Source:http://linkedlifedata.com/resource/pubmed/id/19178351
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Predicate | Object |
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
3
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pubmed:dateCreated |
2009-1-30
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pubmed:abstractText |
Upon heating to 80 degrees C, 11-cis-retinal yields a mixture of all-trans-retinal and 13-cis-retinal. This isomerization has been studied by means of density functional theory methods, and the computational results suggest a close competition between two mechanisms of very different nature. A classical internal rotation around the C11-C12 cis double bond, via a diradical transition state, accounts for the formation of the all-trans isomer. An intricate sequence of pericyclic reactions, namely a reversible [1,7]-H sigmatropic shift and a reversible 6-pi-oxa-electrocyclic reaction, is responsible for the formation of 13-cis-retinal. Experiments using 11-cis-retinal labeled with deuterium at C19 confirmed the mechanistic proposal and also revealed an unprecedented outcome on the product composition of isotopologues.
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pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical | |
pubmed:status |
MEDLINE
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pubmed:month |
Feb
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pubmed:issn |
1520-6904
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pubmed:author | |
pubmed:issnType |
Electronic
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pubmed:day |
6
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pubmed:volume |
74
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
1007-13
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pubmed:meshHeading |
pubmed-meshheading:19178351-Hot Temperature,
pubmed-meshheading:19178351-Isomerism,
pubmed-meshheading:19178351-Kinetics,
pubmed-meshheading:19178351-Ligands,
pubmed-meshheading:19178351-Magnetic Resonance Spectroscopy,
pubmed-meshheading:19178351-Models, Molecular,
pubmed-meshheading:19178351-Molecular Conformation,
pubmed-meshheading:19178351-Retinaldehyde,
pubmed-meshheading:19178351-Rhodopsin,
pubmed-meshheading:19178351-Thermodynamics
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pubmed:year |
2009
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pubmed:articleTitle |
Complex thermal behavior of 11-cis-retinal, the ligand of the visual pigments.
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pubmed:affiliation |
Departamento de Quimica Organica, Facultade de Quimica, Universidade de Vigo, Lagoas Marcosende, E-36310, Vigo, Spain.
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pubmed:publicationType |
Journal Article,
Research Support, Non-U.S. Gov't
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