title: Simulations of structure and vibrational spectra of deoxyoctanucleotides.
abstract: Combined molecular dynamics and ab initio computations were applied for analysis of infrared absorption and vibrational circular dichroism spectra of deoxyoctanucleotides. Unlike for previous idealized models, molecular geometries of these shorter DNA fragments in solutions were obtained as dynamic averages from simulations in a periodic water box. Vibrational spectra for the whole octamers including hydrogen-bonded solvent molecules were simulated on the basis of density-functional calculations on small fragments and subsequent transfer of molecular property tensors. Explicit and continuum solvent models were compared. Apparently, the DNA segments retain an approximate B-conformation in the aqueous solutions, but the terminal base pairs significantly deviate from the planar arrangement and the vibrational circular dichroism spectrum for (CG)(2) nucleotide indicates a larger average helical twist. Sodium counterions moved freely around the molecule during the simulation and do not influence spectral intensities. Simulated absorption spectra faithfully reproduced the experimental signal of principal functional groups, while only qualitative agreement was obtained for the dependence on the basis sequence.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam. 2, 16610, Prague 6, Czech Republic. bour@uochb.cas.cz
authors.forename: Petr
authors.initials: P
authors.lastname: Bour
authors.forename: Valery
authors.initials: V
authors.lastname: Andrushchenko
authors.forename: Martin
authors.initials: M
authors.lastname: Kabelác
authors.forename: Vanitha
authors.initials: V
authors.lastname: Maharaj
authors.forename: Hal
authors.initials: H
authors.lastname: Wieser
mesh_terms: D001483:Base Sequence; D002942:Circular Dichroism; D003198:Computer Simulation; D004247:DNA / Q000737:chemistry*; D008958:Models, Molecular; D009690:Nucleic Acid Conformation; D009838:Oligodeoxyribonucleotides / Q000737:chemistry*; D014732:Vibration
chemical_list: D009838:Oligodeoxyribonucleotides; D004247:DNA