Search for: All records

Abstract Spontaneous ionization/breakup of water at the surface of aqueous droplets has been reported with evidence ranging from formation of hydrogen peroxide and hydroxyl radicals, indicated by ions atm/z36 attributed to OH⋅‐H₃O⁺or (H₂O‐OH₂)⁺⋅ as well as oxidation products of radical scavengers in mass spectra of water droplets formed by pneumatic nebulization. Here, aqueous droplets are formed both by nanoelectrospray, which produces highly charged nanodrops with initial diameters ~100 nm, and a vibrating mesh nebulizer, which produces 2–20 μm droplets that are initially less highly charged. The lifetimes of these droplets range from 10s of μs to 560 ms and the surface‐to‐volume ratios span ~100‐fold range. No ions atm/z36 are detected with pure water, nor are significant oxidation products for the two radical scavengers that were previously reported to be formed in high abundance. These and other results indicate that prior conclusions about spontaneous hydroxyl radical formation in unactivated water droplets are not supported by the evidence and that water appears to be stable at droplet surfaces over a wide range of droplet size, charge and lifetime. 

Laser-heated electrospray ionization with mass spectrometry enables melting temperature measurements of aggregation-prone proteins from which thermochemical and mechanistic information about protein unfolding and ligand loss is deduced. 

Structure-property-processing relationships for model lamellar structured 70 wt.% SLEnS solutions were developed with a combination of rheometry, cross-polarized optical microscopy, calorimetry, small angle X-ray scattering, and rheo-ultrasonic speckle velocimetry. Additives were utilized to maintain high surfactant activity, reduce bulk viscosity and simplify processing. While the bulk flow behavior of neat SLEnS solutions was similar, the effect of some additives was sensitive to the degree of ethoxylation. Linear-chain alcohols (C2-C5) partitioned into inter-bilayer water layers, dehydrating surfactant headgroups and inducing lamellar-to-micellar transitions. Short-chain polyols formed higher-viscosity hexagonal and mixed phases at room temperature through hydrogen bonding with surfactant headgroups. Heating beyond the upper temperature limit weakened these interactions, resulting in low-viscosity solutions. Within the lamellar phase, common salt promoted shear-induced crystallization above the equilibrium temperature range. Propylene glycol suppressed shear-induced crystallization and promoted wall-slip under shear, forming lubrication layers near the wall. These strategies offer practical levers to tune rheology and microstructure of concentrated surfactant systems, with the datasets developed providing a foundation for future modeling. Outcomes from this study inform the sustainable design and efficient processing of concentrated surfactant-based products. 

A recently developed method enables the loss of individual charges from 1 to 10 MDa salt clusters to be resolved using charge detection mass spectrometry. This technique is well suited for investigating the mechanics of late stage ion formation.