No abstract

† Electronic supplementary information (ESI) available: Network formation, synthesis of precursor materials for post-functionalization, UV analysis/Ellman's reagent, DMA curves, calculation of (M c), network post-functionalizations, FT-IR spectra, and SEM images for the molding technique. See

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.

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 fi gure method. The peripheral dendritic functionality is found to infl uence the porous morphologies from closed pored structure with pore size of 1.12 µm 2 to open pore structure with pore size 10.26 µm 2 . 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-effi cient 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.

Dendritic hydrogels from dendritic‐linear‐dendritic (DLD) block copolymers based on PEG and bis‐MPA dendrons were constructed via UV‐initiated thiol‐ene, thiol‐yne, CuAAC, and amine‐NHS crosslinking chemistries. Stoichiometric ratio manipulations, prior to film formation, resulted in functional hydrogels with tuneable compressive moduli. The highest gel fractions for all networks were obtained at off‐stoichiometric ratios with surplus of DLDs. Finally, sustainable networks were fabricated by amalgamating DLD, naturally abundant cellulose nanocrystal, and protein‐based bovine serum albumin.