Rotational dynamics of thiocyanate ions in highly concentrated aqueous solutions

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Abstract

The thiocyanate (SCN -) anion is known as one of the best denaturants, which is also capable of breaking the hydrogen-bond network of water and destabilizing native structures of proteins. Despite prolonged efforts to understand the underlying mechanism of such Hofmeister effects, detailed dynamics of the ions in a highly concentrated solution have not been fully elucidated yet. Here, we used a dispersive IR pump-probe spectroscopic method to study the dependence of vibrational lifetimes and rotational relaxation times of thiocyanate ions on KSCN concentration in D 2O. The nitrile stretch mode is used as a vibrational probe for dispersed IR pump-probe and FTIR measurements. To avoid possible self-attenuation of the IR pump-probe signal by highly concentrated SCN - ions, we added a small amount of 13C-isotope-labeled thiocyanate ions (S 13CN -) and focused on the excited-state absorption contribution to the IR pump-probe signal of the 13C-isotope-labeled nitrile stretch mode. Quite unexpectedly, the vibrational lifetime of S 13CN - ions is independent of the total KSCN concentration in the range from 0.46 m (molality) to 11.8 m while the rotational relaxation time of S 13CN - ions is linearly dependent on the total KSCN concentration. By combining the present experimental findings with the fact that the dissolved ions of KSCN salt have a strong tendency to form a large ion cluster in a highly concentrated aqueous solution, we believe that the ion clusters consisting of potassium and thiocyanate ion pairs in D 2O behave like ionic liquids and the ions inside ion clusters are weakly bound by electrostatic Coulombic interactions. The ability of SCN - ions to form ion clusters in aqueous protein solutions seems to be a key to understand the Hofmeister ion effect. We anticipate that the present experimental results provide a clue for further elucidating the underlying mechanism of the Hofmeister ion effects on protein stability in the future.

Original languageEnglish
Pages (from-to)6233-6240
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number18
DOIs
Publication statusPublished - 2012 May 14

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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