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Fluorescence Properties of 5‐(5,6‐Dimethoxybenzothiazol‐2‐yl)‐2′‐deoxyuridine (d bt U) and Oligodeoxyribonucleotides Containing d bt U
Author(s) -
Hirose Wataru,
Sato Kousuke,
Matsuda Akira
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201100818
Subject(s) - fluorescence , chemistry , delocalized electron , quantum yield , sequence (biology) , yield (engineering) , deoxyuridine , ab initio , stereochemistry , organic chemistry , physics , dna , biochemistry , quantum mechanics , thermodynamics
We describe the synthesis and photophysical properties of 11 substituted 5‐(benzothiazol‐2‐yl)‐2′‐deoxyuridine derivatives and oligodeoxyribonucleotides (ODNs) containing 5‐(5,6‐dimethoxybenzothiazol‐2‐yl)‐2′‐deoxyuridine (d bt U), which was the strongest fluorescent derivative among those prepared. The fluorescence properties of d bt U itself and ODNs containing d bt U show the same tendency of being weaker in both neutral and acidic solution and stronger in basic solution. The ODNs (15mer) containing 16 combinations of 5′‐X bt U‐3′ and 5′‐ bt UY‐3′, where X, Y = A, T, G, or C, were synthesized, and their fluorescence intensity and quantum yield in basic solution were compared. On average, only the ODN with the 5′‐G bt U‐3′ sequence shows a 7.9‐fold lower fluorescence intensity than the other sequences. Ab initio calculations of 5′‐G bt U‐3′ and 5′‐ bt UG‐3′ as models under basic conditions suggest that the lower fluorescence of the ODN containing the 5′‐G bt U‐3′ sequence is caused by a wider overlap between stacked guanine (Gua) and bt Ura than that of the 5′‐ bt UG‐3′ sequence and that the HOMO is delocalized not only on bt Ura but also on Gua.