On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory
- Autores
- Berdakin, Matias; Steinmetz, Vincent; Maitre, Philippe; Pino, Gustavo Ariel
- Año de publicación
- 2015
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- The gas-phase structures of cytosine–Ag+ [CAg]+ and cytosine–Ag+–H2O [CAg–H2O]+ complexes have been studied by mass-selected infrared multiphoton dissociation (IRMPD) spectroscopy in the 900–1800 cm−1 spectral region using the Free Electron Laser facility in Orsay (CLIO). The IRMPD experimental spectra have been compared with the calculated IR absorption spectra of the different low-lying isomers (computed at the DFT level using the B3LYP functional and the 6-311G++(d,p) basis set for C, H, N and O atoms and the Stuttgart effective core potential for Ag). For the [CAg]+ complex, only one isomer with cytosine in the keto-amino (KA) tautomeric form and Ag+ interacting simultaneously with the C(2)[double bond, length as m-dash]O(7) group and N(3) of cytosine was observed. However, the mono-hydration of the complex in the gas phase leads to the stabilization of a two quasi-isoenergetic structure of the [CAg–H2O]+ complex, in which Ag+ interacts with the O atom of the water molecule and with the N(3) or C(2)[double bond, length as m-dash]O(7) group of cytosine. The relative populations of the two isomers determined from the IRMPD kinetics plot are in good agreement with the calculated values. Comparison of these results with those of protonated cytosine [CH]+ and its mono-hydrated complex [CH–H2O]+ shows some interesting differences between H+ and Ag+. In particular, while a single water molecule catalyzes the isomerization reaction in the case of [CH–H2O]+, it is found that in the case of [CAg–H2O]+ the addition of water leads to the stabilization of two isomers separated by small energy barrier (0.05 eV).
Fil: Berdakin, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Steinmetz, Vincent. Université Paris Sud; Francia
Fil: Maitre, Philippe. Université Paris Sud; Francia
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina - Materia
-
Dna Silver Interaction
Fel Laser
Icr Mass Spectrometry
Irmpd Spectroscopy - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/47461
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On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theoryBerdakin, MatiasSteinmetz, VincentMaitre, PhilippePino, Gustavo ArielDna Silver InteractionFel LaserIcr Mass SpectrometryIrmpd Spectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The gas-phase structures of cytosine–Ag+ [CAg]+ and cytosine–Ag+–H2O [CAg–H2O]+ complexes have been studied by mass-selected infrared multiphoton dissociation (IRMPD) spectroscopy in the 900–1800 cm−1 spectral region using the Free Electron Laser facility in Orsay (CLIO). The IRMPD experimental spectra have been compared with the calculated IR absorption spectra of the different low-lying isomers (computed at the DFT level using the B3LYP functional and the 6-311G++(d,p) basis set for C, H, N and O atoms and the Stuttgart effective core potential for Ag). For the [CAg]+ complex, only one isomer with cytosine in the keto-amino (KA) tautomeric form and Ag+ interacting simultaneously with the C(2)[double bond, length as m-dash]O(7) group and N(3) of cytosine was observed. However, the mono-hydration of the complex in the gas phase leads to the stabilization of a two quasi-isoenergetic structure of the [CAg–H2O]+ complex, in which Ag+ interacts with the O atom of the water molecule and with the N(3) or C(2)[double bond, length as m-dash]O(7) group of cytosine. The relative populations of the two isomers determined from the IRMPD kinetics plot are in good agreement with the calculated values. Comparison of these results with those of protonated cytosine [CH]+ and its mono-hydrated complex [CH–H2O]+ shows some interesting differences between H+ and Ag+. In particular, while a single water molecule catalyzes the isomerization reaction in the case of [CH–H2O]+, it is found that in the case of [CAg–H2O]+ the addition of water leads to the stabilization of two isomers separated by small energy barrier (0.05 eV).Fil: Berdakin, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Steinmetz, Vincent. Université Paris Sud; FranciaFil: Maitre, Philippe. Université Paris Sud; FranciaFil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaRoyal Society of Chemistry2015-05-29info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/47461Berdakin, Matias; Steinmetz, Vincent; Maitre, Philippe; Pino, Gustavo Ariel; On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 17; 39; 29-5-2015; 25915-259241463-90761463-9084CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/CP/C5CP02221E#info:eu-repo/semantics/altIdentifier/doi/10.1039/c5cp02221einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:27:29Zoai:ri.conicet.gov.ar:11336/47461instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:27:29.249CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
title |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
spellingShingle |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory Berdakin, Matias Dna Silver Interaction Fel Laser Icr Mass Spectrometry Irmpd Spectroscopy |
title_short |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
title_full |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
title_fullStr |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
title_full_unstemmed |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
title_sort |
On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory |
dc.creator.none.fl_str_mv |
Berdakin, Matias Steinmetz, Vincent Maitre, Philippe Pino, Gustavo Ariel |
author |
Berdakin, Matias |
author_facet |
Berdakin, Matias Steinmetz, Vincent Maitre, Philippe Pino, Gustavo Ariel |
author_role |
author |
author2 |
Steinmetz, Vincent Maitre, Philippe Pino, Gustavo Ariel |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
Dna Silver Interaction Fel Laser Icr Mass Spectrometry Irmpd Spectroscopy |
topic |
Dna Silver Interaction Fel Laser Icr Mass Spectrometry Irmpd Spectroscopy |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
The gas-phase structures of cytosine–Ag+ [CAg]+ and cytosine–Ag+–H2O [CAg–H2O]+ complexes have been studied by mass-selected infrared multiphoton dissociation (IRMPD) spectroscopy in the 900–1800 cm−1 spectral region using the Free Electron Laser facility in Orsay (CLIO). The IRMPD experimental spectra have been compared with the calculated IR absorption spectra of the different low-lying isomers (computed at the DFT level using the B3LYP functional and the 6-311G++(d,p) basis set for C, H, N and O atoms and the Stuttgart effective core potential for Ag). For the [CAg]+ complex, only one isomer with cytosine in the keto-amino (KA) tautomeric form and Ag+ interacting simultaneously with the C(2)[double bond, length as m-dash]O(7) group and N(3) of cytosine was observed. However, the mono-hydration of the complex in the gas phase leads to the stabilization of a two quasi-isoenergetic structure of the [CAg–H2O]+ complex, in which Ag+ interacts with the O atom of the water molecule and with the N(3) or C(2)[double bond, length as m-dash]O(7) group of cytosine. The relative populations of the two isomers determined from the IRMPD kinetics plot are in good agreement with the calculated values. Comparison of these results with those of protonated cytosine [CH]+ and its mono-hydrated complex [CH–H2O]+ shows some interesting differences between H+ and Ag+. In particular, while a single water molecule catalyzes the isomerization reaction in the case of [CH–H2O]+, it is found that in the case of [CAg–H2O]+ the addition of water leads to the stabilization of two isomers separated by small energy barrier (0.05 eV). Fil: Berdakin, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Steinmetz, Vincent. Université Paris Sud; Francia Fil: Maitre, Philippe. Université Paris Sud; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina |
description |
The gas-phase structures of cytosine–Ag+ [CAg]+ and cytosine–Ag+–H2O [CAg–H2O]+ complexes have been studied by mass-selected infrared multiphoton dissociation (IRMPD) spectroscopy in the 900–1800 cm−1 spectral region using the Free Electron Laser facility in Orsay (CLIO). The IRMPD experimental spectra have been compared with the calculated IR absorption spectra of the different low-lying isomers (computed at the DFT level using the B3LYP functional and the 6-311G++(d,p) basis set for C, H, N and O atoms and the Stuttgart effective core potential for Ag). For the [CAg]+ complex, only one isomer with cytosine in the keto-amino (KA) tautomeric form and Ag+ interacting simultaneously with the C(2)[double bond, length as m-dash]O(7) group and N(3) of cytosine was observed. However, the mono-hydration of the complex in the gas phase leads to the stabilization of a two quasi-isoenergetic structure of the [CAg–H2O]+ complex, in which Ag+ interacts with the O atom of the water molecule and with the N(3) or C(2)[double bond, length as m-dash]O(7) group of cytosine. The relative populations of the two isomers determined from the IRMPD kinetics plot are in good agreement with the calculated values. Comparison of these results with those of protonated cytosine [CH]+ and its mono-hydrated complex [CH–H2O]+ shows some interesting differences between H+ and Ag+. In particular, while a single water molecule catalyzes the isomerization reaction in the case of [CH–H2O]+, it is found that in the case of [CAg–H2O]+ the addition of water leads to the stabilization of two isomers separated by small energy barrier (0.05 eV). |
publishDate |
2015 |
dc.date.none.fl_str_mv |
2015-05-29 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/47461 Berdakin, Matias; Steinmetz, Vincent; Maitre, Philippe; Pino, Gustavo Ariel; On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 17; 39; 29-5-2015; 25915-25924 1463-9076 1463-9084 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/47461 |
identifier_str_mv |
Berdakin, Matias; Steinmetz, Vincent; Maitre, Philippe; Pino, Gustavo Ariel; On the Ag+-Cytosine interaction: effect of microhydration probed by IR optical spectroscopy and density functional theory; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 17; 39; 29-5-2015; 25915-25924 1463-9076 1463-9084 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/CP/C5CP02221E# info:eu-repo/semantics/altIdentifier/doi/10.1039/c5cp02221e |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1844614276743954432 |
score |
13.070432 |