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论文类型：期刊论文

发表时间：2017-04-03

发表刊物：EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

收录刊物：SCIE

卷号：2017

期号：13

页面范围：1845-1854

ISSN号：1434-1948

关键字：Dioxygen activation; Enzyme models; Carboxylate ligands; Copper

摘要：To obtain insights into the role of the carboxylate group of Glu73 in the active site of quercetin 2,4-dioxygenase (2,4-QD), the copper(II) complexes [Cu(II)Ln(AcO)] [1 (Ln = L1), 2 (Ln = L2), 3 (Ln = L3), and 4 (Ln = L4)] supported by a series of carboxylate-containing ligands [L1H = 2-{[bis(pyridin-2ylmethyl) amino] methyl} benzoic acid; L2H = 3-{[bis(pyridin-2ylmethyl) amino] methyl} benzoic acid,; L3H = 2-({bis[2-(pyridin-2yl) ethyl] amino} methyl) benzoic acid; L4H = 3-({bis[2-(pyridin-2yl) ethyl] amino} methyl) benzoic acid] as well as the ternary Cu-II flavonolate (fla-) complexes [Cu(II)Ln(fla)] [5 (Ln = L1), 6 (Ln = L2), 7 (Ln = L3), and 8 (Ln = L4)] were synthesized and characterized as structural and functional models for the active site of 2,4-QD. The ternary complexes [Cu(II)Ln(fla)] showed different reactivities in the dioxygenation of bound flavonolate to benzoic acid, salicylic acid, and N,N-dimethylbenzamide at 75-90 degrees C (single- turnover reaction) in the order 5 >> 7 > 8 approximate to 6. A similar reactivity tendency was found in the catalytic dioxygenation of the substrate flavonol (multiturnover reaction) by the binary complexes. The different reactivities of the copper complexes could be attributed to the different Lewis acidities of the copper(II) ions induced by the different coordination environments of the ligands. The results will provide important insights into the pivotal catalytic role of the carboxylate group of Glu73 in 2,4-QD.