Molecular dynamics simulations of random quaternary mixtures of protein-water-CO2-fluorosurfactants show the self-assembly of reverse micelles in supercritical carbon dioxide where the protein becomes entrapped inside the aqueous pool. Analyses show that the protein native state remains intact in the water pool. This is because of the bulk nature of the enclosed water that provides a suitable environment for the extracted protein. Results from ab initio calculations imply that the existing fluorosurfactants can be made more effective in stabilizing water-in-CO2 microemulsions by a partial hydrogenation in their tails. A Lewis acid-Lewis base interaction among CO2 and the surfactant tails enhances the stability of the aqueous droplets substantially. The study can help accelerate the search for surfactant process for environmentally benign applications in dense CO2.

A bio‐inspired method is used to render controlled wrinkling surface patterns on supramolecular architectures assembled from polyoxometalate (POM) clusters. It involves a polyamine‐multivalent anion interaction generating positively charged coacervates, which while dictating the assembly of POM into spherical structures further facilitate an interesting surface morphogenesis with wrinkling patterns. This spontaneous surface wrinkling depends on the type of multivalent anion and the pH. As the polyamine‐anion interaction becomes stronger, the wrinkles turn denser with lesser depth, which eventually undergoes post‐buckling to engender a complex surface pattern. Interestingly, the order of influence exerted by different anions on the morphology follows the Hofmeister series. Moreover, the mild synthesis conditions keep the functional POM units dispersed in the sphere with a structural transformability to their lacunary form.

A polyamine-mediated bioinspired method is demonstrated to heterogenize and stabilize isolated phosphotungstic acid (PTA) Keggin units, which allows formation of a multicomponent microcapsule structure under ambient conditions. Utilizing the supramolecular aggregation property of polyamines in the presence of suitable multivalent anions, it is shown that the resulting aggregates, while facilitating the encapsulation of negatively charged Fe 3 O 4 nanoparticles (magnetic component), further facilitate the assembly of PTA nanoclusters (catalytic component) to generate magnetic microcapsule structures (PTA@MMS). As revealed from a detailed analysis, the interaction of polyamines with PTA is the key for the Keggin units to remain stable and isolated as desirable for catalytic applications. Investigation on the catalytic activity in oxidation of benzyl alcohol with H 2 O 2 as the oxidant in water shows that these isolated PTA units render better catalytic activity and product selectivity toward aldehyde under green conditions compared to the other reported PTA-based noble-metal-free catalysts. Moreover, the presence of magnetic nanoparticles leads to convenient catalyst separation and reuse. Therefore, the method is believed to provide ways for further developments in POM-based heterogeneous catalysts with opportunities to impart multifunctionality for sustainable organic transformations.

A bio‐inspired method is used to render controlled wrinkling surface patterns on supramolecular architectures assembled from polyoxometalate (POM) clusters. It involves a polyamine‐multivalent anion interaction generating positively charged coacervates, which while dictating the assembly of POM into spherical structures further facilitate an interesting surface morphogenesis with wrinkling patterns. This spontaneous surface wrinkling depends on the type of multivalent anion and the pH. As the polyamine‐anion interaction becomes stronger, the wrinkles turn denser with lesser depth, which eventually undergoes post‐buckling to engender a complex surface pattern. Interestingly, the order of influence exerted by different anions on the morphology follows the Hofmeister series. Moreover, the mild synthesis conditions keep the functional POM units dispersed in the sphere with a structural transformability to their lacunary form.