Linked Life Data

19235982

Source:http://linkedlifedata.com/resource/pubmed/id/19235982

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
5
pubmed:dateCreated
2009-2-24
pubmed:abstractText
The active sites of mononuclear molybdenum-containing enzymes contain a low-symmetry Mo(V)-dithiolene intermediate whose structure can be probed using electron paramagnetic resonance (EPR). The relationship between experimental EPR spectra and the electronic and geometric structure of the active site can be difficult to establish, not least because of the low molecular symmetry. When density functional theory is used, it is possible to assess this relationship by systematically varying the geometric structure and comparing the theoretical EPR parameters with those obtained experimentally. We employed this approach to examine the relationship between the metal-dithiolate fold angle and the monoclinic spin Hamiltonian parameters (g, A, beta) of a prototypical mononuclear molybdenyl model complex. By comparing the experimental EPR parameters with these results, we show that the metal-dithiolate fold angle of the complex in solution may be obtained from the non-coincidence angle beta that transforms the principal axes of g to those of A. This will provide a useful method for probing the structure of the Mo(V) intermediate of mononuclear molybdenum enzymes, where the electronic structure of the active site is modulated by the fold angle of the dithiolate ligand (the "metal-dithiolate folding effect").
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Mar
pubmed:issn
1520-510X
pubmed:author
pubmed:issnType
Electronic
pubmed:day
2
pubmed:volume
48
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2224-32
pubmed:meshHeading
pubmed:year
2009
pubmed:articleTitle
Determination of the metal-dithiolate fold angle in mononuclear molybdenum(V) centers by EPR spectroscopy.
pubmed:affiliation
The University of Queensland, Centre for Magnetic Resonance and Centre for Metals in Biology, Queensland 4072, Australia.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't