The ability to control nanostructure shape and dimensions presents opportunities to design materials in which their macroscopic properties are dependent upon the nature of the nanoparticle. Although particle morphology has been recognized as a crucial parameter, the exploitation of the potential shape-dependent properties has, to date, been limited. Herein, we demonstrate that nanoparticle shape is a critical consideration in the determination of nanocomposite hydrogel properties. Using translationally relevant calcium-alginate hydrogels, we show that the use of poly(L-lactide)-based nanoparticles with platelet morphology as an adhesive results in a significant enhancement of adhesion over nanoparticle glues comprised of spherical or cylindrical micelles. Furthermore, gel nanocomposites containing platelets showed an enhanced resistance to breaking under strain compared to their spherical and cylindrical counterparts. This study opens the doors to a change in direction in the field of gel nanocomposites, where nanoparticle shape plays an important role in tuning mechanical properties.
18 December 2020 in Angewandte Chemie International Edition
Enzyme loading of polymersomes requires permeability to enable them to interact with the external environment, typically requiring addition of complex functionality to enable porosity. Herein, we describe a synthetic route toward intrinsically permeable polymersomes loaded with functional proteins using initiator-free visible light-mediated polymerization-induced self-assembly (photo-PISA) under mild, aqueous conditions using a commercial monomer. Compartmentalization and retention of protein functionality was demonstrated using green fluorescent protein as a macromolecular chromophore. Catalytic enzyme-loaded vesicles using horseradish peroxidase and glucose oxidase were also prepared and the permeability of the membrane toward their small molecule substrates was revealed for the first time. Finally, the interaction of the compartmentalized enzymes between separate vesicles was validated by means of an enzymatic cascade reaction. These findings have a broad scope as the methodology could be applied for the encapsulation of a large range of macromolecules for advancements in the fields of nanotechnology, biomimicry, and nanomedicine.