Off‐Stoichiometric Thiol‐Ene Chemistry to Dendritic Nanogel Therapeutics

A novel platform of dendritic nanogels is herein presented, capitalizing on the self‐assembly of allyl‐functional polyesters based on dendritic‐linear‐dendritic amphiphiles followed by simple cross‐linking with complementary monomeric thiols via UV initiated off‐stoichiometric thiol‐ene chemistry. The facile approach enabled multigram creation of allyl reactive nanogel precursors, in the size range of 190–295 nm, being readily available for further modifications to display a number of core functionalities while maintaining the size distribution and characteristics of the master batch. The nanogels are evaluated as carriers of a spread of chemotherapeutics by customizing the core to accommodate each individual cargo. The resulting nanogels are biocompatible, displaying diffusion controlled release of cargo, maintained therapeutic efficacy, and decreased cargo toxic side effects. Finally, the nanogels are found to successfully deliver pharmaceuticals into a 3D pancreatic spheroids tumor model.     

Beyond State of the Art Honeycomb Membranes: High Performance Ordered Arrays from Multiprogrammable Linear‐Dendritic Block Copolymers

A new generation of honeycomb membranes is herein described from a novel library of multipurpose linear‐dendritic block copolymers. These are accomplished by combining atom transfer radical polymerization together with dendrimer chemistry and click reactions. The resulted amorphous block copolymers, with T_g between 30 and 40 °C, display three important functions, i.e., pore generating aromatic groups, crosslinking azides, and multiple dendritic functional groups. All block copolymers enable the successful fabrication of honeycomb membranes through the facile breath figure method. The peripheral dendritic functionality is found to influence the porous morphologies from closed pored structure with pore size of 1.12 μm² to open pore structure with pore size 10.26 μm². Facile UV crosslinking of the azides yields membranes with highly durable structural integrity. Upon crosslinking, the pH and thermal stability are extended beyond the noncrosslinked membranes in which the porous integrity is maintained up to 400 °C and pH 1–14. Taking into account the straightforward and cost‐efficient strategy to generate ordered, functional, and structurally stable honeycomb membranes on various solid substrates, it is apparent that these multipurpose block copolymers may unlock future applications including use as molds for soft lithography.