Source:http://linkedlifedata.com/resource/pubmed/id/17680569
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
32
|
| pubmed:dateCreated |
2007-10-30
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| pubmed:abstractText |
Dinuclear zinc(II) complexes [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) (1) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3) (2) (H-BPMP=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 ((1)H, (31)P 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.
|
| pubmed:language |
eng
|
| pubmed:journal | |
| pubmed:citationSubset |
IM
|
| pubmed:chemical | |
| pubmed:status |
MEDLINE
|
| pubmed:issn |
0947-6539
|
| pubmed:author | |
| pubmed:issnType |
Print
|
| pubmed:volume |
13
|
| pubmed:owner |
NLM
|
| pubmed:authorsComplete |
Y
|
| pubmed:pagination |
9093-106
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| pubmed:dateRevised |
2009-8-4
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| pubmed:meshHeading |
pubmed-meshheading:17680569-Binding Sites,
pubmed-meshheading:17680569-Crystallography, X-Ray,
pubmed-meshheading:17680569-Enzyme Activation,
pubmed-meshheading:17680569-Hydrogen-Ion Concentration,
pubmed-meshheading:17680569-Kinetics,
pubmed-meshheading:17680569-Magnetic Resonance Spectroscopy,
pubmed-meshheading:17680569-Models, Biological,
pubmed-meshheading:17680569-Models, Molecular,
pubmed-meshheading:17680569-Molecular Structure,
pubmed-meshheading:17680569-Organometallic Compounds,
pubmed-meshheading:17680569-Phosphoric Diester Hydrolases,
pubmed-meshheading:17680569-Reference Standards,
pubmed-meshheading:17680569-Ribonucleases,
pubmed-meshheading:17680569-Sensitivity and Specificity,
pubmed-meshheading:17680569-Spectrometry, Mass, Electrospray Ionization,
pubmed-meshheading:17680569-Spectrophotometry, Ultraviolet,
pubmed-meshheading:17680569-Stereoisomerism,
pubmed-meshheading:17680569-Zinc
|
| pubmed:year |
2007
|
| pubmed:articleTitle |
Structural, kinetic, and theoretical studies on models of the zinc-containing phosphodiesterase active center: medium-dependent reaction mechanisms.
|
| pubmed:affiliation |
Département de Chimie Moléculaire, Université J. Fourier, Grenoble I, UMR-5250, ICMG FR-2607, CNRS BP-53, 38041 Grenoble, France.
|
| pubmed:publicationType |
Journal Article,
Research Support, Non-U.S. Gov't
|