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    Please use this identifier to cite or link to this item: http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/32681


    Title: 銅錯合物之合成、構造、磁性與兒茶酚酶活性之研究,和兒茶酚加氧酶模型鐵錯合物之合成與研究
    Other Titles: Syntheses, structures, magnetic properties and catecholase-like activity of copper(II) complexes and studies on the model catechol 1,2-dioxygenase iron(III) complexes
    Authors: 鄭勝權;Cheng, Sheng-chuan
    Contributors: 淡江大學化學學系博士班
    魏和祥;Wei, Ho-hsiang
    Keywords: 銅錯合物;結構;磁性;鐵錯合物;兒茶酚酶;反應性;copper (Ⅱ) complexes;STRUCTURES;magnetic properties;catecholase-like reactivity;iron (Ⅲ) complexes;catechol 1,2-dioxygenase
    Date: 2005
    Issue Date: 2010-01-11 02:32:58 (UTC+8)
    Abstract: 本論文研究主題是討論化學結構、磁性行為與催化活性的關係。內容分成兩部分,第一部分是二價單一架橋雙核銅及雙重架橋雙核或四核銅,合成、構造、磁性行為與兒茶酚酶反應活性探討。第二部份為高自旋鐵(Ⅲ)錯合物的合成、構造與滴定兒茶酚通氧進行1,2-加氧酶反應時,可見光譜的特性與加氧酶催化反應關聯性。

    第一部分:
    本論文合成出來,十二個二價單一架橋雙核銅錯合物與十個雙重架橋雙核或四核銅錯合物,經由X-ray單晶繞射儀的分析,錯合物 1 ~ 6 為烷氧架橋的雙核銅錯合物,7 ~ 12 為酚氧架橋的錯合物。變溫磁性2 ~ 300 K的測量顯示這十二個錯合物都是反鐵磁性的交換作用。以3,5-di-tert-butylcatechol作為類兒茶酚酶反應研究的受質,發現當雙銅間的距離在2.9 ~ 3.0 A 時會有較高的反應性,而且反應速率並不會隨著pH值上升而提高,以錯合物 1 ~ 6進行Michaelis-Menten model的研究得到符合此一模型的動力學參數。錯合物 15、16為雙重架橋四核銅錯合物,其餘均為雙重架橋雙核銅錯合物,變溫磁性2 ~ 300 K的測量顯示雙銅配位面具有屋頂型的 15、16、21和22會有鐵磁性交換作用,其餘則為反鐵磁性交換作用,以3,5-di-tert-butylcatechol作為類兒茶酚酶反應研究的受質,由於雙銅的距離大於3.1 A所以在未改變pH值時不會有太好的反應性,當pH值增加到10.5 後以酸根為第二架橋基的錯合物13 ~ 16反應性會明顯增強。
    第二部份:
    以四芽配位基合成出三個鐵(Ⅲ)的錯合物:
    [Fe(L1 ~ 3)Cl2]
    HL1: 2-{[2-(2-Diethylamino-ethylamino)-ethylimino]-methyl}-phenol
    HL2:2,4-Di-tert-butyl-6-{[2-(2-diethylamino-ethylamino)-ethylimino]-methyl}-phenol
    HL3:2-{[2-(2-Diethylamino-ethylamino)-ethylimino]-methyl}-4-methoxy-phenol
    加入三種不同的兒茶酚陰離子tetrachlorocatechol ( TCC ),catechol ( CAT )和3,5-di-tert-butylcatechol ( 3,5-DTBC )後,得到一個[Fe(L1)TCC]的晶體,經由X-ray單晶繞射儀分析此錯合物為N3O3六配位扭曲的正八面體,從電子吸收光譜的研究發現當[Fe(L1 ~ 3)Cl2]與三種不同的兒茶酚陰離子反應時,除了[Fe(L2)Cl2]的立體障礙較大外,其餘都可清楚看見兩個新生成兒茶酚到鐵(Ⅲ)的電子轉移,根據吸收位置對應其路易士酸性可以發現,路易士酸性越強的[Fe(L3 )3,5-DTBC]進行兒茶酚1,2-雙加氧酶的催化反應性越佳。
    The present thesis has been divided into two parts: Ⅰ. Twenty two single bridged dinuclear, double bridged dinuclear, and tetranuclear copper (Ⅱ) complexes have been prepared and characterized. The crystal structures of all complexes are obtained from single crystal X-ray analysis. The magneto- structural correlations and catecholase activities of these complexes are investigated.

    Ⅱ.A series of high spin Fe(Ⅲ) complexes are prepared and characterized . The crystal structure of this series complexes also obtained from single crystal X-ray analysis. The catechol 1,2-dioxygenase activities of these iron(III) complexes are performed by electronic absorption spectroscopy.
    Part Ⅰ:
    The single crystal X-ray analysis show that the structures of complexes 1 ~ 6 are alkoxo-bridged dinuclear complexes and 7 ~ 12 are phenoxo-bridged dinuclear complexes. Magnetic susceptibility measurements in the temperature range 2-300K for complexes 1 ~ 12 indicate significant antiferromagnetic coupling between two copper (Ⅱ) atoms in all case. The kinetic studies on catecholase activity of complexes 1~ 12 for the oxidation of 3,5-di-tert- butylcatechol by O2 show that the complexes with the bond distance of Cu-Cu located near 2.9 ~ 3.0 A exhibit a high catecholase activity. For complexes 1 ~ 6 the reaction rate constants of the catecholase activity are obtained by Michaelis-Menten model.
    Complexes 15、16 are double bridged tetranuclear complexes and the others are double bridged dinuclear complexes. Magnetic susceptibility measurements in the temperature range 2-300K for 15、16、21、22 roof-shaped complexes indicate significant ferromagnetic coupling between two copper (Ⅱ) atoms and the others are significant antiferromagnetic coupling. Complexes 13-22, due to their Cu-Cu distances of >3.1A, show low catecholase-like activity of the oxidation of 3,5-di-tert-butylcatechol by O2 at low pH value solutions. However, increase the pH value up to 10.5, the high catecholase activities are found, especially the second carboxylato -bridged complexes exhibit more catecholase reactivity.

    Part Ⅱ:
    Series iron(Ⅲ) complexes with tetradentate ligands:
    [Fe(L1 ~ 3)Cl2]
    HL1: 2-{[2-(2-Diethylamino-ethylamino)-ethylimino]-methyl}-phenol
    HL2:2,4-Di-tert-butyl-6-{[2-(2-diethylamino-ethylamino)-ethylimino]-methyl}-phenol
    HL3:2-{[2-(2-Diethylamino-ethylamino)-ethylimino]-methyl}-4-methoxy-phen
    Only single crystal of [Fe(L1)TCC] (TCC =tetrachlorocatechol) has been isolated and X-ray analysis shows that iron(III) atom is distorted octahedral with N3O3 coordination sphere. Catechol 1,2-dioxgenase reactivity has been performed by electronic absorption of dmf (dimethylfomate) solutions of these iron(III) complexes and three kinds of catecholate anions tetrachlorocatechol ( TCC ), catechol ( CAT ), and 3,5-di-tert-butylcatechol ( 3,5-DTBC ) (dimethylfomate). The results show that the high Lewis acidity iron(III) complexes [Fe(L3 )3,5-DTBC] exhibits the highest catechol 1,2-dioxgenase reactivity.
    Appears in Collections:[化學學系暨研究所] 學位論文

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