Keiichiro Shiraga, Koichiro Tanaka, Yuichi Ogawa, Takuro Tajima
https://www.researchgate.net/publication/322148885_Coexistence_of_Kosmotropic_and_Chaotropic_Impacts_of_Urea_on_Water_as_Revealed_by_Terahertz_Spectroscopy
Whether urea can serve as a kosmotrope or chaotrope has long been a topic of debate. In this study, broadband THz spectroscopy (from 0.2 to 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 THz, 4 THz, 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 the urea concentrations up to 5 M and this number is close agreement with that of water constrained by the 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 the urea’s NH2 inversion. These experimental results point to 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.
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