Chemical Society Reviews最新文献

Radical-mediated organic synthesis offers mild and sustainable routes to complex molecules, but conventional metal catalysts often suffer from limited activity, selectivity and recyclability. Single-atom catalysts, featuring atomically dispersed metal centres and well-defined coordination environments, provide an efficient platform for single-electron transfer, radical generation and intermediate stabilisation. This review summarises recent advances in single-atom-catalysed radical transformations, with emphasis on catalyst design, characterisation and mechanistic insight, and outlines key challenges and opportunities for developing sustainable radical methodologies based on single-atom catalysis.

Polyoxometalates (POMs), a versatile class of molecular metal oxides with well-defined structures and tunable physicochemical properties, have recently emerged as powerful platforms for the precise design of metal nanoparticles. In this review, we provide a comprehensive overview and a critical perspective on POM-hybridized metal nanoparticles, highlighting key milestones and recent advances in this rapidly evolving field of catalysis. We classify their synthetic approaches into four representative categories-precursor transformation, direct reduction, hydrothermal synthesis, and general complexation-and summarize characterization strategies from five complementary perspectives to elucidate their complex structures and functions. Beyond a descriptive survey, we establish a unified framework for understanding how POMs orchestrate catalytic behavior through four principal roles: electrosteric stabilization, electronic ligand effects, geometric and interfacial control, and synergistic catalysis. These features enable POMs to bridge the gap between conventional ligand-protected and metal-oxide-supported nanoparticle systems, offering unique opportunities for achieving high activity, stability, and selectivity. Finally, we discuss emerging directions and critical challenges, including operando characterization, the limits of atomic precision, and practical implementation, and provide our perspectives on extending POM-based design principles to broader applications in energy conversion, functional materials, and advanced device applications.

Toll-like receptors (TLRs) comprise a family of transmembrane pattern-recognition receptors that sense pathogen-associated molecular patterns (PAMPs) and damage-associated molecular patterns (DAMPs), thereby orchestrating innate immune responses. Over the past decade, TLRs have emerged as promising therapeutic targets for infectious, inflammatory, autoimmune, and oncological diseases. This review provides a comprehensive overview of TLR agonists and antagonists reported in the last ten years, highlighting an exceptional range of chemical classes, including peptides, nucleic acids, glycolipids, lipopeptides, and small molecules. We discuss the structural determinants underlying receptor selectivity, the design strategies enabling functional modulation, and the progress in preclinical and clinical development. We also address emerging trends, remaining challenges, and opportunities for the rational design of next-generation TLR modulators with improved selectivity and therapeutic potential.

Narrow-spectrum, strong-absorptive fluorescent dyes are effectively meeting the requirements of organic light-emitting diodes (OLEDs) for colour purity and exciton energy utilisation, showing considerable potential for future display applications. As typified by cyanine dyes, the absorption and emission spectral behaviors are strongly correlated with their intrinsic electronic structural features: homogeneous bond lengths and alternating atomic charges. Further studies reveal that these electronic structural features arise from the resonance balance of two ground-state resonance forms, and this balance can be modulated by donor-acceptor substituents. On this basis, this review comprehensively summarizes the molecular design strategies of fluorescent dyes for OLEDs, followed by a systematic overview of their inherent advantages, remaining challenges, and future application prospects in electroluminescent devices.

Nitrenium ions (NIs) are divalent nitrogen species with an N^⊕ centre; many of them are reactive intermediates, and the number of identified stable, catalytic NIs has been surging. Open-chain nitrenium ions (ONIs) generally have very short half-lives and are non-isolable. Therefore, they can only be generated and characterized under suitable reaction conditions. Only a few ONIs have been isolated and structurally characterized. Many ONIs exhibit carcinogenic properties under biological conditions. A few ONIs are therapeutically important. On the other hand, cyclic nitrenium ions (CNIs) are bench-stable and are available in various ring sizes. Several CNIs have been characterized by single-crystal X-ray diffraction and electronic structure analyses. A few CNIs were reported to exhibit catalytic properties (Lewis acid catalysis, phase-transfer catalysis and photocatalysis), and they are also valuable cationic species in biomedical applications. A few biocatalytic CNIs are recognised, and their analogues are designed as useful organocatalysts. Some CNIs participate as reactive intermediates in various biochemical reactions. CNIs are isoelectronic to N-heterocyclic carbenes (NHCs), but their chemical characteristics are distinct. This review provides a comprehensive account of NIs, whose importance in chemical research is proliferating across all branches of chemistry.

Green printing has emerged as a powerful additive manufacturing strategy for fabricating functional materials and devices over large areas, while reducing material consumption, processing steps, production costs and chemical waste. By precisely controlling droplet movement, fluid transport, and interfacial assembly, printing enables the direct patterning of highly integrated structures on various substrates. Over the past five years, rapid advances in functional ink design, printing processes, device integration, and artificial intelligence (AI) have accelerated the transition of printed materials and technologies from laboratory demonstrations towards industrial manufacturing. Nevertheless, their broader deployment remains limited by persistent trade-offs between resolution, throughput, scalability and reproducibility. In this review, we first summarize recent developments in inkjet printing, template-guided printing, 3D printing, transfer printing, roll-to-roll manufacturing and other emerging printing techniques, with emphasis on improving material utilization, simplifying processing procedures, and achieving large-scale production. We then discuss printable functional materials, including quantum dots, nanomaterials, perovskites, polymers, and their composites, highlighting the roles of material composition, rheology, and stability in determining their final functionalities. On this basis, we introduce representative applications in electronics, photonics, biomedical engineering, microfluidics and soft robotics. We further examine the effect of AI on green printing in various aspects such as ink formulations, process optimization, structural design, and closed-loop control. Finally, we discuss the challenges and future prospects for achieving green and sustainable printing in practical use.

The escalating global freshwater crisis demands next-generation, high-performance water purification technologies. Heterocyclic covalent organic framework membranes (HC-COFMs) have emerged as a transformative platform. By strategically integrating nitrogen-, oxygen-, and sulfur-containing heteroatoms into crystalline framework architectures, HC-COFMs achieve unparalleled control over pore chemistry, surface functionality, and molecular transport channels. This comprehensive review systematically explores the structure-property-performance relationships governing HC-COFMs in water-energy-environment applications. We critically examine rational molecular design strategies centered on heterocyclic monomers and robust linkages, alongside state-of-the-art fabrication techniques, including interfacial polymerization, in situ growth, covalent organic nanosheet (CON) stacking, and matrix blending. Furthermore, we highlight the multifunctional utility of HC-COFMs across five key application domains: molecular separation, ion sieving, membrane catalysis, solar-driven water purification, and emerging applications including critical metal recovery and remediation of emerging organic microcontaminants. All these functionalities are underpinned by the exceptional anti-fouling properties and chemical stability intrinsic to heterocyclic COF architectures. Finally, we outline current bottlenecks and future research directions, offering a strategic roadmap to guide the rational design of next-generation HC-COFMs for sustainable, cross-disciplinary water-energy-environment applications.

Metal-sulfur batteries are attracting broad interest as next-generation energy-storage systems because sulfur offers a high theoretical capacity, low cost, and natural abundance. Among them, lithium-sulfur (Li-S) batteries remain the most extensively studied, while room-temperature sodium-sulfur (Na-S) batteries are emerging as attractive alternatives for low-cost and large-scale storage. However, their practical implementation remains limited by inefficient sulfur utilization, sluggish redox kinetics, severe interfacial and chemo-mechanical degradation, and the distinct challenges imposed by different electrolyte environments. In this review, sulfur cathode design is examined as the central enabling factor for translating the theoretical advantages of metal-sulfur chemistry into practical high-energy-density batteries. We first discuss the key cell-level parameters that govern practical energy density and the fundamental reaction and degradation processes in liquid and solid electrolyte systems. We then analyze how sulfur cathode design has evolved from simple sulfur confinement toward multiscale architectures that regulate sulfur chemistry, transport, and structural stability, spanning both liquid electrolyte and all-solid-state configurations. By comparing these two regimes within a unified framework, this review highlights which design principles are broadly transferable, which must be redefined, and how sulfur cathodes should be coupled with electrolytes and realistic cell constraints. Finally, we outline the major challenges and future opportunities for advancing metal-sulfur batteries toward practical implementation.