Calorimetric and acoustic study of binary mixtures containing an isomeric chlorobutane and butyl ethyl ether or methyl tert-butyl ether

Densities and speeds of sound in the temperature range 283.15-313.15 K have been measured for the binary mixtures formed by an isomeric chlorobutane (1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, or 2-chloro-2-methylpropane) and butyl ethyl ether or methyl tert-butyl ether. Excess isentropic compressibilities were calculated from the experimental data. Excess enthalpies at T = 298.15 K are also included for the same binary mixtures. All these properties provide an insight into the nature of interactions operating on the present systems. Finally, the Prigogine-Flory-Patterson theory has been used to analyze the H E results and to estimate the isentropic compressibility values of the mixtures at T = 298.15 K

Protein Conformation and Supercharging with DMSO from Aqueous Solution

The efficacy of dimethyl sulfoxide (DMSO) as a supercharging reagent for protein ions formed by electrospray ionization from aqueous solution and the mechanism for supercharging were investigated. Addition of small amounts of DMSO to aqueous solutions containing hen egg white lysozyme or equine myoglobin results in a lowering of charge, whereas a significant increase in charge occurs at higher concentrations. Results from both near-UV circular dichroism spectroscopy and solution-phase hydrogen/deuterium exchange mass spectrometry indicate that DMSO causes a compaction of the native structure of these proteins at low concentration, but significant unfolding occurs at ~63% and ~43% DMSO for lysozyme and myoglobin, respectively. The DMSO concentrations required to denature these two proteins in bulk solution are ~3–5 times higher than the concentrations required for the onset of supercharging, consistent with a significantly increased concentration of this high boiling point supercharging reagent in the ESI droplet as preferential evaporation of water occurs. DMSO is slightly more basic than m-nitrobenzyl alcohol and sulfolane, two other supercharging reagents, based on calculated proton affinity and gas-phase basicity values both at the B3LYP and MP2 levels of theory, and all three of these supercharging reagents are significantly more basic than water. These results provide additional evidence that the origin of supercharging from aqueous solution is the result of chemical and/or thermal denaturation that occurs in the ESI droplet as the concentration of these supercharging reagents increases, and that proton transfer reactivity does not play a significant role in the charge enhancement observed