Linked Life Data

12803080

Source:http://linkedlifedata.com/resource/pubmed/id/12803080

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
5
pubmed:dateCreated
2003-6-13
pubmed:abstractText
A detailed analysis of the photophysical behaviour of uranyl ion in aqueous solutions at room temperature is given using literature data, together with results of new experimental and theoretical studies to see whether the decay mechanism of the lowest excited state involves physical deactivation by energy transfer or a chemical process through hydrogen atom abstraction. Comparison of the radiative lifetimes determined from quantum yield and lifetime data with that obtained from the Einstein relationship strongly suggests that the emitting state is identical to that observed in the lowest energy absorption band. From study of the experimental rate and that calculated theoretically, from deuterium isotope effects and the activation energy for decay support is given to a deactivation mechanism of hydrogen abstraction involving water clusters to give uranium(v) and hydroxyl radicals. Support for hydroxyl radical formation comes from electron spin resonance spectra observed in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide and tert-butyl-N-phenylnitrone and from literature results on photoinduced uranyl oxygen exchange and photoconductivity. It has previously been suggested that the uranyl emission above pH 1.5 may involve an exciplex between excited uranyl ion and uranium(v). Evidence against this mechanism is given on the basis of quenching of uranyl luminescence by uranium(v), together with other kinetic reasoning. No overall photochemical reaction is observed on excitation of aqueous uranyl solutions, and it is suggested that this is mainly due to reoxidation of UO2+ by hydroxyl radicals in a radical pair. An alternative process involving oxidation by molecular oxygen is analysed experimentally and theoretically, and is suggested to be too slow to be a major reoxidation pathway.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
May
pubmed:issn
1474-905X
pubmed:author
pubmed:issnType
Print
pubmed:volume
2
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
569-75
pubmed:year
2003
pubmed:articleTitle
Deactivation processes of the lowest excited state of [UO2(H2O)5]2+ in aqueous solution.
pubmed:affiliation
Departamento de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal.
pubmed:publicationType
Journal Article