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Optical properties of guanine nanowires: Experimental and theoretical study (41 views)

Changenet-Barret P, Emanuele E, Gustavsson T, Improta R, Kotlyar AB, Markovitsi D, Vaya I, Zakrzewska K, Zikich D

J Phys Chem C (ISSN: 1932-7447), 2010 Sep 2; 114(34): 14339-14346.

Abstract
Long nanowires formed by ca. 800 guanine tetrads (G4-wires) are studied in phosphate buffer containing sodium cations. Their room temperature optical properties are compared to those of the monomeric chromophore 2-deoxyguanine monophosphate (dGMP). When going from dGMP to G4-wires, both the absorption and the fluorescence spectra change. Moreover, the fluorescence quantum yield increases by a factor of 7.3 whereas the average fluorescence lifetime increases by more than 2 orders of magnitude, indicating emission associated with weakly allowed transitions. The behavior of G4-wires is interpreted in the light of a theoretical study performed in the frame of the exciton theory combining data from molecular dynamics and quantum chemistry. These calculations, carried out for a quadruplex composed of three tetrads, reveal the existence of various exciton states having different energies and oscillator strengths. The degree of delocalization of the quadruplex Franck-Condon excited states is larger than those found for longer duplexes following the same methodology. The slower excited-state relaxation in G4-wires compared to dGMP is explained by emission from exciton states, possibly limited on individual tetrads, whose coherence is preserved by the reduced mobility of guanines due to multiple Hoogsteen hydrogen bonds. © 2010 American Chemical Society.

Affiliations ▼
*** IBB - CNR Affiliation

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

Department of Biochemistry, Georges S. Wise Faculty of Life Sciences, Tel Aviv University, Ramat Aviv 69978, Israel

Institut de Biologie et Chimie des Protéines, UMR5086, 69367 Lyon, France

Istituto Biostrutture e Bioimmagini, CNR, Via Mezzocannone 16, I-80134 Napoli, Italy

Details ▼
Impact factor: 4.524, 5-year impact factor: 4.733

Paper type: Journal Article,

Keywords: Delocalizations, Deoxyguanine, Exciton State, Exciton Theory, Fluorescence Lifetimes, Fluorescence Quantum Yield, Fluorescence Spectra, Franck-Condon, Monophosphates, Orders Of Magnitude, Oscillator Strengths, Phosphate Buffers, Room Temperature, Sodium Cations, Theoretical Study, Chromophores, Excited States, Hydrogen Bonds, Molecular Dynamics, Nanowires, Positive Ions, Quantum Theory, Optical Properties,

Url: http://www.scopus.com/inward/record.url?eid=2-s2.0-77956166006&partnerID=40&md5=48260499ddccd6e4d90c81eeff025bd7

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Miannay, F. A., Gustavsson, T., Banyasz, A., Markovitsi, D., (2010) J. Phys. Chem. A, 114, pp. 3256-3263

Vay, I., Miannay, F. A., Gustavsson, T., Markovitsi, D., (2010) ChemPhysChem, 11, pp. 987-989

Starikov, E. B., (2004) Mod. Phys. Lett. B, 18, pp. 825-831

Starikov, E. B., Cuniberti, G., Tanaka, S., (2009) J. Phys. Chem. B, 113, pp. 10428-10435

Lange, A. W., Herbert, J. M., (2009) J. Am. Chem. Soc., 131, pp. 3913-3922


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