Tumor-associated macrophages (TAMs) have emerged as a promising immunotherapeutic target in non-small cell lung cancer (NSCLC). However, the indiscriminate cytotoxicity of chemotherapies and the immunosuppressive tumor microenvironment paradoxically impede this potential. To overcome these limitations, we engineered β-selenoester-crosslinked nanocapsules delivering Gefitinib, designed to induce opposite cell fates in cancer cells and macrophages. In cancer cells, the Se-C bond in β-selenoester is ultrasensitive under the intrinsic reactive oxygen species (ROS) level. It generates acrylates through selenoxide elimination reaction, which further depletes intracellular GSH to regenerate cytotoxic ROS. The ROS-triggered positive-feedback induces nanocapsule disassembly, enabling rapid Gefitinib release and apoptosis induction. The released Gefitinib also disrupts the CD47-SIRPα "don't eat me" axis to enhance macrophage phagocytic activity. In macrophages, low ROS level limits Gefitinib exposure, but the selenium metabolites generated from the elimination reaction are sufficient to promote macrophage activation. This selective cell fate programming yielded no macrophage toxicity at cancer-cell IC50 levels and a 91.1 % tumor suppression in vivo. Collectively, this work demonstrates a divergent cell fate induction strategy based on β-selenoester-crosslinking for integrated TAM-mediated immunotherapy.

Early burst ion release of biodegradable alloys, such as Zn-2(+), often triggers inflammation and impairs bone formation, which affects the clinical application of biodegradable alloys. Here, a multifunctional hydrophilic selenium-containing polyurea (SePUA) is designed with a tunable ratio of selenium-containing groups to hydrophilic groups. The SePUA can form stable Se-metal coordination, achieving controlled ion release of biodegradable alloys, and simultaneously leverages the biological functions of selenium to realize immuno-osteogenic synergistic modulation. Single-cell RNA sequencing reveals that SePUA accelerates the shift from acute inflammation to a healing-permissive immune environment. It reduces early Zn-2(+) release and achieves controllable selenium release, thereby suppressing neutrophil chemotaxis and maturation, recruiting macrophages, activating the KEAP1-NRF2-SEPP1 pathway to decrease intracellular reactive oxygen species (ROS) and drive M2 polarization. Simultaneously, SePUA upregulates the stemness-associated NR2F2-SOX2/NANOG axis in MSCs and enhances their osteogenic differentiation capacity, thereby promoting new bone formation around the implants. This work develops a facile, multifunctional bioactive hydrophilic SePUA for the coating of biodegradable alloys that integrates ion release control, immunomodulation, and osteogenesis, offering critical support for the clinical translation of biodegradable alloys.

Radioprotection remains a critical challenge in biomedicine and space exploration. As the fundamental building blocks of organisms, amino acids are gaining momentum in chemical design for in vivo radioprotection, yet their low atomic number (Z) and rapid metabolism restrict practical applications. This study addresses these limitations through the melanin-inspired polymerization of the higher Z-tellurocysteine. Motivated by the superior catalytic activity and higher Z of tellurium over selenium in both enzyme mimics and microbial systems, we hypothesized that tellurium-containing amino acid polymers could demonstrate enhanced photon interaction and radical scavenging. The exceptional nucleophilic substitution capability of tellurocysteine, which arises from its soft polarizable character, drives its bisubstitution with o-benzoquinone. The heteroatom enrichment and high-Z effect make the novel materials far exceed natural amino acid polymers in radiation shielding. The melanin-mimetic polymeric structure demonstrates enhanced radiation stability and broad-spectrum free radical scavenging ability. Following oral administration, the tellurocysteine-based polymers achieve prolonged intestinal retention, mitigating radiation-induced intestinal injury. Our work establishes a new paradigm in amino acid engineering, demonstrating how strategic non-metallic heavy atom incorporation can transform biological molecules into advanced radioprotective materials. This approach opens possibilities for developing next-generation, amino acid-derived agents with tailored pharmacokinetics and multifunctional activity.

ABSTRACT Dynamic covalent chemistry has enabled adaptive behavior in organic polymer networks and molecular crystals, yet analogous control in inorganic crystalline solids remains largely unexplored. Here we show that elemental selenium can operate as a dynamic covalent inorganic crystal, whose architectural and functional adaptability arises from dynamic covalent Se─Se bonds within the trigonal selenium backbone. External mechanical (or optical) stimuli drive Se─Se bond cleavage and reformation, mediating structural reconfiguration of the crystalline framework. Embedding selenium in a crosslinked polymer matrix creates a mechanically programmable environment that exerts real‐time and persistent mechanical signals in situ. Under this chemo‑mechanical coupling, crystal branching frequency and three‐dimensional architecture respond to matrix stiffness and external light, and these translate directly into tunable dielectric behavior in polymer‐selenium composites. This work expands dynamic covalent chemistry from organic to inorganic crystalline materials, and reveals dynamic covalent inorganic crystals as a new class of adaptive materials.

The construction and integration of curvature govern the structure and function of materials based on 2D sheets, yet achieving ultrafast and scalable curvature programming remains a major challenge. We rapidly generate large stress mismatches by combining an ultrafast stress-relaxing diselenide-containing polyurethane with an ultraslow stress-relaxing disulfide-containing polyurethane. Coupled with modular components and compression, this mismatch enables localized, directional loading of high stress with excellent scalability. Using this strategy, 2D polymer sheets achieve 180° bending within 10 s of UV irradiation, yielding a curvature-programming rate 15-fold faster than state-of-the-art methods. Furthermore, origami modules, which display a 37-fold enhancement in compressive performance, can be obtained through mass production and assembled into complex 3D architectures. This rapid, high-curvature programming approach offers efficiency, mechanical robustness, and scalability, advancing the practical deployment of origami-based metamaterials.

The fusion and fission of cellular membranes are fundamental dynamic processes in living systems, the precise regulation of which largely depends on the redox microenvironment. Constructing biomimetic model systems capable of reversible regulation under mild conditions is of great significance for understanding membrane dynamics. In this work, a class of amphiphilic block copolymers containing selenium/tellurium (Se/Te) motifs was designed and synthesized, which can self-assemble in aqueous solution into stable nanostructures. Under oxidative conditions, tellurium sites form Te-O-Te covalent crosslinks, driving inter-assembly connections and hierarchical structural evolution; in contrast, under reductive conditions, these crosslinks can be cleaved, allowing the system to revert to its initial dispersed state and exhibiting excellent reversibility. Furthermore, a fluorescence "turn-on" compartmentalized reaction model demonstrates that oxidative stimuli enable inter-compartmental substrate mixing and trigger the reaction. This work establishes a redox-controllable dynamic assembly system that recapitulates key features of redox-regulated membrane fusion and fission, providing a biomimetic platform for understanding membrane dynamics and a molecular design strategy for constructing adaptive compartmentalized reaction systems.

Periodontitis causes progressive destruction of both periodontal soft and hard tissues, leading to tooth loss and functional impairment. Conventional treatments, such as mechanical debridement and antibiotic therapy, are often insufficient for effective regeneration due to persistent local inflammation and the complex architecture of gingival and alveolar bone defects. In this study, we developed a thermo-responsive, injectable hydrogel composed of hydroxybutyl chitosan (HBC) and selenium-containing polyurethane (SePU), which undergoes rapid sol-gel transition at physiological temperature. SePU/HBC not only facilitated the adhesion and migration of human gingival fibroblasts but also effectively inhibited osteoclast formation and resorptive activity. Mechanistically, it efficiently scavenged intracellular reactive oxygen species and activated an ATF6-mediated protective unfolded protein response, thereby re-establishing endoplasmic reticulum function and preventing apoptosis. By integrating targeted stress modulation with bifunctional cellular regulation, SePU/HBC offers an innovative strategy for coordinated periodontal tissue regeneration, offering potential benefits in both early inflammation control and late-stage defect repair.

Silicone materials are indispensable across industrial and consumer domains, yet their robust Si-O-Si backbones resist depolymerization and typically require chemical crosslinking to attain elastomeric properties. Here we report a modular synthesis to access non-carbon heteroatomic backbone polymers (PTeSiO) featuring periodic Si-O-Te-O linkages. This copolymerization merges Si-O and Te-O as building blocks, enabling a one-pot, room-temperature aqueous route to high-molecular-weight, transparent elastomers with precise control over backbone composition and side-chain architecture. Main-chain engineering via redox-labile Te-O motifs enables chemoselective backbone scission under mild reductive conditions, affording on-demand polymerization-depolymerization cycles with efficient monomer recovery. The semi-flexible backbones and chain entanglement impart elasticity, thermoplastic processability, and side-chain-dependent mechanical performance. This work establishes a modular and general chemical strategy for creating non-carbon heteroatomic backbones as a design principle for sustainable and recyclable silicone materials.

Shape morphing materials possess an enhanced adaptability to diverse environments while minimizing material usage and energy consumption. The main challenge in this area lies in applying the driving force and stimuli in a rapid, precise, and cost-effective manner to enhance the efficiency of mass production with more variety, lower cost, and better sustainability. This perspective summarizes methods and strategies developed recently for polymer shape morphing via dynamic chemistries, from the traditional method using externally applied force to unconventional preloaded force or force mismatch. We further highlight representative efforts and contributions from our research group in this area. These newly developed strategies strive to balance the competing demands of scalability, transformation efficiency, and structural fidelity and complexity of the resulting architectures, thereby extending shape morphing into previously inaccessible regimes.

ABSTRACT Diabetic wound healing impairment, a common complication of diabetes, has limited clinical treatment options and poor therapeutic outcomes, causing significant physical pain and psychological burden for patients. This study aims to accelerate wound healing by modulating cellular stress responses, offering a safe and efficient new therapeutic strategy. Herein, a selenium‐containing polyurethane (SePU) thermo‐sensitive hydrogel was synthesized, and its mechanism for promoting diabetic wound healing by activating the unfolded protein response (UPR) was elucidated. Hydroxybutyl chitosan (HBC) offers a more convenient application for SePU, with its high hydroxybutyl substitution enabling the hydrogel to undergo a rapid sol–gel transition at physiological temperatures. In vitro experiments showed that SePU thermo‐sensitive hydrogel (SePU/HBC), at appropriate concentrations, significantly promoted the proliferation, spreading, migration, and adhesion of human skin fibroblasts (HSFs), while inhibiting inflammation. In vivo diabetic mouse model, SePU/HBC exhibited a significant wound‐healing effect, promoting re‐epithelialization, collagen formation and maturation. Mechanistic studies revealed that SePU/HBC alleviated endoplasmic reticulum stress under hyperglycemic conditions by activating the UPR‐related gene ATF6 to alleviate endoplasmic reticulum stress (ERS) and inhibit apoptosis. This study offers a novel strategy for diabetic wound treatment using SePU/HBC, which activates the UPR and inhibits apoptosis, demonstrating promising clinical applications for wound healing.

Can artificial polymer materials exhibit the characteristic of "evolution" over time, similar to biological tissue? The limitations arise from their inherently static nature and the absence of dynamic structures. A strategy is proposed for designing polymer materials whose phases and mechanical properties can be continuously transformed and enhanced temporally. Specifically, the polymer phases experience a sequence of transitions involving generation, separation, and fusion. Each period enhances mechanical properties in distinct and significant ways, demonstrating a mechanical evolution. This evolution is initiated through in situ polymerization within the material and can be precisely controlled using visible light. Applied to a hydrogel system, this approach achieves a record-breaking increase in Young's modulus by over 2400-fold, from 18.5 kPa to 44.5 MPa. The findings highlight the potential for tailoring mechanical properties on demand and constructing metamaterials with multilevel moduli and composite architectures.

The escalating utilization of ionizing radiation across medicine and industry underscored the paramount urgency of effective radioprotective materials. Conventional materials such as lead and concrete are widely used, and lead-free materials have also emerged to solve the problems of cumbersome and toxic lead, such as metal-containing micro/nano materials and polymers. Nevertheless, there is still a significant challenge in meeting the urgent need for lightweight and biocompatible alternatives. To tackle this challenge, this work utilizes molecular engineering of melanin to develop a panel of metal-free melanin materials with enhanced conjugation, heightened physical shielding against radiation and effective antioxidant properties. Furthermore, engineered melanin materials demonstrated in vivo γ-ray protection, increasing mice survival from ~12% to 100% after 6 Gy total body irradiation.

Despite advances in immunotherapy, its efficacy against postoperative glioma recurrence remains limited. Here, we present a neoantigen-targeting peptide nanoshield that synergizes with glioma resection to eliminate residual tumor cells and prevent relapse. The nanoshield architecture is constructed using a multicationic protein (MCP) as the structural scaffold, which is assembled with the mutated isocitrate dehydrogenase 1 (muIDH1) neoantigen. The nanoshield vaccine enables lysosome-escaping muIDH1 delivery and inflammasome-mediated immune activation, generating polyfunctional CD8+ T cells. The results demonstrate superior and durable immunogenicity, with a 3-fold increase in CD8+ T cells and a 6-fold in vivo retention profile compared to free peptide controls, respectively. This leads to significant reduction in tumor size in prophylactic and therapeutic glioma models. Notably, it achieves over 40% improvement in terms of postoperative recurrence-free survival through combining the nanovaccine with antiprogrammed death-1 (aPD-1) therapy. Our immunotherapeutic strategy induces potent antitumor immunity, offering promising clinical potential for postoperative management.

Fluorescent polymeric materials have recently gained significant attention in diverse fields, including biological imaging, luminescent sensing, encryption, and anti-counterfeiting. However, the patterning of many materials mentioned above has primarily been achieved through soft lithography technology using ultraviolet light, which can cause unnecessary damage to the materials and is limited by a shallow penetration depth. Herein, we introduce oligo(p-phenylene vinylene) derivatives (cyano-OPVs) as fluorescent molecules into diselenide-containing polyurethane (PUSeSe). Upon swelling, OPV molecules transition from aggregates to monomers, resulting in a blue shift in fluorescence spectra. By leveraging diselenide metathesis within the material, we successfully stabilized the monomeric state of OPV, enabling the inscription of green fluorescent images in illuminated regions, distinct from the original orange emission of the aggregated state. These materials can be effectively patterned within ten minutes under gentle and harmless visible light illumination. This visible light-induced fluorescence patterning method offers a convenient approach for designing advanced anti-counterfeiting materials with broader applications.

In recent decades, significant advancements have been achieved in the field of polymer self-assembly. Among various polymer assemblies, the unique chemical properties of selenium and tellurium have established a robust foundation for the development of functional polymer assemblies that incorporate these elements. Polymer assemblies containing selenium and tellurium have garnered significant attention due to their sensitive responsiveness to stimuli and their precise biological functions. In this review, we summarize the research findings on selenium- and tellurium-containing polymer assemblies. The article elaborates on the applications of selenium- and tellurium-containing polymer assemblies in redox responsive materials, gamma-ray (γ-Ray) responsive materials, light responsive materials, and coordination responsive materials. Finally, the research on selenium and tellurium-containing polymer assemblies lays a methodological foundation for the development of new functional materials driven by elemental characteristics.

Intelligent adaptive materials constitute a vital component of modern advanced material systems.Compared to other stimuli such as temperature and pH, light exhibit advantageous characters including cleanliness,renewability, and high spatiotemporal resolution. As a result, light-responsive intelligent adaptive materials have witnessed significant development in recent years, both in fundamental research and technological applications.They are now widely applied in frontier fields such as manufacturing, optoelectronics, and bio-nano applications.Polymer topology network, as a decisive factor in material properties, directly influences the material intelligence level through its dynamic reconfiguration capability. This review begins with systematically summarizing the photochemical/physical reaction mechanisms of commonly used photosensitive moieties in light-responsive materials. It then focuses on the multi-level response processes involved in light-controlled topological [Graphics] transformations:through analysis of representative cases, the review elucidates the modulation mechanisms of photo-induced behaviours in photosensitive groups (including isomerization, dissociation/recombination) on material topological structures across multiple molecular-scale aspects-including polymer chain segments (e.g.,alteration of crosslinking density), network architecture (e.g., three-dimensional topological reconfiguration),network integrity (e.g., chain scission and degradation), and interface engineering. Finally, the review analyzes current bottlenecks in light-controlled topology reconfigurable materials-such as insufficient response rates, low efficiency, and challenges in mitigating phototoxicity and biotoxicity, and envision their applications in fields like adaptive coatings and programmable soft robotics

Extreme ultraviolet (EUV) lithography has become the essence of advanced semiconductor manufacturing processes. While enabling smaller feature sizes, EUV lithography imposes increasingly stringent requirements on the comprehensive performance and stochastic defect suppression of photoresist. The widely recognized strategy to minimize these defects is a material that integrates high EUV absorption and energy utilization into a homogeneous system based on molecular building blocks-the ideal formulation for EUV photoresist. However, achieving these integrated characteristics within a single molecule has remained an unresolved challenge. Here, we address all these requirements by polytelluoxane using an organic telluride monomer polymerized via Te─O bonds. This polymeric photoresist, operating through a main chain scission mechanism, demonstrates high-performance positive-tone lithography. Attributed to this ideal formulation, our photoresist achieves a comprehensive 18-nm line width at a dose of 13.1 mJ/cm2 with a line edge roughness of 1.97 nm. We believe that this strategy establishes a framework for the design of next-generation EUV photoresists.

Titanium implants, although widely used in clinical applications, are still facing challenges of inflammation and compromised osseointegration, especially in diabetic and osteoporotic patients. Existing titanium modification techniques are confronted with problems of complicated manufacturing processes, poor bonding strength, and difficulties in dual regulation of immunity and osteogenesis. Here, a selenium-containing polyurethane (SePU) is synthesized and modified the titanium surface with SePU via a convenient soaking method. Notably, SePU formed a coordination bond with Ti, induced M2 polarization of macrophages, promoted osteogenic differentiation, inhibited osteoclast formation, and enhanced peri-implant bone formation in diabetic and osteoporotic rats. Tissue RNA-sequencing and validation reveal SePU regulated NRF2-mediated oxidative stress by upregulating GSTM3, enhancing ROS scavenging, reducing oxidative damage, thus creating a pro-regenerative immune microenvironment. These findings provide a novel approach using the essential element selenium to solve intractable clinical bottlenecks of titanium implants, especially for systemic backgrounds unfavorable to osteogenesis, such as diabetes and osteoporosis.