Effect of Ag+ on the Excited-State Properties of a Gas-Phase (Cytosine)2Ag+ Complex: Electronic Transition and Estimated Lifetime

Recently, DNA molecules have received great attention because of their potential applications in material science. One interesting example is the production of highly fluorescent and tunable DNA–Agn clusters with cytosine (C)-rich DNA strands. Here, we report the UV photofragmentation spectra of gas...

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Detalles Bibliográficos
Autores: Berdakin, Matias, Féraud, Geraldine, Dedonder Lardeux, Claude, Jouvet, Christophe, Pino, Gustavo Ariel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2014
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/31368
Acceso en línea:http://hdl.handle.net/11336/31368
Access Level:acceso abierto
Palabra clave:Dna Bases
Dna−Agn Cluster
Excited State
Metal-Mediated Base Pairs
Photofragmentation Spectroscopy
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:Recently, DNA molecules have received great attention because of their potential applications in material science. One interesting example is the production of highly fluorescent and tunable DNA–Agn clusters with cytosine (C)-rich DNA strands. Here, we report the UV photofragmentation spectra of gas-phase cytosine···Ag+···cytosine (C2Ag+) and cytosine···H+···cytosine (C2H+) complexes together with theoretical calculations. In both cases, the excitation energy does not differ significantly from that of isolated cytosine or protonated cytosine, indicating that the excitation takes place on the DNA base. However, the excited-state lifetime of the C2H+ (τ = 85 fs), estimated from the bandwidth of the spectrum, is at least 2 orders of magnitude shorter than that of the C2Ag+ (τ > 5000 fs). The increased excited-state lifetime upon silver complexation is quite unexpected, and it clearly opens the question about what factors are controlling the nonradiative decay in pyrimidine DNA bases. This is an important result for the expanding field of metal-mediated base pairing and may also be important to the photophysical properties of DNA-templated fluorescent silver clusters.