The abundant quantities and strong binding energies of inner-shell electrons (ISEs) make them an ideal energy storage medium to break through the energy density limitation of conventional batteries relying on the transfer of valence electrons. However, since the ISEs are strongly bound by the Coulomb potential of the nuclei, the production of highly charged ions through conventional chemical methods becomes unfeasible. Herein, by trapping the charged ions within an electric and magnetic field under vacuum, we present a new energy storage paradigm based on the ISE transition to overcome the fundamental limitations of batteries. Multiple ions, including highly charged barium and oxygen ions, generated via the electron impact ionization within a high-density, magnetically confined electron beam, are utilized as a proof-of-concept. The integration of the photovoltaic module thus enables the efficient conversion of the potential energy into electrical power, which is validated by a series of experimental investigations, including electron beam current and trap voltage modulations. The resulting cell achieves stable current and voltage output with a high energy density of 1.5 × 10⁴ Wh·kg^–1 according to the ion population and mass.

The separation of xenon and krypton gas mixtures presents a significant yet challenging task due to the close molecular sizes and similar physical properties of these gases. In this study, we present a novel microporous hydrogen-bonded organic framework, designated as HOF-SCU-1, which is constructed from a carboxylic acid-based organic linker, 3,3′,5,5′-tetrakis(3,5-dicarboxyphenyl)-2,2′,4,4′,6,6′-hexamethylbiphenyl (H₈TDHB). HOF-SCU-1 demonstrates exceptional separation performance for xenon and krypton mixtures, as evidenced by dynamic breakthrough curves. Grand canonical Monte Carlo (GCMC) simulation results indicate that the effects of pore confinement and the abundance of accessible binding sites work synergistically to facilitate this challenging gas separation.

Silicon oxide (SiO_x) is a high-capacity anode candidate for lithium-ion batteries, yet its widespread adoption is hindered by poor conductivity and interfacial instability. Traditional carbon-coating methods often suffer from uneven coverage and weak adhesion, leading to rapid capacity fading. Herein, we propose a novel Zn-anchored interfacial growth strategy to fabricate a hollow double-shell SiO_x/C composite (HSiO_x/C-1@NC). By utilizing surface-grafted Zn species as uniform nucleation sites, a conformal ZIF-8 shell is grown directly on SiO_x/C and subsequently converted—through a single carbonization step—into a porous, nitrogen-doped carbon layer with strong interfacial adhesion and tailored porosity. The resulting HSiO_x/C-1@NC anode exhibits exceptional long-cycle stability, delivering a high reversible capacity of 811.8 mAh·g^–1 at 1 A·g^–1 after 1500 cycles, which ranks among the best performances reported for SiO_x-based materials. The unique hollow dual-shell architecture not only accommodates volume expansion and shortens Li⁺ diffusion paths, but also establishes a robust and continuous conductive network that ensures efficient electron transfer and interfacial stability. This work provides a scalable and versatile interfacial engineering approach to designing high-performance SiO_x anodes, with potential applicability to other oxide-based electrode systems.

Glycans are essential biomolecules across species, and a thorough understanding of their structure-function relationships heavily depends on high-quality samples obtained through chemical or enzymatic synthesis. Solid-phase glycan synthesis (SPGS) is a powerful technique for preparing well-defined glycans. However, assembling structures with multiple cis-glycosidic bonds, particularly cis-glycosamines, remains a significant challenge for SPGS. In this study, we targeted heparan sulfate (HS) backbone oligosaccharides, which contain two types of 1,4-cis linkages between glucosamine (GlcN) and D-glucuronic acid (GlcA) or L-iduronic acid (IdoA). We evaluated ten 2-azido-2-deoxy-thioglucopyranosides with diverse C3-OH/C6-OH functionalities as potential building blocks for glucosamine residues. Considering reactivity and stereoselectivity, a candidate with a bulky tert-butyldiphenylsilyl group at C6-OH demonstrated superior performance compared to 3,6-diesterified species in our study. This silyl building block also proved to be well-compatible with SPGS, facilitating the successful preparation of four disaccharides and four tetrasaccharides containing GlcN-GlcA or GlcN-IdoA on solid-phase. Finally, for the first time, we successfully synthesized a Fondaparinux-type pentasaccharide backbone containing GlcN, GlcA, and IdoA residues simultaneously by directly installing all types of cis-linkages on solid-phase without using disaccharide building blocks or special reagents.

The successful development of the organocatalyzed asymmetric [3+2] cyclization of chromone derivatives with γ-hydroxyenones has enabled the efficient synthesis of 3-tetrahydrofuran-chromones featuring three contiguous stereogenic centers. This reaction proceeds with excellent efficiency, delivering high yields (up to 98%), diastereoselectivities (up to 95 : 5 dr), and enantioselectivities (up to 99% ee). Notably, a diastereodivergent transformation is achieved by treating the initial cycloadduct with DBU, which triggers a sequence of retro-Michael reaction, C–C bond rotation, and intramolecular cyclization to afford the thermodynamically more stable diastereomer. DFT calculations support this mechanistic pathway, identifying the ring-closing step as the rate-determining transition state and confirming the overall exothermic nature of the transformation. The protocol enables access to four stereoisomers and represents the diastereodivergent synthesis of 3-tetrahydrofuran-chromones, providing a library of compounds for biological activity screening. Furthermore, synthetic transformations of the products were performed to enhance the synthetic effectiveness of the protocol. This work advances asymmetric catalysis by offering a versatile approach to complex chiral heterocycles with tunable stereochemistry.

Photodynamic antibacterial therapy (PDAT), with its advantages of high efficiency, controllability, and low drug resistance, has emerged as a promising research focus in the field of antibacterial treatment. Herein, we design an m-xylylene-bridged benzothioxanthene imide dimer (m-Dimer) to regulate molecular aggregation behavior. Notably, the aggregated m-Dimer exhibits a reduced singlet-triplet energy gap (ΔE_ST), which effectively facilitates the intersystem crossing (ISC) process and efficiently generates singlet oxygen (¹O₂) under visible light. Consequently, m-Dimer achieves exceptional antibacterial efficacy, eradicating both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) at a low concentration of 10 μM upon white-light irradiation. Moreover, its excellent photostability, straightforward synthesis, and low-cost underscore high potential for scalable PDAT applications.

The development of efficient electrocatalysts for the reduction of nitrate (NO₃^-) to ammonia (NH₃) offers a sustainable alternative to the energy-intensive Haber–Bosch process, positioning this approach as a key focus in low-carbon and environmental research. However, practical implementation of the nitrate reduction reaction (NO₃^-RR) remains challenging due to the complexity of proton-coupled electron transfer and the sluggish kinetics arising from diverse reaction intermediates. In this work, we present an asymmetric Fe/Mn diatomic catalyst anchored on a metal–organic framework (MOF)-derived carbon skeleton, which exhibits outstanding catalytic performance for NH₃ synthesis, achieving a Faradaic efficiency of 98.7% at −0.4 V vs. RHE. Through combined in situ X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, we reveal that in the asymmetric Fe-Mn/SNC structure, strong electronic coupling between Fe and Mn active sites, together with synergistic modulation by S and N atoms, effectively optimizes the electronic structure, enhances structural stability, and ensures optimal atomic dispersion. The proposed transverse coordination-asymmetric heteronuclear diatomic cooperation mechanism provides a novel design strategy for advancing nitrate reduction and electrocatalytic ammonia synthesis.

Air-stable organic radicals with their open-shell electronic configuration possess attractive optoelectronic properties and hold great potential for a wide array of applications. Among luminescent radicals, polychlorinated triarylmethyl (PTM) radicals and their derivatives are the most extensively studied due to the protection provided by the polychloroaryl groups. In this study, a phenothiazine unit was employed to substitute one polychloroaryl group in PTM radicals, yielding six new PTZ-BTM (1a–3a, and 1b–3b) radicals. Single-crystal structural analysis revealed that PTZ-BTM radicals adopt a propeller-like configuration, which effectively shields the central carbon radical and contributes to their remarkable stability under air conditions. Their half-lives (18.9–219.4 h) are much longer than that (0.6 h) of classical tri(2,4,6-trichlorophenyl)methyl radical (TTM). Density functional theory (DFT) calculations indicate that approximately 65% of the spin density is localized on the central carbon of PTZ-BTM radicals. HOMO is predominantly situated on the phenothiazine moiety, and LUMO is mainly distributed over the polychlorophenyl unit. Thus, 3a and 3b displayed distinct near-infrared emission at 784 nm and 783 nm, showing a substantial bathochromic shift compared to that (570 nm) of TTM, along with a photoluminescence quantum yield (PLQY) of 1.2% and 1.5% in dichloromethane. Furthermore, cyclic voltammetry revealed that the PTZ-BTM radicals exhibit two reversible redox events, demonstrating their ability to be reversibly reduced to anions and oxidized to cations. This work presents a new type of air-stable, luminescent radicals, implying potential applications in the fields of OLED and NIR-I imaging.

Hypercrosslinked polymers (HCPs) from Friedel–Crafts alkylation have attracted significant attention as promising materials for adsorption and separation due to their abundant porosity, low cost, ease of preparation, and excellent stability. Here, we fabricated a series of composite membranes coated with continuous HCP layers on polyvinylidene fluoride (PVDF) film substrates, using various aromatic monomers as building blocks via an external braiding method. Different HCP structures were constructed by tuning the number of crosslinking sites on the monomers and their structural rigidity, and their effects on organic dye separation were systematically investigated. Benefiting from both physical size sieving and electrostatic effects, the prepared biphenyl-based membranes can effectively block anionic dyes, such as methyl blue, Congo red, Eriochrome black T and methyl orange, achieving a rejection rate exceeding 99% and a water flux of up to 30.2 L·m^–2·h^–1·bar^–1. This study presents an efficient method to uniformly grow hypercrosslinked functional HCP layers on substrate membranes via interfacial polymerization, offering a versatile and straightforward approach to fabricating nanofiltration membranes for the treatment of organic pollutants.

The pivotal roles of fused carbo-/heterocyclic skeletons in medicinal chemistry and fine chemical industry are best exemplified by their ubiquitous presence in marketed drugs and wide applications in organic electronics and luminescence materials. Among them, azafluoren(ol)e, pyridopyrimidin(on)e and isoindole derivatives possess a wide spectrum of biological activities. Moreover, they have also demonstrated strong absorption and emission properties, thus qualifying their uses in dyes and light-emitting materials. Presented herein is a divergent synthesis of CF₃-azafluorenol or CF₃-pyrido[1,2-a]pyrimidine fused isoindole through condition- controlled cascade reactions of 3-alkenyl-1,2,4-oxadiazolone with CF₃-ynone. The formation of the former product involves a C−H activation (CHA)-initiated formal [4 + 2] annulation followed by an intramolecular enamine aldol-type reaction. The formation of the latter product firstly goes through a formal [4 + 2] annulation but with different regio-selectivity, followed by an intermolecular condensation and an intramolecular Friedel-Crafts type reaction, or followed by C−H alkenylation, N-intramolecular Michael addition, N-nucleophilic addition and water elimination. To our knowledge, this is the first report on CHA-initiated double or triple annulation of 3-alkenyl-1,2,4-oxadiazolone with CF₃-ynone to furnish different polycyclic products. In general, these synthetic protocols feature redox-neutral reaction conditions, good compatibility with labile functional groups, excellent step-/atom-economy, valuable products, intriguing reaction pathways, diverse structural derivation and ready scalability. To explore the potential application of the products thus obtained in pharmaceutical field, the anti-cancer activity of selected products against two human cancer cell lines (HCT-116 and Hela) was evaluated by using 5-fluorouracil (5-FU) as the positive control. The results showed that most of them possess moderate to good anti-cancer activity.

QS-21 is one of the most potent saponin immunoadjuvants. However, its wide applications in subunit vaccine development are seriously restricted by its limited availability. Among the factors causing the scarcity of QS-21, the difficult acquisition of quillaic acid (QA) on large scale is the fundamental one. Based on two steps of C–H functionalization, the Sanford C–H acetoxylation and the Yu modified Schonecker-Baran C–H oxidation, scalable (gram-scale) and concise (20 steps) synthesis of QA from oleanolic acid (OA) was accomplished. Moreover, based on the versatile 23,24-Me-diacetoxylized side product, the divergent synthesis of QA derivatives, including hederagenin analogues, oxetane-containing OA, as well as 24-Me-nor-OA, was conveniently accomplished.

The size of perovskites is a crucial factor to impact third-order nonlinear optical (NLO) properties. The inherent channels of metal-organic frameworks (MOFs) can be utilized for achieving the size reduction of perovskites. Confining small-sized perovskites within the MOFs channels to form composite materials helps to regulate the NLO properties of perovskites. In this work, a self-assembly strategy was employed to confine MBAPbBr₃ (MBA = Methylphenylethylamine) within the 1D channels of a Zn-MOF {[Zn_1.75L_0.625(Pz-NH₂)_0.25(μ₃-O)_0.25(μ₂-O)_0.25(H₂O)_1.25]·4CH₃CN}_n (L = 5,5'-(1H-2,3,5-triazole-1,4-diyl)di-isophthalic acid), obtaining small-sized perovskites. At the excitation wavelengths of 532, 900, or 1064 nm, the NLO absorption coefficient and NLO refractive index of MBAPbBr₃@Zn-MOF were enhanced by an order of magnitude compared with those of intrinsic MBAPbBr₃. Femtosecond transient absorption spectroscopy and theoretical calculations indicate that the strong charge interactions and bandgap coupling between the Zn-MOF and perovskite enhance the light absorption cross-section and the lifetime of photogenerated carriers, thereby facilitating the multi-photon absorption-induced excited-state absorption process and enabling the materials to achieve higher energy conversion. This work explores the influence of the tiny size of perovskites and the charge interaction with MOFs on the third-order NLO properties, providing a new perspective for the design and regulation of third-order NLO materials.

This study addresses the critical need for efficient methods to synthesize 2-trifluoromethylated aromatic azacycles, which are pivotal targets in drug and agrochemical development. While direct C–H trifluoromethylation using trimethyl(trifluoromethyl)silane (TMSCF₃) offers a facile route for C2-regioselective incorporation, its limitations in yield and substrate scope present a significant challenge. To overcome this, we introduce a novel concept by modifying the reagent structure: utilizing Me₂(CH₂Cl)SiCF₃, a bifunctional silyl reagent that enhances its reactivity compared to existing silyl reagents. Under a modified Kanai & Kuninobu procedure involving sequential nucleophilic addition and oxidative aromatization, this approach demonstrates substantial theoretical and methodological progress. It successfully delivers an array of 2-CF₃ substituted quinoline derivatives (24 examples) in yields significantly superior to those of TMSCF₃ (with increments of ≥20% for 10 examples), while also expanding the scope to include naphthyridines and phenanthrolines. These results advance beyond current methodologies by establishing that polar modification of the silyl methyl group can generate more powerful reagents, thereby providing a robust framework for the selective and high-yielding synthesis of valuable fluorinated aromatic azacycles.

The pentafluorosulfanyl (SF₅) moiety has garnered significant attention as a fluorinated functional group in the fields of medicinal chemistry, agrochemistry, and materials science, attributable to its distinctive physicochemical properties. In comparison to its structural analogue, trifluoromethyl, the SF₅ group demonstrates notably increased lipophilicity and pronounced electron-withdrawing capacity. However, the direct pentafluorosulfanylation of unactivated alkenes remains challenging due to the intrinsic propensity of SF₅Cl to undergo spontaneous chloropentafluorosulfanylation. Herein, we report a photoinduced radical pentafluorosulfanylation-cyclization of alkenes enabled by an in situ substrate-derived radical moderator strategy. Upon irradiation with LEDs, homolytic cleavage of the S–Cl bond in SF₅Cl affords an electrophilic SF₅ radical, which undergoes addition to the alkene unit of the sulfinamide substrate, thereby generating a carbon-centered radical intermediate. Subsequent intramolecular S_Hi cyclization yields the cyclic sulfinamide product, while a tert-butyl radical partakes in an XAT process with SF₅Cl to regenerate the SF₅ radical and perpetuate the radical chain mechanism. Intriguingly, intramolecular hydrogen-bonding interactions between the sulfinyl group and the CH₂SF₅ moiety are posited to be responsible for the exceptional stereocontrol observed. Furthermore, the resulting SF₅-containing motifs are readily amenable to further functionalization, thereby highlighting the broad synthetic utility and potential applications of these cyclic sulfinamides in pharmaceutical and materials science research.

An innovative and highly regioselective strategy has been developed for synthesizing Heck-type products of (E)- and (Z)-prop-1-ene-1,3-diyldiaryls by benzylation of alkynes through cleaving the carbon-carbon triple bond of terminal alkynes. This method involves using a functionalized heterogeneous ruthenium-chitosan based catalyst, which can be easily recycled by filtering and washing with solvent post-reaction. By adopting this approach, the need for highly toxic alkyl halides, oxidants, and activation reagents is eliminated, while ensuring excellent E/Z selectivity in the formation of desired Heck-type benzylation products in satisfactory yields. To further investigate the reaction mechanism, comprehensive step-by-step control experiments and DFT calculations were conducted, shedding light on potential implications for the synthesis of biologically active (Z)- and (E)-prop-1-ene-1,3-diyldiarenes.

The 2,7-dioxabicyclo[3.2.1]octane scaffold is a novel and pivotal structural motif found in many natural products and bioactive compounds. Despite its significance, efficient synthetic routes to this framework still remain underdeveloped. Herein, a Brønsted acid catalyzed strategy enabling concise, highly stereo- and chemoselective synthesis of the 2,7-dioxabicyclo[3.2.1]octane scaffold from γ-hydroxy enones with phenolic compounds and other enol partners using simple hydrochloric acid as the catalyst is reported. In this strategy, HCl might act as a bifunctional catalyst to suppress competing furan formation via α-addition to selectively generate the bridged ketal product. Utilizing this approach, a series of polysubstituted 2,7-dioxabicyclo[3.2.1]octanes were successfully synthesized, showcasing its broad substrate scope and functional group compatibility. Mechanistic studies support HCl's dual role in carbonyl activation by acidic proton and nucleophilic 1,4-addition ensured by chloride anion to afford the key 2,5-dihydrofuran-2-ol intermediate. Further stability test validated the scaffold's robustness, and bioactivity test disclosed an anti-proliferative activity against 4T1 cells in vitro with compound 3da showing an IC₅₀ of 35.15 ± 0.78 μM. These findings motivate the ongoing design and application of ketal-bridged scaffolds in a more concise and efficient manner.

As a fundamental feature of physiological regulation in living systems, chirality has emerged as a critical factor in the rapid development of nanomaterials for biomedical applications. Through precise structural design, chiral nanomaterials enable high-precision biological analysis and efficient therapeutic interventions by exploiting handedness-dependent interactions at chiral organic–inorganic hybrid interfaces or through chiral light–matter coupling. This review systematically outlines synthetic strategies for diverse chiral nanomaterials, spanning three primary material categories: inorganic (e.g., chiral metal nanoparticles, nanographenes, carbon nanotubes, mesoporous silica nanoparticles, and quantum dots), organic (e.g., chiral covalent organic frameworks and DNA nanomaterials), and organic–inorganic hybrid systems (e.g., chiral metal nanoclusters and metal−organic frameworks). For each category, we undertake a comprehensive discussion of established methodologies for imparting or controlling chirality, including direct synthesis, post-synthetic modification, and template-guided assembly, among others. Furthermore, we summarize the applications of these chiral nanomaterials across several frontier biomedical domains, including biosensing, antitumor therapy, antibacterial treatment, as well as tissue engineering and regeneration. Particularly, the focus is on elucidating how nanoscale chirality influences fundamental biological processes, including molecular signaling, cellular uptake, proliferation, and immune responses in order to establish structure-activity relationships that link the design of chiral nanomaterials with their macroscopic biological functions. Finally, we examine the key challenges impeding clinical translation, including the unclear mechanisms governing the interactions of chiral nanomaterials with biological systems, the paucity of diverse functional chiral ligands, and unresolved issues concerning long-term biosafety. We also offer perspectives on future directions for chiral nanomaterials, including AI-driven design and advanced biorelevant testing platforms to study systematic structure–activity relationships, thereby accelerating the development of enantioselective nanomedicine. This work aims to provide theoretical guidance for the rational design of chiral nanomaterials with tailored biological functionalities, thereby advancing solutions to pressing challenges in life sciences.

Nanoimprint Lithography (NIL) stands as a high-efficiency patterning technique capable of sub-diffraction resolution by replicating nanostructures from a mold. The performance of its core functional material, the NIL resist, critically governs the resolution and quality of the imprinted nanostructures. This review systematically explores functional patterning through resist design for nanoimprinting. It begins with an in-depth comparison of the two primary lithography material systems: thermal NIL (T-NIL) resists, which rely on thermoplastic flow or thermosetting crosslinking, and ultraviolet NIL (UV-NIL) resists, driven by UV-induced photopolymerization. The discussion encompasses their chemical compositions (including resins like epoxies, acrylates, and vinyl ethers), imprint mechanisms, advantages, and limitations. Subsequently, recently developed functional resist materials are examined, highlighting innovations in resins, crosslinking chemistries, and nanomaterial-incorporated formulations. The critical applications of functionalized NIL resists in advanced fields are thoroughly discussed. In semiconductor device patterning, optimized resists enable high-density circuit fabrication. For optical devices, tailored photopolymerization and crosslinking in UV-NIL resists facilitate precise nanostructure replication for metasurfaces. Biomedical applications leverage biocompatible resists for creating drug delivery systems. Each domain attains enhanced nanostructure fidelity through application-specific optimization of resist properties. Finally, future development trends for NIL resists are outlined, emphasizing sustainable chemistries, stimuli-responsive crosslinking, hybrid organic-inorganic resins, and defect-minimized resists. Advancements in nanoimprinting lithography are poised to expand patterning capabilities toward sub-10 nm nanostructures, multifunctional devices, and intelligent manufacturing paradigms. This review serves as a foundational reference for designing next-generation high-performance NIL resists and functional patterning strategies.