00759nas a2200229 4500008004100000022001400041245007900055210006900134260000900203300001600212490000700228653002700235653002400262653001500286100002700301700001800328700002100346700002000367700001800387700001800405856010600423 2024 eng d a2040-336400aProbing surface interactions in CdSe quantum dots with thiocyanate ligands0 aProbing surface interactions in CdSe quantum dots with thiocyana cAUG  a14922-149310 v1610aCOLLOIDAL NANOCRYSTALS10aSTRUCTURAL DYNAMICS10aThin-films1 aDeshmukh, Samadhan, H.1 aYadav, Sushma1 aChowdhury, Tubai1 aPathania, Akhil1 aSapra, Sameer1 aBagchi, Sayan uhttps://library.ncl.res.in/content/probing-surface-interactions-cdse-quantum-dots-thiocyanate-ligands02491nas a2200133 4500008004100000245006900041210006900110260000800179490000600187520202800193100002002221700001802241856009802259 2024 eng d00aSlowdown of solvent structural dynamics in aqueous DMF solutions0 aSlowdown of solvent structural dynamics in aqueous DMF solutions cDEC0 v93 a

This study presents a comprehensive investigation into the molecular dynamics of solvation environments through an integrated approach combining Fourier-transform infrared (FTIR) spectroscopy, molecular dynamics (MD) simulations, and two-dimensional infrared (2D IR) spectroscopy. We explore the solvation of an ionic solute (ammonium thiocyanate) in various solvent systems, including N,N-dimethylformamide (DMF), water, and a 0.5 mole fraction of DMF in water, aiming to unravel the intricate interplay between solute-solvent interactions and solvent dynamics across diverse solvation environments. By integrating FTIR spectral analysis with radial distribution functions and coordination numbers obtained from MD simulations, we decipher the solvent composition around the solute molecule. Analysis of 2D IR spectra and hydrogen bond, as well as dipolar autocorrelation function from MD simulations, further elucidates the nuances of solute-solvent interactions, highlighting the impact of solvent dynamics on solvation structures. Our results reveal a significant slowdown of the solvent structural dynamics in the equimolar binary solvent mixture compared to the neat solvents. This slowdown underscores the complex relationship between solute-solvent interactions and solvent dynamics. The integration of FTIR, MD simulations, and 2D IR spectroscopy provides a unified framework for obtaining a holistic understanding of solvation dynamics, offering valuable insights into the underlying molecular mechanisms governing solute-solvent interactions in complex systems. These results pave the way for future studies to delve deeper into the molecular intricacies of solvation phenomena.

1 aPathania, Akhil1 aBagchi, Sayan uhttps://library.ncl.res.in/content/slowdown-solvent-structural-dynamics-aqueous-dmf-solutions01901nas a2200181 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520123800266100002101504700002001525700002601545700001801571856013001589 2025 eng d a0021-960600aProbing solvent fluctuations in deep eutectic solvents: Influence of probe charge and nano-domain localization0 aProbing solvent fluctuations in deep eutectic solvents Influence cJUL a0445060 v1633 a

Deep eutectic solvents (DESs) segregate into hydrogen bond acceptor or hydrogen bond donor (HBD) rich nano-domains, leading to molecular heterogeneity. Understanding how this heterogeneity affects the DES structure and dynamics is essential. In this study, we used two-dimensional nuclear magnetic resonance (2D NMR) and two dimensional infrared (2D IR) spectroscopies, combined with molecular dynamics (MD) simulations, to investigate solvation structure and dynamics in two choline chloride-based DESs with different HBDs-levulinic acid and glycolic acid. We introduced two thiocyanate vibrational probes, methyl thiocyanate (CH3SCN, neutral) and ammonium thiocyanate (NH4SCN, anionic), which selectively localize in specific nano-domains. 2D NMR provided insights into solvent structure and probe location, while 2D IR captured solvation dynamics. Our results show that these small probes do not alter the solvent structure, regardless of charge. However, solvation dynamics depend on long-range electrostatic ordering in the DES and the local shielding effects of the nano-domain where the probe resides. MD simulations complement experimental findings, providing a molecular-level understanding of solvation in DESs.

1 aChowdhury, Tubai1 aPathania, Akhil1 aRavindranathan, Sapna1 aBagchi, Sayan uhttps://library.ncl.res.in/content/probing-solvent-fluctuations-deep-eutectic-solvents-influence-probe-charge-and-nano-domain