Geometry-dependent phosphodiester hydrolysis catalyzed by binuclear copper complexes

被引：83

作者：

Zhu, L ^{[1
]}

dos Santos, O ^{[1
]}

Koo, CW ^{[1
]}

Rybstein, M ^{[1
]}

Pape, L ^{[1
]}

Canary, JW ^{[1
]}

机构：

[1] NYU, Dept Chem, New York, NY 10003 USA

来源：

INORGANIC CHEMISTRY | 2003年 / 42卷 / 24期

关键词：

D O I：

10.1021/ic0340985

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Two isomeric binuclear ligands PBTPA and MBTPA and their copper(II) complexes were prepared and examined for hydrolysis of a model phosphodiester substrate: bis(p- nitrophenyl) phosphate. A bell-shaped pH vs rate profile, which is in agreement with one mechanism proposed for bimetallonucleases/phosphatases, was observed for the binuclear complex of copper(II) and PBTPA. At pH 8.4, a maximum rate of 1.14 x 10(-6) s(-1) -more than 10(4)-fold over uncatalyzed reactions-was achieved. However, the analogous complex of MBTPA did not show significant rate enhancement. The binuclear complex of copper(II) and PBTPA also showed 10-fold acceleration over mononuclear complex of copper(II) and tris(2-pyridylmethyl)amine (TPA) catalyzed reaction. A phage phiX174 DNA assay showed that the complex of copper(II) and PBTPA promoted supercoiled phage phiX174 DNA relaxation under both aerobic and anaerobic conditions, in contrast to the hydrolytic inactivity of the mononuclear complex of copper(II) and TPA.

引用

页码：7912 / 7920

页数：9

共 69 条

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