Chemical Society Reviews最新文献

Selective modifications of native proteins provide powerful opportunities to study and manipulate biological systems, yet achieving site-selective functionalization remains challenging due to the surfeit of competing amino acids, often addressed by genetic engineering of target proteins. Ligand-directed protein modification addresses these limitations by exploiting reversible molecular recognition to position reactive groups in proximity to a defined protein site, thereby enabling selective covalent modification of native proteins under physiological conditions. Importantly, ligand-directed protein modification is evolving from a specialized labeling methodology into a versatile platform for the selective manipulation of protein function in native biological environments. In this review, we discuss recent advances in ligand-directed strategies that employ synthetically accessible small molecules and peptides as recognition elements. Current approaches are categorized into (i) ligation reactions, in which the ligand remains attached to the protein, (ii) transfer reactions, which install a functional moiety while releasing the ligand, and (iii) ligand-directed catalysis, where ligand-tethered catalysts promote protein-substrate reactions with catalytic turnover. For each strategy, employed chemical reactions, amino acid selectivities, and applications in chemical biology and biotechnology are described. We further compare the strengths and limitations of these approaches considering the balance between reactivity, selectivity, and biocompatibility.

Sequential double hydrofunctionalization of alkynes (SDHFA) represents an atom- and pot-economical strategy to access geminal- and vicinal-difunctionalized compounds, which are widespread in drug molecules, bioactive natural products, and functional polymers and materials. However, the multiple-step nature of SDHFA brings more challenges associated with chemo-, regio- and stereoselective control; meanwhile, the one-pot setting may introduce incompatibility between the two steps. Metal catalysis has played an important role in modern organic chemistry, and various catalytic systems have been applied to solve the above-mentioned challenges. Over the past decades, considerable advances have been made in metal-catalyzed SDHFA. This review provides a comprehensive summary of this field, covering the addition reactions of O-H, N-H, C-H, P-H, S-H, B-H, and Si-H bonds, and highlights representative mechanisms and synthetic applications with the aim of providing useful insight into this area and promoting its further development.

Chemistry is deeply connected to nearly every aspect of our lives and will therefore play a key role in addressing global challenges related to health, materials, and energy. In this context, the design and synthesis of new molecular materials remains at the forefront of research aimed at delivering transformative advances. A leading example for such shifts in existing scientific paradigms is surpassing the "thermodynamic limit for single-junction solar cells", which limits the maximum solar conversion efficiency achievable by a single p-n junction solar cell to just over 30%.

The selective activation of C(sp³)-H bonds in a molecule possessing multiple inequivalent hydrogens remains a critical challenge in organic synthesis. One method to achieve such activation is via well-explored 1,5-hydrogen atom transfer (HAT) processes of heteroatom-centered radicals. In contrast to 1,5-HAT, the emerging field of heteroatom-centered radical-mediated 1,2-HAT offers a complementary strategy for the selective activation of C-H bonds positioned α to heteroatoms (mostly N and O). In this review, we systematically outline recent progress in O- and N-centered radical net-1,2-HAT pathways, covering mechanisms and synthetic applications under transition-metal catalysis, photoredox, electrochemical, and super-electron-donor (SED) promoted conditions. The core mechanism, involving the translocation of a radical site from a heteroatom to an α-carbon atom, enables subsequent coupling reactions or can be used to initiate cascade reactions. The utility of this strategy is highlighted by its mild conditions, excellent functional group compatibility, and applicability to complex substrates, establishing it as a robust method for heteroatom-directed α-C-H functionalization. The scope, limitations, gaps in the literature and possible future directions are discussed.

Covalent organic frameworks (COFs) are atomically precise, crystalline platforms for efficient solar-to-chemical energy conversion. However, their net efficiency is fundamentally limited by severe kinetic competition, in which ultra-fast exciton recombination outpaces the slower multi-electron kinetics required for surface photocatalytic reactions. This review provides a comprehensive analysis of fundamental exciton dynamics in COF photocatalysts, tracing the photophysical cascade from initial photon absorption and bound electron-hole pair generation to long-range carrier migration and interfacial transfer. We have systematically discussed the significant role of various advanced time-resolved and operational spectroscopic techniques, which serve as vital toolkits for quantifying excited-state lifetimes and mapping charge-translocation pathways. Building upon these insights, we critique state-of-the-art structural modulation strategies, highlighting different parameters such as linkage engineering, donor-acceptor architectures, polarization effects, and internal dielectric environment tuning that manipulate carrier behaviour to force efficient charge separation. Finally, we explore how matching bulk photophysics with customized interfacial active sites drives diverse, highly demanding photocatalytic applications, including hydrogen evolution, CO₂ reduction, organocatalysis, H₂O₂ generation, nitrate reduction, and uranium extraction. Ultimately, this review underscores that maximizing quantum efficiency requires a deliberate, multi-scale synergy that balances bulk solid-state photophysics with the reaction-specific kinetics of the catalyst-substrate interface.

Heterogeneous boron-based catalysts represent a distinct class of materials for small molecule upgrading, providing catalytic functions complementary to those of conventional metal-based systems. The structural versatility of boron-containing compounds governs their performance in a range of reactions. A prominent case is the oxidative dehydrogenation of propane, where boron-based systems routinely achieve propylene selectivity in excess of 80% at 20% propane conversion, a regime wherein conventional metal oxide benchmarks are typically limited to selectivity below 60%. Though still in their developmental infancy, heterogeneous boron-based catalysts present an immense potential for industrial applications. This review surveys progress in the preparation of both bulk and supported boron-based catalysts and critically examines their mechanistic roles in small molecule upgrading. Specific emphasis is placed on the selective oxidation of methane, dry and steam reforming of methane to syngas, oxidative dehydrogenation of light alkanes and ethylbenzene, and emerging applications in electrocatalysis. Beyond summarizing recent progress, we address rational design strategies, key characterization techniques, and approaches for reliable performance evaluation. Available evidence indicates that boron species can participate directly in surface reactions, modify metal or support interfaces, stabilize working phases, and influence the formation and propagation of gas-phase radicals. The relative importance of these functions depends on the catalyst structure and reaction conditions. By linking observed catalytic behavior to underlying surface chemistry, this analysis provides a structured perspective to guide future research on heterogeneous boron-based catalysis.

Visible light-driven 3D printing has evolved beyond a mere substitution of ultraviolet irradiation and now represents a mechanistically redefined platform for additive manufacturing. As outlined in this review, the transition to visible wavelengths has required a fundamental reconsideration of photophysical and photochemical principles that govern photopolymerization, reshaping the design of photoinitiating systems, and processing strategies. We first discuss how the transition from ultraviolet to visible irradiation has reshaped molecular design strategies in photopolymerization, prompting the development of new photoinitiating systems tailored to the lower-energy visible regime. This shift has expanded the range of accessible activation pathways and enabled diverse polymerization mechanisms, encompassing free-radical, controlled radical, cationic, and other non-radical processes. We examine how these chemically distinct approaches have been translated into practical visible light-based 3D printing platforms. Beyond reaction mechanisms, we analyze formulation and optical considerations that uniquely influence curing performance under visible light, including spectral matching, light penetration, inhibition effects, and the balance between resolution and build speed. Finally, we highlight strategies that leverage wavelength selectivity and multi-component photochemistry to enable multimaterial fabrication and advanced applications. Collectively, this review integrates mechanistic insight with materials and process design, providing a comprehensive perspective on the current landscape and future directions of visible light-based 3D printing.

Medicinal chemistry sits at the center of modern drug discovery, yet translating molecular designs into approved medicines remains slow, expensive, and prone to high attrition across the pipeline from target identification to clinical validation. Artificial intelligence (AI) is beginning to reshape this landscape by enabling large-scale integration, interpretation, and generation of chemical, biological, and clinical data for hypothesis generation, chemical space exploration, and iterative cycles of model-guided design and experimental validation. In this review, we examine how machine learning, deep learning, natural language processing (NLP), and generative modeling are being applied across medicinal chemistry and drug development. We outline the principles of major AI modalities and detail their roles in target discovery, virtual screening, molecular property prediction, de novo molecular design, fragment-based optimization, safety and absorption, distribution, metabolism, excretion, and toxicity (ADMET) assessment, and clinical trial design. We highlight how multimodal data fusion, predictive modeling, and human-AI collaborative frameworks are supporting more informed decisions in rational drug design. At the same time, we critically assess the limitations that constrain real-world impact, including data scarcity and inconsistency, model generalizability and interpretability, evolving regulatory expectations, and the persistent gap between in silico predictions and experimentally validated drug candidates. While a small but growing number of AI-guided molecules have entered clinical development, systematic evidence on whether AI-driven approaches ultimately deliver better drugs or faster timelines than traditional methods is still accruing. We discuss emerging opportunities at the intersection of AI with automation, robotics, multimodal biology, protein structure prediction, and autonomous discovery. With rigorous validation, high-quality datasets, and appropriate regulatory frameworks, AI can become a dependable tool for discovering safer, more effective, and more personalized medicines.

The emergence of two-dimensional (2D) magnetic materials has revolutionized spintronics, quantum computing, and neuromorphic engineering, challenging conventional paradigms of magnetic ordering. Despite rapid advancements in synthesis, property modulation, and device integration, a holistic understanding of the critical role of reduced dimensions remains elusive. This review summarizes the recent development of 2D magnetic materials, including semiconductors, metals, and insulators of various crystal symmetries, which has broadened the perspective of the magnetic and electronic properties arisen from symmetry breaking. We focus on low-dimensional confined magnetic phenomena, in particular, interfacial effects and external stimuli (strain, gating, and light) enabled control over magnetic phase transitions, skyrmion dynamics, and topological states. Furthermore, we highlight the emergent applications of van der Waals heterostructures in ultracompact spintronic memory and quantum sensors. Finally, we outline unresolved challenges including ambient stability, scalable production, and Curie temperature enhancement, followed by proposal of interdisciplinary strategies to harness 2D magnetism for next-generation technologies. This review aims to provide guidance for the rational design of functional 2D magnetic materials and to accelerate the progress in disruptive quantum and energy-efficient devices.

Pure-silica zeolites have become indispensable in adsorption, separation, and catalysis under demanding conditions, owing to their exceptional structural diversity, hydrophobicity, thermal and chemical stability, and tunable pore architectures. A comprehensive understanding-spanning synthesis, atomic-scale structural determination, and application-is essential for advancing sustainable chemical processes, green catalysis, and next-generation separation technologies. Our review systematically evaluates the structural features of two-dimensional (2D) layered and three-dimensional (3D) framework zeolites, comparatively assesses the advantages, limitations, and applicability of various synthesis strategies, and critically examines the fundamental principles, strengths, inherent limitations, and recent advances in state-of-the-art structural characterization techniques. We further summarize their major applications in adsorption, separation, and catalysis. By uniquely integrating synthesis, structure, and function, our review provides an up-to-date resource that reflects current challenges, emerging opportunities, and promising directions for further research in pure-silica zeolites.