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  • Analytical Chemistry and Spectroscopy  (1)
  • Chemical shift anisotropy  (1)
  • 1
    ISSN: 1432-1017
    Keywords: Chemical shift anisotropy ; 31P relaxation ; DNA dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The five phosphates of the deoxynucleotide d(CpGpTpApCpG)2 have been assigned by two-dimensional heteronuclear NMR spectroscopy. The chemical shift anisotropy and correlation time of each phosphate group has been determined from measurements of the spin-lattice, spin-spin relaxation rate constants and the 31P-{1H} nuclear Overhauser enhancement (NOE) at three magnetic field strengths (4.7 T, 9.4 T, and 11.75 T) and two temperatures (288 K and 298 K). As expected, the relaxation data require two mechanisms to account for the observed rate constants, i.e. dipole-dipole and chemical shift anisotropy. At 9.4 T and 11.75 T, the latter mechanism dominates the relaxation, leading to insignificant NOE intensities. The correlation time, chemical shift anisotropy and effective P-H distance were obtained from least-squares fitting to the data. Comparison of the fitted value for the correlation time with that obtained from 1H measurements shows that the molecule behaves essentially as rigid rotor on the nanosecond timescale. Large amplitude motions observed in long segments of DNA are due to bending motions that do not contribute significantly to relaxation in short oligonucleotides.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 12 (1982), S. 36-48 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared and Raman spectra of methylviologen (1,1′-dimethyl-4,4′-bipyridine dication, MV2+) have been measured from both the solid dichloride and aqueous solutions. The preresonance behaviour of MV2+ Raman bands showed that the absorption at ˜196 nm is mainly responsible for the resonance scattering process in MV2+. In the region below 1700 cm-1, nine polarized (p˜1/3) resonance Raman bands of the methylviologen radical cation, MV+, were assigned to in-plane ring modes. Arguments are given that the chromophore of MV+ may also partially include the methyl groups. The excitation profiles of the MV+fundamentals, measured with laser wavelengths covering the range 350.6-676.4 nm, reveal three main groups of modes, each behaving differently for the excitation in this range. Modes containing largely ν(C—C) ring contributions are mainly coupled with electronic transitions at ˜395, ˜605 and ˜720 nm and yield simple excitation profiles. Modes involving principally the vibrations of the N+—CH3 group show complicated interference peaks in the whole range of the excitation profiles. γ(CCC) is mainly coupled with the absorption at ˜620 nm. Resonance Raman bands of the (MV+)2 dimer have been characterized through studies of the concentration dependence of the spectra.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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