Chemical Reviews最新文献

Nanozymes have shown significant potential in cancer catalytic therapy by strategically catalyzing tumor-associated substances and metabolites into toxic reactive oxygen species (ROS) in situ, thereby inducing oxidative stress and promoting cancer cell death. However, within the complex tumor microenvironment (TME), the rational design of nanozymes and factors like activity, reaction substrates, and the TME itself significantly influence the efficiency of ROS generation. To address these limitations, recent research has focused on exploring the factors that affect activity and developing nanozyme-based cascade catalytic systems, which can trigger two or more cascade catalytic processes within tumors, thereby producing more therapeutic substances and achieving efficient and stable cancer therapy with minimal side effects. This area has shown remarkable progress. This Perspective provides a comprehensive overview of nanozymes, covering their classification and fundamentals. The regulation of nanozyme activity and efficient strategies of rational design are discussed in detail. Furthermore, representative paradigms for the successful construction of cascade catalytic systems for cancer treatment are summarized with a focus on revealing the underlying catalytic mechanisms. Finally, we address the current challenges and future prospects for the development of nanozyme-based cascade catalytic systems in biomedical applications.

Throughout history, we have looked to nature to discover and copy pharmaceutical solutions to prevent and heal diseases. Due to the advances in metabolic engineering and the production of pharmaceutical proteins in different host cells, we have moved from mimicking nature to the delicate engineering of cells and proteins. We can now produce novel drug molecules, which are fusions of small chemical drugs and proteins. Currently we are at the brink of yet another step to venture beyond nature’s border with the use of unnatural amino acids and manufacturing without the use of living cells using cell-free systems. In this review, we summarize the progress and limitations of the last decades in the development of pharmaceutical protein development, production in cells, and cell-free systems. We also discuss possible future directions of the field.

The nascent field of targeted protein degradation (TPD) could revolutionize biomedicine due to the ability of degrader molecules to selectively modulate disease-relevant proteins. A key limitation to the broad application of TPD is its dependence on small-molecule ligands to target proteins of interest. This leaves unstructured proteins or those lacking defined cavities for small-molecule binding out of the scope of many TPD technologies. The use of proteins, peptides, and nucleic acids (otherwise known as “biologics”) as the protein-targeting moieties in degraders addresses this limitation. In the following sections, we provide a comprehensive and critical review of studies that have used proteins and peptides to mediate the degradation and hence the functional control of otherwise challenging disease-relevant protein targets. We describe existing platforms for protein/peptide-based ligand identification and the drug delivery systems that might be exploited for the delivery of biologic-based degraders. Throughout the Review, we underscore the successes, challenges, and opportunities of using protein-based degraders as chemical biology tools to spur discoveries, elucidate mechanisms, and act as a new therapeutic modality.

Vanadium is a transition metal with important industrial, technological, biological, and biomedical applications widespread in the environment and in living beings. The different reactions that vanadium compounds (VCs) undergo in the presence of proteins, nucleic acids, lipids and metabolites under mild physiological conditions are reviewed. In the environment vanadium is present naturally or through anthropogenic sources, the latter having an environmental impact caused by the dispersion of VCs in the atmosphere and aquifers. Vanadium has a versatile chemistry with interconvertible oxidation states, variable coordination number and geometry, and ability to form polyoxidovanadates with various nuclearity and structures. If a VC is added to a water-containing environment it can undergo hydrolysis, ligand-exchange, redox, and other types of changes, determined by the conditions and speciation chemistry of vanadium. Importantly, the solution is likely to differ from the VC introduced into the system and varies with concentration. Here, vanadium redox, hydrolytic and ligand-exchange chemical reactions, the influence of pH, concentration, salt, specific solutes, biomolecules, and VCs on the speciation are described. One of our goals with this work is highlight the need for assessment of the VC speciation, so that beneficial or toxic species might be identified and mechanisms of action be elucidated.

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.