Innovative approaches to sustainable and high-performance luminescent materials have led to the development of narrowband phosphorescent wood-based composites. By embedding narrowband phosphorescent organic molecules into a natural porous wood matrix, this study introduces a novel material with significant potential for green optoelectronic applications. Specifically, narrowband molecules were designed through low-frequency vibronic coupling to synthesize a kind of coronene derivative (CoDe), which was combined with wood to maintain its narrowband emission characteristics, with an equally impressive small full-width at half-maximum (FWHM) of 11 nm and phosphorescence lifetime of 1.46 s under ambient conditions. This composite not only inherits wood's renewability but also benefits from enhanced triplet exciton stability due to the extensive hydrogen bond network within cellulose. This work paves the way for multifunctional applications in flexible electronics, smart building materials, and advanced lighting systems.

Bufogargarizins are a class of unique 19-norbufadienolides isolated from the venom of Bufo bufo gargarizans. Here we report a concise synthesis of bufogargarizin B from inexpensive, commercially available dehydroepiandrosterone by means of a conformation-controlled skeletal reorganization approach. The synthesis features the rapid construction of the 5/7/6/5 tetracyclic core framework by means of a SmI2-mediated ketone-allylic acetate transannular cyclization, and the installation of stereochemically diverse 5,7- and 7,5-fused ring systems through a biomimetic retro-aldol/transannular aldol cascade reaction. In addition, an efficient, scalable synthesis of 2-pyrone-5-boronate, a key building block for the introduction of the side chain of bufadienolides, has been developed, and the highly functionalized all-cis D ring of bufogargarizin B is installed by means of a series of highly chemo- and regioselective redox transformations. This work vividly demonstrates that conformational control plays a critical role in the precise installation of desired stereocenters in transannular cyclization products.

Molecules bearing a fully heteroatom-substituted phosphorus(V) stereocenter exist ubiquitously in medicines, agroscience and catalysis fields. Due to the lack of efficient and robust catalytic asymmetric methods, approaches to achieve fully heteroatom-substituted phosphorus(V) stereocenters usually rely on conventional chiral auxiliary control and resolution pathways. Recent catalytic protocols are built on tedious stepwise synthesis from complex P(V) precursors. Here, we report a streamlined installation strategy to achieve various fully heteroatom-substituted P(V) stereocenters from simple POCl3. Thirteen types of N-, O-, and S-based nucleophiles are adopted for the preparation of six types of P(V) stereocenters. Over 100 examples are provided to show the generality and reliability of the synthetic method. This protocol is also applied to the concise synthesis of twelve bioactive molecules and analogs. The antifungal evaluations of the prepared compounds reveal two new fungicide candidates and also suggest the importance of the stereochemistry for bioactivity. (c) 2026 Science China Press. Published by Elsevier B.V. and Science China Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

In this work, a crystallization-driven co-self-seeding strategy, involving mixed-seed and co-seed co-self-seeding approaches, is developed to prepare heterojunction nanofibers containing a heterogeneous core with controllable length and morphology.

Difluoroamino (NF2) groups are highly valuable in functional materials-particularly energetic materials-yet efficient and general methods for their direct installation remain largely underdeveloped. Here, we report a mild and practical difluoroamination protocol using nitrogen trifluoride (NF3), an inexpensive and bench-stable gas, as a NF2 source for difluoroamination of tertiary organolithium reagents. This method delivers C-NF2 bonds in high yields (up to 86%) and provides a scalable, safer alternative for incorporating NF2 groups into complex molecular architectures.

Narrowband organic emission has traditionally relied on intrinsic molecular design. Here, we report a distinct strategy to achieve narrowband organic afterglow through external environmental modulation of vibronic coupling. By doping coronene derivatives into halogenated organic matrices, narrowband afterglow emission with full width at half maximum (FWHM) values as low as 13.7 nm is realized under ambient conditions, whereas non-halogenated matrices produce broad emission (FWHM >60 nm). Systematic host-dependent studies reveal that halogen environments selectively enhance the 0-0 transition or low-frequency vibronic bands of the locally excited T-1 state, thereby markedly narrowing the emission profile. Time-dependent density functional theory and Franck-Condon simulations corroborate the vibronic origin of spectral narrowing and disclose a nonmonotonic dependence on halogen atomic number arising from the interplay between selective vibronic amplification and the external heavy-atom effect. The resulting materials exhibit bright, high-purity afterglow under ambient conditions and can be readily processed into patterned architectures and large-area polymer panels with high visual contrast. This work establishes external-environment perturbation as a powerful paradigm for narrowband organic afterglow and provides new insight into vibronic regulation of excited-state emission.

A central challenge in on-surface synthesis of topologically unique carbon nanostructures lies in the precise and selective construction of triangular nanorings. Achieving the resulting chirality and the sp2/sp-hybridized state simultaneously from prochiral precursors is critical, yet immensely difficult. Here, we design an asymmetric alpha-cyanostilbene derivative with aggregation-induced emission properties as a prochiral building block to achieve deterministic pathway selection through controlling the substrate- and thermal-directed strategy, allowing for the targeted formation of heterochiral nanorings with defined sp2- and sp-hybridization on Ag(111). Direct thermal deposition onto a hot Ag(111) surface at 443 K drives a highly selective cyclotrimerization, yielding discrete sp2-hybridized heterochiral triangular nanorings. Subsequent annealing induces an elimination reaction, converting these rings into their sp-hybridized analogues while preserving chirality. In contrast, room-temperature deposition and postannealing predominantly produces linear chains. The structural evolution and selective reaction mechanisms are unequivocally characterized by scanning tunneling microscopy (STM), bond-resolution STM, synchrotron radiation photoemission spectroscopy (SRPES), and density functional theory (DFT) calculations. This work establishes a novel strategy for the precise synthesis of chiral triangular nanorings, revealing the critical role of surface-mediated conformational control and dynamic covalent bonding in determining product topology and chirality.

Amphiphilic porphyrin nanomicelles have been established as new single-molecule photodynamic agents (PDAs) for cancer treatment. Further improvement of the photodynamic performance will increase the potential of this class of PDAs for practical application. Here, we prepare four new porphyrin compounds F-TSCnP (n = 5-8) that bear a n-C5F11, n-C6F13, n-C7F15, and n-C8F17 chain, respectively. We demonstrate that, compared with the analogues that bear a shorter perfluoroalkyl or n-C8H17 chain, n-C8F17-bearing compound F-TSC8P can self-assemble into nanomicelles that possess increased stability and uniformity as well as improved intracellular self-delivering capacity. We further illustrate that nanomicelles formed by F-TSC8P form a unique fluorocarbon microphase, which can enrich and deliver O2 to achieve remarkably enhanced photosensitizing activity for 1O2 generation. In vivo assay using a mouse model reveals that, compared with the fluorine-free counterpart, F-TSC8P, which has a therapeutic index of 10, exhibits a 150% increase in photodynamic activity for tumour growth inhibition.

Coordination-driven self-assembly offers a powerful toolkit for constructing sophisticated functional architectures. Rigid ligands are widely employed as building blocks in metallo-supramolecular chemistry due to their structural predictability during self-assembly. In contrast, flexible building blocks-though capable of offering greater structural diversity and stimuli-responsiveness-are rarely used, as their conformational freedom often complicates structural control. Consequently, the integration of flexible ligands into metallo-supramolecular systems remains underexplored. To address this challenge, we employ a postassembly ligand-exchange approach to construct a series of heteroleptic metallo-supramolecular cuboctahedra incorporating both rigid and flexible ligands. Investigations of chain length dependence reveal that flexible alkyl-diamine incorporation affects cage hydrodynamic size and stability, with optimal stability achieved at 8 units. This combined bottom-up and top-down synthetic approach offers a promising strategy for engineering complex architectures from flexible building blocks for further exploration of chemistry within a confined space.

ADP-glucose pyrophosphorylase (AGPase) catalyzes the conversion of glucose-1-phosphate and adenosine 5 '-triphosphate (ATP) to ADP-glucose (ADPG), the dedicated precursor of starch in plants. It is a rate-limiting enzyme of the starch biosynthesis pathway, and its activity is closely linked to crop productivity. Plant AGPase is a heterotetramer composed of two types of subunits, and its activity is subject to allosteric regulation by photosynthetic metabolites, with 3-phosphoglycerate (3-PGA) acting as an activator and phosphate as an inhibitor. Here, we report the cryo-electron microscopy structures of Arabidopsis heterotetrameric AGPase in apo, 3-PGA-bound, phosphate-bound, ATP/3-PGA-bound, and ADPG/3-PGA-bound states. AGPase consists of two small subunits (APS1) and two large subunits (APL1), organized as a dimer of APS1-APL1 heterodimers. Both the small and large subunits comprise an N-terminal catalytic domain and a C-terminal left-handed beta-helix domain. By combining structural analysis with functional characterization, we identified the binding sites of the allosteric modulators and substrate/product in the AGPase and elucidated the mechanism of allosteric regulation, which involves 3-PGA binding-induced conformational changes at the active site. These findings provide critical insights into ADPG synthesis by plant heterotetrameric AGPase and offer clues to engineer the AGPase to enhance starch production and increase crop yields.

The difluoromethylene-bridged cyclopropane-cyclobutane (CP-CF2-CyBu) motif represents a novel fluorinated scaffold that fuses two privileged strained rings, cyclopropane and cyclobutene, both of which constitute valuable structural elements in medicinal chemistry. This unique bicyclic framework offers attractive opportunities for expanding fluorinated chemical space in pharmaceutical design, particularly as compact, three-dimensional bioisosteres capable of enhancing metabolic stability and conferring conformational restriction. However, practical synthetic routes to access these strained bicyclic scaffolds remain underdeveloped. Herein, we report an efficient and operationally straightforward method for the diastereoselective synthesis of the CP-CF2-CyBu scaffold through copper-catalyzed hydrodifluoroalkylation of cyclopropenes, employing 2-(difluoromethylene)cyclobutyl sulfonium salt (CB-DFAS) as the key fluoroalkylating reagent. This reagent is readily prepared in multigram quantities via a concise three-step synthesis. The protocol proceeds through in situ generated copper hydride species, involving CuH-mediated hydrocupration followed by oxidative addition, thereby delivering diverse CP-CF2-CyBu products with high efficiency and diastereoselectivity under mild conditions. Notably, the reaction exhibits ligand-dependent stereodivergence: 1,1-disubstituted cyclopropenes with triphenylphosphine afford syn-diastereomers preferentially via a chelation-controlled transition state, whereas 1,2-disubstituted cyclopropenes with a bulky N-heterocyclic carbene ligand (L8) furnish anti-diastereomers selectively through non-chelation pathway governed by cage strain effect. Both pathways achieve high diastereoselectivities (up to >20 : 1 dr) and exhibit broad functional group tolerance, accommodating sensitive motifs including boronates, nitriles, halides, and nitro groups that remain compatible for downstream elaboration. The synthetic utility of this method is demonstrated by diverse transformations of the CP-CF2-CyBu products, including hydrogenation, reduction, and dihydroxylation, thereby providing streamlined access to complex, medicinally relevant fluorinated bicyclic frameworks previously inaccessible via conventional synthetic strategies. This work establishes a practical platform for expanding fluorinated chemical space in drug discovery.

Mechanosensing interactions between the extracellular matrix (ECM) and the intracellular cytoskeleton are fundamental to cellular functions such as motility, proliferation, and adhesion, driven by the dynamic, bidirectional, tension-regulated maturation of focal adhesion (FA) sites. We demonstrate that native mechanosensing interactions and their downstream functions are precisely controlled using synthetic hydrogels. We introduce a microfluidic-assisted synthesis of imine-crosslinked hyaluronic acid-gelatin copolymer hydrogels (HAG), enabling controlled, predefined gradient viscoelasticity. Specifically, three native tissues (muscle, epidermis, and cartilage)-mimicking HAG hydrogels were prepared, matching their effective Young's modulus (Ymod) and stress relaxation time (tau 1/2). Enhanced cell spreading and directional cell migration are observed, with a preference for substrates with tissue-matching viscoelasticity. These mechanosensing reactions are confirmed by traction force microscopy, revealing a tight correlation between native tissue mechano-properties and the hydrogel viscoelastic parameters. We demonstrate that the signaling efficacies of the FAK and associated YAP/TAZ pathways, central regulators of FA formation and cell migration, are tuned by substrate tissue-matching viscoelasticity. We implement these preprogrammed viscoelastic gradient hydrogels as spatiotemporal cell-separation matrices, enabling viscoelasticity-driven migration of binary cell mixtures. This work provides a potent platform for studying cell-material interactions, offering significant potential applications in tissue engineering, immunotherapy, and regenerative medicine.

The first copper-catalyzed enantioselective allylic C-H cyanation of electron-deficient alkenes was established herein. With a sequential catalytic hydrogenation in a one-pot fashion, the current method provides easy access to structurally diverse gamma-cyanated carbonyls in good yields with excellent enantioselectivity, which are difficult to synthesize by the previously reported methods. Additional mechanistic investigations of the controlling experiments, kinetic study, isotopic effect, and DFT calculations revealed a new reaction pathway. We found that the previously reported Cu(II)-bound N-centered radical (NCR) undergoes dissociation in polar solvents to generate a free NCR species. This free sulfonamidyl radical, derived from the NF reagent, has a greater hydrogen-atom abstraction (HAA) ability, which is crucial for the successful allylic C-H abstraction of electron-deficient alkenes. Although the off-cycle existed to quench free NCR species by the extra Cu(I) catalyst, this side reaction can be effectively suppressed by reducing the catalyst concentration. Therefore, highly selective and efficient allylic C-H cyanation of electron-deficient alkenes could be achieved by using a low catalyst loading (0.25 mol %). These findings highlight the method to adjust the interaction between the copper(II) intermediate and free NCRs, which opens a window to carry out asymmetric C-H bond functionalization reactions across a range of substrate types.