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Commodity PS is synthesized via free radical polymerization, whereas PS in block copolymers (BCPs) is typically synthesized via living anionic polymerization. The purpose of this work is to investigate how the synthesis method impacts important properties such as water sorption and glass transition temperature (Tg). Water sorption is important because the performance of nanostructured polymer membranes in various applications is known to be affected by environmental conditions such as humidity. Tg is important because it dictates processing conditions, both for commodity PS as well as BCPs such as thermoplastic elastomers. Water sorption in commercial PS was found to be 0.5 mgwater/gpolymer at the highest humidities investigated (about 80%), in agreement with literature. On the other hand, syndiotactic PS synthesized anionically at low temperature absorbed more water, up to 1.5 mgwater/gpolymer, due to higher free volume. The greatest impact on water sorption was due to addition of hydrophilic hydroxyl chain ends to atactic PS, which resulted in water sorption of up to 2.3 mgwater/gpolymer. In addition to measuring water sorption and dry Tg separately, the impact of relative humidity on PS Tg was examined. Combined differential scanning calorimetry and dynamic mechanical analysis show that on going from the dry state to high humidity, the Tg of PS decreases by 5 °C. Moreover, the tensile storage modulus of PS decreases from 1.58 GPa at 0% RH to 0.53 GPa at 40% RH. In addition to the practical relevance of this study, this report fills a gap in experimental literature by using a poor solvent system, PS/water, to examine plasticization in the pure polymer limit. 

Nano-porous aerogels are an advantageous approach to produce low-density materials with high surface area, particularly when using biobased materials. Frequently, most biobased aerogels are synthesized through a bottom-up approach, which requires high energy inputs to break and rebuild the raw materials, and for elimination of water. To curb this, this work focused on generating aerogels by a top-down approach through the delignification of a wood substrate while eliminating water by solvent exchange. To diversify the surface chemistry for use in water treatment, the delignified wood–nanowood-was coated with a chitosan–cyclodextrin co-polymer and tested in the capture of microcystin-LR. The generated nanowood structure had 75% porosity after coating, with up to 339% water swelling and an adsorption capacity of 0.12 mg g −1 of the microcystin. This top-down technique enables the generation of low-cost aerogels by reducing steps, using a biobased self-assembled coating with hydrophobic active sites, and avoiding costly energetic input.