Chemical Society Reviews最新文献

MXenes have emerged as highly promising two-dimensional materials for advanced sensing applications owing to their high electrical conductivity, rich surface chemistry, hydrophilicity, mechanical flexibility, and compositional diversity. While many MXene-based sensors have been interpreted primarily from the perspective of surface-mediated interactions on individual flakes, practical sensing devices are typically constructed from assembled architectures, including films, fibers, aerogels, hydrogels, and composite networks. In these systems, inter-flake regions can make important contributions to the generation and transmission of macroscopic sensing signals by influencing charge transport, ion and molecular diffusion, and local interfacial interactions at the device level. This review focuses on inter-flake modulation as a key design principle for MXene-based sensing systems. We begin by briefly outlining the intrinsic material properties that make MXenes attractive for sensing, then discuss the fundamental inter-flake properties of MXene assemblies, including interlayer spacing, flake orientation, structural porosity, and the chemical microenvironment, with emphasis on their characterization, modulation strategies, and impacts on sensing performance. We further summarize representative advances in inter-flake modulation of MXene assemblies for smart sensing scenarios, spanning piezoresistive sensing, chemiresistive sensing, and electrochemical sensing. Finally, we discuss key challenges and opportunities for optimizing inter-flake structures toward future MXene-based sensing systems. We believe this work will provide useful guidance and new perspectives for future advanced MXene materials and devices in smart sensing applications.

Physical mixing is one of the simplest ways to combine catalytic components, yet it has often been treated as an empirical formulation strategy rather than a rational design principle. This Review states that, when distinct solids are arranged to exchange intermediates, products, inhibitors, heat or local chemical potentials, a physical mixture can function as an interfacial reaction network rather than as a simple sum of independent catalysts. We define this concept as interfacial reaction-network catalysis (IRNC), in which complex transformations are spatially partitioned into coupled functional domains and steered through measurable interdomain exchange. After clarifying the boundaries between physical mixing, conventional bifunctional catalysis and chemically integrated architectures, we introduce three network-control modes: intermediate relay, catalytic shunting and thermodynamic cascading. Intermediate relay connects source and receiving domains through relayed intermediates. Catalytic shunting allocates branch-point flux among desired, side, escape and deactivation pathways. Thermodynamic cascading regulates local activities, residence times and deactivation exposure through enrichment, product removal and inhibitor buffering. We then discuss how these functions operate in oxide-zeolite, Fischer-Tropsch-zeolite and multicomponent systems, and how physical separation and chemical integration provide complementary coupling regimes. Finally, we highlight descriptor quantification, operando characterization, multiscale simulation and catalyst-reactor co-design as key requirements for moving IRNC from empirical combination to predictive network programming. This framework establishes physical mixing as a modular and scalable strategy for steering complex catalytic transformations across molecular, particle and reactor scales.

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%.