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The effect of methylation on the excited state dynamics of aminouracils (116 visite)

Gustavsson T, Improta R, Banyasz A, Vaya I, Markovitsi D

J Photochem Photobiol A Chem (ISSN: 1010-6030), 2012 Apr 15; 234: 37-43.

Tipo di articolo: Journal Article, , Impact factor: 2.416, Impact factor a 5 anni: 2.691, Url: http://www.scopus.com/inward/record.url?eid=2-s2.0-84859538922&partnerID=40&md5=898683f4b373b5ad4d870d0e959a0cd9

Parole chiave: Dna, Excited State, Femtosecond, Fluorescence Upconversion, Nucleobases, Td-Dft, Time-Resolved Fluorescence,

Affiliazioni: *** IBB - CNR ***
CNRS, IRAMIS, URA 2453, 91191 Gif-sur-Yvette, France
Istituto Biostrutture e Bioimmagini, CNR, Via Mezzocannone 16, I-80134 Napoli, Italy


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The excited state properties of two amino substituted uracils, 5-aminouracil (5AU) and 5-dimethylaminouracil (5DMAU) have been studied by steady-state and time-resolved fluorescence spectroscopy. In addition, the electronic transitions corresponding to photon absorption and emission were calculated using the TD-DFT/PCM method (with PBE0 and CAM-B3LYP functionals), explicitly including water molecules of the first solvent shell. The fluorescence decays, recorded by fluorescence upconversion, reveal that the emitting states of both molecules are substantially longer-lived than that of uracil. However, while the 5AU fluorescence decays on a picosecond timescale, the 5DMAU fluorescence contains a weak, long-lived component, continuing beyond 100 ps. Calculations show that the excited state deactivation of 5AU is governed by the existence of a minimum on the ππ* excited state potential energy surface. For 5DMAU, on the other hand, a very long-lived but weakly fluorescent intramolecular charge transfer (ICT) state, involving a significant charge transfer between the dimethylamino group and the pyrimidine ring, is found. This stable ICT state is characterized by a rotation of the dimethylamino group towards a quasi-perpendicular geometry. © 2012 Elsevier B.V. All rights reserved.
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Vogt G, Nuernberger P, Gerber G, Improta R, Santoro F, Nuernberger P, Vogt G, Gerber G, Improta R, Santoro F
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Gustavsson T, Lazzarotto E, Markovitsi D, Banyasz AA, Improta R, Scalmani G
* A combined femtosecond fluorescence and TD-DFT study of uracil derivatives in aqueous solution (89 visite)
Femtochemistry Vii Elsevier (ISSN: 9780-4445), 2006; N/D: 254-257.
Impact Factor: 0
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Improta R, Barone V, Scalmani G, Frisch MJ
* A State-Specific Pcm Td-Dft Method For Equilibrium And Non-Equilibrium Excited State Calculations In Solution (119 visite)
J Chem Phys (ISSN: 0897-690online, 0021-9606printed), 2006; 125(5): 54103-54103.
Impact Factor: 3.093
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37 Records (33 escludendo Abstract e Conferenze).
Impact factor totale: 206.562 (196.088 escludendo Abstract e Conferenze).
Impact factor a 5 anni totale: 210.22 (199.62 escludendo Abstract e Conferenze).







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