論文

査読有り 筆頭著者 責任著者
2018年1月

Coexistence of Kosmotropic and Chaotropic Impacts of Urea on Water As Revealed by Terahertz Spectroscopy

Journal of Physical Chemistry B
  • Keiichiro Shiraga
  • ,
  • Yuichi Ogawa
  • ,
  • Koichiro Tanaka
  • ,
  • Takashi Arikawa
  • ,
  • Naotaka Yoshikawa
  • ,
  • Masahito Nakamura
  • ,
  • Katsuhiro Ajito
  • ,
  • Takuro Tajima

122
3
開始ページ
1268
終了ページ
1277
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.jpcb.7b11839
出版者・発行元
AMER CHEMICAL SOC

Whether urea can serve as a kosmotrope or chaotrope has long been a topic of debate. In this study, broad-band THz spectroscopy (0.2-12 THz) of aqueous solutions of urea was used to characterize the hydration state and the hydrogen bond structure of water around urea. Three low-frequency vibration modes of urea were found around 2, 4, and above 12 THz. After eliminating the contribution of these modes, the "urea-vibration-free" complex dielectric constant was decomposed into the relaxation modes of bulk water and the oscillation modes of water. When hydration water is defined to be reorientationally retarded relative to bulk, our analysis revealed that the hydration number is 1.9 independent of urea concentrations up to 5 M, and this number is in close agreement with that of water constrained by strong acceptor hydrogen bonds of urea oxygen. Regarding the hydrogen bond structure, it was found that the tetrahedral-like water structure is mostly preserved (though the hydrogen bond lifetime is significantly shortened) but the population of non-hydrogen-bonded water molecules fragmented from the network is markedly increased, presumably due to urea's NH2 inversion. These experimental results point to the coexistence of apparently two contradictory aspects of urea: dynamical retardation (the kosmotropic aspect) by the -CO group and slight structural disturbance (the chaotropic aspect) by the -NH2 group.

リンク情報
DOI
https://doi.org/10.1021/acs.jpcb.7b11839
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000423652900029&DestApp=WOS_CPL
URL
https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.7b11839
ID情報
  • DOI : 10.1021/acs.jpcb.7b11839
  • ISSN : 1520-6106
  • eISSN : 1520-5207
  • Web of Science ID : WOS:000423652900029

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