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Hydrogen Bonding Effects on the 15N and 1H Shielding Tensors in Nucleic Acid Base Pairs

✍ Scribed by Jiřı́ Czernek; Radovan Fiala; Vladimı́r Sklenář

Publisher
Elsevier Science
Year
2000
Tongue
English
Weight
67 KB
Volume
145
Category
Article
ISSN
1090-7807

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✦ Synopsis

The results of systematic ab initio calculations of 15 N and 1 H chemical shielding tensors in the GC base pair as a function of hydrogen bond length are presented for the first time. The hydrogen bond length characterized by the distance r N. . .N between purine N1 and pyrimidine N3 was varied between 2.57 and 3.50 Å and the chemical shift tensors were calculated by the sum-overstates density functional perturbation theory. It is shown that the hydrogen bond length has a strong effect on the chemical shielding tensor of both imino proton and nitrogen, on their orientation, and, as a consequence, on the relaxation properties of both nuclei. For a nitrogen nucleus not involved in hydrogen bonding, the shielding tensor is nearly axially symmetric and almost collinear with the bond vector. As the length of the hydrogen bond decreases, the least shielding component 11 deflects from the N-H vector and the shielding tensor becomes increasingly asymmetric. The significance of the presented results for the analysis of relaxation data and the efficiency of TROSY effects together with a summary of the relevant shielding parameters are presented and discussed.

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