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• W1974378049 startingPage "7215" @default.
• W1974378049 abstract "Recent measurements of trans-hydrogen bond deuterium isotope effects (DIEs) on 13C chemical shifts in nucleic acids (Vakonakis, I.; LiWang, A. C. J. Biomol. NMR 2004, 29, 65; J. Am. Chem. Soc. 2004, 126, 5688) have led to intriguing results: (i) the DIEs of A:T pairs in DNA are about 5 ppb smaller than those of A:U in RNA and (ii) A:T DIEs vary by as much as 13 ppb among the oligonucleotides. The first observation suggests that inter-base H-bonds in RNA may be stronger than those in DNA, while the second indicates that the conformation of the base pair modulates the transmission of the isotope effect across the hydrogen bond. In an effort at providing a rationale--so far unknown--for the observed DIEs in nucleic acids, density functional theory and hybrid Car-Parrinello/molecular mechanical calculations of DIEs on nucleosides and nucleotides in the gas phase and in aqueous solution have been performed. The calculations suggest that (i) the DIE in an isolated A:T base pair differs from that in an A:U base pair because of the changes in the magnetic properties caused by the replacement of a methyl group on passing from U to T, (ii) the DIEs depend crucially on the conformation of the base pairs, and (iii) the DIEs are strongly affected by magnetic and electrostatic interactions with the surrounding environment." @default.
• W1974378049 created "2016-06-24" @default.
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• W1974378049 date "2006-05-13" @default.
• W1974378049 modified "2023-10-16" @default.
• W1974378049 title "Deuterium Isotope Effects in A:T and A:U Base Pairs: A Computational NMR Study" @default.
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• W1974378049 doi "https://doi.org/10.1021/ja0577903" @default.
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• W1974378049 hasPublicationYear "2006" @default.
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