CHEMICAL COMMUNICATIONS

A MoC-MoP heterostructure enabled catalytic route for high-performance lithium-sulfur batteries
Wu B, Tang X, Xiang Y, Wang H, Tong C, Shao M, Li C and Wei Z
The commercialization of lithium-sulfur (Li-S) batteries is hindered by polysulfide shuttling and the sluggish conversion kinetics. Herein, we report a strategy for regulating the polysulfide conversion pathway a MoC-MoP heterostructure. With moderate adsorption strength and strong orbital coupling, this heterostructure catalyzes the cleavage of LiS into LiS˙ radicals, which subsequently undergo rapid liquid-phase disproportionation to facilitate chemical nucleation of LiS, thereby bypassing the slow liquid-solid conversion step. The S/MoC-MoP@CNF cathode constructed by this mechanism exhibits remarkable electrochemical performance, achieving a high discharge capacity of 1054.2 mAh g at 0.5C with a low capacity fading of only 0.062% per cycle.
Emerging tungsten-based materials for rechargeable metal-ion batteries: progress and perspectives
Xiao C, Liu T, Sun L and Chen L
Tungsten-based (W-based) materials have emerged as promising candidates for electrode materials in the next-generation rechargeable metal-ion batteries (MIBs), owing to their distinctive crystal structure, high theoretical specific capacity, and superior chemical stability. This review systematically reviews the latest research progress of W-based materials in the field of MIBs. Firstly, the representative crystal structures of W-based materials are outlined. Secondly, various synthesis methods and their impacts on the material morphology and electrochemical performance are discussed in depth. Subsequently, specific case studies are analyzed to clarify the potential energy-storage mechanisms. Meanwhile, a comprehensive systematic review and analysis of the applications of W-based materials in various battery systems, including lithium-ion, sodium-ion, potassium-ion, and zinc-ion batteries, have been conducted. Particular emphasis is placed on material modification strategies such as micro/nanostructural engineering, defect engineering, and the development of carbon-based composites. Furthermore, the review offers a comprehensive summary of advanced characterization techniques and computational methodologies currently employed in the field. Key challenges associated with W-based materials, for instance, during the cycling process, such as the limited conductivity and significant volume expansion, are critically examined, along with potential future research directions aimed at addressing these challenges.
Cu-catalyzed selective coupling of alkynes with danB-Bpai
Li Q, Zhang D, Song T, Tang X, Ma JA and Zhang C
A novel diboronic reagent, danB-Bpai, has been designed, and the copper-catalyzed selective transformation reaction between alkynes and this reagent has been investigated. By regulating ligands and additives, the chemoselective reaction of danB-Bpai can be achieved. The reaction exhibits excellent functional group compatibility, and synthetic experiments have confirmed that its products can serve as important synthetic precursors for a series of compounds with complex structures. Additionally, this study further examined the influence of the aromatic ring attached to the alkyne on reaction kinetics and explored the source of protons in the reaction.
Porous carbon nitride photocatalysts prepared by calcination of hydroxyl-substituted melamine derivatives
Miyata K, Shiraishi Y, Ichikawa S, Tanaka S and Hirai T
The carbon nitride powders synthesized by calcination of hydroxyl-substituted melamine derivatives such as ammeline and ammelide exhibited higher photocatalytic H-generation activity than those synthesized from melamine, owing to their large surface areas resulting from defective porous structures.
Bimetallic PtRu alloy nanowires confined on MXene nanosheets for highly efficient methanol electrooxidation
Yang J, Jiang Q, Zhang C, Zhang J, Yang L, He H and Huang H
Herein, we present the oriented synthesis of 1D ultrafine bimetallic PtRu alloy nanowires confined on 2D TiCT MXene nanosheets (PtRu NW/MXene) a convenient and robust solvothermal assembly strategy. Both experimental and theoretical investigations demonstrate that this distinct 1D/2D heterointerface design not only effectively stabilizes the integral hybrid structure through a "line-to-face" contact model, but also significantly ameliorates the electronic structure and catalytic environment of the PtRu component. Accordingly, the newly developed PtRu NW/MXene catalyst exhibits a large electrochemically active surface area of 130.7 m g, a high mass/specific activity of 2083.7 mA mg/1.59 mA cm, and exceptional long-term stability.
Single-atom catalysts for selective electrochemical CO reduction to C products
Zhao Q, Wu Q and Xu ZJ
Conversion of CO into useful products offers promising pathways towards achieving global carbon neutrality, and the development of corresponding advanced catalysts is important but challenging. Many catalysts can facilitate the conversion of CO into mono-carbon C products (such as carbon monoxide and formic acid), while conversion of CO into high-value-added multi-carbon compounds (such as ethylene and ethanol) requires multiple proton-coupled-electron-transfer (PCET) steps and targeted control product selectivity, which remain difficult to achieve in most catalysts. Single atom catalysts (SACs) demonstrate great potential for efficiently electrolyzing CO molecules into high valued chemicals with striking features, including atomically dispersed metal centres, well defined coordination environments, and tuneable electronic structures. In this review, the latest advances in SACs for CO conversion are comprehensively summarized, highlighting how SACs design influences product selectivity in CO reduction reactions, particularly for challenging C products with higher volumetric energy densities and market value. The fundamentals of SACs are first introduced, highlighting their unique advantages and outlining state-of-the-art design strategies and modification methods for performance optimization. The catalytic mechanism of CO on SACs is then delved into and their inspiration for SACs design is elucidated. Most importantly, the latest representative examples of engineered SACs for the electrochemical CO reduction reaction and design principles are presented and how novel SACs engineering enhances their activity, selectivity and stability is discussed, providing guidance for the development of efficient and durable SACs. Finally, the current challenges and limitations in this field are identified and future research opportunities are proposed, suggesting concepts for creating durable and highly active catalytic platforms for CO conversion and further applications.
A heterometallic σ-silane adduct from cooperative reactivity of an iron-aluminium complex
Stadler B and Crimmin MR
Protonation of a heterometallic silanide complex with an alcohol led to formation of a σ-silane complex. This reaction does not require a strong acid or a weakly coordinating anion. Both metals of the heterometallic complex play an important role, with the aluminium centre sequestering the anion generated in the protonation step.
Recent advances in diverse reactions of γ-bromocrotonates and their derived allyl sulfonium salts
Xiong D, Wang L, Qu X, Chen Y, Li L, Yao H, Huang N and Wang N
γ-Bromocrotonates and their derived allyl sulfonium salts serve as versatile synthons because they incorporate both an electron-withdrawing leaving group (bromine atom or sulfonium salt group) and a Michael acceptor (α,β-unsaturated ester group). This combination allows for the generation of various intermediates, leading to a wide range of subsequent transformations. Consequently, these synthons have garnered considerable attention, prompting the development of diverse methodologies and strategies for efficiently constructing functionalized organic molecules. In this review, we systematically summarize and elaborate on recent advances in diverse reactions of such versatile synthons. The discussed reactions are categorized according to γ-bromocrotonates and their derived allyl sulfonium salts acting as C1 synthons, C2 synthons, and C3 synthons, respectively, and provide detailed mechanistic insights. Additionally, this review highlights current challenges and future prospects for research in this field.
Strategies for tailoring clusteroluminescence: from aggregation control to molecular engineering
Wu R, Wu T, Guan W and Lu C
Clusteroluminescence (CL), light emission from non-conventional systems through-space interaction (TSI), offers unique photophysical properties distinct from traditional luminophores. This review outlines dual-level strategies for tailoring CL: aggregation regulation and molecular engineering. Controlling aggregation crystalline or amorphous packing, spatial confinement, and microenvironment design modulates cluster formation and TSI efficiency. Molecular approaches, such as heteroatom incorporation, substituent tuning, and conformational control, enable precise manipulation of electronic structure and emission pathways. Interplay between these levels allows tunable, efficient, and multifunctional CL. By integrating recent advances, we provide a systematic framework to guide rational design of clusteroluminogens (CLgens) toward next-generation luminescent materials.
Red/NIR-emissive AIE nanoprobe to track subcellular dynamics in a photodynamic therapy process
Zhou Y, Jiang Y, Zhang L, Li Y, Hao Y, Zhou P, Wang Z, Zhang Y, Ni JS, Xu Y, Meng L and Dang D
Precise monitoring of cancer treatment at the subcellular level remains a critical challenge. Therefore, a lysosome-specific AIE nanoprobe integrating stimulated emission depletion (STED) imaging and photodynamic therapy is reported here. The probe enables real-time visualization of lysosomal dynamics and reactive oxygen species (ROS)-mediated apoptosis, offering a powerful platform for high-resolution imaging-guided cancer diagnosis and treatment.
Phenolic resin-derived hard carbon for sodium-ion batteries: insights and prospects
Zhu Z, Pan J, Wu B, Li Q, Li W, Duan J and Yin YX
Phenolic resin (PF) has garnered considerable interest as a precursor for anode materials in sodium-ion batteries (SIBs) owing to its high carbonization yield, tunable molecular structure, and well-established synthetic technology. Despite their promise, these materials still face challenges such as low initial Coulombic efficiency, limited rate capability, and inadequate long-term cycling stability. The rational design of high-performance PF-derived carbon anodes necessitates a fundamental understanding of the relationship between their microstructure and sodium storage behavior. In this review, we start from the polymerization and carbonization reaction of PF and discuss the key issues of PF-based hard carbon, along with the sodium storage mechanism. The recent advances in optimizing PF-derived hard carbon are summarized, encompassing the selection of phenolic resin monomers and modification of PF-based hard carbons and their composites. In addition, we offer some perspectives for the design of better PF-based hard carbons for SIBs.
Design, synthesis and biological activity of potential retrometabolic polymyxins thiol-ene chemistry
Smith C, Siow A, Kowalczyk R, Ferguson SA, Smith MJB, Cook GM, Sander V, Davidson AJ, Brimble MA and Harris PWR
Despite their nephrotoxicity, polymyxins remain in clinical use as last-resort antibiotics, underscoring the urgent need for alternatives amid rising antimicrobial resistance. We report herein the total chemical synthesis and further biological evaluation of three polymyxin analogues that possess an ester linkage within the heptapeptide ring. Thioether installation was achieved pre-established vinyl ester formation, permitting a novel intermolecular thiol-ene reaction with a cysteine thiol to form the polymyxin ring. This moiety aims to sensitise the analogue towards esterase enzymes concentrated within the proximal tubule cells of the kidneys, theoretically limiting polymyxin accumulation, mitigating their toxicity.
Inhibition of glycoprotein biosynthesis in the pathogenic bacterium by masked carbohydrate phosphonates
Soleimani E, Chowdhury A, Zhu JS, Ospanow E, Moulton KD, Dube DH and Jakeman DL
The glycan-rich surface of plays a critical role in host-pathogen interactions and represents a promising target for therapeutic intervention. We report the synthesis and biological evaluation of a masked bis(pivaloyloxymethyl) phosphonate analogue of α-D-glucose 1-phosphate designed to inhibit glycoprotein biosynthesis in . This prodrug strategy enhances bacterial uptake by neutralizing the phosphonate's dianionic charge, potentially enabling intracellular esterase-mediated release of the active phosphonate. Using metabolic oligosaccharide engineering (MOE) with AcGlcNAz, we demonstrate that the masked phosphonate exhibits dose-dependent inhibition of glycoprotein biosynthesis, whereas unmasked and cyclic phosphonate analogues show minimal activity. These findings highlight the potential of masked phosphonates as chemical tools for probing bacterial glycosylation and as leads for novel antibacterial agents.
Excited-state intramolecular proton transfer (ESIPT) based metal-organic frameworks for smart sensing and stimuli-responsive applications
Maiti A, Mahato B and Ghoshal D
Excited-state intramolecular proton transfer (ESIPT)-based sensing applications have emerged as a powerful and distinctive strategy for the detection of various analytes, offering matchless advantages over traditional sensing techniques. The ESIPT process is characterized by its ultrafast tautomerization, associated with broad tunability, and large Stokes shifts in fluorescence emission. This is highly desirable for qualitative and quantitative detection, especially in complex environments, reaction intermediates, industrial waste monitoring, fuel purity Several ESIPT-active organic compounds have been reported, but the development of ESIPT-based metal-organic frameworks (MOFs) is still at a rudimentary stage, as the challenge lies in the design, especially in terms of dual-emissive behavior, which is a signature of ESIPT-based effective sensing. This unique characteristic of the ESIPT process is due to the stringent requirement of a narrow energy gap between two tautomeric forms. Incorporating specially designed ESIPT-based organic linkers in MOFs, with their stable and tunable structures, offers a promising platform to realize the distinctive ESIPT-driven dual-emissive behavior. This review article highlights our persistent effort to understand the ESIPT behaviour in MOFs, along with related reports from other groups. In this way, we have tried to articulate our understanding towards the structure-property relationships in ESIPT active MOFs. The effects of external stimuli, such as pressure, temperature, pH, light, solvent polarity, and ionic species, in modulating ESIPT in MOFs have also been taken into consideration for their advanced applications.
Boosting Li-S redox chemistry by the plasmonic effect of MXene
Liu Y, Wang X, Meng X and Wang Z
The plasmonic effect of MXene induces localized photothermal heating and hot-carrier generation, collectively reducing the ionic diffusion resistance and lowering the activation energy of lithium polysulfide conversion. Consequently, the accelerated redox kinetics greatly enhance the capacity and energy efficiency of Li-S cells under near-infrared irradiation.
Recent advances in developing bioactive porous organic cages for fluorescence bioimaging, drug delivery, and therapies
Zhang Y, Liu M, Wang Y and Tang JH
Porous organic cages (POCs) are a class of covalently-linked three-dimensional materials with precise molecular structures, well-defined intrinsic cavities, and versatile tunabilities. Many POCs were primarily linked through dynamic reversible imine bonds, which resulted in limited stability under aqueous and harsh conditions. This instability has restricted their broader research and application potential, particularly in biomedical fields. Recently, significant advancements in the fabrication of water-soluble and stable POCs have opened up opportunities for diverse applications, such as host-guest chemistry, sensing, separation, and biological imaging and therapies. This review focuses on recently emerged POCs for diverse biomedical applications, including fluorescence bioimaging, drug delivery, and therapies. To provide a systematic summary and comprehensive discussion of these newly developed POCs, their synthetic strategies, unique bioactive properties, and biomedical applications are highlighted. The outlook emphasizes the remaining challenges and structural design guidance toward the development of new POCs for further inspiration of future biomedical investigations.
NIR-II photozymes with stoichiometric chemistry-regulated enzyocatalytic activities for multi-modal nanocatalytic therapy
Lin Z, Song Z, Shen H, Shen Y, Chen L and Chen Y
Nanocatalytic therapy faces limitations from low ROS efficiency and high intracellular GSH. We develop trigonal PtTe photozymes (t-PtTe) with stoichiometry-regulated multi-enzymatic (POD-, CAT-, OXD-like) and NIR-II responses. In acidic tumors, t-PtTe generates ˙OH (POD-like), produces O (CAT-like), and depletes GSH to amplify ROS. Under NIR-II, it enhances efficacy photothermal effect and O photodynamic generation, synergizing with enzyme-catalyzed ROS to induce robust tumor apoptosis with minimal systemic toxicity.
Water-assisted SO capture in pyridine-functionalized COFs
Tang Z, Si GR, Chen Q, Lv JA, Wang S, Bai XF, Xie LH, Wang K and Li JR
Covalent organic frameworks (COFs) have emerged as promising materials for gas separation and purification due to their high porosity, structural tunability and chemical stability. However, the practical application of COFs in SO capture is hindered by severe performance loss under humid conditions. To address this challenge, we develop a water-assisted adsorption strategy by incorporating pyridine groups into chemically robust COFs. Two COFs, TpBpy and TpTtp, exhibit high adsorption capacities and cycling stability. Notably, TpTtp exhibits a SO uptake of 0.75 mmol g under dry simulated flue gas (2500 ppm SO, 15% CO in N), which increases by 36% to 1.02 mmol g at 50% relative humidity. Mechanistic analysis confirms that water promotes SO binding through synergistic interactions with pyridine sites. These results demonstrate the potential of COFs for deep desulfurization in humid flue gas streams.
homolytic cleavage of a terminal lanthanum(III)-methyl bond by Cu Kα X-radiation forms a La(II) complex
Stennett CR, Luevano MR, Ziller JW and Evans WJ
A new method for generating La(II) complexes is described in which irradiation of single crystals of the La(III) terminal methyl complex La(SAr)CH, Ar = CH-2,6-(CH-2,4,6-Pr), with Cu Kα X-rays (50 W, 8.04 keV/1.540 Å) during SCXRD experiments results in the homolytic cleavage of the La-C bond and formation of the La(II) complex La(SAr).
Synergy of a 2D/2D TiCT MXene-graphene oxide heterostructure for enhanced hydrogen storage
Ghotia S, Banerjee S, Kumar A and Kumar P
The demand for hydrogen storage materials for fuel cell devices is growing rapidly worldwide, driven by a combination of environmental, economic, and technological factors. 2D MXenes and graphene are crucial for developing efficient and safe hydrogen storage systems. The incorporation of GO into TiCT MXene enhanced its hydrogen storage capacity by ∼57% at 303 K, ∼46% at 273 K, ∼10% at 253 K, and ∼8% at 173 K. This improved performance of TiCT MXene is due to the increased surface area, synergistic interactions, and defect-induced adsorption sites in the TiCT-GO composite. Therefore, this study highlights the promise of MXene-GO hybrids for efficient hydrogen storage applications.
Bridged chemistry of macrocyclic arenes: from sp-carbon bridges to π-conjugation and heteroatom bridging
Jia XX, Wei TB, Lin Q, Shi B, Yao H, Qu WJ and Chen JF
Macrocyclic arenes are a class of host molecules featuring precisely adjustable cavities and abundant recognition sites, which facilitate rich host-guest interactions. Their bridging structures-such as methylene groups, conjugated units, and heteroatoms (, O, S, N, and Si)-can be rationally designed to fine-tune cavity microenvironments, conformational dynamics, and optoelectronic properties. These capabilities make them key building blocks for constructing molecular containers, sensors, and smart supramolecular assemblies. In recent years, macrocyclic arenes constructed from various aromatic building units and bridging groups have gained widespread attention due to their highly symmetrical rigid frameworks, tunable electronic properties, and rich host-guest chemical behaviors. This article systematically reviews the research progress in this class of macrocyclic arenes, focusing on the regulatory effects of different bridging structures on their cavity sizes, conformational features, and optoelectronic properties. It summarizes the latest developments in synthetic strategies such as one-pot methods, fragment coupling, and post-synthetic modifications and discusses their applications in molecular recognition, pollutant adsorption, optoelectronic material construction, and stimuli-responsive systems. Finally, we look ahead to the challenges and development prospects facing macrocyclic arenes in design synthesis and future applications, aiming to provide useful references and insights for research in this field.