Abstract

An extensive analysis of trans-hydrogen bond 2hJNN and 1hJHN scalar couplings, the covalent 1JHN couplings, and the imino proton chemical shifts is presented for Hoogsteen−Watson−Crick T•A−T and C+•G−C triplets of an intramolecular DNA triplex. The 2hJNN coupling constants for the Watson−Crick base pairs have values ranging from 6 to 8 Hz, while the Hoogsteen base paired thymines and protonated cytidines have values of approximately 7 and 10 Hz, respectively. Distinct decreases of 2hJNN are observed at the triplex strand ends. Trans-hydrogen bond J correlations (1hJHN) between the donor 1H nucleus and the acceptor 15N nucleus are observed for this triplex by a novel, simple quantitative J-correlation experiment. These one-bond 1hJHN couplings range between 1 and 3 Hz. A strong correlation is found between the chemical shift of the imino proton and the size of 2hJNN, with stronger J couplings corresponding to downfield chemical shifts. A similar, but inverse correlation is found between the proton chemical...

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