Linked Life Data

20397184

Source:http://linkedlifedata.com/resource/pubmed/id/20397184

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
6
pubmed:dateCreated
2010-6-2
pubmed:abstractText
Density Functional Theory and post-Hartree Fock calculations reveal an unusual energy profile for Zn-S and Zn-N bond dissociation reactions in several [Zn(SR)(4)](2-) and [Zn(Im)(SR)(3)](-) complexes. The Zn-S bond dissociation in tetrathiolate dianions, which is highly exothermic in the gas phase, proceeds through a late transition state which can be rationalized on the basis of an avoided crossing resulting from Coulomb repulsion between the anionic fragments and ligand-to-metal charge-transfer in the [Zn(SR)(4)](2-) complexes. When solvation models for water, DMSO, or acetonitrile are included, some complexes become stable while others are metastable, so this constitutes the first theoretical model which is in full agreement with the experimental data for various [Zn(SR)(4)](2-), [Zn(SR)(3)](-), and [Zn(Im)(SR)(3)](-) complexes. The analysis given here indicates that the Zn(Cys)(4) and Zn(His)(Cys)(3) cores of numerous proteins are metastable with respect to Zn-S and Zn-N bond dissociation, respectively. This is consistent with the kinetic lability at the zinc-centers and illustrates that in nature, thermodynamic stability is imparted upon the zinc cores by the protein environment.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Jun
pubmed:issn
1861-471X
pubmed:author
pubmed:issnType
Electronic
pubmed:day
1
pubmed:volume
5
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
1445-54
pubmed:year
2010
pubmed:articleTitle
Thermodynamic stability versus kinetic lability of ZnS4 core.
pubmed:affiliation
Laboratoire des Mécanismes Réactionnels, Département de Chimie, Ecole Polytechnique and CNRS, 91128 Palaiseau Cedex, France.
pubmed:publicationType
Journal Article