Geometry-Dependent Phosphodiester Hydrolysis Catalyzed by Binuclear Copper Complexes

Lei Zhu, Osvaldo Dos Santos, Chi Wan Koo, Marc Rybstein, Louise Pape, James Canary

Research output: Contribution to journalArticle

Abstract

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 × 10-6 s-1-more than 104-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 φX174 DNA assay showed that the complex of copper(II) and PBTPA promoted supercoiled phage φX174 DNA relaxation under both aerobic and anaerobic conditions, in contrast to the hydrolytic inactivity of the mononuclear complex of copper(II) and TPA.

Original languageEnglish (US)
Pages (from-to)7912-7920
Number of pages9
JournalInorganic Chemistry
Volume42
Issue number24
DOIs
StatePublished - Dec 1 2003

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hydrolysis
Copper
Hydrolysis
copper
Geometry
geometry
Bacteriophages
deoxyribonucleic acid
phosphatases
DNA
Phosphoric Monoester Hydrolases
bells
Assays
amines
phosphates
Ligands
ligands
augmentation
Substrates
profiles

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Geometry-Dependent Phosphodiester Hydrolysis Catalyzed by Binuclear Copper Complexes. / Zhu, Lei; Dos Santos, Osvaldo; Koo, Chi Wan; Rybstein, Marc; Pape, Louise; Canary, James.

In: Inorganic Chemistry, Vol. 42, No. 24, 01.12.2003, p. 7912-7920.

Research output: Contribution to journalArticle

Zhu, Lei ; Dos Santos, Osvaldo ; Koo, Chi Wan ; Rybstein, Marc ; Pape, Louise ; Canary, James. / Geometry-Dependent Phosphodiester Hydrolysis Catalyzed by Binuclear Copper Complexes. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 24. pp. 7912-7920.
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