Measurement of Long-Range 1H-19F Scalar Coupling Constants and Their Glycosidic Torsion Dependence in 5-Fluoropyrimidine-Substituted RNA Export

@article{citeulike:2670169, abstract = {Abstract: Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-,-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented.}, address = {Contribution from the Department of Molecular Biology and The Skaggs Institute of Chemical Biology, The Scripps Research Institute, MB 33, 10550 North Torrey Pines Road, La Jolla, California 92037, National Centre for Biomolecular Research, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic, and Bruker Biospin GmbH, Rheinstetten, Germany}, author = {Hennig, M. and Munzarova, M. L. and Bermel, W. and Scott, L. G. and Sklenar, V. and Williamson, J. R.}, citeulike-article-id = {2670169}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/ja060165t}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/ja060165t}, day = {3}, doi = {10.1021/ja060165t}, journal = {J. Am. Chem. Soc.}, keywords = {19f, j-couplings, rna, torsion-angles}, month = {May}, number = {17}, pages = {5851--5858}, posted-at = {2008-04-14 19:02:27}, priority = {2}, title = {Measurement of Long-Range 1H-19F Scalar Coupling Constants and Their Glycosidic Torsion Dependence in 5-Fluoropyrimidine-Substituted RNA}, url = {http://dx.doi.org/10.1021/ja060165t}, volume = {128}, year = {2006} }

TY - JOUR ID - citeulike:2670169 L3 - citeulike-article-id:2670169 N2 - Abstract: Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-,-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented. IS - 17 JF - J. Am. Chem. Soc. AD - Contribution from the Department of Molecular Biology and The Skaggs Institute of Chemical Biology, The Scripps Research Institute, MB 33, 10550 North Torrey Pines Road, La Jolla, California 92037, National Centre for Biomolecular Research, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic, and Bruker Biospin GmbH, Rheinstetten, Germany EP - 5858 TI - Measurement of Long-Range 1H-19F Scalar Coupling Constants and Their Glycosidic Torsion Dependence in 5-Fluoropyrimidine-Substituted RNA VL - 128 SP - 5851 KW - 19f KW - j-couplings KW - rna KW - torsion-angles AU - Hennig, M AU - Munzarova, ML AU - Bermel, W AU - Scott, LG AU - Sklenar, V AU - Williamson, JR PY - 2006/05/03/ UR - http://dx.doi.org/10.1021/ja060165t ER -