Specific ion interactions with aromatic rings in aqueous solutions: Comparison of molecular dynamics simulations with a thermodynamic solute partitioning model and Raman spectroscopy

Micelle Structure and Hydrophobic Hydration

“…59−62 Thus, our observation of an anomalously large red-shift of the CD stretch of benzene-d 6 in C 10 TAB micelles suggests that benzene may also interact with the bromide (Br − ) counteranions, which are known to red-shift the CH stretch of benzene in aqueous salt solutions. 63 Thus, our results suggest that benzene molecules near the micelle surface interact with both the −N(CH 3 ) 3 + head groups and Br − counterions.…”

OH-Stretch Raman Multivariate Curve Resolution Spectroscopy of HOD/H2O Mixtures

“…25,27 Raman MCR has been used to study solutions of acetonitrile in water, 27 πhydrogen bond formation between liquid water and benzene, 28 dangling hydroxyl groups of water around benzyl alcohol, 29 the hydration shell structure of CO 2 and hydrogen bonding between CO 2 and water, 30 hydrophobic hydration shells of nalcohols, 31 phase transitions in mixed lipid aggregates, 32 aqueous proton solvation, 33 the affinity of ions for hydrophobic hydration shells, 34 and for solutions of benzene and pyridine in water. 35 Raman MCR has also been used to decompose temperature-dependent Raman spectra of liquid H 2 O and D 2 O into linear combinations of two spectral components with temperature-independent shapes but temperature-dependent intensities, corresponding to water molecules in different local tetrahedral environments. 36,37 Matt and Ben-Amotz 22 used Raman MCR to probe the influence of intermolecular OH (OD) stretching vibrational couplings on water OH (OD) stretching band shapes and intensities in isotopically dilute liquid water.…”

“…One of the two spectral components is equivalent to a pure solvent spectrum, whereas the other contains SC spectral features . However, no assumptions regarding the spectral shape are required. , Raman MCR has been used to study solutions of acetonitrile in water, π-hydrogen bond formation between liquid water and benzene, dangling hydroxyl groups of water around benzyl alcohol, the hydration shell structure of CO 2 and hydrogen bonding between CO 2 and water, hydrophobic hydration shells of n -alcohols, phase transitions in mixed lipid aggregates, aqueous proton solvation, the affinity of ions for hydrophobic hydration shells, and for solutions of benzene and pyridine in water . Raman MCR has also been used to decompose temperature-dependent Raman spectra of liquid H 2 O and D 2 O into linear combinations of two spectral components with temperature-independent shapes but temperature-dependent intensities, corresponding to water molecules in different local tetrahedral environments. , …”

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

“…However, it is becoming increasingly evident that these areas do in fact frequently overlap; two prime examples being the accumulation of large polarizable anions at the air-water interface, 1-5 and the favorable interactions of polarizable anions with non-polar surfaces. [6][7][8][9][10][11][12][13][14][15] Thus the hydrophobic and Hofmeister effects are but part of a greater continuum of aqueous supramolecular chemistry, with many important and outstanding questions regarding the influence of the different kinds of non-covalent interactions involved.Studies of water and aqueous solutions have mostly been driven by the physical sciences community, a broad range of scientists whose expertise in spectroscopy, computer modeling, and biochemistry (to name just three areas) has generally not involved macrocycles or host molecules in general. However, for some time now, supramolecular chemists -with their expertise in macrocyclic synthesis and measuring weak non-covalent interactions -have been travelling a parallel course of exploration.…”