Fabrication of Light-Triggered Soft Artificial Muscles via a Mixed-Matrix Membrane Strategy.

Artificial muscles triggered by light are of great importance, especially for the development of non-contact and remotely controlled materials. Common materials for synthesis of photoinduced artificial muscles typically rely on polymer-based photomechanical materials. Herein, we are able to prepare artificial muscles using a mixed-matrix membrane strategy to incorporate photomechanical molecular crystals with connective polymers (e.g. PVDF). The formed hybrid materials inherit not only the advantages of the photomechanical crystals, including faster light response, higher Young's modulus and ordered structure, but also the elastomer properties from polymers. This new type of artificial muscles demonstrates various muscle movements, including lifting objects, grasping objects, crawling and swimming, triggered by light irradiation. These results open a new direction to prepare light-driven artificial muscles based on molecular crystals.

Tuning Pore Heterogeneity in Covalent Organic Frameworks for Enhanced Enzyme Accessibility and Resistance against Denaturants.

Achieving high-performance biocomposites requires knowledge of the compatability between the immobilized enzyme and its host material. The modular nature of covalent organic frameworks (COFs), as a host, allows their pore geometries and chemical functionalities to be fine-tuned independently, permitting comparative studies between the individual parameters and the performances of the resultant biocomposites. This research demonstrates that dual pores in COFs have profound consequences on the catalytic activity and denaturation of infiltrated enzymes. This approach enforces a constant pore environment by rational building-block design, which enables it to be unequivocally determined that pore heterogeneity is responsible for rate enhancements of up to threefold per enzyme molecule. More so, the enzyme is more tolerant to detrimental by-products when occupying the larger pore in a dual-pore COF compared to a corresponding uniform porous COF. Kinetic studies highlight that pore heterogeneity facilitates mass transfer of both reagents and products. This unparalleled versatility of these materials allows many different aspects to be designed on demand, lending credence to their prospect as next-generation host materials for various enzyme biocomposites catalysts.

Porous Ionic Polymers as a Robust and Efficient Platform for Capture and Chemical Fixation of Atmospheric CO2.

Direct use of atmospheric CO2 as a C1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO2 uptake capacity of the PIPs facilitates the enrichment of CO2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO2 .