Structural, kinetic, and theoretical studies on models of the zinc-containing phosphodiesterase active center: medium-dependent reaction mechanisms.
Dinuclear Zn(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) were synthesized, structurally characterized, and pH-driven changes in metal coordination obsd. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a H2O/DMSO (70:30) mixt. and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was obsd. A detailed mechanistic study by kinetic studies, spectroscopic measurements (1H, 31P NMR spectroscopy), and ESI-MS anal. in conjunction with ab initio calcns. 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. [on SciFinder(R)]
Références
- Titre
- Structural, kinetic, and theoretical studies on models of the zinc-containing phosphodiesterase active center: medium-dependent reaction mechanisms.
- Type de publication
- Article de revue
- Année de publication
- 2007
- Auteurs
- Selmeczi, Katalin, Michel Carine, Milet Anne, Gautier-Luneau Isabelle, Philouze Christian, Pierre Jean-Louis, Schnieders David, Rompel Annette, and Belle Catherine
- Revue
- Chem. - A Eur. J.
- Volume
- 13
- Pagination
- 9093–9106
- ISSN
- 0947-6539
- Mots-clés
- crystal structure zinc pyridylmethylaminomethylphenol dinuclear complex geometry optimized zinc pyridylmethylaminomethylphenol phosphate complex kinetics transesterification hydroxypropyl nitrophenyl phosphate zinc pyridylmethylaminomethylphenol catalyst phosphodiesterase model zinc pyridylmethylaminomethylphenol phosphate complex catalyst transesterification zinc pyridylmethylaminomethylphenol dinuclear complex prepn structure
Soumis le 12 avril 2018