Chemical Society Reviews最新文献

Organic transformation driven by heterogeneous catalysis is of crucial significance in both fundamental research and modern industrial production of fine chemicals. Thermocatalysis offers excellent applications due to its high activity and excellent scalability, yet still faces significant challenges toward the goals of high efficiency, energy-saving and sustainability. Recently, photocatalysis has emerged as a promising alternative for addressing these issues in a green and economical manner. In practice, the selection of an appropriate catalytic system is a critical factor that can influence the chemical process on multiple levels significantly. In this review, we aim to present a tutorial demonstration about the critical comparison between thermo- and photocatalytic terms for organic transformation. We begin by outlining the basic principles in thermo- and photocatalytic fundamentals, together with summarizing the general advantages and disadvantages of each. Subsequently, given the high sustainability and potentiality exhibited by the photocatalytic process, we present its representative applications including oxidation, reduction, coupling, and cleavage series. The general reaction conditions and activities observed in thermocatalysis for similar reactions are also introduced for comparison. The understanding of reaction mechanisms and the resulting regulations toward activity and selectivity are specifically discussed. Finally, future perspectives of heterogeneous photocatalytic terms for practical applications are elucidated.

Acetylene, a traditional industrial raw material, has garnered increasing attention in modern organic synthesis over the past two decades. Its catalytic transformation has emerged as an atom-economical and efficient strategy for producing a variety of high value-added compounds. This review comprehensively summarizes recent advancements and breakthroughs in the catalytic conversion of acetylene, focusing on two main categories: transition-metal-catalyzed transformations and photo-catalyzed/promoted transformations. The discussions center on various reaction intermediates, including alkenylmetals, acetylides, metallacyclopentadienes or heterometallacycles, gold carbenes, alkenyl-Ni complexes, and vinyl radicals. Furthermore, this review delves into the detailed mechanisms and diverse derivatizations of these reactions, highlighting their significance in the development of versatile acetylene catalytic transformations.

In this review, we provide an overview of research efforts to integrate carbon dioxide capture specifically using amino acid-based sorbents with its thermocatalytic hydrogenation promoted by homogeneous metal complexes. Carbon capture and utilization (CCU) is a promising strategy for the production of fuels, chemicals and materials using CO₂ scrubbed from point sources and the atmosphere as a C1 feedstock while mitigating CO₂ emissions. Compared to established (alkanol)amines, amino acids offer some advantages as CO₂ capture agents due to their lower volatility, higher oxygen stability and lower regeneration energies. We report how the structural diversity of amino acids and the possibility of combining them with cations in salts and ionic liquids have been exploited in the design of absorbers for improved absorption kinetics and capacity. Furthermore, we discuss selected examples from the literature illustrating the use of 1°/2° (poly)amines, since the 1°/2° amino groups are mainly responsible for CO₂ chemisorption in amino acid-based capture media, the nature of the corresponding adducts, and the most promising catalysts capable of converting the latter to formate and methanol while regenerating the scrubber. General trends regarding the influence of catalyst structure and reaction parameters on the efficiency, productivity, and selectivity of such processes will be highlighted. We will detail how this knowledge has informed the design of novel processes in which CO₂ is chemisorbed by amino acid-based solvents and hydrogenated in situ to formate and methanol, or alternatively used as a fuel to implement a “hydrogen battery” where, after metal-catalyzed H₂ release from formate, CO₂ is retained by the amino acid-based solvent in the “spent battery” which can then be recharged by hydrogenation of the retained CO₂ promoted by the same catalyst. The topic is still in its infancy, and several issues have emerged that will be critically discussed in the final section of this review. These issues need to be addressed in order to improve performance and provide a playground for researchers whose interest we hope to have aroused with this review.

Light serves as an excellent external stimulus due to its high spatial and temporal resolution. The use of light to regulate biological processes has evolved into a vibrant field over the past decade. Employing light on chemical substances such as bioactive molecules and drug delivery systems offers a promising therapeutic approach to achieve precise control over biological processes. In this review, we provide an overview of the advancements in optochemical technologies for controlling bioactive molecules (photopharmacology) and drug delivery systems (photoresponsive drug delivery), with an emphasis on their relationship and biomedical applications. Gaining a deeper understanding of the underlying mechanisms and emerging research will facilitate the development of optochemically controlled bioactive molecules and photoresponsive drug delivery systems, further enhancing light technologies in biomedical applications.

The fabrication of structures with designated topologies at the nanoscale is an intriguing issue, attributed to the possibility of both imparting unique properties to functional materials and unravelling the codes that lie in many natural systems. As a significant bottom-up approach, the self-assembly strategy is potent in formulating various exquisite structures. While the building of common types of miniaturized structures such as tubes, twists and spheres has been investigated in depth to gain insight into the intrinsic principles that dictate their formation and functions, the preparation of peculiar topological nanostructures is still scattered and unsystematic. In parallel, chirality is among the most ubiquitous phenomena of fundamental significance in nature and is in close relationship with the origin of life. Essentially, chirality represents a type of orderliness and thus may interplay with peculiar topologies in an orchestrated and serendipitous way. In this review, we describe the development of constructing emergent chiral and topological nanoarchitectures via the self-assembly method, mainly focusing on structures including toroids, catenanes, Möbius strips, spirals and fractals. In addition, other types involving toruloids/kebabs, trumpets and bamboos, screws, dendritic and lamellar twists are also exemplified. The design of building blocks and various self-assembling strategies towards these target architectures are highlighted in this review, in an effort to provide an overview of the feasible approaches that facilitate the tailored construction of mesoscopic structures.

N-heterocyclic carbenes (NHCs) have emerged as a versatile and powerful class of ligands in surface chemistry, offering remarkable stability and tunability when bound to surfaces, including metals, metal oxides, and semiconductors. Understanding their surface and interfacial mechanisms at the atomic-level is essential for precise control of molecule–surface interaction, as well as intermolecular interactions, which directly influence material performance and functionalities. Research in surface chemistry focusing on molecular binding modes, self-assembly, on-surface reactions, and electronic properties is crucial for the rational design of efficient catalysts, customized materials, and high-performance devices. This review highlights these critical aspects of NHCs on surfaces, beginning with their robust and multiple binding modes, which underpin their stability and versatility. The covalent NHC–surface bonds allow NHCs to form stable attachments, often surpassing the strength of traditional thiol-based modifiers, promoting robust anchoring across diverse materials. Another focus is the self-assembly of NHCs into highly ordered monolayers, which facilitates the design of functional nanostructures. Emerging topics also include on-surface reactions, surface electronic properties, and interfacial charge transfer of NHCs, emphasizing their dependence on the substrate and NHC molecular structure. By consolidating recent advancements in the study of NHCs on surfaces, we aim to provide a comprehensive overview of their transformative potential in surface chemistry at the atomic scale, while also identifying key challenges and future directions in the field.

In vivo diagnostics obtains real-time physiological information directly from the site of interest in a patient's body, providing more accurate disease diagnosis compared with ex vivo diagnostics. Particularly, in vivo dynamic diagnostics allows the continuous monitoring of physiological signals over a period of time, offering deeper insights into disease pathogenesis and progression. However, achieving in situ dynamic diagnostics in deep tissues presents challenges related to energy and signal penetration as well as dynamic monitoring. Bioengineered nanomaterials serve as an ideal platform for in vivo dynamic diagnostics, leveraging energy conversion and biofunctionalization to enable continuous acquisition of physiological information across temporal and spatial scales. In this review, with reference to the studies from the last five years, we summarize the fundamental components that are essential for dynamic diagnosis in vivo. Firstly, an input energy source with high tissue penetration is needed, such as near-infrared (NIR) light, X-rays, magnetic field and ultrasound. Secondly, a nanomaterial class that is responsive to such an energy source to provide a readable output signal is chosen. Thirdly, bioengineered nanoprobes are designed to exhibit spatial, temporal or spatiotemporal changes in the output signal. Finally, different methods are used to analyse the output signal of nanoprobes, such as detecting changes in optical, radiation, magnetic and ultrasound signals. This review also discusses the obstacles and potential solutions for advancing these bioengineered nanomaterials toward clinical translational applications.

From accelerating simulations and exploring chemical space, to experimental planning and integrating automation within experimental labs, artificial intelligence (AI) is changing the landscape of chemistry. We are seeing a significant increase in the number of publications leveraging these powerful data-driven insights and models to accelerate all aspects of chemical research. For example, how we represent molecules and materials to computer algorithms for predictive and generative models, as well as the physical mechanisms by which we perform experiments in the lab for automation. Here, we present ten diverse perspectives on the impact of AI coming from those with a range of backgrounds from experimental chemistry, computational chemistry, computer science, engineering and across different areas of chemistry, including drug discovery, catalysis, chemical automation, chemical physics, materials chemistry. The ten perspectives presented here cover a range of themes, including AI for computation, facilitating discovery, supporting experiments, and enabling technologies for transformation. We highlight and discuss imminent challenges and ways in which we are redefining problems to accelerate the impact of chemical research via AI.

Electrocatalytic technologies, such as water electrolysis and metal–air batteries, enable a path to sustainable energy storage and conversion into high-value chemicals. These systems rely on electrocatalysts to drive redox reactions that define key performance metrics such as activity and selectivity. However, conventional electrocatalysts face inherent trade-offs between activity, stability, and scalability particularly due to the reliance on noble metals. Asymmetrically tailored electrocatalysts (ATEs) – systems that are being exploited for non-symmetric designs in composition, size, shape, and coordination environments – offer a path to overcome these barriers. Here, we summarize recent developments in ATEs, focusing on asymmetric coupling strategies employed in designing these systems with non-precious transition metal catalysts (TMCs). We explore tailored asymmetries in composition, size, and coordination environments, highlighting their impact on catalytic performance. We analyze the electrocatalytic mechanisms underlying ATEs with an emphasis on their roles in water-splitting and metal–air batteries. Finally, we discuss the challenges and opportunities in advancing the performance of these technologies through rational ATE designs.

Ammonia is an essential chemical due to its immense usage in agriculture, energy storage, and transportation. The synthesis of “green” ammonia via carbon-free routes and renewable energy sources is the need of the hour. In this context, photo- and/or electrocatalysis proves to be highly crucial. Low-dimensional materials (LDMs), owing to their unique properties, play a significant role in catalysis. This review presents a vast library of LDMs and broadly categorizes their catalytic performance according to their dimensionality, i.e., zero-, one-, and two-dimensional catalysts. The rational design of LDMs can significantly improve their catalytic performance, particularly in reducing small molecules like dinitrogen, nitrates, nitrites, and nitric oxides to synthesize ammonia via photo- and/or electrocatalysis. Additionally, converting nitrates and nitrites to ammonia can be beneficial in wastewater treatment and be coupled with CO₂ co-reduction or oxidative reactions to produce urea and other valuable chemicals, which are also discussed in this review. This review collates the works published in recent years in this field and offers some fresh perspectives on ammonia synthesis. Through this review, we aim to provide a comprehensive insight into the catalytic properties of the LDMs, which are expected to enhance the efficiency of ammonia production and promote the synthesis of value-added products.