中文摘要
將合成出的兩種模擬胜肽AAHAHAA (A=Ala，H=His)以及RYAYR (R=Arg，Y= Tyr)分別在適合的pH值緩衝溶液中和水溶性六配位DNIC [(1-MeIm)2(η2-ON O)Fe(NO)2]反應可生成[Fe(AAHAHAA)2(NO)2]+(1)及[Fe(RYAYR)(NO)2]+(2)。另外將未上保護基的His和Tyr兩種胺基酸分別和六配位DNIC及[PPN][Fe(NO)2 (NO 2)2]反應可生成[Fe(His)2(NO)2]+(3)及[Fe(Tyr)2(NO)2]3-(4)。並利用EPR、ESI- MS和UV/ VIS等儀器證實[NHis/NHis]、[Otyr/Otyr]胺基酸鍵及胜肽鍵DNICs的存在。
化合物1在室溫下半生期僅五小時，而化合物2相對較穩定。化合物2和4的298 K EPR光譜並非單純的五線分裂，但兩者77 K光譜卻和小分子DNIC中的[Fe(NO)2(OPh)2]-相同。在UV/VIS光譜上化合物1及3有相似的兩組吸收，可將此吸收視為含[NHis/NHis] DNICs的特殊吸收峰；化合物3之EPR光譜經模擬後可得aN(NO) =2.35 G，aN(Im)=2.48 G，aH1= 2.0 G，aH2=1.7 G，而化合物1的耦合常數為aN(NO) =2.4 G，aN(Im)= 2.45 G，aH1= 1.9 G，aH2=1.5 G，兩者在EPR光譜中皆為十線分裂，不同於小分子DNIC中[Fe(C3H3N2)2(NO)2]-所看到的九線分裂，此為第一次看到有Imidazole環上氫耦合的現象。

目錄
謝誌…………………………………………………………………………………….i
中文摘要……..……………………………………………………………………….iii
Abstract……………………………………………………………………………….iv
目錄………………………………………………………..…………………………..v
圖表目錄…………………………………………………………………………….viii
表目錄………………………………………………………………………………...xi
第一章 緒論
1-1 一氧化氮在生物體內的重要性...........................................................................1
1-2 NO在生物體的儲存與傳輸................................................................................2
1-3 生物體內蛋白質鍵結的雙亞硝基鐵錯合物.......................................................5
1-4 水溶性雙亞硝基鐵錯合物與雙鐵核四亞硝基錯合物.....................................11
1-5 胜肽鍵雙亞硝基鐵錯合物.................................................................................13
1-6 研究方向.............................................................................................................14
第二章 實驗部分
2-1 一般實驗.............................................................................................................15
2-2 儀器.....................................................................................................................15
2-3 藥品.....................................................................................................................16
2-4 模擬胜肽的合成、純化與分析............................................................................18
2-4-1合成模擬胜肽.............................................................................................18
vi
2-4-2 樣品的純化與分析...................................................................................24
2-4-3 模擬胜肽的定量.......................................................................................25
2-5 化合物的合成、反應與鑑定...............................................................................26
2-5-1 化合物[PPN][Fe(NO)2(NO2)2]的製備......................................................26
2-5-2 化合物[(1-MeIm)2(η2-ONO)Fe(NO)2]的製備…………………………27
2-5-3 化合物[PPN][Fe(NO)2(NO2)2]與acetyl-L-tyrosine-ethyl ester…………27
hydrate反應
2-6水溶性雙亞硝基鐵錯合物的合成、反應與鑑定.................................................28
2-6-1 緩衝液(20ml)之製備..............................................................................28
2-6-2 [PPN][Fe(NO)2(NO2)2]與L-tyrosine ( pKa=10.13 )之反應...................28
2-6-3 [(1-MeIm)2(η2-ONO)Fe(NO)2]與L-Histidine(pKa1=6.0........................29
，pKa2=14.3)反應
2-6-4 [(1-MeIm)2(η2-ONO)Fe(NO)2]與AAYAYAA之反應............................29
2-6-5 [(1-MeIm)2(η2-ONO)Fe(NO)2]與KYAYK( pKa值=10.79 )之反應......30
2-6-6 [(1-MeIm)2(η2-ONO)Fe(NO)2]與KAAAK ( pKa=10.79 )之反應.........30
2-6-7 [(1-MeIm)2(η2-ONO)Fe(NO)2]與RYAYR之反應..................................31
2-6-8 [(1-MeIm)2(η2-ONO)Fe(NO)2]與AAHAHAA之反應..........................32
2-6-9水溶性雙亞硝基鐵錯合物的純化.............................................................32
2-6-10水溶性雙亞硝基鐵錯合物的鑑定方法...................................................33
第三章 結果與討論
3-1 模擬胜肽的設計、純化與分析結果...................................................................36
vii
3-2 [PPN][Fe(NO)2(NO2)2]與L-tyrosine之反應與光譜性質.................................38
3-3 [(1-MeIm)(NO2)Fe(NO)2]與AAYAYAA之反應與光譜性質...........................40
3-4 [(1-MeIm)(NO2)Fe(NO)2]與KYAYK之反應與光譜性質................................44
3-5 [(1-MeIm)(NO2)Fe(NO)2]與RYAYR之反應與光譜性質.................................38
3-6 [(1-MeIm)(NO2)Fe(NO)2]與L-Histidine之反應與光譜性質...........................50
3-7 [(1-MeIm)(NO2)Fe(NO)2]與AAHAHAA之反應與光譜性質.........................52
3-8 [PPN][Fe(NO)2(NO2)2]與acetyl-L-tyrosine-ethyl ester hydrate之反................56
應與[Fe(NO)2(OPh)2]-和[Fe(NO)2 (TyrEt)2]-兩者光譜性質比較
3-9 化合物[Fe(NO)2(Tyr)2]-，[Fe(RYAYR)(NO)2]+與[Fe(NO)2(OPh)2]-..................60
的EPR光譜比較
3-10 化合物[Fe(NO)2(Im)2]+，[Fe(AAHAHAA)(NO)2]+與[Fe(C3H3N2)2(NO)2]-......62
的EPR光譜比較
3-11 [Fe(AAHAHAA)(NO)2]+和[Fe(RYAYR)(NO)2]+胜肽鍵雙亞硝基鐵............64
錯合物穩定性之探討
第四章 結果與討論....................................................................................................66
參考文獻……………………………………………………………………………..68

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