In E. coli, the committed step of proline biosynthesis is initiated by γ-glutamate kinase (GK); however, the regulatory logic governing this enzyme remains poorly understood. E. coli GK (EcGK) possesses an enigmatic C-terminal PUA domain—a motif historically linked to RNA binding but uncharacterized in this context. Here, we demonstrate that EcGK forms metabolic filaments and further assembles into four-stranded metabolic cables. Cryo-EM structures of EcGK filaments reveal two assembly interfaces: one analogous to the eukaryotic P5CS “hook” motif and a novel interface mediated by the PUA domain. Filament formation hinders substrate binding, whereas higher-order cable assembly introduces additional cooperativity in substrate binding. Moreover, we resolve the first proline-bound EcGK structure, revealing the function of the PUA domain and the E135-D148 loop in proline feedback inhibition. Thus, the PUA domain plays dual roles in EcGK regulation: it drives filament/cable assembly to reshape substrate binding kinetics, and also facilitates the E135–D148 loop to enable high sensitivity to proline feedback inhibition. In E. coli, the PUA domain thus modulates proline biosynthesis within physiological ranges of substrates and products.

In situ identification and spatially resolved analysis of multicomponent species on complex heterogeneous surfaces remain formidable challenges in surface science, advanced manufacturing, and cultural heritage conservation. Although surface-enhanced Raman scattering (SERS) provides highly sensitive molecular fingerprints, existing platforms often struggle to simultaneously achieve robust interfacial contact and discriminable responses on rough, porous, and compositionally heterogeneous solids. Here, we report a programmable interfacial energy-alignment strategy by integrating a core–shell plasmonic metal-organic framework (MOF) heterojunction, Fe₃O₄@SiO₂@UiO-66(X)@Ag triangular nanoplates (Ag TNs), into an injectable poly(vinyl alcohol) (PVA) microgel matrix to construct a self-adaptive SERS chip. The microgel fills surface asperities and establishes semipermeable conformal contact. Upon dehydration, it locally densifies interfacial nanogaps and reconstructs hotspot networks, thereby promoting more effective interfacial coupling within accessible pores and cracks while improving signal stability and reproducibility. Meanwhile, ligand engineering of UiO-66(X) modulates the interfacial electronic structure and favors phase-dependent charge-transfer-assisted enhancement, whereas tuning the tip sharpness of Ag TNs regulates localized surface plasmon resonance (LSPR) coupling under different excitation wavelengths. Excitation- and ligand-controlled SERS experiments, together with density functional theory calculations, provide an electronic-structure rationale for the observed preferential responses and support the involvement of cooperative electromagnetic and charge-transfer-assisted enhancement contributions. As a result, the chip enables phase-resolved identification and spatial mapping of corrosion products in model multilayer systems, as well as low-disturbance in situ analysis and interval-based corrosion-state estimation of excavated bronze artifacts. This work provides a general materials-design framework for programmable interfacial energy-level regulation toward molecular sensing and chemical imaging on complex solid surfaces.

Chronic wounds remain a major clinical challenge due to persistent inflammation, excessive oxidative stress, and impaired tissue regeneration. Herein, we developed a multifunctional hydrogel dressing (GX/ML) by integrating a reactive oxygen species (ROS)-responsive dynamic borate ester cross-linking network with electrocatalytic MXene nanosheets and anti-inflammatory luteolin. The hydrogel enables real-time monitoring of wound inflammation through electrochemical sensing of H₂O₂ levels, while on-demand drug release is triggered by either high ROS or near-infrared irradiation. In vitro and in vivo results demonstrated exceptional ROS-scavenging capability, efficient antibacterial activity (>96% against S. aureus and E. coli), and promotion of macrophage polarization toward the pro-healing M2 phenotype. In a diabetic mouse wound model, the GX/ML hydrogel accelerated wound closure (98.1% healing rate by day 19), enhanced angiogenesis, collagen deposition, and re-epithelialization, and modulated immune responses via cytokine signaling pathways (e.g., NF-κB and NOD-like receptor pathways). Transcriptomic analysis confirmed regulation of genes related to immune inflammation and tissue remodeling. This work provides a synergistic strategy through a smart hydrogel platform that integrates real-time inflammatory monitoring with condition-triggered drug release, offering a feedback-responsive approach for chronic wound management.

Chiral organic thin films are emerging as key materials in advanced optoelectronic and chiroptical technologies, where the straightforward, solution-processed fabrication of chiroptically active neat films from small π-conjugated helical molecules is highly desirable for sustainable and scalable device integration. However, in such densely packed systems, the intrinsic chiroptical response is often compromised by macroscopic anisotropies (e.g., linear dichroism and birefringence) and aggregation-induced effects, which obscure genuine molecular signatures and induce or alter chiral exciton coupling. Here, we demonstrate that a readily accessible and conformationally flexible helically chiral boron-dipyrromethene dimer (helicoBODIPY) platform enables the reproducible fabrication of robust solution-processed neat thin films exhibiting a unique behavior: chiroptical isotropy while retaining the characteristic molecular chiroptical response arising from intramolecular chiral exciton coupling. Through systematic structural tuning, these systems exhibit enhanced electronic circular dichroism (ECD) and circularly polarized luminescence in solution. Remarkably, the sharp ECD couplets and absorption dissymmetry values measured in the corresponding films closely reproduce those observed in solution, indicating minimal contribution from anisotropic contributions and negligible perturbation of excitonic interactions in the condensed phase. These unique findings point to helically flexible helicoBODIPYs as an excellent molecular platform that bridges molecular design and thin-film performance, offering a potential tool for disentangling aggregation effects in chiral thin films and advancing the rational design of chiral organic materials with predictable chiroptical properties.

Hydrogels with rapid mechanical energy-dissipation capability are highly desirable for protective and shock-absorbing applications. However, conventional systems often suffer from irreversible network damage, slow recovery, and mechanical fatigue. Herein, we report a biodegradable supramolecularly crosslinked polymer hydrogel (AGK) engineered through the synergistic integration of boronate ester covalent networks and G4-quartet supramolecular assemblies. The coupled covalent–supramolecular interactions promote reversible network dissociation and adaptive molecular reorganization under mechanical stress, enabling rapid self-healing, enhanced structural integrity, and efficient energy dissipation. The AGK hydrogel withstands compressive loads up to ∼5.4 kg, significantly outperforming the pristine biopolymer hydrogel (∼2.9 kg). Dynamic impact analyses reveal a remarkably low coefficient of restitution (∼0.21), substantially lower than those of conventional polymeric materials, demonstrating superior impact attenuation and rapid mechanical energy dissipation. Consequently, the hydrogel effectively protects fragile objects from both static compression and free-fall impact damage while maintaining mechanical resilience over repeated damage–recovery cycles. This work establishes a sustainable supramolecular engineering strategy for designing adaptive self-healable hydrogels with efficient energy-dissipation capability, offering promising opportunities for advanced protective, impact-mitigating, and mechanically adaptive soft materials.

Hybrid glasses have emerged as a promising class of functional materials with tunable physicochemical properties, yet systematic anion-size engineering to modulate glass-forming ability (GFA) remains challenging due to the lack of well-defined comparative platforms. By assembling the (4-fluorobenzyl)(triphenyl)phosphonium cation (FBTPP⁺) with tetrahedral cadmium(II) anions, we present four new hybrids, (FBTPP)₂[CdX₄] (X = Cl⁻, Br⁻, I⁻, NCS⁻ for 1–4), forming a textbook-style comparative system to elucidate crystal-glass phase transformations. This series enables synergistic control over core properties: a centrosymmetric-to-noncentrosymmetric evolution (Pbca → P2₁/c → Cc → Cc), a 146 K melting point depression (515 → 369 K), a decreasing fragility index (41.8 → 30.3), and a marked GFA enhancement (0.70 → 0.83). These systematic trends originate from anion enlargement and electronic polarization, which weaken intermolecular contacts, reduce lattice cohesion, lower the melting barrier, and promote diffuse charge distributions, thus broadening structural relaxation near the glass transition and enhancing kinetic stability against recrystallization. The bulky, charge-delocalized NCS⁻ anion further induces a polar crystal packing with an open, loosened structure and greatly increased molecular separation. We further demonstrate a novel strategy that bypasses the kinetic limitation of recrystallization: a polar glass-ceramic thin film (4-GC) was fabricated under ambient conditions via direct consolidation of its glassy phase with polycrystalline 4 above the vitrification temperature, exhibiting a 2.4-fold enhanced second-harmonic generation response. This work provides a programmable ion-engineering strategy for high-performance nonlinear-optical hybrid glass-ceramics.

Dissociative networks comprising reversible Diels-Alder bonds have received increasing attention due to their potential for end-of-life recyclability. Here, we demonstrate that a tetraphenylethylene-based probe can act as a universal self-reporting additive for scalable Diels–Alder networks, enabling reversible optical monitoring of network conversion and thermal history at loadings below 0.8 wt%. Upon Diels–Alder reaction, suppression of photoinduced electron transfer activates a clear light-blue fluorescence, enabling direct optical tracking of network formation. The luminogen is homogeneously distributed within the polymer matrix and exhibits fully reversible fluorescence upon repeated heating–cooling cycles, reflecting the reversible nature of the crosslinks. Importantly, the fluorescence intensity evolves with Diels–Alder conversion, providing a direct indicator of the network state and its thermal history. This work establishes a general approach for reaction conversion tracking in dynamic covalent polymer networks and offers new opportunities for monitoring processing, self-healing, and recycling of sustainable thermosets.

Photosynthetic biohybrid systems (PBSs), which integrate microorganisms with inorganic semiconductors, offer a sustainable platform for solar-to-chemical conversion. However, most PBSs are hindered by the limited light absorption and inefficient charge separation of semiconductor. Herein, a biohybrid system featuring an intracellular in-situ synthesized CuS/CdS plasmonic nano-heterojunction (CuS/CdS@yeast) is developed for wide spectrum–driven photocatalysis. Regulated by the organism, biogenic CuS/CdS nano-heterojunctions achieve efficient electron-hole separation by forming an S-scheme heterostructure, driven by a substantial electrostatic potential difference. Furthermore, in-situ intracellular synthesis strategy enables a coupling between yeast cells and the nano-heterojunction, allowing photoelectrons of the semiconductor to directly participate in bioenergetic pathways, resulting in a significant elevation of intracellular reduction equivalents (nicotinamide adenine dinucleotide [NADH]) and available energy (adenine nucleoside triphosphate [ATP]), which are essential to sustain microbial biosynthesis. By synergizing a heterojunction with biological components, this biohybrid achieves superior photocatalytic reduction under full-spectrum illumination. Notably, it delivers an ammonia synthesis rate of 93.94 µmol·g⁻¹·h⁻¹ (without sacrificial agents) and a hydrogen production of 3803.47 µmol·g⁻¹, representing ∼13-fold and ∼27-fold enhancements over pure cells. This work presents novel insights into the rational design of efficient biohybrid systems for sustainable biomanufacturing.

Layered double hydroxides (LDHs) are promising photocatalysts but suffer from wide bandgaps and rapid recombination of photogenerated charge carriers, resulting in poor visible-light activity. Conventional metal nanoparticle sensitization represents a useful means to improve the photocatalytic performance of LDHs, while its mechanism is scarcely understood at the atomic level. Herein, we report a sensitization strategy based on interfacial reactions between metal nanoclusters (NCs) and LDHs to enhance visible-light-driven photocatalysis. Au_29-43(SG)_27–37 NCs (SG denotes glutathione) were introduced into the regeneration process of MgAl-based layered double oxides (MgAl-LDOs), where strong electrostatic interactions between positively charged hydroxide layers and negatively charged carboxylate ligands induced cluster motif reconstruction and size conversion into Au₂₂(SG)₁₈ NCs. The resulting Au₂₂/LDH composites exhibit a significantly narrowed bandgap (2.21 eV), extended visible-light absorption up to 561 nm, and 4.3 times increase in specific surface area. These synergistic effects lead to markedly enhanced photocatalytic degradation of methylene blue, achieving 20.3% removal within 120 min under visible light. Radical scavenging experiments demonstrate that H₂O₂ and hydroxyl radicals (·OH) are the dominant reactive species in this system. This work demonstrates an effective route for LDHs sensitization and underscores the critical role of interfacial reconstruction in regulating photocatalytic performance.

Emerging optoelectronic tasks such as night-vision imaging and wearable health monitoring call for near-infrared (NIR) photodetectors that operate without external bias, exhibit minimal dark current, and respond within nanoseconds. Organic photodetectors (OPDs) have yet to meet these benchmarks, hindered by the scarcity of NIR-absorbing molecules and poor control over active-layer crystallinity. Here we report a unified approach that couples molecular engineering, morphology tuning, and trap-state suppression to accelerate charge dynamics in OPDs. Three non-fullerene acceptors-CA1, CA2, and CA3 were constructed by extending the π-backbone of an imidazole-centered core. DFT calculations and single-crystal analyses show that each additional fused ring systematically modulates backbone planarity and intermolecular packing, which in turn governs charge mobility and defect density. CA2 strikes an optimal balance: its moderate rigidity and favorable surface energy match the donor polymer, producing a bicontinuous fibrillar network with low energetic disorder. Conversely, the highly crystalline CA1 readily self-aggregates, introducing grain boundaries that act as recombination centers. Consequently, the PM6:CA2 blends deliver outstanding OPD performance, with a record-low dark current of 2.54 × 10⁻¹² A cm⁻² at zero bias. They also feature a total noise current of 8.51 × 10⁻¹⁵ A·Hz^−1/2, yielding a detectivity peak of 1.08 × 10¹³ Jones (specific detectivity from real noise) at 840 nm. In addition, the devices exhibit a wide linear dynamic range of 167.8 dB and fast transient responses of 307 ns (rise) and 319 ns (fall). The detector enables cuff-free deep-tissue photoplethysmography and a 10 Mbps optical data link, underscoring the potential of imidazole-extended acceptors for sensitive, ultrafast NIR OPDs.

Constructing flexible ultralong room-temperature phosphorescence (URTP) materials is highly attractive yet challenging, as flexible matrices struggle to suppress the nonradiative decay of triplet excitons. Herein, self-protective carbonized polymer dots (CPDs) derived from carbonized polyvinyl alcohol (PVA), were embedded in a gel matrix to create flexible URTP materials. Simply tuning the alcoholysis degree of PVA to 88% and reacting it with ethylenediamine under hydrothermal conditions yields NCD₈₈, which exhibits a phosphorescence lifetime of 1.05 s. This benefits from carbonyl/nitrogen clusters that promote intersystem crossing (ISC) and incompletely carbonized PVA chains that restrain nonradiative decay. This strategy effectively resolves the trade-off between ISC efficiency and triplet exciton stabilization, enabling URTP in PVA-based CPDs. Furthermore, by combining freeze–thaw cycling with a solvent exchange strategy, a PVA-based deep eutectic gel was prepared, exhibiting a URTP lifetime of 0.86 s, along with high tensile strength and high toughness. Thus, this study not only resolves the challenge of nonradiative decay in PVA-based self-protective CPDs via simple alcoholysis regulation, but also successfully integrates URTP properties with high mechanical performance into a single gel system, providing a new strategy for developing flexible URTP materials.

The advancement of organic near-infrared-II (NIR-II) photothermal agents is impeded by complex structural designs and arduous synthetic procedures. While supramolecular charge-transfer complexes (CTCs) offer a facile assembly route, efficient NIR-II-absorbing CTCs remain scarce. Crucially, a fundamental paradox arises: tight planar stacking for narrow-bandgap NIR-II absorption inevitably induces severe aggregation-caused quenching (ACQ), suppressing reactive oxygen species generation and disabling synergistic photothermal/photodynamic therapy. Herein, we identified DBTTF (D₂) as the optimal electron donor through a systematic screening against a TFTQ acceptor. Significantly, the 2A-D₂ assembly with a 2-to-1 acceptor-to-donor ratio was established as the optimal candidate due to its highest molar extinction coefficient by deciphering the stoichiometry-property relationship. Molecular dynamics simulations revealed that this acceptor-rich environment induces looser molecular packing and weaker intermolecular interactions. This unique configuration successfully resolved the ACQ bottleneck, enabling efficient reactive oxygen species generation while maintaining a high photothermal conversion efficiency of 40.3%. Driven by these synergetic effects, 2A-D₂ induced severe mitochondrial dysfunction and DNA damage under 1064 nm irradiation, achieving robust 94.5% tumor inhibition and suppressing pulmonary metastasis. Thus, this study established a robust framework for developing advanced NIR-II CTCs by integrating donor screening with precise stoichiometric engineering to harmonize photothermal and photodynamic modalities for tumor ablation.

The increasing demand for high-speed X-ray imaging requires scintillators with high light yield, rapid decay, and structural stability. Metal halide nanowires (NWs) have emerged as promising candidates due to their distinctive optical properties, high surface-area-to-volume ratio, high light yield, and high spatial resolution. However, their practical application is hindered by complex synthesis routes and performance degradation during the liquid–solid phase transition. Here, using CsCu₂I₃ NWs as a model system, we develop a streamlined low-temperature crystallization synthesis method and further introduce a surface protective agent strategy that significantly enhances scintillation performance. Through the use of tailored protective agents, the photoluminescence quantum yield of NWs increases from 12.78% to 21.65%, while the X-ray light yield improves by approximately ninefold, reaching ∼77,500 photons MeV⁻¹. The optimized scintillator achieves a low detection limit of 59.20 nGy_air·s⁻¹, which is approximately 93-fold lower than the typical dose rate of standard medical X-ray diagnostics. Identical SPA treatment delivers uniform luminescence improvement across zero-and one-dimensional copper halide systems, confirming the generalizable regulatory effect of the proposed ligand coordination framework. This efficient and scalable approach not only advances nanowire-based scintillators but also provides a generalizable pathway for stabilizing solution-processed nanomaterials and accelerating their commercial adoption.

Organic small-molecule phototheranostic agents (OPTAs) with second near-infrared (NIR-II, 1000–1700 nm) absorption show great potential for precise cancer theranostics. However, achieving simultaneous NIR-IIb (1500–1700 nm) emission and high photothermal conversion efficiency (PCE) under low-power 1064 nm excitation remains challenging due to competing radiative and nonradiative decay pathways. Herein, we report a facile molecular design strategy using noncovalent conformational locks (NoCLs) to develop efficient NIR-II excitable OPTAs with both bright NIR-IIb emission and superior PCE. Two A–D–A'–D–A type molecules (NCF and QCF) are synthesized. By introducing S···N NoCLs, QCF adopts a more planar and rigid conformation, facilitating compact J-aggregation and enhanced intramolecular charge transfer. Therefore, QCF nanoparticles (NPs) exhibit a strong NIR-II absorption at 1143 nm, dual emission at 1338/1550 nm, and a high PCE of 75% under low-power 1064 nm laser irradiation (0.3 W cm⁻²). Single-crystal and theoretical analyses confirm that S···N NoCLs promote planarization, suppress nonradiative decay, and strengthen intermolecular interactions. In vivo, QCF NPs enable high-resolution NIR-IIb vascular/tumor imaging and effective tumor ablation with excellent biosafety. This work establishes NoCLs as a generalizable design principle for next-generation NIR-II OPTAs with synergistic optical and therapeutic properties, advancing imaging-guided cancer theranostics.