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rdf:type |
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lifeskim:mentions |
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pubmed:issue |
17
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pubmed:dateCreated |
2010-8-30
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pubmed:abstractText |
The mechanism of the reaction of CuFL1 (FL1 = 2-{2-chloro-6-hydroxy-5-[(2-methylquinolin-8-ylamino)methyl]-3-oxo-3H-xanthen-9-yl}benzoic acid) with nitric oxide (NO) to form the N-nitrosated product FL1-NO in buffered aqueous solutions was investigated. The reaction is first-order in [CuFL1], [NO], and [OH(-)]. The observed rate saturation at high base concentrations is consistent with a mechanism in which the protonation state of the secondary amine of the ligand is important for reactivity. This information provides a rationale for designing faster-reacting probes by lowering the pK(a) of the secondary amine. Activation parameters for the reaction of CuFL1 with NO indicate an associative mechanism (DeltaS(double dagger) = -120 +/- 10 J/mol.K) with a modest thermal barrier (DeltaH(double dagger) = 41 +/- 2 kJ/mol; E(a) = 43 +/- 2 kJ/mol). Variable-pH electron paramagnetic resonance experiments reveal that, as the secondary amine of CuFL1 is deprotonated, electron density shifts to yield a new spin-active species having electron density localized on the deprotonated amine nitrogen atom. This result suggests that FL1-NO formation occurs when NO attacks the deprotonated secondary amine of the coordinated ligand, followed by inner-sphere electron transfer to Cu(II) to form Cu(I) and release of FL1-NO from the metal.
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pubmed:grant |
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pubmed:commentsCorrections |
http://linkedlifedata.com/resource/pubmed/commentcorrection/20704359-11134509,
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http://linkedlifedata.com/resource/pubmed/commentcorrection/20704359-9482858
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
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pubmed:status |
MEDLINE
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pubmed:month |
Sep
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pubmed:issn |
1520-510X
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pubmed:author |
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pubmed:issnType |
Electronic
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pubmed:day |
6
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pubmed:volume |
49
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
8025-33
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pubmed:dateRevised |
2011-9-13
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pubmed:meshHeading |
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pubmed:year |
2010
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pubmed:articleTitle |
Mechanism of nitric oxide reactivity and fluorescence enhancement of the NO-specific probe CuFL1.
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pubmed:affiliation |
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
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pubmed:publicationType |
Journal Article,
Research Support, U.S. Gov't, Non-P.H.S.,
Research Support, N.I.H., Extramural
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