Water-Soluble Reversible Photo-Cross-Linking Polymer Dielectrics.

Effective recycling of mixed materials requires the separation of the different components without the need for toxic solvents. One approach involves utilizing a water-soluble coating with reversible photo-cross-linkers, making it robust until end of life where it can then be dissolved in water after de-cross-linking. Here, a novel coumarin methacrylate monomer and its nitroxide-mediated copolymerization to create poly((methacrylic acid)-co-(styrene sulfonate)-co-(coumarin methacrylate)) for water-soluble thin films are reported. Under exposure to light, the coumarin functional groups produce reversible [2+2] cycloadditions which cross-link the resulting polymer films, making them no longer water soluble. Characterization of reversible cross-linking behavior is reported through changes in contact angle and in situ rheological characterization. The resulting polymers are successfully integrated into metal-insulator-metal capacitors, demonstrating the potential use for water-soluble reversible photo-cross-linkable dielectric materials for organic electronics.

Facile, Energy-Efficient Microscale Fibrillation of Polyacrylamides under Ambient Conditions.

Insight into fiber formation can provide new rationale for the design and preparation of fibers with programmed mechanical properties. While synthetic bioinspired fibers have shown impressive tensile properties, the fiber formation process remains poorly understood. Moreover, these systems are highly complex and their formation is environmentally and economically costly. Controlled fiber formation under ambient conditions from polyacrylamide solutions with properties comparable to natural fibers such as wool and coir is demonstrated. Photopolymerization and subsequent microscale fibrillation of different acrylamides in water/ethanol mixtures yield a simple and energy-efficient route to fiber formation. This strategy reduces required processing energy by two-to-three orders of magnitude. Through extensive experimental elucidation, insight into precise fiber forming conditions of polymeric solutions is achieved. Ethanol is utilized as a chain transfer agent to control the molecular weight of the polyacrylamides, and the entanglement regimes of the solutions are determined through rheological characterization showing fiber formation above the entanglement concentration. Unique from previously reported hydrogel microfibers, it is shown that fibers with good mechanical properties can be obtained without the need for composites or crosslinkers. The reported approach offers a platform for fiber formation under ambient conditions with molecular-level understanding of their assembly.

A Platform Approach to Protein Encapsulates with Controllable Surface Chemistry.

The encapsulation of proteins into core-shell structures is a widely utilised strategy for controlling protein stability, delivery and release. Despite the recognised utility of these microstructures, however, core-shell fabrication routes are often too costly or poorly scalable to allow for industrial translation. Furthermore, many scalable routes rely upon emulsion-techniques implicating denaturing or environmentally harmful organic solvents. Herein, we investigate core-shell protein encapsulation through single-feed, aqueous spray drying: a cheap, industrially ubiquitous particle-formation technology in the absence of organic solvents. We show that an excipient's preference for the surface of the spray dried particle is well-predicted by its hydrodynamic diameter (Dh) under relevant feed buffer conditions (pH and ionic strength) and that the predictive power of Dh is improved when measured at the spray dryer outlet temperature compared to room temperature (R2 = 0.64 vs. 0.59). Lastly, we leverage these findings to propose an adaptable design framework for fabricating core-shell protein encapsulates by single-feed aqueous spray drying.

Formation of 2D and 3D multi-tori mesostructures via crystallization-driven self-assembly.

The fabrication of three-dimensional (3D) objects by polymer self-assembly in solution is extremely challenging. Here, multi-tori mesostructures were obtained from the crystallization-driven self-assembly of a coil-crystalline block copolymer (BCP) in mixed solvents. The formation of these structures follows a multistep process. First, the BCP self-assembles into amorphous micrometer-large vesicles. Then, the BCP confined in these mesosized vesicles crystallizes. This second step leads to the formation of objects with shapes ranging from closed 3D multi-tori spherical shells to 2D toroid mesh monolayers, depending on the solvent mixture composition. This approach demonstrates how topological constraints induced by the specific interactions between coil-crystalline BCP and solvents can be used to prepare mesostructures of complex morphologies.

Glass wool: a novel support for heterogeneous catalysis.

Heterogeneous catalysis presents significant advantages over homogeneous catalysis such as ease of separation and reuse of the catalyst. Here we show that a very inexpensive, manageable and widely available material - glass wool - can act as a catalyst support for a number of different reactions. Different metal and metal oxide nanoparticles, based on Pd, Co, Cu, Au and Ru, were deposited on glass wool and used as heterogeneous catalysts for a variety of thermal and photochemical organic reactions including reductive de-halogenation of aryl halides, reduction of nitrobenzene, Csp3-Csp3 couplings, N-C heterocycloadditions (click chemistry) and Csp-Csp2 couplings (Sonogashira couplings). The use of glass wool as a catalyst support for important organic reactions, particularly C-C couplings, opens the opportunity to develop economical heterogeneous catalysts with excellent potential for flow photo-chemistry application.

Visualizing Nanoscale Coronal Segregation in Rod-Like Micelles Formed by Co-Assembly of Binary Block Copolymer Blends.

Mixed micelles formed by co-assembly of pairs of block copolymers (BCPs) can develop novel morphologies and generate useful properties not accessible from homomicelles. For micelles consisting of two different polymers in the corona, identifying the location of the corona chains is a critical part of morphology characterization. Coronal segregation in mixed micelle is often characterized by transmission electron microscopy in combination with selective staining of individual polymers. In this study, Karstedt's catalyst is used for selective Pt(0)-olefin coordination staining of polyisoprene (PI) and poly(methylvinylsiloxane) (PMVS) corona chains in the presence of poly(dimethylsiloxane) (PDMS) corona chains in cylindrical mixed micelles with a crystalline poly(ferrocenyldimethylsilane) (PFS) core. Previous experiments using OsO4 as a stain did not enable visualization of nanoscale coronal segregation in mixed micelles obtained from co-assembly of PFS-b-PI and PFS-b-PDMS, as well as PFS-b-PMVS and PFS-b-PDMS.