anionic [{Fe(NO)2}9-{Fe(NO)2}10] Roussin’s Red Ester with the fully delocalized mixed-valence core. The better water soluble’s complex [Fe(μ-SCys)(NO)2]2 (12), [Fe(μ-SCysMe)(NO)2]2 (13) and [Fe(SCysMe)2(NO)2] (14) were then synthesized. Complex 12 - 14 were characterized by IR、UV-vis. Reaction of complex 12 and excess L-Cysteine in DI-water produces the 13-line hyperfine splitting spectra－[H3O+][Fe(SCys)2(NO)2]. The transformation of complex 14 into complex 13 in DI-water was observed identified with EPR spectroscopy.

謝誌 i
摘要 ii
Abstract iii
目錄 iv
圖目錄 vi
表目錄 viii
Scheme viii
第一章 緒論 1
1-1 一氧化氮(Nitric oxide) 1
1-2 一氧化氮在生物體內的重要性 3
1-3 NO在生物體的儲存與傳輸 7
1-4 NO降解[2Fe2S]對酵素活性之改變 13
1-5 樹枝狀高分子(Dendrimer) 16
1-6 實驗研究方向 19
第二章 實驗部份 20
2-1 一般實驗 20
2-2 儀器 20
2-3 藥品 22
2-4 化合物的合成、鑑定與反應 23
2-4-1 合成methyl 3,5-bis(benzyloxy)benzoate (1) 23
2-4-2 合成3,5-di(benzyloxy)benzyl alcohol ( [G-1]-OH ) (2) 24
2-4-3 合成3,5-di(benzyloxy)benzyl bromide ( [G-1]-Br ) (3) 24
2-4-4 合成[G-2]-OH (4) 25
2-4-5 合成[G-2]-Br (5) 25
2-4-6 合成[K-18-crown-6-ether]2[Fe2(μ-S)2(NO)4] ( RRS ) (6) 26
2-4-7 合成[Fe(μ-SR)(NO)2]2 (R = [G-2]) ( [G-2]-RRE ) (7) 27
2-4-8 合成[Na-18-crown-6-ether][Fe(S-[G-2])(R)(NO)2](R= Im (8a)， R = SPh (8b)) 27
2-4-9 合成[Fe2(μ-S-[G-2])(μ-S)(NO)4]- (cation=[K-18-crown-6-ether] (9a)，cation=[PPN] (9b) ) 28
2-4-10 合成[Fe(μ-SR)(NO)2]2 (R = [G-1]) ( [G-1]-RRE ) (10) 28
2-4-11 合成[Na-18-crown-6-ether] [Fe(μ-SR)(NO)2]2 (R = [G-1]) ( [G-1]-RRE-1 ) (11) 29
2-4-12 合成水溶性[Fe(μ-SR)(NO)2]2 ( SR = L-Cysteine ) ([Fe(μ-SCys)(NO)2]2 )(12) 30
2-4-13 合成水溶性[Fe(μ-SR)(NO)2]2 (SR = L-Cysteine methyl ester) (13) 30
2-4-14 合成水溶性[Fe(SR)2(NO)2] (SR = L-Cysteine methyl ester) (14) 31
2-5 晶體結構解析(Crystallography) 32
第三章 結果與討論 34
3-1 Dendrimer Ligand的合成([G-1]-Br(3)、[G-1]-Br(5)) 34
3-2 [Fe(μ-SR)(NO)2]2 (R = [G-2]) ( [G-2]-RRE ) (7) 、[Fe(μ-SR)(NO)2]2 (R = [G-1]) ( [G-1]-RRE ) (10) 的合成與光譜性質 37
3-3 含[G-2]之DNIC的合成與光譜性質 41
3-4 不對稱的Roussin’s red ester 44
3-5 [G-1]-RRE-1的合成與光譜探討 46
3-6 L-Cysteine的反應與光譜討論 53
3-7 L-Cysteine methyl ester hydrochloride (簡稱CysMe)的反應 與光譜討論 58
第四章 結論 68
參考文獻 71
圖目錄
圖 1-1-1 一氧化氮之分子軌域圖 1
圖 1-2-1 一氧化氮合成酶之催化機制 3
圖 1-2-2 guanylyl cyclase 活化中心與血基質作用之示意圖 5
圖 1-3-1 Cys-NO and GSNO 8
圖 1-3-2 兩種一氧化氮儲存模式互相轉換之示意圖 8
圖 1-3-3 The structural formulas of classical DNICs. 11
圖 1-3-4 The structural formulas of Non-classical DNICs and Se-containing DNICs. 11
圖 1-3-5 NO與高電位之鐵硫蛋白值（HiPIP）的反應 12
圖 1-4-1 一氧化氮影響ferrochelatase所造成免疫系統反應 14
圖 1-4-2 SoxR活化RNA轉譯的兩種方式 14
圖 1-4-3 [2Fe2S] cluster被一氧化氮修飾及回復示意圖 15
圖 1-5-1 Divergent合成法 16
圖 1-5-2 Convergent合成法 17
圖 1-5-3 含Zn之DPs結構 18
圖 1-5-4 水溶性dendrimer 18
圖 3-2-1 [G-2]-RRE (7) (THF) 之IR光譜圖(THF) 38
圖 3-2-2 [G-1]-RRE (10) (THF) 之IR光譜圖(THF) 38
圖 3-2-3 Ligand之吸收光譜 39
圖 3-2-4 RRE之吸收光譜 40
圖 3-2-5 SEt-RRE之吸收光譜 40
圖 3-3-1 [Na-18-crown-6-ether][Fe(S-[G-2])(Im)(NO)2] (8a) (THF)之IR 光譜 42
圖 3-3-2 [Na-18-crown-6-ether][Fe(S-[G-2])(SPh)(NO)2] (8b) (THF)之IR 光譜 42
圖 3-4-1 [K-18-crown-6-ether] [Fe2(μ-S -[G-2])( μ-S)(NO)4] (9a)之 IR 光譜 45
圖 3-4-2 [PPN] [Fe2(μ-S -[G-2])(μ-S)(NO)4] (9b)之 IR 光譜 45
圖 3-5-1 [Na-18-crown-6-ether][[G-1]-RRE] (11) (THF)之 IR 光譜 47
圖 3-5-2 [Na-18-crown-6-ether][[G-1]-RRE] (11)之X-ray結構ORTEP圖 47
圖 3-5-3 [Na-18-crown-6-ether][[G-1]-RRE] (11)之結構圖 48
圖 3-5-4 EPR spectrua of aRRE-S-[G-1] (THF) 50
圖 3-5-5 EPR spectrua of aRRE-SEt (THF) 50
圖 3-5-6 EPR spectrua of aRRE-StBu (THF) 50
圖 3-5-7 aRRE吸收光譜 52
圖 3-6-1 [Fe(μ-SCys)(NO)2]2 (12) (H2O)之 IR 光譜 54
圖 3-6-2 [Fe(μ-SCys)(NO)2]2 (12)之吸收光譜(H2O, RT) 54
圖 3-6-3 [H3O+][Fe(SCys)2(NO)2]之EPR (H2O) 56
圖 3-7-1 [Fe(μ-SCysMe)(NO)2]2 (13) (THF)之 IR 光譜 59
圖 3-7-2 [Fe(μ-SCysMe)(NO)2]2 (13) (MeOH)之 IR 光譜 59
圖 3-7-3 [Fe(μ-SCysMe)(NO)2]2 (13) (H2O)之 IR 光譜 60
圖 3-7-4由[Na-18-crown-6-ether] [Fe(SC7H4SN)2(NO)2]轉變成 [Fe(μ-SCysMe)(NO)2]2(13)之IR光譜 61
圖 3-7-5 由[Fe(μ-SCysMe)(NO)2]2轉變成 [Fe(SCysMe)2(NO)2] (14)之IR光譜 62
圖 3-7-6 [Fe(SCysMe)2(NO)2] (14)吸收光譜 (THF, RT) 62
圖 3-7-7 [Fe(SCysMe)2(NO)2] (14)之EPR (H2O) 66
圖 3-7-8 [Fe(SCysMe)2(NO)2] (14) 在水中測得的吸收光譜(H2O, RT) 66
圖 3-7-9 [Fe(SCysMe)2(NO)2] (14) 在室溫下水中測得的EPR光譜與過1.5hr, 4.5hr, 18.5hr測得的EPR光譜 67




表目錄
表 1-1 NO的鍵長及紅外線光譜震動能量 2
表 2-1 [Na-18-crown-6-ether] [ [G-1]-RRE] (11)之元素分析(EA) 29
表 2-1 Crystal data of [Na-18-crown-6-ether][Fe(μ-S-[G-1])(NO)2]2 ([G-1]-RRE-1) (11) 33
表 3-1 aRRE-S-[G-1] (11)、aRRE-SEt、aRRE-StBu之鍵長鍵角 49


Scheme
Scheme 1 Convergent methodology 34
Scheme 2 Ligand 合成 36
Scheme 3 化合物8a與8b的反應機制 43
Scheme 4 [Fe2(SCys)2(NO)4] (12)變成[H3O+][Fe(SCys)2(NO)2]之機制 57
Scheme 5 由[Na-18-crown-6-ether][Fe(SC7H4SN)2(NO)2]經由 [Fe(μ-SCysMe)(NO)2]2 (13)轉變成[Fe(SCysMe)2(NO)2](14) 63
Scheme 6 Dendrimer complexes 之合成 69
Scheme 7 Cysteine complexes 之合成 70

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