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Solvent effect on the singlet excited-state lifetimes of nucleic acid bases: A computational study of 5-fluorouracil and uracil in acetonitrile and water (41 views)

Santoro F, Barone V, Gustavsson T, Improta R

J Am Chem Soc (ISSN: 0002-7863, 0002-2786, 1520-5126), 2006 Dec 20; 128(50): 16312-16322.

Abstract
The first comprehensive quantum mechanical study of solvent effects on the behavior of the two lowest energy excited states of uracil derivatives is presented. The absorption and emission spectra of uracil and 5-fluorouracil in acetonitrile and aqueous solution have been computed at the time-dependent density-functional theory level, using the polarizable continuum model (PCM) to take into account bulk solvent effects. The computed spectra and the solvent shifts provided by our method are close to their experimental counterpart. The S0/S1 conical intersection, located in the presence of hydrogen-bonded solvent molecules by CASSCF (8/8) calculations, indicates that the mechanism of ground-state recovery, involving out-of-plane motion of the 5 substituent, does not depend on the nature of the solvent. Extensive explorations of the excited-state surfaces in the Franck-Condon (FC) region show that solvent can modulate the accessibility of an additional decay channel, involving a dark n/π* excited state. This finding provides the first unifying explanation for the experimental trend of 5-fluorouracil excited-state lifetime in different solvents. The microscopic mechanisms underlying solvent effects on the excited-state behavior of nucleobases are discussed. © 2006 American Chemical Society.

Affiliations ▼
*** IBB - CNR Affiliation

Istituto per i Processi Chimico-Fisici, CNR, Area della Ricerca del CNR di Pisa, via Moruzzi 1, I-56124 Pisa, Italy

Dipartimento di Chimica, Università Federico II, Complesso Universitario Monte S. Angelo, Via Cintia, I-80126 Napoli, Italy

Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM-CNRS URA 2453, CEA Saclay, F-91191 Gif-sur-Yvette, France

Istituto di Biostrutture e Bioimmagini, CNR, Via Mezzocannone 6, I-80134 Napoli, Italy

Details ▼
Impact factor: 7.696, 5-year impact factor: 11.015

Paper type: Journal Article,

Keywords: Absorption, Acetonitrile, Emission Spectroscopy, Mathematical Models, Microscopic Examination, Probability Density Function, Quantum Theory, Solvents, Water, Excited States, Lowest Energy Excited States, Polarizable Continuum Model (pcm), Uracil, Nucleic Acids, Fluorouracil, Nucleic Acid Base, Aqueous Solution, Article, Calculation, Density Functional Theory, Flame Photometry, Hydrogen Bond, Molecular Dynamics, Quantum Mechanics, Computer Simulation, Fluorine, Molecular Conformation, Time Factors,

Url: http://www.scopus.com/inward/record.url?eid=2-s2.0-33845573545&partnerID=40&md5=2e2651b7040fe5b1f92e2f4892f8589f

References ▼
Crespo-Hernandez, C.E., Cohen, B., Hare, P.M., Kohler, B., (2004) Chem. Rev., 104, pp. 1977-202

Bensasson, R.V., Land, E.J., Truscott, T.G., (1993) Excited States and Free Radicals in Biology and Medicine, , Oxford University Press: Oxford

Sinha, R.P., Hader, D.-P., (2002) Photochem. Photobiol. Sci., 1, pp. 225-236

Pecourt, J.-M.L., Peon, J., Kohler, B., (2000) J. Am. Chem. Soc., 122, pp. 9348-9349

Malone, R.J., Miller, A.M., Kohler, B., (2003) Photochem. Photobiol., 77, p. 158

Cohen, B., Crespo-Hernandez, C.E., Kohler, B., (2004) Faraday Discussions of the Chemical Society, 127, pp. 137-147

Crespo-Hernández, C.E., Kohler, B., (2004) J. Phys. Chem. B, 108, pp. 11182-11188

Biancafort, L., Cohen, B., Hare, P.M., Kohler, B., Robb, M.A., (2005) J. Phys. Chem. A, 109, pp. 4431-4436

Peon, J., Zewail, A.H., (2001) Chem. Phys. Lett., 348, pp. 255-262

Gustavsson, T., Sharonov, A., Markovitsi, D., (2002) Chem. Phys. Lett., 351, pp. 195-200

Onidas, D., Markovitsi, D., Marguet, S., Sharonov, A., Gustavsson, T., (2002) J. Phys. Chem. B, 106, pp. 11367-11374

Pancur, T., Schwalb, N.K., Renth, F., Temps, F., (2005) Chem. Phys., 313, pp. 199-212

Improta, R., Barone, V., (2004) J. Am. Chem. Soc., 126, pp. 14320-14321

Gustavsson, T., Banyasz, A., Lazzarotto, E., Markovitsi, D., Scalmani, G., Frisch, M.J., Barone, V., Improta, R., (2006) J. Am. Chem. Soc., 128, pp. 607-619

Gustavsson, T., Sarkar, N., Lazzarotto, E., Markovitsi, D., Barone, V., Improta, R., (2006) J. Phys. Chem. B, 110, pp. 12843-12847

Matsika, S., (2004) J. Phys. Chem. A, 108, pp. 7584-7590

Matsika, S., (2005) J. Phys. Chem. A, 109, pp. 7538-7545

Zgierski, M.Z., Patchkovskii, S., Fujiwara, T., Lim, E.C., (2005) J. Phys. Chem. A, 109, pp. 9384-9387

Ismail, N., Blancafort, L., Olivucci, M., Kohler, B., Robb, M.A., (2002) J. Am. Chem. Soc., 124, pp. 6818-6819

Merchan, M., Serrano-Andres, L., Robb, M.A., Blancafort, L., (2005) J. Am. Chem. Soc., 127, pp. 1820-1825

Blancafort, L., Robb, M.A., (2004) J. Phys. Chem. A, 108, pp. 10609-10614

Marian, C.M., (2005) J. Chem. Phys., 122, p. 104314

Marian, C., Nolting, D., Weinkauf, R., (2005) Phys. Chem. Chem. Phys., 7, pp. 3306-3316

Nielsen, S.B., Søiling, T.I., (2005) ChemPhysChem, 6, pp. 1276-1281

Perun, S., Sobolewski, A.L., Domcke, W., (2005) Chem. Phys., 313, pp. 107-112

Canuel, C., Mons, M., Piuzzi, F., Tardivel, B., Dimicoli, I., Elhanine, M., (2005) J. Chem. Phys., 122, pp. 743161-743166

Markovitsi, D., Onidas, D., Gustavsson, T., Talbot, F., Lazzarotto, E., (2005) J. Am. Chem. Soc., 127, pp. 17130-17131

Markovitsi, D., Talbot, F., Gustavsson, T., Onidas, D., Lazzarotto, E., Marguet, S., (2006) Nature, 441, pp. E7

Tsolakidis, A., Kaxiras, E., (2005) J. Phys. Chem. A, 109, pp. 2373-2380

Burghardt, I., Cederbaum, L.S., Hynes, J.T., (2004) Faraday Discussions, 127, p. 395

Yamazaki, S., Kato, S., (2005) J. Chem. Phys., 123, p. 114510

Toniolo, A., Olsen, S., Manohar, L., Martinez, T.J., (2004) Faraday Discussions, 127, p. 149

Sorgues, S., Mestdagh, J.M., Soep, B., (2004) Chem. Phys. Lett., 399, p. 234

Burghardt, I., Hynes, J.T., Gindensperger, E., Cederbaum, L.S., (2006) Phys. Scr., 73, pp. C42

Muller, A.M., Lochbrunner, S., Schmid, W.E., Fuss, W., (1998) Angew. Chem., Int. Ed., 37, p. 505

Fuss, W., (2002) Photochem. Photobiol. Sci., 1, p. 255

Marian, C.M., Schneider, F., Kleinschmidt, M., Tatchen, J., (2002) Eur. Phys. J. D, 20, pp. 357-367

Becker, R.S., Kogan, G., (1980) Photochem. Photobiol., 31, pp. 5-13

Colarusso, P., Zhang, K., Guo, B., Bernath, P.F., (1997) Chem. Phys. Lett., 269, pp. 39-48

Adamo, C., Barone, V., (1999) J. Chem. Phys., 110, pp. 6158-6170

Adamo, C., Scuseria, G.E., Barone, V., (1999) J. Chem. Phys., 111, pp. 2889-2899

Cossi, M., Barone, V., (2000) J. Phys. Chem. A, 104, pp. 10614-10622

Bearpark, M.J., Robb, M.A., Schlegel, H.B., (1994) Chem. Phys. Lett., 223, pp. 269-274

Tomasi, J., Mennucci, B., Cammi, R., (2005) Chem. Rev., 105, p. 2999

Cossi, M., Scalmani, G., Rega, N., Barone, V., (2002) J. Chem. Phys., 117, p. 43

Barone, V., Cossi, M., Tomasi, J., (1997) J. Chem. Phys., 107, p. 2310

He, Y., Wu, C., Kong, W., (2004) J. Phys. Chem. A, 108, pp. 943-949

Chahinian, M., Seba, H.B., Ancian, B., (1998) Chem. Phys. Lett., 285, pp. 337-345

Gaigeot, M.-P., Sprik, M., (2004) J. Phys. Chem. B, 108, pp. 7458-7467

Frisch, M.J., (2005) Gaussian Development Version, Revision D.02, , Gaussian, Inc.: Wallingford CT

Billinghurst, B.E., Yeung, R., Loppnow, G.R., (2006) J. Phys. Chem. A, 110, pp. 6185-6191

Peticolas, W.R., Rush III, T., (1995) J. Comput. Chem., 16, p. 1262

Fodor, S.P.A., Fava, R.P., Hays, T.R., Spiro, T.G., (1985) J. Am. Chem. Soc., 107, p. 1520

Hare, P.M., Crespo-Hernandez, C.E., Kohler, B., (2006) J. Phys. Chem. B, 110, pp. 18641-18650

Improta, R. In preparationLim, E.C., (1986) J. Phys. Chem., 90, p. 6770

Bensasson, R. V., Land, E. J., Truscott, T. G., (1993) Excited States and Free Radicals in Biology and Medicine, , Oxford University Press: Oxford

Sinha, R. P., Hader, D. -P., (2002) Photochem. Photobiol. Sci., 1, pp. 225-236

Pecourt, J. -M. L., Peon, J., Kohler, B., (2000) J. Am. Chem. Soc., 122, pp. 9348-9349

Malone, R. J., Miller, A. M., Kohler, B., (2003) Photochem. Photobiol., 77, p. 158

Crespo-Hern ndez, C. E., Kohler, B., (2004) J. Phys. Chem. B, 108, pp. 11182-11188

Zgierski, M. Z., Patchkovskii, S., Fujiwara, T., Lim, E. C., (2005) J. Phys. Chem. A, 109, pp. 9384-9387

Marian, C. M., (2005) J. Chem. Phys., 122, p. 104314

Nielsen, S. B., S iling, T. I., (2005) ChemPhysChem, 6, pp. 1276-1281

Muller, A. M., Lochbrunner, S., Schmid, W. E., Fuss, W., (1998) Angew. Chem., Int. Ed., 37, p. 505

Marian, C. M., Schneider, F., Kleinschmidt, M., Tatchen, J., (2002) Eur. Phys. J. D, 20, pp. 357-367

Becker, R. S., Kogan, G., (1980) Photochem. Photobiol., 31, pp. 5-13

Bearpark, M. J., Robb, M. A., Schlegel, H. B., (1994) Chem. Phys. Lett., 223, pp. 269-274

Gaigeot, M. -P., Sprik, M., (2004) J. Phys. Chem. B, 108, pp. 7458-7467

Frisch, M. J., (2005) Gaussian Development Version, Revision D. 02, , Gaussian, Inc.: Wallingford CT

Billinghurst, B. E., Yeung, R., Loppnow, G. R., (2006) J. Phys. Chem. A, 110, pp. 6185-6191

Peticolas, W. R., Rush III, T., (1995) J. Comput. Chem., 16, p. 1262

Fodor, S. P. A., Fava, R. P., Hays, T. R., Spiro, T. G., (1985) J. Am. Chem. Soc., 107, p. 1520

Hare, P. M., Crespo-Hernandez, C. E., Kohler, B., (2006) J. Phys. Chem. B, 110, pp. 18641-18650


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* A joint experimental/theoretical study of the ultrafast excited state deactivation of deoxyadenosine and 9-methyladenine in water and acetonitrile (51 views)
Gustavsson T, Sarkar S, Vaya I, Jimenez MC, Markovitsi D, Improta R
Photochem Photobiol Sci (ISSN: 1474-905x), 2013; 12(8): 1375-1386.

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1 Records (1 excluding Abstracts and Conferences).
Total impact factor: 2.939 (2.939 excluding Abstracts and Conferences).
Total 5-year impact factor: 2.793 (2.793 excluding Abstracts and Conferences).



Your bibliography query: (([btitle, keywords, abstract] ABSORPTION AND [btitle, keywords, abstract] ACETONITRILE AND [btitle, keywords, abstract] EMISSION AND [btitle, keywords, abstract] SPECTROSCOPY)) AND NOT [id] = 9456



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