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Bulge‐like Asymmetric Heterodye Clustering in DNA Duplex Results in Efficient Quenching of Background Emission Based on the Maximized Excitonic Interaction
Author(s) -
Fujii Taiga,
Hara Yuichi,
Osawa Takuya,
Kashida Hiromu,
Liang Xingguo,
Yoshida Yasuko,
Asanuma Hiroyuki
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201365
Subject(s) - chemistry , fluorophore , quenching (fluorescence) , exciton , photochemistry , fluorescence , photoluminescence , antiparallel (mathematics) , duplex (building) , crystallography , dna , materials science , optoelectronics , physics , optics , quantum mechanics , magnetic field , biochemistry
Asymmetric dye clusters with a single fluorophore (Cy3) and multiple quenchers (4′‐methylthioazobenzene‐4‐carboxylate, methyl red, and 4′‐dimethylamino‐2‐nitroazobenzene‐4‐carboxylate) were prepared. The dye and one‐to‐five quenchers were tethered through D ‐threoninol to opposite strands of a DNA duplex. NMR analysis revealed that the clusters with a single fluorophore and two quenchers formed a sandwich‐like structure (antiparallel H‐aggregates). The melting temperatures of all the heteroclusters were almost the same, although structural distortion should become larger, as the number of quenchers increased. An asymmetric heterocluster of a single fluorophore and two quenchers showed larger excitonic interaction (i.e., hypochromicity of Cy3), than did a single Cy3 and a single quencher. Due to the larger exciton coupling between the dyes, the 1:2 heterocluster suppressed the background emission more efficiently than the 1:1 cluster. However, more quenchers did not enhance quenching efficiency due to the saturation of exciton coupling with two quenchers. Finally, this asymmetric 1:2 heterocluster was introduced into the stem region of a molecular beacon (MB; also known as an in‐stem MB) targeting the fusion site in the L6 BCR‐ABL fusion gene. With this MB design, the signal/background ratio was as high as 68 due to efficient suppression of background emission resulting from the maximized excitonic interaction.