| 摘要: | 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. |
