Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes

Laser Flash Photolysis (LFP) experiments carried out on 2-azidofluorene in aqueous systems generate 2-fluorenyl nitrenium ion (λmax = 450 nm) which decays with first order rate constant and is quenched with 2′-deoxyguanosine originating an intermediate, namely the C8 adduct of 2-fluorenyl nitrenium...

Descripción completa

Detalles Bibliográficos
Autores principales: McClelland, Robert A., Postigo, Al
Formato: Artículo
Lenguaje:Inglés
Publicado: Universidad de Belgrano - Facultad de Ciencias Exactas y Naturales - Proyectos de Investigación 2014
Materias:
Fluorenyl nitrenium ion
Photochemistry
Laser flash photolysis
Flash fotólisis láser
Fotoquímica
fluorenilo nitrenium ion
Acceso en línea:http://repositorio.ub.edu.ar/handle/123456789/2728
Aporte de:
Repositorio Institucional - Universidad de Belgrano (UB) de Universidad de Belgrano
id I36-R142-123456789-2728
record_format dspace
institution Universidad de Belgrano
institution_str I-36
repository_str R-142
collection Repositorio Institucional - Universidad de Belgrano (UB)
language Inglés
topic Fluorenyl nitrenium ion
Photochemistry
Laser flash photolysis
Flash fotólisis láser
Fotoquímica
fluorenilo nitrenium ion
spellingShingle Fluorenyl nitrenium ion
Photochemistry
Laser flash photolysis
Flash fotólisis láser
Fotoquímica
fluorenilo nitrenium ion
McClelland, Robert A.
Postigo, Al
Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes
topic_facet Fluorenyl nitrenium ion
Photochemistry
Laser flash photolysis
Flash fotólisis láser
Fotoquímica
fluorenilo nitrenium ion
description Laser Flash Photolysis (LFP) experiments carried out on 2-azidofluorene in aqueous systems generate 2-fluorenyl nitrenium ion (λmax = 450 nm) which decays with first order rate constant and is quenched with 2′-deoxyguanosine originating an intermediate, namely the C8 adduct of 2-fluorenyl nitrenium ion, with bimolecular rate constant in the order of 1.3 × 109 M− 1 s− 1 in pure water. This intermediate very likely mimics the intermediate formed from carcinogens (i.e.: arylnitrenium ions formed through metabolic activation pathways from aminoaromatic substrates) and DNA rests in vivo. Solvent effects demonstrate and support the further stabilization of this intermediate (with respect to fluorenyl nitrenium ion) through hydrogen bonding as compared to other probe systems, and accounts for the enhanced metabolic carcinogenecity observed for this type of compounds. Diverse solvent systems, such as mixtures of water with acetonitrile, 1,1,1-trifluoroethanol, and 1,1,1,3,3,3-hexafluoroisopropanol, are used to interpret solvent–complex interactions.
format Article
author McClelland, Robert A.
Postigo, Al
author_facet McClelland, Robert A.
Postigo, Al
author_sort McClelland, Robert A.
title Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes
title_short Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes
title_full Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes
title_fullStr Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes
title_full_unstemmed Solvent effects on the reactivity of fluorenyl nitrenium ion with DNA-like probes
title_sort solvent effects on the reactivity of fluorenyl nitrenium ion with dna-like probes
publisher Universidad de Belgrano - Facultad de Ciencias Exactas y Naturales - Proyectos de Investigación
publishDate 2014
url http://repositorio.ub.edu.ar/handle/123456789/2728
work_keys_str_mv AT mcclellandroberta solventeffectsonthereactivityoffluorenylnitreniumionwithdnalikeprobes
AT postigoal solventeffectsonthereactivityoffluorenylnitreniumionwithdnalikeprobes
bdutipo_str Repositorios
_version_ 1764820529263411201

Ejemplares similares