Chemical Reviews最新文献

The application of external electric fields to influence chemical reactions at electrode interfaces has attracted considerable interest in recent years. However, the design of electric fields to achieve highly efficient and selective catalytic systems, akin to the optimized fields found at enzyme active sites, remains a significant challenge. Consequently, there has been substantial effort in probing and understanding the interfacial electric fields at electrode/electrolyte interfaces and their effect on adsorbates. In this review, we examine recent advances in experimental, computational, and theoretical studies of the interfacial electric field, the origin of the vibrational Stark effect of adsorbates on electrode surfaces, and the effects of electric fields on reactions at electrode/electrolyte interfaces. We also discuss recent advances in control of charge transfer and chemical reactions using magnetic fields. Finally, we outline perspectives on key areas for future studies.

Heterogeneous catalysts are pivotal to the chemical and energy industries, which are central to a multitude of industrial processes. Large-scale industrial catalytic processes rely on special structures at the nano- or atomic level, where reactions proceed on the so-called active sites of heterogeneous catalysts. The complexity of these catalysts and active sites often lies in the interfacial regions where different components in the catalysts come into contact. Recent advances in synthetic methods, characterization technologies, and reaction kinetics studies have provided atomic-scale insights into these critical interfaces. Achieving atomic precision in interfacial engineering allows for the manipulation of electronic profiles, adsorption patterns, and surface motifs, deepening our understanding of reaction mechanisms at the atomic or molecular level. This mechanistic understanding is indispensable not only for fundamental scientific inquiry but also for the design of the next generation of highly efficient industrial catalysts. This review examines the latest developments in atomic-scale interfacial engineering, covering fundamental concepts, catalyst design, mechanistic insights, and characterization techniques, and shares our perspective on the future trajectory of this dynamic research field.

Cells contain thousands of different lipids. Their rapid and redundant metabolism, dynamic movement, and many interactions with other biomolecules have justly earned lipids a reputation as a vexing class of molecules to understand. Further, as the cell’s hydrophobic metabolites, lipids assemble into supramolecular structures─most commonly bilayers, or membranes─from which they carry out myriad biological functions. Motivated by this daunting complexity, researchers across disciplines are bringing order to the seeming chaos of biological lipids and membranes. Here, we formalize these efforts as “synthetic lipid biology”. Inspired by the idea, central to synthetic biology, that our abilities to understand and build biological systems are intimately connected, we organize studies and approaches across numerous fields to create, manipulate, and analyze lipids and biomembranes. These include construction of lipids and membranes from scratch using chemical and chemoenzymatic synthesis, editing of pre-existing membranes using optogenetics and protein engineering, detection of lipid metabolism and transport using bioorthogonal chemistry, and probing of lipid–protein interactions and membrane biophysical properties. What emerges is a portrait of an incipient field where chemists, biologists, physicists, and engineers work together in proximity─like lipids themselves─to build a clearer description of the properties, behaviors, and functions of lipids and membranes.

Template-directed synthesis has become a powerful methodology to access complex molecules. Noncovalent templating has been widely used in the last few decades, but less attention has been paid to covalent template-directed synthesis, despite the fact that this methodology was used for the first reported synthesis of a catenane. This review highlights the evolution of covalent templating over the last 60 years, thereby providing a toolbox for the design of efficient covalent templating processes. Covalent templating represents a useful synthetic tool for accessing complex molecules, and the examples described here include the synthesis of macrocycles, mechanically interlocked molecules, linear oligomers, polydisperse linear polymers, and cross-linked polymer networks.

N-Sulfonyl hydrazones have been extensively used as operationally safe carbene precursors in modern organic synthesis due to their ready availability, facile functionalization, and environmental benignity. Over the past two decades, there has been tremendous progress in the carbene chemistry of N-sulfonyl hydrazones in the presence of transition metal catalysts, under metal-free conditions, or using photocatalysts under photoirradiation conditions. Many carbene transfer reactions of N-sulfonyl hydrazones are unique and cannot be achieved by any alternative methods. The discovery of novel N-sulfonyl hydrazones and the development of highly enantioselective new reactions and skeletal editing reactions represent the notable recent achievements in the carbene chemistry of N-sulfonyl hydrazones. This review describes the overall progress made in the carbene chemistry of N-sulfonyl hydrazones, organized based on reaction types, spotlighting the current state-of-the-art and remaining challenges to be addressed in the future. Special emphasis is devoted to identifying, describing, and comparing the scope and limitations of current methodologies, key mechanistic scenarios, and potential applications in the synthesis of complex molecules.