Optical Properties of Guanine Nanowires: Experimental and Theoretical Study

详细信息    查看全文

• 作者：Pascale Changenet-Barret ; Emanuela Emanuele ; Thomas Gustavsson ; Roberto Improta ; Alexander B. Kotlyar ; Dimitra Markovitsi ; Ignacio Vay ; Krystyna Zakrzewska ; Dragoslav Zikich
• 刊名：Journal of Physical Chemistry C
• 出版年：2010
• 出版时间：September 2, 2010
• 年：2010
• 卷：114
• 期：34
• 页码：14339-14346
• 全文大小：303K
• 年卷期：v.114,no.34(September 2, 2010)
• ISSN：1932-7455

文摘

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.