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研究生： 陳虹伶
Hong-Ling Chen
論文名稱： 具不同軸取代之脯胺醇配位基於含鎳超氧化物歧化酶擬態化合物之合成、鑑定及對超氧離子活性探討
Synthesis, Characterization and Superoxide Reactivity of Prolinol-based NiSOD Mimics with Various Axial Ligands.
指導教授： 李位仁
Lee, Way-Zen
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2014
畢業學年度： 102
語文別： 英文
論文頁數： 75
中文關鍵詞： 含鎳超氧化物歧化酶 、鎳二聚體錯合物
英文關鍵詞： NiSOD, Ni-dimer complex
論文種類： 學術論文
相關次數： 點閱：117  下載：1 
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    • 本實驗室之前發表了Ni(BDPP)作為NiSOD 的擬態化合物，而本研究為了改良擬態化合物對超氧離子的活性及提升配位基的可變性，利用2,6-bis(((S)-2-(bis(4-methylphenyl)hydroxymethyl)-1-pyrrolidinyl)-methyl)-pyridine (H2BDPMeP) 及(S, S)-bis[2-(diphenylmethanol)-pyrrolidine]dipropylaniline (H2BDPPA) 兩種配位基， 分別得到了Ni(BDPMeP) (1)、[Ni(HBDPMeP)](ClO4)·(CH2Cl2)2 (2)和Ni2(BDPPA)2 (3)等幾種不同的NiSOD 擬態化合物。這些NiSOD 擬態化合物以X 光單晶繞射儀、紫外光可見光光譜儀及循環伏安法所鑑定。錯合物1 為Ni(BDPP) 的衍生物， 其在249.5 mV (versus Ag/AgCl inDCM, E = 124 mV)有一可逆的NiIII/NiII 氧化還原峰，而錯合物3 在714 mV (versus Ag/AgCl in DCM, E = 192 mV)也顯示了一組准可逆的NiIII/NiII 氧化還原峰，由錯合物1 和3 的電化學分析可知，他們可藉由二茂鐵離子或1,1’-二溴二茂鐵離子氧化生成三價鎳錯合物[NiIII(BDPMeP)](BF4) (4)及NiIII2(BDPPA)2(BF4)2 (5)。更重要的是錯合物4 和5 能將超氧離子轉化為氧氣，並分別還原回二價鎳錯合物1和3。

    Recently, the complex Ni(BDPP) was reported as a NiSOD model compound. In this study, we would like to improve the superoxidere activity of the NiSOD mimics and to augment the ligand alterability. The alternative NiSOD model compounds, Ni(BDPMeP) (1),[Ni(HBDPMeP)](ClO4)·(CH2Cl2)2 (2), and Ni2(BDPPA)2 (3), were supported by a new ligand, 2,6-bis(((S)-2-(bis(4-methylphenyl)-hydroxymethyl)-1-pyrrolidinyl)methyl)-pyridine (H2BDPMeP) or (S,S)-bis[2-(diphenylmethanol)- pyrrolidine]dipropylaniline (H2BDPPA),respectively. These NiSOD mimics were characterized by X-raycrystallography, UV-vis spectroscopy, and cyclic voltammetry. Complex1, a derivative of Ni(BDPP), demonstrated a reversible NiIII/NiII redoxcouple at E1/2 = 249.5 mV versus Ag/AgCl in DCM (ΔE = 124 mV). In addition, complex 3 showed a quasi-reversible NiIII/NiII redox couple atE1/2 = 714 mV versus Ag/AgCl in DCM (ΔE = 192 mV). Complex 1 and3 can be oxidized to nickel(III) species, [NiIII(BDPMeP)](BF4) (4) and NiIII2(BDPPA)2(BF4)2 (5), by ferrocenium salt and 1,1’-dibromoferrocenium salt respectively. Importantly, complexes 4 and 5 have shown the ability to convert O2– into O2 along with the formation of 1 and 3.

    Abstract I Abstract (Chinese version) II List of Figures III List of Tables V List of Figures VI CHAPTER ONE: INTRODUCTION 1 1.1 Significance and Specific Objectives of the This Work 1 1.2 Superoxide Dismutases (SODs) 2 1.2.1 Cu/ZnSOD 2 1.2.2 MnSOD. 3 1.2.3 FeSOD. 4 1.2.4 NiSOD 5 1.3 Literature Survey of NiSOD Analogues 9 1.2.1 Structural NiSODred Mimics 9 1.2.2 Structural NiSODox Mimics 12 1.2.3 Functional Models of NiSOD 14 CHAPTER TWO: EXPERIMENTAL SECTION 18 2.1 Synthetic Materials and Methods 18 2.2 Synthesis and Characterization of Ligands and Complexes 20 2.2.1 Synthesis and Characterization of H2BDPMeP 20 2.2.2 Synthesis and Characterization of Ni(BDPMeP) (1) 24 2.2.3 Synthesis and Characterization of [Ni(HBDPMeP)](ClO4)·(CH2Cl2)2 (2) 25 2.2.4 Synthesis and Characterization of H2BDPPA 26 2.2.5 Ni2(BDPPA)2 (3) 30 2.2.6 Synthesis and Characterization of 1,1’-Dibromoferrocene (FcBr2) 31 2.2.7 Synthesis and Characterization of [FcBr2](BF4) 32 2.2.8 Synthesis and Characterization of [NiIII(BDPMeP)](BF4) (4) 32 2.2.9 Synthesis and Characterization of NiIII2(BDPPA)2(BF4)2 (5) 33 2.3 Reaction of NiIII-complexes with KO2 34 2.3.1 [NiIII(BDPMeP)](BF4) (4) 34 2.3.2 NiIII2(BDPPA)2(BF4)2 (5) 34 CHAPTER THREE: RESULTS AND DISCUSSION 36 3.1 Synthesis and Discussion of Ni(BDPMeP) (1) 39 3.2 Synthesis and Discussion of [NiIII(BDPMeP)](BF4) (4) 47 3.3 Synthesis and Discussion of NiBDPPA (3) 53 3.4 Synthesis and Discussion of NiIII2(BDPPA)2(BF4)2 (5) 57 3.5 Discussion between Nickel-complexes and Superoxide 62 3.5.1 [NiIII(BDPMeP)](BF4) (4) 62 3.5.2 NiIII2(BDPPA)2(BF4)2 (5) 65 CHAPTER FOUR: CONCLUDING REMARKS 68 REFERENCE 70 APPENDIX

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