Despite the key roles of L-glutathiones (GSHs) inbiology and nano-biotechnology, understanding their labile structures and hydrogen bond interactions with nanoparticles has posed a critical challenge to the scientific community. The structural conformation of GSH as a capping layer on gold nanoparticle (AuNP) and silver nanoparticle (AgNP) surfaces is investigated. In this report, we attempt to explore the material-dependent interaction of GSH with different spherical nanoparticle surfaces by employing Fourier transform infrared (FTIR) spectroscopy. The infrared signal of amide I of GSH is studied as a function of different materials' spherical nanoparticles with comparable size. We revealed the β-sheet secondary structure of GSH on AgNPs and the random structure on AuNPs even though both the nanoparticles have comparable shapes and sizes and belong to the same group of the periodic table. The GSH is firmly anchored on the gold and silver surface via the thiol of the cys part. However, our experimental data designate a further interaction with the AgNP surface via the carboxylic acid group of the gly-and glu-end of the molecule. It is observed that enhancement of IR absorption of amide I of GSH is pronounced by a factor of 10 on AuNP but, in contrast, on the same-sized AgNP, the suppression is perceived by a factor of 2, even though both are plasmonic materials with respect to free GSH. This study can be used as a point of reference for understanding the structural conformation of the capping layer on nanoparticle surfaces as well as surface enhancement of the IR absorption of amide I. We would like to emphasize that molecular self-assembly on the nanoparticle surfaces is definitely of very broad interest for chemists working in nearly any subdiscipline, spanning from the nanoparticle-based medicine to surfaceenhanced spectroscopy to heterogeneous catalysis, etc.

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.

Solvatochromic shifts of SO vibrational probes describe the strength of the surrounding electric fields and the hydrogen bonding status. Herein, we demonstrated how the solvents alter the infrared (IR) spectra of the SO vibrating mode. The experimental measurement of the involvement of α-H/D isotopic interactions with different solvents and their effects on the IR absorbance spectra of the vibrational probe provides detailed knowledge of the microsolvation environment despite the complexity of overlapping bands in the spectra. Herein, we discover how the solvents interact differently with DMSO and DMSO-d 6, while being electronically and structurally the same. Interestingly, the IR spectrum of the SO mode remains unaltered during α-isotopic replacement in the presence of aprotic solvents (acetone, acetonitrile, and dichloromethane), but in strongly coordinating polar solvents (D2O), it is altered remarkably. There is a lack of quantitative information about the influence of the α-H atom or α-isotopic substitution on the vibrational probe in the literature. Our experiments provide a detailed molecular understanding of the structure of DMSO in DMSO–solvent binary mixtures. As DMSO plays an important role in virtually all subdisciplines of chemistry and biology, we believe that our work will be of interest to a large diversity of studies in these fields.

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The involvement of amide I in vibrational coupling with symmetric and asymmetric CC modes of different phenolic derivatives.