Observation of the DNA ion-phosphate vibrations

TL;DR

This study uses low-frequency Raman spectroscopy to investigate counterion vibrations in DNA, revealing that cesium ions significantly influence vibrational modes compared to sodium ions, with implications for understanding DNA-ion interactions.

Contribution

The paper provides experimental evidence of ion-phosphate vibrational modes in DNA and distinguishes the effects of cesium and sodium counterions on these vibrations.

Findings

Cs-DNA spectra show a doubled intensity of the 100 cm-1 band compared to Na-DNA.

The 100 cm-1 band in Cs-DNA involves both H-bond stretching and cesium ion vibrations.

Na+ counterion vibrations occur at 180 cm-1 and do not contribute to the 100 cm-1 band.

Abstract

The low-frequency Raman spectra of Na-and Cs-DNA water solutions have been studied to determine the mode of counterion vibrations with respect to phosphate groups of the DNA double helix. The obtained spectra are characterized by the water band near 180 cm-1 and by several DNA bands near 100 cm-1. The main difference between Na- and Cs-DNA spectra is observed in case of the band 100 cm-1. In Cs-DNA spectra this band has about twice higher intensity than in Na-DNA spectra. The comparison of obtained spectra with the calculated frequencies of Na- and Cs-DNA conformational vibrations [Perepelytsya S.M., Volkov S.N. Eur. Phys. J. E. 24, 261 (2007)] show that the band 100 cm-1 in the spectra of Cs-DNA is formed by the modes of both H-bond stretching vibrations and vibrations of caesium counterions, while in Na-DNA spectra the band 100 cm-1 is formed by the mode of H-bond stretching vibrations only. The modes of sodium counterion vibrations have a frequency 180 cm-1, and they do not rise above the water band. Thus, the increase in intensity of the band 100 cm-1 in the spectra of Cs-DNA as compared with Na-DNA is caused by the mode of ion-phosphate vibrations.