Robust Hydrogel Actuators Functioning in Multi-Environments Enabled by Thermo-Responsive Polymer Nanoparticle Coatings on Hydrogel Surfaces.

Hydrogel actuators with anisotropic structures exhibit reversible responsiveness upon the trigger of various external stimuli, rendering them promising for applications in many fields including artificial muscles and soft robotics. However, their effective operation across multiple environments remains a persistent challenge, even for widely studied thermo-responsive polymers like poly(N-isopropyl acrylamide) (PNIPAm). Current attempts to address this issue are hindered by complex synthetic procedures or specific substrates. This study introduces a straightforward methodology to grow a thin, dense PNIPAm nanoparticle layer on diverse hydrogel surfaces, creating a highly temperature-sensitive hydrogel actuator. This actuator demonstrates adaptability across various environments, including water, oil, and open air, owing to its distinct structure facilitating self-water circulation during actuation. The thin PNIPAm layer consists of interconnected PNIPAm nanoparticles synthesized via in situ interfacial precipitation polymerization, seamlessly bonded to the hydrogel substrate through an interfacial layer containing hybrid hydrogel/PNIPAm nanoparticles. This unique anisotropic structure ensures exceptional structural stability without interfacial delamination, even enduring harsh treatments such as freezing, ultrasonic irradiation, and prolonged water immersion. Remarkably, PNIPAm films on hydrogel surfaces which enable programmable 3D actuation can also be precisely patterned. This synthetic approach opens a novel pathway for fabricating advanced hydrogel actuators with broad-ranging applications.

Rapid, Tough, and Trigger-Detachable Hydrogel Adhesion Enabled by Formation of Nanoparticles In Situ.

Integrating hydrogel with other materials is always challenging due to the low mass content of hydrogels and the abundance of water at the interfaces. Adhesion through nanoparticles offers characteristics such as ease of use, reversibility, and universality, but still grapples with challenges like weak bonding. Here, a simple yet powerful strategy using the formation of nanoparticles in situ is reported, establishing strong interfacial adhesion between various hydrogels and substrates including elastomers, plastics, and biological tissue, even under wet conditions. The strong interfacial bonding can be formed in a short time (60 s), and gradually strengthened to 902 J m-2 adhesion energy within an hour. The interfacial layer's construction involves chain entanglement and other non-covalent interactions like coordination and hydrogen bonding. Unlike the permanent bonding seen in most synthetic adhesives, these nanoparticle adhesives can be efficiently triggered for removal by acidic solutions. The simplicity of the precursor diffusion and precipitation process in creating the interfacial layer ensures broad applicability to different substrates and nanoparticle adhesives without compromising robustness. The tough adhesion provided by nanoparticles allows the hydrogel-elastomer hybrid to function as a triboelectric nanogenerator (TENG), facilitating reliable electrical signal generation and output performance due to the robust interface.

Smart Galactosidase-Responsive Antimicrobial Dendron: Towards More Biocompatible Membrane-Disruptive Agents.

Antimicrobial resistance is a global healthcare challenge that urgently needs the development of new therapeutic agents. Antimicrobial peptides and mimics thereof are promising candidates but mostly suffer from inherent toxicity issues due to the non-selective binding of cationic groups with mammalian cells. To overcome this toxicity issue, this work herein reports the synthesis of a smart antimicrobial dendron with masked cationic groups (Gal-Dendron) that could be uncaged in the presence of ß-galactosidase enzyme to form the activated Enz-Dendron and confer antimicrobial activity. Enz-Dendron show bacteriostatic activity toward Gram-negative (P. aeruginosa and E. coli) and Gram-positive (S. aureus) bacteria with minimum inhibitory concentration values of 96 µm and exerted its antimicrobial mechanism via a membrane disruption pathway, as indicated by inner and outer membrane permeabilization assays. Crucially, toxicity studies confirmed that the masked prodrug Gal-Dendron exhibited low hemolysis and is at least 2.4 times less toxic than the uncaged cationic Enz-Dendron, thus demonstrating the advantage of masking the cationic groups with responsive immolative linkers to overcome toxicity and selectivity issues. Overall, this study highlights the potential of designing new membrane-disruptive antimicrobial agents that are more biocompatible via the amine uncaging strategy.

Visible-Light-Driven MADIX Polymerisation via a Reusable, Low-Cost, and Non-Toxic Bismuth Oxide Photocatalyst.

The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation (RDRP) processes has initiated a rapidly propagating area of polymer research in recent years. We introduce bismuth oxide (Bi2 O3 ) as a heterogeneous photocatalyst for polymerisations, operating at room temperature with visible light. We demonstrate formidable control over degenerative chain-transfer polymerisations, such as macromolecular design by interchange of xanthate (MADIX) and reversible addition-fragmentation chain-transfer (RAFT) polymerisation. We achieved narrow molecular weight distributions and attribute the excellent temporal control of a photo-induced electron transfer (PET) process. This methodology was employed to synthesise diblock copolymers combining differently activated monomers. The Bi2 O3 catalyst system has the additional benefits of low toxicity, reusability, low-cost, and ease of removal from the reaction mixture.

Pyrazole carbodithiolate-driven iterative RAFT single-additions.

In this Communication, we comprehensively investigated substituent effects relevant to iterative reversible activation fragmentation chain transfer (RAFT) single unit monomer insertion (SUMI) reactions. Through the use of the pyrazole carbodithiolate (PCDT) "Z-group" as the chain transfer component in RAFT SUMI, we show the importance of "Z-group" effects and its interplay with "R-group" (the carbon-centred radical precursor) effects. We also expanded the scope of RAFT SUMI to new monomer types and sequences thereof. As such, the C-S bond dissocation/reformation steps were found to be crucial factors in SUMI, and it was found that general substituent effects must be wholistically examined for every step of this reaction. This stands in contrast with conventional knowledge of RAFT polymerisation, where the main consideration is often centred around the propagation stage, i.e., the key C-C bond formation step. Indeed, contrary to SUMI, the latter characteristic was observed in the analogous alternating copolymerisation.

Biomimetic Electronic Skin through Hierarchical Polymer Structural Design.

Human skin comprises multiple hierarchical layers that perform various functions such as protection, sensing, and structural support. Developing electronic skin (E-skin) with similar properties has broad implications in health monitoring, prosthetics, and soft robotics. While previous efforts have predominantly concentrated on sensory capabilities, this study introduces a hierarchical polymer system that not only structurally resembles the epidermis-dermis bilayer structure of skin but also encompasses sensing functions. The system comprises a polymeric hydrogel, representing the "dermis", and a superimposed nanoporous polymer film, forming the "epidermis". Within the film, interconnected nanoparticles mimic the arrangement of interlocked corneocytes within the epidermis. The fabrication process employs a robust in situ interfacial precipitation polymerization of specific water-soluble monomers that become insoluble during polymerization. This process yields a hybrid layer establishing a durable interface between the film and hydrogel. Beyond the structural mimicry, this hierarchical structure offers functionalities resembling human skin, which includes (1) water loss protection of hydrogel by tailoring the hydrophobicity of the upper polymer film; (2) tactile sensing capability via self-powered triboelectric nanogenerators; (3) built-in gold nanowire-based resistive sensor toward temperature and pressure sensing. This hierarchical polymeric approach represents a potent strategy to replicate both the structure and functions of human skin in synthetic designs.

Comparison of protein quantification methods for protein encapsulation with ZIF-8 metal-organic frameworks.

The use of metal-organic frameworks (MOFs) as delivery systems for biologically functional macromolecules has been explored widely in recent years due to their ability to protect their payload from a wide range of harsh conditions. Given the wide usage and diversity of potential applications, optimising the encapsulation efficiency by MOFs for different biological is of particular importance. Here, several protein quantitation methods and report were compared on the accuracy, practicality, limitations, and sensitivity of these methods to assess the encapsulation efficiency of zeolitic imidazolate frameworks (ZIF)-8 MOFs for two common biologicals commonly used in nanomedicine, bovine serum albumin (BSA), and the enzyme catalase (CAT). Using these methods, ZIF-8 encapsulation of BSA and CAT was confirmed to enrich for high molecular weight and glycosylated protein forms. However, contrary to most reports, a high degree of variance was observed across all methods assessed, with fluorometric quantitation providing the most consistent results with the lowest background and greatest dynamic range. While bicinchoninic acid (BCA) assay has showed greater detection range than the Bradford (Coomassie) assay, BCA and Bradford assays were found to be susceptible to background from the organic "MOF" linker 2-methylimidazole, reducing their overall sensitivity. Finally, while very sensitive and useful for assessing protein quality SDS-PAGE is also susceptible to confounding artifacts and background. Given the increasing use of enzyme delivery using MOFs, and the diversity of potential uses in biomedicine, identifying a rapid and efficient method of assessing biomolecule encapsulation is key to their wider acceptance.