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Author: 鄭惠文
Cheng Hui Wen
Thesis Title: 槲黃素氧化酶活性中心之雙銅擬態化合物的合成、結構及其對3-羥基黃銅醇催化反應之研究
Synthesis and Structure of Dicopper(II) Complex Relevant to the Active Site of Quercetin 2,3-dioxygenase and Its Catalysis towards 3-Hydroxyflavone.
Advisor: 李位仁
Lee, Way-Zen
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2009
Academic Year: 97
Language: 中文
Number of pages: 82
Keywords (in Chinese): 槲黃素氧化酶
Thesis Type: Academic thesis/ dissertation
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  • 為了合成槲黃素氧化酶活性中心的擬態化合物,本研究設計了一個對稱性的多牙基配子2,6-bis[(2-di(2-pyridylmethyl)aminoethoxy)]- benzoic acid (BDPABH),並由此配子成功地合成出擬態化合物[Cu2(BDPAB)(CH3CN)(ClO4)](ClO4)2 (1) 及其鋅衍生物[Zn2(BDPAB)- (CH3CN)2](ClO4)3 (2)。兩個錯合物皆利用紅外光光譜和電灑質譜及X-光結構解析法進行鑑定。錯合物1為具有雙銅中心的分子結構,每個銅金屬中心的配位環境皆為扭曲的八面體。兩個銅離子間的距離為5.73 Å。在77 K下偵測錯合物1的電子順磁共振光譜,發現在g‖區域具有七隻分裂的精細結構線,且其平均精細偶合常數為72 G,並推測雙銅之間具有微弱的磁性交互作用。此外,錯合物1在乙腈電解質溶液中由循環伏安法顯示出有兩個擬可逆(quasireversible)的過程,分別為一個電子的氧化還原反應。錯合物1進行3-羥基黃銅醇的氧化斷裂催化反應時,會產生2-(dimethylamino)-2-phenylbenzofuran-3(2H)-one、3-(dimethylamino)-3-phenyl-3H-chromene-2,4-dione、benzoic acid及2-hydroxybenzil四種產物。當催化劑1的劑量提升至10 mol%時,反應24小時後,受質會被消耗完畢,且主要產物為benzoic acid;然而當受質濃度稀釋為1 × 10-4 M時,主要產物會變為3-(dimethylamino)-3-phenyl-3H-chromene-2,4-dione。

    In order to mimic the active site of quercetine-2,3-dioxygenase, a symmetric ligand, 2,6-bis[(2-di(2-pyridylmethyl)aminoethoxy)]benzoic
    acid (BDPABH), was designed to synthesize a model complex, [Cu2(BDPAB)(CH3CN)(ClO4)](ClO4)2 (1), and a zinc derivative, [Zn2(BDPAB)(CH3CN)2](ClO4)3 (2). Both complexes 1 and 2 were characterized by IR and ESI-MS spectroscopies, and X-ray crystallography. The molecular structure of 1 revealed a dicopper core, in which the two copper centers were separated with a distance of 5.73 Å. Each copper center possessed a distorted octahedral geometry. The EPR spectrum of complex 1 recorded at 77 K has shown seven hyperfine lines in the g‖ region, with an average hyperfine coupling constant of 72 G. A weak magnetic exchange interaction between two copper centers of 1 was proposed. Cyclic voltammetry experiments recorded in CH3CN electrolytic solution of 1 exhibited two successive one-electron electrochemical events, which are quasireversible processes. Complex 1 can catalyze the oxidative cleavage of 3-hydroxyflavone to form 2-(dimethylamino)-2-phenylbenzofuran-3(2H)-one, 3-(dimethylamino)-3- phenyl-3H-chromene-2,4-dione, benzoic acid, and 2-hydroxybenzil. When catalyst 1 was increased to 10 mol%, the substrate was completely consumed within 24 hours, and the major product was benzoic acid. However, 3-(dimethylamino)-3-phenyl-3H-chromene-2,4-dione would become the major product as the concentration of the substrate was decreased to 1.4 × 10-4 M.

    中文摘要 Ι 英文摘要 II 圖索引 III 表索引 VII 附錄索引 VIII 第一章 緒論 第一節 研究動機與目的………………………..….………………...1 第二節 槲黃素氧化酶的相關文獻探討……………………….……...3 第三節 二價銅錯合物的性質…...………………………………....16 第二章 實驗部分 第一節 實驗儀器、藥品及條件……………..…………...………..19 第二節 配位基的合成與鑑定……………..………………………...27 第三節 金屬錯合物的合成……………………...…………………..31 第四節 含氮氧多牙基二價銅錯合物與受質之氧化反應…...……..35 第五節 含氮氧多牙基二價銅錯合物與受質之催化反應……….....37 第三章 槲黃素氧化酶模擬化合物的研究與討論 第一節 配子的合成探討……………………………………...……..43 第二節 錯合物的結果與探討……………………………..………...45 第三節 紫外光/可見光光譜……………………………………......50 第四節 紅外光光譜……………………………………………….....51 第五節 電子順磁共振光譜……………………………………….....53 第六節 含氮氧多牙基二價銅錯合物之還原電位的探討….........58 第七節 雙核金屬錯合物與受質催化反應之研究…………….......62 第八節 含氮氧多牙基二價銅錯合物對受質催化反應之討論….....73 第四章 結論與展望………...…………………………………….….79 參考文獻…………………………………………………………….…...82 附錄

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