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Structural and spectroscopic studies of a model for catechol oxidase

Smith, S. J. and Noble, C. J. and Palmer, R. C. and Hanson, G. R. and Schenk, Gerhard and Gahan, L. R. and Riley, M. J. (2008) Structural and spectroscopic studies of a model for catechol oxidase. Journal of Biological Inorganic Chemistry, 13 (4). pp. 499-510. ISSN 0949-8257

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Abstract

A binuclear copper complex, [Cu2(BPMP) (OAc)2][ClO4] x H2O, has been prepared using the binucleating ligand 2,6-bis[bis(pyridin-2-ylmethylamino)methyl]-4-methylphenol (H-BPMP). The X-ray crystal structure reveals the copper centers to have a five-coordinate square pyramidal geometry, with the acetate ligands bound terminally. The bridging phenolate occupies the apical position of the square-based pyramids and magnetic susceptibility, electron paramagnetic resonance (EPR) and variable-temperature variable-field magnetic circular dichroism (MCD) measurements indicate that the two centers are very weakly antiferromagnetically coupled (J = -0.6 cm(-1)). Simulation of the dipole-dipole-coupled EPR spectrum showed that in solution the Cu-O-Cu angle was increased from 126 degrees to 160 degrees and that the internuclear distance was larger than that observed crystallographically. The high-resolution spectroscopic information obtained has been correlated with a detailed ligand-field analysis to gain insight into the electronic structure of the complex. Symmetry arguments have been used to demonstrate that the sign of the MCD is characteristic of the tetragonally elongated environment. The complex also displays catecholase activity (k(cat) = 15 +/- 1.5 min(-1), K(M) = 6.4 +/- 1.8 mM), which is compared with other dicopper catechol oxidase models.

Item Type: Article
Keywords: Catechol oxidase; Copper dimer; Magnetic circular dichroism; Electron paramagnetic resonance; Angular overlap model;
Subjects: Science & Engineering > Chemistry
Item ID: 3692
Depositing User: Gary Schenk
Date Deposited: 29 May 2012 08:48
Journal or Publication Title: Journal of Biological Inorganic Chemistry
Publisher: Springer Verlag
Refereed: Yes
URI:

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