0181426 - UFCH-W 20020092 RIV US eng J - Journal Article
Sychrovský, Vladimír - Vacek, Jaroslav - Hobza, Pavel - Žídek, L. - Sklenář, V. - Cremer, D.
Exploring the Structure of a DNA Hairpin with the Help of NMR Spin-Spin Coupling Constants: An Experimental and Quantum Chemical Investigation.
Journal of Physical Chemistry A. Roč. 106, - (2002), s. 10242-10250. ISSN 1089-5639. E-ISSN 1520-5215
R&D Projects: GA MŠMT LN00A032
Institutional research plan: CEZ:AV0Z4040901
Keywords : DNA * help of NMR spin-spin coupling constants * quantum chemical investigation
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.765, year: 2002

A 13C, 15N-labeled DNA hairpin molecule of the sequence d(GCGAAGC) = d(G1C2G3A4A5G6C7) is investigated by NMR spectroscopy to determine one-bond and two-bond NMR spin-spin coupling constants 1J(X, H) (X= C, N), 1J(C, X) (X= C, N), and 2J(X,H) (X=C,N). Measured J values for the Watson-Crick (WC) base-pairs G1C7, G6C2, the mismatched base-pair G3A5 and the unpaired base A4 were compared with calculated J values to verify sign and magnitude. For the J-calculations, coupled perturbed density functional theory (CP-DFT) in connection with the B3LYP hybrid functional and basis sets (9s5p1d/5s,1p)[6s,4p,1d/3s,1p] as well as (11s,7p,2d/6s,2p)[7s,6p,2d/4s,2p] was employed to determine diamagnetic spin-orbit (DSO), paramagnetic spin-orbit (PSO), Fermi contact (FC), and spinůdipolar (SD) contributions to the total isotropic coupling constant J. Coupling constants 1J(C,H) and 2J(N,H) turn out to be very sensitive to the position of C and N in the pyrimidine or purine rings .
Permanent Link: http://hdl.handle.net/11104/0001885