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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
3
pubmed:dateCreated
2006-1-30
pubmed:abstractText
This report describes the synthesis, spectroscopy, and photochemistry of a new fluorescein-derivatized iron sulfur nitrosyl compound, the Roussin's red salt ester bis-((mu-S,mu-S')-fluorescein-2-thioethyl-ester)-tetranitrosyldiiron (Fluor-RSE). Under continuous photolysis Fluor-RSE decomposes with moderate quantum yields (0.0036 +/- 0.0005 at lambda(irr) = 436 nm) with the corresponding release of most of the NO carried by the Fe2S2NO4 cluster. Large changes in the optical absorptivity occur upon photolysis of the Fluor-RSE, and these changes have been attributed to the different protic forms available to the fluorescein chromophore as it is separated from the cluster. Steady-state luminescence experiments have shown that the fluorescence of Fluor-RSE is about 85% quenched relative to the model compound ethyl fluorescein (Fluor-Et). Thus, it is clear that excitation of the fluorescein chromophore antennae is followed by energy transfer to the Fe/S/NO cluster at a rate at least comparable to fluorescence. However, the effect of the iron-sulfur core on the fluorescent lifetimes from fluorescein chromophore is much smaller. A single-exponential decay (tau = 3.3 ns) was seen for Fluor-RSE that is only modestly shorter than that for Fluor-Et (tau = 4.5 ns), and this is the effect of the smaller radiative rate constant (k(r)) for the former. These systems further demonstrate that attachment of a pendant dye chromophore as an antenna significantly improves the effective rate for photochemical NO generation from the Roussin's red salt esters at longer excitation wavelengths.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Feb
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
6
pubmed:volume
45
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
1192-200
pubmed:meshHeading
pubmed:year
2006
pubmed:articleTitle
Toward development of water soluble dye derivatized nitrosyl compounds for photochemical delivery of NO.
pubmed:affiliation
Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93106-9510, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S.