Understanding the interfacial interactions between covalent organic frameworks (COFs) and polymer matrices remains a critical challenge for the development of high-performance mixed matrix membranes (MMMs) for gas separation and mechanical robustness. Here, we systematically study MMMs made of highly crystalline and monodispersed 2D PDA-HTA COF and 3D-Py-COF with commonly used PIM-1 and 6FDA-DAM as matrix. A comprehensive gas permeation, electron microscopy and mechanical properties analysis revealed that the incorporation of these porous fillers universally decreased gas permeability, which is mainly due to polymer chain infiltration. The large pores of the 2D COF promote deep polymer penetration, leading to pore blockage and the formation of a rigidified, selective interfacial region. In contrast, the small pores of the 3D COF largely prevent infiltration, resulting in a more classic, weakly-adhered filler. Crucially, this same infiltration mechanism dictates the composite's mechanical properties, inducing complex plasticization and reinforcement phenomena that are highly dependent on the specific COF-polymer pairing. These findings offer mechanistic insights and design principles for optimizing the interface in MMMs, paving the way for advanced membranes with both excellent separation and mechanical performance.

Deploying aqueous Zn batteries as next-generation energy storage systems requires simultaneous improvements in calendar and cycle life, which remain hindered by side reactions such as corrosion and dendrite formation. While recent studies have enhanced cycling stability to some degree, they have largely overlooked calendar life and rarely provided quantified insights into corrosion-induced capacity loss. In this work, we introduce the nonionic surfactant fatty alcohol polyoxyethylene ether (AEO) into a Zn(OTf)₂-based electrolyte to improve calendar and cycle life by inhibiting Zn corrosion and optimizing Zn deposition homogeneity. Owing to its amphiphilic molecular structure, AEO forms a zinc-philic and hydrophobic adsorption layer and spontaneously regulates Zn²⁺ solvation/desolvation structure through enhanced interactions with lone pair electrons, mediating corrosion pathways by limiting solvated and interfacial water molecules. Therefore, the AEO electrolyte suppresses corrosion current by 74.9% and Coulombic efficiency loss by 18.48% after 24-hour aging in a Zn||Cu configuration. Furthermore, a Zn-powder-based full cell with a low negative to positive (N/P) ratio of 2.5 achieves a high capacity retention of 83.37% over 100 cycles, including 20 times of 24-hour intermittent aging. This work sheds light on the mechanism of the surfactant-modified electrolyte and offers a scalable approach for practical long-life aqueous Zn batteries.

Perylenediimide (PDI) radical anions have been extensively investigated and applied in photothermal therapy. However, the current PDI radical anions show poor photothermal conversion efficiency owing to the intrinsic ambient instability and unfavorable aggregation of PDI units, restricting their subsequent practical application. Herein, an N-heterocyclic carbene (NHC) metallacycle was employed to fabricate a discrete π-stacked PDI dimer (PDI₂), which was subsequently reduced to the PDI radical dimer (PDI₂-RD) by glutathione (GSH). The well-defined dimer packing endows PDI₂-RD with robust ambient stability over 30 days, suppresses the quenching of PDI radical anions, and facilitates intramolecular electron transfer. As a result, the PDI₂-RD achieves a photothermal conversion efficiency of 84.9%, which is 13.1 times higher than that of the monomeric PDI radical anion under 808 nm laser irradiation. For in vitro and in vivo experiments, the GSH-induced PDI₂-RD within tumor cells showed excellent photothermal therapeutic efficacy as well as good biocompatibility. This study presents an alternative strategy to develop stable and discrete radical dimers for efficient photothermal therapy.

Three-dimensional covalent organic frameworks (3D COFs) have attracted significant research interest due to their unique structures. However, the interpenetration phenomenon exists in most 3D COFs, which compresses pore space, reduces effective pore volume and specific surface area, and thus limits the performance of these materials in fields such as adsorption and catalysis. Therefore, developing non-interpenetrated 3D COFs is challenging yet of great significance. In this study, a symmetry reduction strategy was employed to construct a jca topological 3D COF (JUC-643) with a unique double-helix structure. Powder X-ray diffraction (PXRD) and topological analysis confirmed it as a non-interpenetrated [4+3(+2)]-c net, overcoming the interpenetration tendency of traditional [8(+2)]-c or [6(+2)]-c net. Benefiting from the non-interpenetrated characteristic, the framework retains sufficient pore space, providing ample accommodation for molecular adsorption. At 298 K and 1 bar, JUC-643 exhibits adsorption capacities of 2.47 mmol·g^–1 for C₃H₈ and 3.32 mmol·g^–1 for n-C₄H₁₀. This study not only offers a generalizable method for the design of non-interpenetrated 3D COFs but also confirms their application potential in light hydrocarbon adsorption.

Quantum dot color conversion (QDCC) technology holds significant promise for next-generation virtual reality/augmented reality displays due to its low cost, high efficiency, and high resolution. However, its advancement is impeded by two primary challenges: the need for high blue light absorption and photo conversion efficiency, and the difficulty of achieving high-resolution patterning of the color conversion layer. This study addresses these challenges by developing a novel bis(2-methacryloxyethyl) phosphate (BMEP)- based photoresist incorporating a high concentration (30 wt%) of perovskite quantum dots (PQDs). The marked superiority of BMEP fundamentally arises from its unique dual functionality. The phosphate group in BMEP exhibits strong affinity for undercoordinated Pb²⁺ sites on nascent PQD surfaces, providing exceptional passivation of surface defects and effectively suppressing ion migration. Concurrently, the photopolymerizable methacrylate end groups of BMEP enable the formation of a densely cross-linked network upon UV exposure, which creates a pronounced spatial confinement effect, physically restricting uncontrolled growth and agglomeration of PQDs. By optimizing exposure time, anti-solvent selection, and annealing parameters, monodisperse PQDs were obtained, resulting in a high blue-light absorption of 99.45% in a 6.3 μm thick film and a high photo conversion efficiency exceeding 41%. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses confirmed that BMEP suppresses PQDs growth distortion through spatial confinement. Using in situ photolithography, red, green, and blue pixel arrays were fabricated, exhibiting photoluminescence quantum yield larger than 80% and covering 91.37% of the Rec. 2020 color gamut. This work introduces a novel strategy for designing high-concentration PQDs photoresists, advancing the development of high-resolution, wide-color-gamut QDs displays.

Advanced fluorescent anti-counterfeiting technologies have garnered widespread attention due to the insufficient security of traditional anti-counterfeiting methods. Addressing the ongoing demand for more secure anti-counterfeiting methods, we pioneered a simple and effective strategy for the on-demand fabrication of CsPbBr₃ nanocrystalline patterns via direct laser writing on CsPbBr_1.8I_1.2 perovskite thin films. The resulting films were comprehensively characterized in terms of morphology, structure, elemental composition, and optical properties. Our investigation reveals that mild laser irradiation induces a reaction between iodide ions and ambient oxygen, leading to iodide depletion and local bromide enrichment with replacing the lattice positions of these iodide vacancies. This halide exchange facilitates the formation of CsPbBr₃ nanocrystals, which exhibit bright green luminescence under 365 nm UV excitation. At higher laser intensities, blue luminescence can also be achieved, attributed to the smaller crystal sizes. By leveraging programmable design, we successfully generate green- and dual-emissive patterns within otherwise non-luminescent CsPbBr_1.8I_1.2 films, offering a promising route for optical anti-counterfeiting applications. This work demonstrates a novel, laser-assisted technique for the controlled creation of fluorescent security features.

Organosilicon compounds have garnered significant attention due to their unique physicochemical properties and broad applications in pharmaceuticals, materials science, and synthetic chemistry. The construction of C–Si bonds represents a fundamental challenge in this field, with silylboronates emerging as particularly versatile reagents. Conventional catalytic systems heavily rely on precious transition metals (e.g., Pd, Pt, Au) to activate Si–B bonds through oxidative addition or transmetalation pathways. While effective, these methods suffer from limitations in sustainability, cost, and functional group compatibility. The emergence of photoredox and electrocatalytic approaches has opened new avenues for metal-free Si–B bond activation. These strategies enable controlled generation of silyl radicals under mild conditions through single-electron transfer processes, including anodic oxidation or photoinduced electron transfer. This paradigm shift has facilitated diverse radical silylation transformations, such as hydrosilylation and radical-mediated functionalization. Despite these advancements, the integration of silylboronates with photocatalytic Truce-Smiles rearrangements remains unexplored. Herein, we report a visible-light-promoted tandem silylation reaction that addresses this gap. Using silylboronates as silicon sources, our methodology proceeds via a novel Truce-Smiles rearrangement pathway to efficiently construct two distinct types of silylated products from methacrylamide substrates. The optimized reaction conditions employ a photocatalyst and operate at ambient temperature without stoichiometric oxidants, demonstrating excellent functional group tolerance, broad substrate scope, and scalability. The practical utility of this protocol is further verified through successful late-stage functionalization of complex drug molecules. This work not only provides a general strategy for C–Si bond construction but also underscores the potential of photoredox catalysis in expanding the toolbox for sustainable, metal-free synthetic organic chemistry.

Allylic sulfones represent important structural motifs frequently found in bioactive molecules and serve as versatile synthetic intermediates. Consequently, the development of efficient synthetic routes to these valuable scaffolds remains a significant and ongoing pursuit in chemistry. Conventional synthetic methods often rely on noble-metal catalysts or pre-functionalized substrates and are predominantly limited to the formation of allylic aryl sulfones. Recently, multicomponent sulfonylation strategy involving sulfur dioxide insertion has emerged as an attractive alternative. However, existing approaches within this paradigm generally still require pre-functionalized alkene substrates, and general examples of multicomponent sulfonylation reactions that employ readily available alkenes via SO₂ insertion to afford allylic alkyl sulfones remain scarce. Herein, we report an earth-abundant cobalt metallaphotoredox catalyzed three-component allylic C–H sulfonylation reaction that enables direct and complementary access to allylic alkyl sulfones. This method employs readily available alkenes, DABSO as a sulfur dioxide surrogate, and cyclobutanone oxime esters as radical precursors. Mechanistic investigations reveal that the cobaloxime catalyst plays a dual role, combining photoredox and hydrogen atom transfer (HAT) capabilities, which is critical for driving the transformation. This approach operates without noble-metal catalyst and pre-functionalization, and exhibits operational simplicity, broad functional group tolerance, and high chemo- and regioselectivity. The utility of this methodology is demonstrated through scalable synthesis and late-stage functionalization of pharmaceutical derivatives. This protocol thus provides a novel and complementary route for the direct synthesis of allylic alkyl sulfones from unfunctionalized alkenes.

D- and L-glycero-L-Heptopyranosyl residues are essential structural motifs in glycans and glycoconjugates, yet they remain challenging to obtain from natural sources. Herein, we disclose an efficient protocol for synthesizing D- and L-glycero-L-heptopyranosyl thioglycosides, which are recognized as powerful glycosyl donors. Our strategy pivots on a C1-to-C5 switch strategy, commencing from readily accessible allyl α-C-glycosides. The key transformations include a DBU-catalyzed anomerization of easily available α-C-glycosylethanals, an imidazolidinone-catalyzed α-oxyamination of the aldehydes to install a chiral hydroxy group with high selectivity, and a decarboxylative transformation of the resulting uronic acids into the target thioglycosides. We found that the efficiency of the anomerization step is significantly influenced by the electronic nature of the protecting groups and the conformation of a sugar ring. Intriguingly, the stereoselectivity of the key oxyamination step was found to be independent of the catalyst's chirality. To demonstrate the practical application of this protocol, we synthesized three distinct thioglycosides, including 6-O-methyl-D-glycero-L-gluco-heptopyranosyl thioglycoside, L-glycero-L-galacto-heptopyranosyl thioglycoside and L-glycero-L-manno-heptopyranosyl thioglycoside from the corresponding allyl α-C-glycosides. The ready access to these glycosyl donors paves the way for synthesizing biologically relevant targets, such as Campylobacter jejuni NCTC11168 capsular oligosaccharides, septacidin/spicamycin-type nucleosides, and their analogues.

Cyclodepsipeptides represent a distinctive family of natural cyclic peptides endowed with diverse and potent biological activities, making them promising scaffolds for drug development and agrochemical applications. Incorporation of N-methylated amino acids further enhances their metabolic stability and oral bioavailability by resisting proteolytic degradation. However, the synthesis of such cyclodepsipeptides, especially those containing multiple sterically hindered N-methylated residues, remains a significant challenge for conventional solid-phase peptide synthesis (SPPS) due to inefficient on-resin acylation, sluggish coupling kinetics, and conformational constraints. Herein, we report the first successful application of a novel solid-phase peptide synthesis (SPPS) strategy based on immobilized ribosome-mimicking molecular reactors (RMMRs) for the efficient synthesis of two representative bioactive cyclodepsipeptides: destruxin B (a hexadepsipeptide with two consecutive N-methylated amino acids) and [2S,3S-Hmp]-aureobasidin L (a nonapeptide featuring four N-methylated amino acids). A crucial approach is the use of pre-assembled depsidipeptide building blocks, which mitigate side reactions associated with on-resin esterification, combined with the RMMR platform that accelerates the coupling of sterically hindered residues via an artificial pseudo-intramolecular acyl-transfer mechanism. The linear precursors were efficiently assembled on Oxyma-C RMMR-HMPA resin with high/moderate crude purities (90% for destruxin B, 45% for [2S,3S-Hmp]-aureobasidin L) and much reduced synthesis times (≈15 h and ≈60 h, respectively). Subsequent solution-phase macrocyclization using HATU/DIPEA yielded the target compounds in satisfactory yields (75% for destruxin B, 50% for [2S,3S-Hmp]-aureobasidin L). This robust and time-economic methodology overcomes key limitations of conventional methods, providing a broadly applicable platform for the synthesis of complex cyclodepsipeptides and facilitating future medicinal chemistry exploration of this valuable class of bioactive molecules.

Indenophenanthrenes have remained largely overlooked as photocatalysts because their intrinsically high exciton binding energies and low molar absorption coefficients restrict both light-harvesting efficiency and single-electron transfer (SET) capability. In this work, we introduce a twisted indenophenanthrene derivative that overcomes these long-standing limitations through intentional distortion of its π-conjugated framework. The resulting nonplanar geometry enhances light absorption and substantially decreases electron–hole pair binding energy, thereby enabling efficient photoinduced SET for the first time within this molecular family. This structurally engineered chromophore functions as a robust metal-free photoredox catalyst. Its catalytic performance was validated through a prototypical decarboxylative coupling reaction between α-amino acids and electron-deficient alkenes. Under mild visible-light irradiation, the catalyst delivers the desired C–C bond-forming products in high yields across a broad substrate scope. A wide range of natural and synthetic amino acids, as well as diverse alkene acceptors, are well tolerated, demonstrating the generality and versatility of this newly developed catalyst platform. Mechanistic studies comprising radical trapping, fluorescence quenching, Stern–Volmer analysis, and a series of control experiments collectively provide compelling evidence for an oxidative quenching pathway mediated by radical intermediates. Over-all, this study establishes a modular design principle for engineering the photophysical and electrochemical properties of purely organic photocatalysts through geometric twisting. By demonstrating that twisted indenophenanthrenes can mediate challenging redox transformations under mild, metal-free conditions, this work positions them as a promising new class of sustainable organic photoredox catalysts for advanced synthetic applications.

Biomass-based materials (BBMs), derived from renewable natural resources such as cellulose, hemicellulose, lignin, chitin, and proteins, have recently attracted great attention in the field of sustainable energy storage owing to their intrinsic abundance, structural diversity, and environmental compatibility. BBMs can be transformed into advanced carbon materials and other derivatives through functional design, demonstrating promising applications in various components of rechargeable batteries, including electrode materials, solid-state electrolytes, separators, current collectors, and electrolyte additives. Their tunable pore structures, abundant functional groups, and heteroatom doping enable efficient ion transport, enhanced conductivity, and stable framework. Recent research progress has revealed that biomass derived carbon materials exhibit controllable micro-structures and hierarchical porosity suitable for Li⁺, Na⁺, and K⁺ storage. The introduction of BBMs into solid-state electrolytes has improved ionic conductivity and mechanical robustness through hydrogen-bond networks and inter-molecular forces. Meanwhile, cellulose and chitosan- based separators provide excellent wettability, mechanical strength, and dendrite suppression ability, which promote the development of long- term batteries. However, the poor batch-to-batch repeatability, unsatisfactory oxidation stability at high voltages of BBMs still restrained their practical applications in secondary batteries. This review systematically summarizes the molecular structure and functional groups of different types of biomasses. Then, the influence of nano/micro structures on determining specific utilization of BBMs in different battery systems is mainly discussed. Following this, the key scientific challenges of modulating the structures of BBMs and the gap in their functional realization for high-performance batteries are emphatically discussed. Finally, we provide an outlook on potential structural design strategies and chemical treatment approaches for biomass materials to enhance their electrochemical performance in various roles, which will accelerate the development of these green resources and their practical applications in energy storage.

In recent years, two-photon excited luminescence (TPEL) and multi-photon excited luminescence (MPEL) materials have attracted increasing attention due to their unique nonlinear optical (NLO) properties, particularly in the realm of metal−organic frameworks (MOFs). MOFs, as a type of flourishing framework materials linked by coordination bonds, have distinguished themselves with their outstanding TPEL/MPEL performances, providing innovative tools for the exploration of mysterious nonlinear optics and promising applications. This review systematically introduces the basic mechanisms of TPEL/MPEL materials, emphasizing the role of photoluminescence quantum yield (PLQY), two-photon absorption (TPA)/multi-photon absorption (MPA) cross-sections, and photostability in material design. Then, recent progresses in the rational construction of MOFs with tailored NLO properties is highlighted, including strategies such as linear/tripodal/quadrupodal ligand engineering, guest@MOF host-guest systems, and post-synthetic modifications. These advancements have unlocked diverse applications, such as anti-counterfeiting via 3D coding and patterning, bioimaging with deep-tissue penetration and high spatial resolution, stimulated emission for low-threshold lasing, and optical data storage. Furthermore, the potential challenges in enhancing MOFs’ NLO efficiency, structural stability, and biocompatibility are addressed, and perspectives in the forthcoming development of this field are proposed. The insights presented herein aim to inspire innovative approaches in the design and application of MOF-based NLO materials across disciplines, fostering advancements in photonics, biomedical engineering, and materials science.

The field of TPEL/MPEL and MOF research has been significantly advanced by a group of outstanding scientists. In 1931, Göppert-Mayer made the theoretical prediction of the two-photon absorption (TPA) phenomenon, laying the cornerstone for future research in this area.^[1] Decades later, in 1990, Denk and co-workers developed the first two-photon excitation microscope, which revolutionized imaging techniques in biological and materials science.^[2] In 2012, the Pan group contributed to the development of functional MOF materials by working on lanthanide MOFs with TPEL.^[3] In 2013, the Qian group pushed the boundaries of MOF applications in optoelectronics by developing a two-photon-pumped micro-laser using dye-encapsulated MOFs.^[4] In 2014, the Zhou group achieved a remarkable feat by synthesizing a MOF with a photoluminescent quantum yield (PLQY) of 99.9%.^[5] In 2015, Vittal and co-workers further enhanced the optical properties of MOFs by improving 4PEL via Förster resonance energy transfer (FRET).^[6] In 2017, Fischer and co-workers deepened the understanding of photophysical properties of MOFs by studying intrinsic stimulated emission (STE) and MPEL.^[7-8] In 2022, the Jiang group set a new record by achieving the highest TPA action cross-section value of MOFs to date.^[9] In the same year, Wang and co-workers introduced interpretable machine learning techniques to TPA research, opening up new avenues for data analysis in this field.^[10] More recently, in 2024, the Bu group provided new insights into the TPA process by investigating its mechanism under low-power density non-coherent excitation.^[11] Collectively, these contributions have significantly propelled the field forward.

Inorganic ionic compounds are widely existed in nature and applied in construction, energy, biomedical and optical fields. However, the inherent ionic bonding characteristics lead to brittle fracture of these inorganic materials under mechanical force, which significantly limits their application scopes. Overcoming the inherent brittleness of these materials represents a long-standing challenge in chemistry and materials science. In recent years, significant advances have been made to turn inorganic materials into flexible ones. In this review, we summarize the emerging strategies for enhancing the flexibility (e.g., deformability, resilience, plasticity, ductility, etc.) of inorganic materials composited by inorganic ionic compounds, by the regulation of bulk solid phase structures and morphologies. For the regulation of bulk solid phase structures, specific strategies involve regulating ionic bonding and slip systems, alongside leveraging dynamic phase transition. Among these, modulating ionic bonds reduces the stiffness of inorganic ionic materials by weakening the interactions between ions, thereby enhancing their moldable ability. Regulating slip systems improves ductility and plasticity by increasing dislocation density and the number of effective slip systems while maintaining the integrity of structure to facilitate slip. Utilizing dynamic phase transition of materials enhances plasticity by dissipating stress through stress- or thermally-induced dynamic cyclic phase transformations. For the regulation of morphologies, approaches focus on constructing nanowires, sub-1 nm architectures, and molecular-scale structures. High aspect ratios and amplified surface effects endow one-dimensional nanowires with exceptional bending flexibility. This feature becomes even more pronounced in sub-1 nm and molecular-scale structures, even imparting polymer-like characteristics. In this review, we aim to deepen the fundamental understanding in turning brittle inorganic ionic compounds to flexible one from a structural-property relationship view, and creates avenues for their potential applications in structural materials, flexible electronics and novel biomaterials.