Studies on Iron(Ⅲ) Catechol 1,2-Dioxygenase model Complexes and Iron(Ⅲ) Catecholase Reactivity Complexes

博士 === 淡江大學 === 化學學系博士班 === 100 === 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, el...

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Bibliographic Details
Main Authors: Jian-Wei Lu, 呂建緯
Other Authors: 魏和祥
Format: Others
Language:zh-TW
Published: 2012
Online Access:http://ndltd.ncl.edu.tw/handle/24847950755399199252
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Summary:博士 === 淡江大學 === 化學學系博士班 === 100 === 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.