title: Vibrational analysis of nucleic acids. I. The phosphodiester group in dimethyl phosphate model compounds: (CH3O)2PO2-, (CD3O)2PO2-, and (13CH3O)2PO2-.
abstract: Normal coordinate analyses and vibrational assignments are presented for the dimethyl phosphate anion [(CH3O)2PO2-] and its deuteriomethyl [(CD3O)2PO2-] and carbon-13 [(13CH3O)2PO2-] derivatives in the gauche-gauche conformation. The dimethyl phosphate anion, which is the simplest model for the nucleic acid phosphodiester moiety, exhibits many of the spectral complexities of DNA and RNA and has previously resisted a complete and consistent vibrational analysis. In the present study we make use of new experimental data on the dimethyl phosphate isotopomers, including Raman depolarization measurements, to develop a consistent valence force field for normal modes of the C--O--P--O--C phosphodiester network and its hydrogenic substituents, as well as for stretching and bending modes of the O--P--O network of the anionic phosphodioxy group (PO2-). The force field established for dimethyl phosphate incorporates one significant nonbonded force constant, introduced from ab initio calculations, to account for interaction between the two ester C--O bonds. This study resolves previous problematic assignments for conformation-sensitive symmetric (in-phase) and asymmetric (out-of-phase) skeletal stretching modes of the ester linkages and demonstrates substantial anharmonicity in the hydrogen-stretching vibrations of the methyl substituents. New assignments are proposed for Raman bands of the phosphodioxy group, which may serve as potential indicators of structure and interaction of the DNA phosphates.
authors.affiliation: Division of Cell Biology and Biophysics, School of Biological Sciences, University of Missouri-Kansas City 64110-2499.
authors.forename: Y
authors.initials: Y
authors.lastname: Guan
authors.forename: C J
authors.initials: CJ
authors.lastname: Wurrey
authors.forename: G J
authors.initials: GJ
authors.lastname: Thomas
mesh_terms: D002247:Carbon Isotopes; D004247:DNA / Q000737:chemistry; D003903:Deuterium; D008968:Molecular Conformation; D009696:Nucleic Acids / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman; D013329:Structure-Activity Relationship; D014732:Vibration
chemical_list: D002247:Carbon Isotopes; D009696:Nucleic Acids; D009943:Organophosphorus Compounds; D004247:DNA; D003903:Deuterium; C007477:dimethyl phosphate