Deuterium Isotope Effects in A:T and A:U Base Pairs: A Computational NMR Study
MetadataShow full item record
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. NMR2004, 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 s so far unknown s for the observed DIEs in nucleic acids, density functional theory and hybrid Car Parrinello/molecular mechanical calculations 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.
Open access to this article available via the website of the American Chemical Society. http://acswebcontent.acs.org/home.html
The website for the Journal of the American Chemical Society is available at:
Showing items related by title, author, creator and subject.
Natgunanathan, I.; Xiang, Y.; Rong, Yue; Zhou, W.; Guo, S. (2012)This paper presents a novel patchwork-based embedding and decoding scheme for digital audio watermarking. At the embedding stage, an audio segment is divided into two subsegments and the discrete cosine transform (DCT) ...
Properties of lithium under hydrothermal conditions revealed by in situ Raman spectroscopic characterization of Li2O-SO3-H2O (D2O) systems at temperatures up to 420 °CWang, X.; Wang, X.; Chou, I.; Hu, W.; Wan, Y.; Li, Zhen (2017)© 2017 Elsevier B.V.Lithium (Li) is an important component of hydrothermal fluids, especially submarine hydrothermal fluids. Investigation of the species and ion complexation of Li+ at elevated temperature and pressure ...
INCITE: A randomised trial comparing constraint induced movement therapy and bimanual training in children with congenital hemiplegiaBoyd, Roslyn; Sakzewski, L.; Ziviani, J.; Abbott, D.; Badawy, R.; Gilmore, R.; Provan, K.; Tournier, J.; Macdonell, R.; Jackson, G. (2010)Background: Congenital hemiplegia is the most common form of cerebral palsy (CP) accounting for 1 in 1300 live births. These children have limitations in capacity to use the impaired upper limb and bimanual coordination ...