Synthesis of Oxazoline/Methacrylate-Based Graft-Copolymers <i>via</i> Grafting-Through Method and Evaluation of Their Self-Assembly in Water and Dodecane

Well-defined graft-copolymers of poly(2-ethyl-2-oxazoline)methacrylate macromonomer (PEtOxMM), n-butyl methacrylate, and n-lauryl methacrylate were synthesized via the grafting-through method. The effect of composition on the thermal properties and solution behavior was investigated. Differential scanning calorimetry and thermogravimetric analysis showed little dependency of the thermal properties on the terpolymer composition, while the solution properties were found to be strongly dependent. Varying the PEtOxMM content, the resulting graft- copolymers were found to be soluble in water or n-dodecane. A thermoresponsive behavior was observed only for the graft-copolymers in water, as shown by turbidity measurements and dynamic light scattering analysis. Small-angle X-ray scattering measurements at different temperatures were performed to investigate the self-assembly behavior of the graft-copolymers in both n-dodecane and water. A range of temperature-triggered morphological transitions was observed in both solvents depending on the graft-copolymer composition. These graft-copolymers were able to self-assemble into different morphologies in both n-dodecane and water, exhibiting a high temperature stability

Exploring the Nanostructures Accessible to an Organic Surfactant Atmospheric Aerosol Proxy

The composition of atmospheric aerosols varies with time, season, location, and environment. This affects key aerosol properties such as hygroscopicity and reactivity, influencing the aerosol’s impact on the climate and air quality. The organic fraction of atmospheric aerosol emissions often contains surfactant material, such as fatty acids. These molecules are known to form three-dimensional nanostructures in contact with water. Different nanostructures have marked differences in viscosity and diffusivity that are properties whose understanding is essential when considering an aerosol’s atmospheric impact. We have explored a range of nanostructures accessible to the organic surfactant oleic acid (commonly found in cooking emissions), simulating variation that is likely to happen in the atmosphere. This was achieved by changing the amount of water, aqueous phase salinity and by addition of other commonly coemitted compounds: sugars and stearic acid (the saturated analogue of oleic acid). The nanostructure was observed by both synchrotron and laboratory small/wide angle X-ray scattering (SAXS/WAXS) and found to be sensitive to the proxy composition. Additionally, the spacing between repeat units in these nanostructures was water content dependent (i.e., an increase from 41 to 54 Å in inverse hexagonal phase d-spacing when increasing the water content from 30 to 50 wt %), suggesting incorporation of water within the nanostructure. A significant decrease in mixture viscosity was also observed with increasing water content from ∼104 to ∼102 Pa s when increasing the water content from 30 to 60 wt %. Time-resolved SAXS experiments on levitated droplets of this proxy confirm the phase changes observed in bulk phase mixtures and demonstrate that coexistent nanostructures can form in droplets. Aerosol compositional and subsequent nanostructural changes could affect aerosol processes, leading to an impact on the climate and urban air pollution