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Article Dans Une Revue Chemistry - A European Journal Année : 2007

Structural, Kinetic and Theoretical Studies on modeling Zn-containing phosphodiesterase Active Center: medium-dependent Reaction Mechanisms

Résumé

Dinuclear zinc(II) complexes [Zn2(bpmp)(µ-OH)](ClO4)2 (1) and [Zn2(bpmp)(H2O)2](ClO4)3 (2) ( -HBPMP=2,6-bis[bis(2-pyridylmethyl)- aminomethyl]-4-methylphenol) have been synthesized, structurally characterized, and pH-driven changes in metal coordination observed. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a water/ DMSO (70:30) mixture and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was observed. A detailed mechanistic investigation by kinetic studies, spectroscopic measurements (1H, 31P NMR spectroscopy), and ESI-MS analysis in conjunction with ab initio calculations was performed on 1. Based on these results, two medium-dependent mechanisms are presented and an unusual bridging phosphate intermediate is proposed for the process in DMSO.

Dates et versions

hal-00942240 , version 1 (04-02-2014)

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Katalin Selmeczi, Carine Michel, Anne Milet, Isabelle Gautier-Luneau, Christian Philouze, et al.. Structural, Kinetic and Theoretical Studies on modeling Zn-containing phosphodiesterase Active Center: medium-dependent Reaction Mechanisms. Chemistry - A European Journal, 2007, 13 (32), pp.9093-9106. ⟨10.1002/chem.200700104⟩. ⟨hal-00942240⟩
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