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    Please use this identifier to cite or link to this item: http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/77372


    Title: 鐵(Ⅲ)兒茶酚雙加氧酶模型錯合物及鐵(Ⅲ)具兒茶酚酶活性錯合物之研究
    Other Titles: Studies on iron(Ⅲ) catechol 1,2-dioxygenase model complexes and iron(Ⅲ) catecholase reactivity complexes
    Authors: 呂建緯;Lu, Jian-Wei
    Contributors: 淡江大學化學學系博士班
    魏和祥
    Keywords: 兒茶酚雙加氧酶;兒茶酚酶;鐵(III)錯合物;X-ray結構;Intradiol cleavage;Catechol 1,2-dioxygenase;Iron(III) complexes;X-ray structure;Catecholase Activity
    Date: 2012
    Issue Date: 2012-06-21 06:37:58 (UTC+8)
    Abstract: 第一部份: 鐵(Ⅲ)兒茶酚雙加氧酶模型錯合物
    本論文合成一系列兒茶酚1,2-雙加氧酶之功能性模型鐵(III)錯合物且物理性質由X-ray單晶繞射儀、UV-Vis光譜、元素分析儀及電化學方法來分析,並藉由GC-Mass進行反應產物之量測。
    酵素、酵素-受質型錯合物及配位基:
    (1) [Fe(HL1)Cl3]2
    (2) [Fe(HL2)Cl3].CH3CN
    (3) [Fe(HL3)Cl3].CH3CN
    (4) [Fe(HL5)Cl3]2.CH3CN
    (5) [Fe(HL6)Cl3]
    (6) [Fe(HL4)(H2O)Cl2]Cl
    (7) [Fe(HL5)(H2O)Cl2]Cl
    (8) [Fe(L1)(C6Br4O2)]
    (9) [Fe(L2)(C6Cl4O2)]
    (10) [Fe(L6)(C6Cl4O2)]
    (11) [Fe(HL6)(C6Br4O2)Cl].CH3CN
    (12) [Fe(HL6)2]Cl3.2 CH3CN.H2O

    加入3,5-di-tert-butylcatechol(3,5-DTBC)的兒茶酚陰離子與Complex(1) ~ Complex(7)反應,可藉由電子吸收光譜發現兩個新生成兒茶酚到鐵(III)的電子轉移,根據吸收位置與路易士酸性的關係可發現,路易士酸性越強的錯合物有較佳的兒茶酚1,2-雙加氧酶的催化反應性。含有較弱配位能力的H2O或Cl-的配位基團易被小分子或溶劑分子取代而改變其反應途徑。

    第二部份: 鐵(Ⅲ)具兒茶酚酶活性錯合物之研究
    合成一系列具苯酚四牙配位基之錯合物,且性質由X-ray單晶繞射儀、UV-Vis光譜、元素分析儀及電化學方法來分析。
    酵素-受質型錯合物及配位基:

    (1) [Fe(L1)(C6Br4O2)]
    (2) [Fe(L2)(C6Cl4O2)]2
    (3) [Fe(L3)(C6Br4O2)].2CH3OH
    (4) [Fe(L4)(C6Br4O2)]
    (5) [Fe(L5)(C6Cl4O2)].CH3CN

    加入兒茶酚陰離子3,5-di-tert-butylcatechol(3,5-DTBC)與[Fe(L1~5)Cl2]反應,可藉由UV-Vis光譜測量,根據其吸收位置(λ=400nm)可發現有Diquinone的生成,表示這一系列的鐵(III)錯合物具有兒茶酚酶活性,且路易士酸性越強的錯合物具有較佳的兒茶酚酶催化反應性。
    Part Ⅰ: Iron(Ⅲ) Catechol 1,2-Dioxygenase model Complexes
    A seiries of iron(III) complexes as funtionl model compounds for catechol 1,2-dioxygenases (intradiol cleavage) were synthesized and characterized by X-ray single crystal diffraction, UV-Vis spectroscopy, element analyzer, Gas chromatography –Mass and electronchemical analysises.
    Enzyme, enzyme-substrate complexes and ligands:

    (1) [Fe(HL1)Cl3]2
    (2) [Fe(HL2)Cl3].CH3CN
    (3) [Fe(HL3)Cl3].CH3CN
    (4) [Fe(HL5)Cl3]2.CH3CN
    (5) [Fe(HL6)Cl3]
    (6) [Fe(HL4)(H2O)Cl2]Cl
    (7) [Fe(HL5)(H2O)Cl2]Cl
    (8) [Fe(L1)(C6Br4O2)]
    (9) [Fe(L2)(C6Cl4O2)]
    (10) [Fe(L6)(C6Cl4O2)]
    (11) [Fe(HL6)(C6Br4O2)Cl].CH3CN
    (12) [Fe(HL6)2]Cl3.2 CH3CN.H2O

    Catechol 1,2-dioxygenase reactivity had been performed by electronic spectrum in methanol/acetonitrile solutions. The solutions were contained Complex(1)~Complex(7) with catecholate anions of 3,5-di-tert-butylcatechol(3,5-DTBC). The results show that the high lewis acidity iron(III) complexes exhibits the higher catechol 1,2-dioxygenase reactivity. The product distribution of Catechol 1,2-dioxygenase reaction was found to be very solvent dependent.


    Part Ⅱ: Iron(Ⅲ) Catecholase Reactivity Complexes
    A seiries iron(III) complexes of the monophenolate ligands for catecholase activity were synthesized and characterized by X-ray single crystal diffraction, UV-Vis spectroscopy, element analyzer, and electronchemical analysises.

    Enzyme-substrate complexes and ligands:
    (1) [Fe(L1)(C6Br4O2)]
    (2) [Fe(L2)(C6Cl4O2)]2
    (3) [Fe(L3)(C6Br4O2)].2CH3OH
    (4) [Fe(L4)(C6Br4O2)]
    (5) [Fe(L5)(C6Cl4O2)].CH3CN

    A seiries iron(III) compounds of the monophenolate ligands with catecholase activity had been performed by UV-Vis spectrum in DMF solutions. The solutions were contained [Fe(L1~5)Cl2] which reacted with catecholate anions of 3,5-di-tert-butylcatechol(3,5-DTBC). The results show that the high lewis acidity of iron(III) complexes exhibits the higher Catecholase reactivity.
    Appears in Collections:[化學學系暨研究所] 學位論文

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