4.6 Article

New insights into a hydrogen bond: hyper-Raman spectroscopy of DMSO-water solution

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 23, Issue 41, Pages 24047-24051

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp02387j

Keywords

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Funding

  1. National Science Foundation (NSF) [DBI-1455671, ECCS-1509268, CMMI-1826078]
  2. Air Force Office of Scientific Research (AFOSR) [FA9550-15-1-0517, FA9550-20-1-0366, FA9550-20-1-0367]
  3. Army Medical Research Grant [W81XWH2010777]
  4. National Institutes of Health (NIH) [1R01GM127696-01, 1R21GM142107-01]
  5. Cancer Prevention and Research Institute of Texas (CPRIT) [RP180588]
  6. NSF Graduate Research Fellowship Program (NSF GRFP)
  7. China Scholarship Council (CSC)
  8. National Natural Science Foundation of China [11934011]
  9. National Science Foundation Graduate Research Fellowship Program [DGE 1746932]
  10. U.S. Department of Defense (DOD) [W81XWH2010777] Funding Source: U.S. Department of Defense (DOD)

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Hydrogen bonding is crucial in biological processes for stabilizing proteins, lipids, and controlling enzyme reactions. Hyper-Raman scattering was used to study molecular interactions in the DMSO-H2O system for the first time, revealing evidence of intermolecular bonds between water and DMSO. This demonstrates the potential of hyper-Raman spectroscopy in investigating model system bonding.
Hydrogen bonding plays an essential role in biological processes by stabilizing proteins and lipid structures as well as controlling the speed of enzyme catalyzed reactions. Dimethyl sulfoxide-water (DMSO-H2O) solution serves as a classical model system by which the direct and indirect effects of hydrogen bonding between water hydrogens and the sulfoxide functional group can be explored. The complex transition from self-bonding to heterogeneous bonding is important, and multiple spectroscopic approaches are needed to provide a detailed assessment of those interactions. In this report, for the first time, hyper-Raman scattering was successfully employed to investigate molecular interactions in DMSO-H2O system. We measured the improper blueshift of the C-S and C-H stretching modes of DMSO caused by partial charge transfer and enhanced bond polarization. By detecting differences in the frequency shifts of C-S and C-H modes for low DMSO concentrations (<33 mol%) we find evidence of the intermolecular bonds between water and the DMSO methyl groups. We exploit the high sensitivity of hyper-Raman scattering to the low frequency librations of H2O to observe a change in librational mode population providing insight into existing questions about the coordination of H2O around DMSO molecules and the formation of the H2O shell around DMSO molecules proposed in prior simulation studies. These results demonstrate that hyper-Raman spectroscopy can be a practical spectroscopic technique to study the intermolecular bonding of model systems and test claims about model system bonding generated by theoretical calculations.

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