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High-Energy Long-Lived Mixed Frenkel-Charge-Transfer Excitons: From Double Stranded (AT)n to Natural DNA (53 views)

Vayá I, Brazard J, Huix-rotllant M, Thazhathveetil AK, Lewis FD, Gustavsson T, Burghardt I, Improta R, Markovitsi D

Chemistry (ISSN: 0947-6539, 1521-3765, 1521-3765electronic), 2016; 22(14): 4904-4914.

The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV-induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine-thymine double-stranded structures (AT)n. Fluorescence measurements on (AT)n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale. Time-dependent (TD)-DFT calculations, performed for two base pairs and exploring various relaxation pathways, allow the assignment of this emission band to excited states resulting from mixing between Frenkel excitons and adenine-to-thymine charge-transfer states. Emission from such high-energy long-lived mixed (HELM) states is in agreement with their fluorescence anisotropy (0.03), which is lower than that expected for π-π∗ states (≥0.1). An increase in the size of the system quenches π-π∗ fluorescence while enhancing HELM fluorescence. The latter process varies linearly with the hypochromism of the absorption spectra, both depending on the coupling between π-π∗ and charge-transfer states. Subsequently, we identify the common features between the HELM states of (AT)n structures with those reported previously for alternating (GC)n: High emission energy, low fluorescence anisotropy, nanosecond lifetimes, and sensitivity to conformational disorder. These features are also detected for calf thymus DNA in which HELM states could evolve toward reactive π-π∗ states, giving rise to delayed fluorescence. High-energy long-lived mixed (HELM) excitons are populated during excited-state relaxation in (AT)n duplexes. They result from mixing between Frenkel excitons and adenine-to-thymine charge-transfer states and extend over at least four bases on both strands. The properties of HELM states (high emission energy, low fluorescence anisotropy, nanosecond lifetime, and sensitivity to conformational disorder) are also detected for natural DNA. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Affiliations ▼
*** IBB - CNR Affiliation

LIDYL, CEA, CNRS, Université Paris Saclay, Gif-sur-Yvette, France

Institut für Physikalische und Theoretische Chemie, Goethe-Universität, Max-von-Laue-Str. 7, Frankfurt am Main, Germany

Department of Chemistry, Northwestern University, Evanston, IL, United States

Istituto Biostrutture e Bioimmagini-Consiglio, Nazionale Delle Ricerche, Via mezzocannone 16, Napoli, Italy

Details ▼
Impact factor: 5.731, 5-year impact factor: 5.608

Paper type: Journal Article,

Keywords: Dna, Excitons, Fluorescence Spectroscopy, Hypochromism, Quantum Chemistry,

Url: https://www2.scopus.com/inward/record.uri?eid=2-s2.0-84961730181&partnerID=40&md5=22e242fce4f2130ecd20c2a49167a4f6

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* Stabilization of mixed frenkel-charge transfer excitons extended across both strands of guanine-cytosine DNA duplexes (62 views)
Huix-Rotllant M, Brazard J, Improta R, Burghardt I, Markovitsi D
J Phys Chem Lett (ISSN: 1948-7185, 1948-7185electronic), 2015; 6(12): 2247-2251.

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* Multi-pathway excited state relaxation of adenine oligomers in aqueous solution: A joint theoretical and experimental study (42 views)
Banyasz A, Gustavsson T, Onidas D, Changenet-Barret P, Markovitsi D, Improta R
Chemistry (ISSN: 0947-6539, 1521-3765, 1521-3765electronic), 2013 Mar; 19(11): 3762-3774.

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* Electronic excited states responsible for dimer formation upon UV absorption directly by thymine strands: Joint experimental and theoretical study (53 views)
Banyasz A, Douki T, Improta R, Gustavsson T, Onidas D, Vaya I, Perron M, Markovitsi D
J Am Chem Soc (ISSN: 0002-7863, 0002-2786, 1520-5126), 2012 Sep 12; 134(36): 14834-14845.

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* Cation effect on the electronic excited states of guanine nanostructures studied by time-resolved fluorescence spectroscopy (50 views)
Hua Y, Changenet-Barret P, Improta R, Vaya I, Gustavsson T, Kotlyar AB, Zikich D, Sket P, Plavec J, Markovitsi D
J Phys Chem C (ISSN: 1932-7447), 2012 Jul 12; 116(27): 14682-14689.

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4 Records (4 excluding Abstracts and Conferences).
Total impact factor: 29.433 (29.433 excluding Abstracts and Conferences).
Total 5-year impact factor: 29.4 (29.4 excluding Abstracts and Conferences).

Your bibliography query: (([btitle, keywords, abstract] EXCITONS AND [btitle, keywords, abstract] FLUORESCENCE AND [btitle, keywords, abstract] SPECTROSCOPY)) AND NOT [id] = 53215

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