Reply to “Comment on ‘Arresting an Unusual Amide Tautomer Using Divalent Cations’”

Kashid, Somnath M.; Singh, Reman Kumar; Kwon, Hyejin; Seol, Jin Gyu; Kim, Yung Sam; Mukherjee, Arnab; Bagchi, Sayan

doi:10.1021/acs.jpcb.0c06005

Cited by 1 publication

(2 citation statements)

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“…The simulations reveal the hydrogen-bond formation and breaking mechanisms of DMSO in neat water. The hydrogen-bond analysis from the MD simulation trajectories demonstrates that SO can form zero, one, or two HB complexes with the surrounding water molecules. − Interestingly, the free DMSO (0.35%) and 1HB complexes (3.5%) are found to be negligibly small in comparison to 2HB (96.15%) populations. Similarly, TPSO predominantly forms 2HB populations (92%) compared to 1HB (8%) and 0HB (0%) in neat water.…”

Section: Resultsmentioning

confidence: 99%

“…To this end, similar behavioral changes can be found in molecules containing a carbonyl (CO) moiety where the less polarizable C atom replaces the S atom. Furthermore, studies on hydrogen-bond occupancy have shown that SO- and CO-containing molecules can form one or more hydrogen bonds in a protic solvent. − Recently, a temperature- and concentration-dependent study on DMSO/water mixtures indicated the presence of four distinct forms of DMSO, namely self-associated (aggregated), free-monomer (0HB), singly hydrogen-bonded (1HB), and doubly hydrogen-bonded (2HB) species. , On the contrary, a recent study has shown that CO-containing esters are exclusively doubly hydrogen-bonded in water . The reported differences in structures’ hydrogen-bond occupancies upon changing the C atom in CO to the S atom in SO warrants a detailed study of DMSO in the solution state.…”

Section: Introductionmentioning

confidence: 99%

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On–Off Infrared Absorption of the S═O Vibrational Probe of Dimethyl Sulfoxide

et al. 2022

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Dimethyl sulfoxide (DMSO), a polar solvent molecule, is used in a wide range of therapeutic and pharmacological applications. Different intermolecular interactions, such as dimerization and hydrogen bonding with water, are crucial to understanding the role of DMSO in applications. Herein, we study DMSO in various solvation environments to decipher the environment-dependent dimerization and hydrogen-bonding propensity. We use a combination of infrared spectroscopy, quantum mechanical calculations, and molecular dynamics simulations to reach our conclusions. Although DMSO can exist in a dynamic equilibrium between monomers and dimers, our results show that the relative intensity of the SO stretch and the CH3 rocking modes is a spectroscopic indicator of the extent of DMSO dimerization in solution. The dimerization (self-association) is seen to be maximum in neat DMSO. When dissolved in different solvents, the dimerization propensity decreases with increasing solvent polarity. In the presence of a protic solvent, such as water, DMSO forms a hydrogen bond with the solvent molecules, thereby reducing the extent of dimerization. Further, we estimate the hydrogen-bond occupancy of DMSO. Our results show that DMSO predominantly exists as doubly hydrogen-bonded in water.

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