Chemical Society Reviews最新文献

Electrochemistry has emerged as a powerful means to facilitate redox transformations in modern chemical synthesis. This review focuses on organo-mediators that facilitate electrochemical reactions via outer-sphere electron transfer (ET) between active mediators and substrates, offering advantages over direct electrolysis due to their availability, ease of modification, and simple post-processing. They prevent overoxidation/reduction, enhance selectivity, and mitigate electrode passivation during the electrosynthesis. By modifying the structure of organo-mediators, those with tunable redox potentials enable electrosynthesis and avoid metal residues in the final products, making them promising for further application in synthetic chemistry, particularly in pharmacochemistry, where the maximum allowed level of the metal residue in synthetic samples is extremely strict. This review highlights the recent advancements in this rapidly growing area within the past two decades, including the electrochemical organo-mediated oxidation (EOMO) and electrochemical organo-mediated reduction (EOMR) events. The organo-mediator enabled electrochemical transformations are discussed according to the reaction type, which has been categorized into oxidation and reduction organic mediators.

Compared with the costly and toxic LiCoO₂ cathode in lithium-ion batteries (LIBs), nickel-based layered oxide (NLO) cathode materials exhibit the advantages of high capacity, natural abundance, environment-friendliness, and low cost, displaying tremendous application potentials in power batteries for automobiles and aircrafts. This review comprehensively introduces the challenges faced by NLO cathode materials in all alkali-ion batteries (AIBs) in their material synthesis, cation mixing, particle cracking, phase changes, cation dissolution of Mn, and oxygen loss Various strategies, including heteroatom doping, surface coating, and concentration gradient, are applied to tackle these problems by developing layered LiNi_1−xM_xO₂ (M: metal; 0 < x < 1) and LiNi_xCo_yMn_zO₂ (x + y + z = 1) materials. The successful commercial application of NLO cathode materials in LIBs has further driven their developments in sodium/potassium-ion batteries via the synthesis of (Na/K)Ni_1−xM_xO₂. Moreover, many sophisticated techniques, including in situ X-ray diffraction, scanning/transmission electron microscopy, operando neutron diffraction, and elemental analysis, are used to simultaneously monitor real-time phase changes, lattice variations, structural distortions, and elemental dissolutions of NLO-based materials. Furthermore, density functional theory (DFT) calculations are discussed as a powerful tool for predicting structural evolution, energy band structures, optimal doping concentrations, and ion diffusion pathways, thereby guiding the reasonable design of these materials. Finally, this review provides perspectives on future research directions and modification strategies for NLO cathode materials in AIBs, aiming to accelerate their deployment in electric vehicles and other energy storage devices. These efforts are expected to contribute significantly to the advancement of sustainable energy technologies and the global pursuit for carbon neutrality.

Surfaces are well known to be complex entities that are extremely difficult to study, and any phenomenon that is related to them is consequently challenging to approach. Moving from the bulk to the nanoscale adds a further layer of complexity to the problem. Because SERS relies on surfaces at the nanoscale, a rigorous understanding of the chemical phenomena that concur in the observation of the SERS signal is still limited or disorganized at best. Specifically, the lack of understanding of the chemical properties of nanoparticle surfaces has direct consequences on the development of SERS-based devices, causing a widespread belief that SERS is an inherently unreliable and fundamentally irreproducible analytical technique. Herein, we discuss old and new literature from SERS and related fields to accompany the reader through a journey that explores the chemical nature and architecture of colloidal plasmonic nanoparticles as the most popular SERS-active surfaces. By examining the chemistry of the surface landscape of the most common SERS colloids and the thermodynamic equilibria that characterize it, we aim to paint a chemically realistic picture of what a SERS analyst deals with on a daily basis. Thus, our goal for this review is to provide a centralized compilation of key, state-of-the-art surface chemistry information that can guide the rational development of analytical protocols and contribute an additional path through which our community can continue to advance SERS as a reliable and robust analytical tool.

In recent years, superhard covalently bonded materials have drawn a great deal of attention due to their excellent mechanical properties and potential applications in various fields. This review focuses on the self-healing behavior of these materials, outlining state-of-the-art research results. In detail, we discuss current self-healing mechanisms of self-healing materials including extrinsic healing mechanisms (such as microencapsulation, oxidative healing, shape memory, etc.) and intrinsic healing (dynamic covalent bonding, supramolecular interactions, diffusion, defect-driven processes, etc.). We also provide an overview of the progress in the self-healing behavior of superhard covalently bonded materials and the mechanisms of permanent covalent bonding healing. Additionally, we analyze the factors that influence the healing properties of these materials. Finally, the main findings and an outlook on the future directions and challenges of this emerging field are summarized in the Conclusion section.

The growing interest in the catalytic activity of earth-abundant 3d transition-metals has led to the development of new and more sustainable methods for C–H bond functionalization reactions. However, this is an emerging field which involves considerable mechanistic complexity as the mode of action of 3d transition metals differs markedly from the well-studied mechanisms of precious metals. In this review, we present an overview of the research efforts in Ni-, Cu-, Fe- and Co-catalyzed directed C(sp³)–H bond functionalization reactions, covering design principles and mechanistic discussions, along with potential applications and limitations. To conclude, the unresolved challenges and future viewpoints are highlighted. We aspire for this review to serve as a relevant and valuable reference for researchers in this swiftly progressing field, helping to inspire the development of more original and innovative strategies.

Natural products have applications as biopharmaceuticals, agrochemicals, and other high-value chemicals. However, there are challenges in isolating natural products from their native producers (e.g. bacteria, fungi, plants). In many cases, synthetic chemistry or heterologous expression must be used to access these important molecules. The biosynthetic machinery to generate these compounds is found within biosynthetic gene clusters, primarily consisting of the enzymes that biosynthesise a range of natural product classes (including, but not limited to ribosomal and nonribosomal peptides, polyketides, and terpenoids). Cell-free synthetic biology has emerged in recent years as a bottom-up technology applied towards both prototyping pathways and producing molecules. Recently, it has been applied to natural products, both to characterise biosynthetic pathways and produce new metabolites. This review discusses the core biochemistry of cell-free synthetic biology applied to metabolite production and critiques its advantages and disadvantages compared to whole cell and/or chemical production routes. Specifically, we review the advances in cell-free biosynthesis of ribosomal peptides, analyse the rapid prototyping of natural product biosynthetic enzymes and pathways, highlight advances in novel antimicrobial discovery, and discuss the rising use of cell-free technologies in industrial biotechnology and synthetic biology.

Rechargeable multivalent metal batteries (MMBs) are considered as promising alternatives to Li-ion and Pb-acid batteries for grid-scale energy storage applications due to the multi-electron redox capability of metal anodes. However, the conventional inorganic cathodes used in MMBs face challenges with the sluggish diffusivity and poor storage of charge-dense multivalent cations in their crystal lattice. Organic electrode materials (OEMs), on the other hand, offer several advantages as MMB cathodes, including flexible structural designability, high resource availability, sustainability, and a unique ion-coordination storage mechanism. This review explores the intrinsic connection between the structural features of OEMs and their charge storage performance, aiming to unveil key design principles for organic molecules used in various MMB applications. We begin with an overview of the fundamental aspects of different MMBs (i.e., Zn/Mg/Ca/Al batteries), covering electrolyte selection, metal stripping/plating electrochemistry, and the fundamentals of cathode operation. From a theoretical understanding of redox activities, we summarize the properties of different redox sites and correlate the electrochemical properties of OEMs with various structural factors. This analysis further leads to the introduction of critical design considerations for different types of OEMs. We then critically review a wide range of organic compounds for MMBs, from small organic molecules to redox-active polymers and covalent-organic frameworks, focusing on their structure–property relationships, key electrochemical parameters, and strengths and shortcomings for multivalent ion storage. Finally, we discuss the existing challenges and propose potential solutions for further advancing OEMs in MMBs.

This review offers a critical and exhaustive examination of the current state and innovative advances in high-voltage Li, Na, K, and Zn aqueous rechargeable batteries, an area poised for significant technological breakthroughs in energy storage systems. The practical issues that have traditionally hampered the development of aqueous batteries, such as limited operating potential windows, challenges in stable solid–electrolyte interphase (SEI) formation, the need for active materials optimized for aqueous environments, the misunderstood intercalation chemistry, the unreliable assessment techniques, and the overestimated performance and underestimated physicochemical and electrochemical drawbacks, are highlighted. We believe that this review not only brings together existing knowledge but also pushes the boundaries by providing a roadmap for future research and development efforts aimed at overcoming the longstanding challenges faced by the promising aqueous rechargeable batteries.

With the rates of infectious diseases and (pan)drug-resistant pathogens constantly increasing, there is a pressing need for the development of new drug candidates. To fight this global health crisis, new medicines should propose improved or novel modes of action. A successful strategy to fight microbial resistance is the incorporation of metallocenes into drug scaffolds. This review aims at encouraging the scientific community to follow this approach by giving an overview of all published synthetic strategies either for the derivatization of anti-infective drug scaffolds with metallocenes or for the de novo synthesis of original metallocenyl anti-infectives. This should facilitate future research as published articles are classified depending on the reaction type that is employed for the incorporation of the metallocenes, namely addition–elimination, condensation, “click” chemistry, cross-coupling, nucleophilic substitution and other methods. Overall, this review exhibits the impressive but somewhat unexploited potential of anti-infective metallocenyl compounds to treat infectious diseases.

The remarkable optoelectronic properties of metal halide perovskites (MHPs) have established them as highly promising photovoltaic absorber materials, propelling the rapid advancement of perovskite solar cells (PSCs) that outperform many traditional alternatives in terms of power conversion efficiency (PCE). However, despite their advancements, PSC devices encounter significant non-radiative recombination losses, encompassing trap-assisted (Shockley–Read–Hall) recombination in bulk and interfaces of PSCs, which restricts their open-circuit voltage (V_OC) and overall PCE, dragging it below the Shockley–Queisser (SQ) limit. The ongoing debate regarding the role of grain boundary (GB) recombination, whether it primarily manifests as bulk or surface recombination, has spurred extensive research aimed at elucidating these mechanisms. This review provides a critical comprehensive analysis of the thermodynamic correlations related to V_OC losses, bridging the gap between the theoretical SQ limit and practical device performance. Subsequently, it delves into recent findings that aim to decipher the multifaced nature and origin of radiative and non-radiative recombination-induced losses within the device stack, assessing their impacts on overall performance. Furthermore, this review emphasizes the application of advanced machine learning techniques to discern dominant recombination mechanisms in PSCs. Finally, it summarizes the notable advanced strategies to mitigate undesirable non-radiative recombination losses, which pave the way to the thermodynamic efficiency limit.