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Abstract α‐Lipoic acid (LA) has recently emerged as an attractive, inexpensive monomer for synthesizing degradable polymers via ring‐opening of its 1,2‐dithiolane, introducing easily cleavable disulfide linkages into polymer backbones. Reversible addition–fragmentation chain transfer (RAFT) copolymerization with vinyl monomers enables access to degradable poly(disulfide)s with controlled molecular weights. However, conventional thermal RAFT methods suffer from oxygen sensitivity, limited LA incorporation (<40 mol%), and modest degrees of polymerization (DP < 300). Here, we report an oxygen‐tolerant, red‐light‐driven RAFT approach using methylene blue (MB⁺) as a photosensitizer, and triethanolamine (TEOA) as a sacrificial electron donor. This photoRAFT strategy affords well‐defined LA–vinyl copolymers with DPs exceeding 6000, relatively low dispersities (Đ= 1.1–1.6), and LA incorporations up to 68 mol%. The method is compatible with a broad range of functional comonomers, including hydrophilic, charged, and zwitterionic acrylates and acrylamides, yielding water‐soluble degradable polymers. The resulting copolymers are readily degradable by disulfide‐reducing agents, UV light, and ambient sunlight. Overall, this mild and efficient platform overcomes the limitations of thermal RAFT, providing improved access to functional, high‐molecular‐weight degradable LA copolymers, suggesting potential applications as biocompatible plastics and biomedical materials.more » « lessFree, publicly-accessible full text available October 27, 2026
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Abstract Polymer materials suffer mechano-oxidative deterioration or degradation in the presence of molecular oxygen and mechanical forces. In contrast, aerobic biological activities combined with mechanical stimulus promote tissue regeneration and repair in various organs. A synthetic approach in which molecular oxygen and mechanical energy synergistically initiate polymerization will afford similar robustness in polymeric materials. Herein, aerobic mechanochemical reversible-deactivation radical polymerization was developed by the design of an organic mechano-labile initiator which converts oxygen into activators in response to ball milling, enabling the reaction to proceed in the air with low-energy input, operative simplicity, and the avoidance of potentially harmful organic solvents. In addition, this approach not only complements the existing methods to access well-defined polymers but also has been successfully employed for the controlled polymerization of (meth)acrylates, styrenic monomers and solid acrylamides as well as the synthesis of polymer/perovskite hybrids without solvent at room temperature which are inaccessible by other means.more » « less
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Abstract In this study, some copper catalysts used for atom transfer radical polymerization (ATRP) were explored as efficient anti‐tumor agents. The aqueous solution of copper‐containing nanoparticles with uniform spheric morphology was in situ prepared through a copper‐catalyzed activator generated by electron transfer (AGET) ATRP in water. Nanoparticles were then directly injected into tumor‐bearing mice for antitumor chemotherapy. The copper nanodrugs had prolonged blood circulation time and enhanced accumulation at tumor sites, thus showing potent antitumor activity. This work provides a novel strategy for precise and large‐scale preparation of copper nanodrugs with high antitumor activity.more » « less
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Abstract Bottlebrush polymers (BB) have emerged as compelling candidates for biosystems to face tribological challenges, including friction and wear. This study provides a comprehensive assessment of an engineered triblock BB polymer's affinity, cell toxicity, lubrication, and wear protection in both in vitro and in vivo settings, focusing on applications for conditions like osteoarthritis and dry eye syndrome. Results show that the designed polymer rapidly adheres to various surfaces (e.g., cartilage, eye, and contact lens), forming a robust, biocompatible layer for surface lubrication and protection. The tribological performance and biocompatibility are further enhanced in the presence of hyaluronic acid (HA) both in vitro and in vivo. The exceptional lubrication performance and favorable interaction with HA position the synthesized triblock polymer as a promising candidate for innovative treatments addressing deficiencies in bio‐lubricant systems.more » « less
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Abstract Nanoparticle reinforcement is a general approach toward the strengthening of elastomer nanocomposite in large‐scale applications. Extensive studies and efforts have been contributed to demonstrating the property reinforcement of polymer nanocomposites in relation to matrix‐filler and filler‐filler interaction. Here, a facile synthetic method is creatively reported to synthesize SiO2,15/120‐g‐polyisoprene (SiO2‐g‐PI) particle brushes using atom transfer radical polymerization (ATRP). The dispersion and microstructures of the nanoparticles in the nanocomposites are investigated by morphological characterizations, whereas the reinforcing mechanism is studied through mechanical measurements as well as computational simulation. Remarkably, compared with the cured bulk elastomers and matrix(M)/SiO2blends, M/particle brushes (PB) exhibit significant improvement in mechanical properties, including tensile strength, elongation at break, modules, and rolling resistance. This elastomer nanocomposites afford a novel prospect for the practical application of next‐generation automobile tires with enhanced performance.more » « less
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Abstract This present study illustrates the synthesis and preparation of polyoxanorbornene‐based bottlebrush polymers with poly(ethylene oxide) (PEO) side chains by ring‐opening metathesis polymerization for solid polymer electrolytes (SPE). In addition to the conductive PEO side chains, the polyoxanorbornene backbones may act as another ion conductor to further promote Li‐ion movement within the SPE matrix. These results suggest that these bottlebrush polymer electrolytes provide impressively high ionic conductivity of 7.12 × 10−4S cm−1at room temperature and excellent electrochemical performance, including high‐rate capabilities and cycling stability when paired with a Li metal anode and a LiFePO4cathode. The new design paradigm, which has dual ionic conductive pathways, provides an unexplored avenue for inventing new SPEs and emphasizes the importance of molecular engineering to develop highly stable and conductive polymer electrolytes for lithium‐metal batteries (LMB).more » « less
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Abstract Liquid‐metal embedded elastomers (LMEEs) have been demonstrated to show a variety of excellent properties, including high toughness, dielectric constant, and thermal conductivity, with applications across soft electronics and robotics. However, within this scope of use cases, operation in extreme environments – such as high‐temperature conditions – may lead to material degradation. While prior works highlight the functionality of LMEEs, there is limited insight on the thermal stability of these soft materials and how the effects of liquid metal (LM) inclusions depend on temperature. Here, the effects on thermal stability, including mechanical and electrical properties, of LMEEs are introduced. Effects are characterized for both fluoroelastomer and other elastomer‐based composites at temperature exposures up to 325 °C, where it is shown that embedding LM can offer improvements in thermo‐mechanical stability. Compared to elastomer like silicone rubber that has been previously used for LMEEs, a fluoroelastomer matrix offers a higher dielectric constant and significant improvement in thermo‐mechanical stability without sacrificing room temperature properties, such as thermal conductivity and modulus. Fluoroelastomer‐LM composites offer a promising soft, multi‐functional material for high‐temperature applications, which is demonstrated here with a printed, soft heat sink and an endoscopic sensor capable of wireless sensing of high temperatures.more » « less
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Free, publicly-accessible full text available December 1, 2026
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Free, publicly-accessible full text available November 10, 2026
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Free, publicly-accessible full text available October 24, 2026
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