VIBRATIONAL RELAXATION ON HYDROGEN BONDING IN DINUCLEOSIDE PHOSPHATE

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The specific interactions between bases, which depend on the dinucleoside phosphate conformations, were studied in terms of the vibrational dynamics of hydrogen-bonding. The hydrogen-bond stretching vibrations of the nucleotide complexes and dinucleoside phosphates were observed in the polycrystalline state by the Raman spectroscopy. The vibrational dynamics were investigated by measuring the line broadenings of hydrogen-bonding vibration observed in near 100cm^<-1>. The half band-widths of vibrational lines took their magnitudes from 4cm^<-1> to 10cm^<-1>. The calculations for the relaxation processes revealed that the broadening of the vibrational lines was considered to originate in process, in which the vibrational energy was transferred among the lattice modes. The doublet spectra observed in the GpC, ApT and GMP-CMP samples were rather symmetrical, in contrast to the asymmetric two peaks of the TpT, ApA, CpC, GpT and AMP-TMP. The relaxation time for the former group was 1.22×10^<-12> sec, whereas that for the latter group was 2.01×10^<-12> sec on the average. The difference between the relaxation times was attributed to that of the sugar-phosphate conformations in a crystal, on the basis of calculating coupled oscillator frequencies with respect to the sugar-phosphate conformations. The relaxation time, 1.27×10^<-12>sec for the ApT crystal was faster than the one, 1.82×10^<-12>sec for the AMP-TMP crystal. This fact could be also explained by the relaxation processes depending on their crystal structures. The Watson-Crick A-T pairing in the ApT become highly stabilized dynamically, but is in low thermodynamic stability, since this type of pairing is found in the least interaction energy among the possible four base-pairings.
1983-03-15

VIBRATIONAL RELAXATION ON HYDROGEN BONDING IN DINUCLEOSIDE PHOSPHATE

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