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Entangling strands in a well-ordered manner can produce useful effects, from shoelaces and fishing nets to brown paper packages tied up with strings. At the nanoscale, non-crystalline polymer chains of sufficient length and flexibility randomly form tangled mixtures containing open knots of different sizes, shapes and complexity. However, discrete molecular knots of precise topology can also be obtained by controlling the number, sequence and stereochemistry of strand crossings: orderly molecular entanglements. During the last decade, substantial progress in the nascent field of molecular nanotopology has been made, with general synthetic strategies and new knotting motifs introduced, along with insights into the properties and functions of ordered tangle sequences. Conformational restrictions imparted by knotting can induce allostery, strong and selective anion binding, catalytic activity, lead to effective chiral expression across length scales, binding modes in conformations efficacious for drug delivery, and facilitate mechanical function at the molecular level. As complex molecular topologies become increasingly synthetically accessible they have the potential to play a significant role in molecular and materials design strategies. We highlight particular examples of molecular knots to illustrate why these are a few of our favourite things. [ABSTRACT FROM AUTHOR]

Descriptors play a crucial role in electrocatalysis as they can provide valuable insights into the electrochemical performance of energy conversion and storage processes. They allow for the understanding of different catalytic activities and enable the prediction of better catalysts without relying on the time-consuming trial-and-error approaches. Hence, this comprehensive review focuses on highlighting the significant advancements in commonly used descriptors for critical electrocatalytic reactions. First, the fundamental reaction processes and key intermediates involved in several electrocatalytic reactions are summarized. Subsequently, three types of descriptors are classified and introduced based on different reactions and catalysts. These include d-band center descriptors, readily accessible intrinsic property descriptors, and spin-related descriptors, all of which contribute to a profound understanding of catalytic behavior. Furthermore, multi-type descriptors that collectively determine the catalytic performance are also summarized. Finally, we discuss the future of descriptors, envisioning their potential to integrate multiple factors, broaden application scopes, and synergize with artificial intelligence for more efficient catalyst design and discovery. [ABSTRACT FROM AUTHOR]

Elevated levels of carbon dioxide (CO2) in the atmosphere and the diminishing reserves of fossil fuels have raised profound concerns regarding the resulting consequences of global climate change and the future supply of energy. Hence, the reduction and transformation of CO2 not only mitigates environmental pollution but also generates value-added chemicals, providing a dual remedy to address both energy and environmental challenges. Despite notable advancements, the low conversion efficiency of CO2 remains a major obstacle, largely attributed to its inert chemical nature. It is imperative to engineer catalysts/materials that exhibit high conversion efficiency, selectivity, and stability for CO2 transformation. With unparalleled precision at the atomic level, atomic layer deposition (ALD) and molecular layer deposition (MLD) methods utilize various strategies, including ultrathin modification, overcoating, interlayer coating, area-selective deposition, template-assisted deposition, and sacrificial-layer-assisted deposition, to synthesize numerous novel metal-based materials with diverse structures. These materials, functioning as active materials, passive materials or modifiers, have contributed to the enhancement of catalytic activity, selectivity, and stability, effectively addressing the challenges linked to CO2 transformation. Herein, this review focuses on ALD and MLD’s role in fabricating materials for electro-, photo-, photoelectro-, and thermal catalytic CO2 reduction, CO2 capture and separation, and electrochemical CO2 sensing. Significant emphasis is dedicated to the ALD and MLD designed materials, their crucial role in enhancing performance, and exploring the relationship between their structures and catalytic activities for CO2 transformation. Finally, this comprehensive review presents the summary, challenges and prospects for ALD and MLD-designed materials for CO2 transformation. [ABSTRACT FROM AUTHOR]

Cost-effective and high-efficiency catalysts play a central role in various sustainable electrochemical energy conversion technologies that are being developed to generate clean energy while reducing carbon emissions, such as fuel cells, metal–air batteries, water electrolyzers, and carbon dioxide conversion. In this context, a recent climax in the exploitation of advanced earth-abundant catalysts has been witnessed for diverse electrochemical reactions involved in the above mentioned sustainable pathways. In particular, polymer catalysts have garnered considerable interest and achieved substantial progress very recently, mainly owing to their pyrolysis-free synthesis, highly tunable molecular composition and microarchitecture, readily adjustable electrical conductivity, and high stability. In this review, we present a timely and comprehensive overview of the latest advances in organic polymers as emerging materials for powerful electrocatalysts. First, we present the general principles for the design of polymer catalysts in terms of catalytic activity, electrical conductivity, mass transfer, and stability. Then, the state-of-the-art engineering strategies to tailor the polymer catalysts at both molecular (i.e., heteroatom and metal atom engineering) and macromolecular (i.e., chain, topology, and composition engineering) levels are introduced. Particular attention is paid to the insightful understanding of structure–performance correlations and electrocatalytic mechanisms. The fundamentals behind these critical electrochemical reactions, including the oxygen reduction reaction, hydrogen evolution reaction, CO2 reduction reaction, oxygen evolution reaction, and hydrogen oxidation reaction, as well as breakthroughs in polymer catalysts, are outlined as well. Finally, we further discuss the current challenges and suggest new opportunities for the rational design of advanced polymer catalysts. By presenting the progress, engineering strategies, insightful understandings, challenges, and perspectives, we hope this review can provide valuable guidelines for the future development of polymer catalysts. [ABSTRACT FROM AUTHOR]

Benefiting from low costs, structural diversities, tunable catalytic activities, feasible modifications, and high stability compared to the natural enzymes, reactive oxygen nanobiocatalysts (RONBCs) have become dominant materials in catalyzing and mediating reactive oxygen species (ROS) for diverse biomedical and biological applications. Decoding the catalytic mechanism and structure--reactivity relationship of RONBCs is critical to guide their future developments. Here, this timely review comprehensively summarizes the recent breakthroughs and future trends in creating and decoding RONBCs. First, the fundamental classification, activity, detection method, and reaction mechanism for biocatalytic ROS generation and elimination have been systematically disclosed. Then, the merits, modulation strategies, structure evolutions, and state-of-art characterisation techniques for designing RONBCs have been briefly outlined. Thereafter, we thoroughly discuss different RONBCs based on the reported major material species, including metal compounds, carbon nanostructures, and organic networks. In particular, we offer particular insights into the coordination microenvironments, bond interactions, reaction pathways, and performance comparisons to disclose the structure--reactivity relationships and mechanisms. In the end, the future challenge and perspectives for RONBCs are also carefully summarised. We envision that this review will provide a comprehensive understanding and guidance for designing ROS-catalytic materials and stimulate the wide utilisation of RONBCs in diverse biomedical and biological applications. [ABSTRACT FROM AUTHOR]

Planar chirality is an important form of molecular chirality that can be utilized to induce enantioselectivity when incorporated into transition metal catalysts. However, due to synthetic constraints, the use of late transition metal planar chiral complexes to conduct enantioselective transformations has been limited. Additionally, the published methods surrounding the stereochemical assignment of planar chiral compounds are sometimes conflicting, making proper assignment difficult. This review aims to provide clarity on the methods available to assign planar chirality and provide an overview on the synthesis and use of late transition metal planar chiral complexes as enantioselective catalysts. [ABSTRACT FROM AUTHOR]

Site-specific protein modification is a widely-used biochemical tool. However, there are many challenges associated with the development of protein modification techniques, in particular, achieving site-specificity, reaction efficiency and versatility. The engineering of peptide ligases and their substrates has been used to address these challenges. This review will focus on sortase, peptidyl asparaginyl ligases (PALs) and variants of subtilisin; detailing how their inherent specificity has been utilised for site-specific protein modification. The review will explore how the engineering of these enzymes and substrates has led to increased reaction efficiency mainly due to enhanced catalytic activity and reduction of reversibility. It will also describe how engineering peptide ligases to broaden their substrate scope is opening up new opportunities to expand the biochemical toolkit, particularly through the development of techniques to conjugate multiple substrates site-specifically onto a protein using orthogonal peptide ligases. [ABSTRACT FROM AUTHOR]

Due to inherent structural defects, common nanocatalysts always display limited catalytic activity and selectivity, making it practically difficult for them to replace natural enzymes in a broad scope of biologically important applications. By decreasing the size of the nanocatalysts, their catalytic activity and selectivity will be substantially improved. Guided by this concept, the advances of nanocatalysts now enter an era of atomic-level precise control. Single-atom catalysts (denoted as SACs), characterized by atomically dispersed active sites, strikingly show utmost atomic utilization, precisely located metal centers, unique metal-support interactions and identical coordination environments. Such advantages of SACs drastically boost the specific activity per metal atom, and thus provide great potential for achieving superior catalytic activity and selectivity to functionally mimic or even outperform natural enzymes of interest. Although the size of the catalysts does matter, it is not clear whether the guideline of "the smaller, the better" is still correct for developing catalysts at the single-atom scale. Thus, it is clearly a new, urgent issue to address before further extending SACs into biomedical applications, representing an important branch of nanomedicine. This review begins by providing an overview of recent advances of synthesis strategies of SACs, which serve as a basis for the discussion of emerging achievements in improving the enzyme-like catalytic properties at an atomic level. Then, we carefully compare the structures and functions of catalysts at various scales from nanoparticles, nanoclusters, and few-atom clusters to single atoms. Contrary to conventional wisdom, SACs are not the most catalytically active catalysts in specific reactions, especially those requiring multi-site auxiliary activities. After that, we highlight the unique roles of SACs toward biomedical applications. To appreciate these advances, the challenges and prospects in rapidly growing studies of SACs-related catalytic nanomedicine are also discussed in this review. [ABSTRACT FROM AUTHOR]

In view of their unique characteristics and properties, silver nanomaterials (Ag NMs) have been used not only in the field of nanomedicine but also for diverse advanced catalytic technologies. In this comprehensive review, light is shed on general synthetic approaches encompassing chemical reduction, sonochemical, microwave, and thermal treatment among the preparative methods for the syntheses of Ag-based NMs and their catalytic applications. Additionally, some of the latest innovative approaches such as continuous flow integrated with MW and other benign approaches have been emphasized that ultimately pave the way for sustainability. Moreover, the potential applications of emerging Ag NMs, including sub nanomaterials and single atoms, in the field of liquid-phase catalysis, photocatalysis, and electrocatalysis as well as a positive role of Ag NMs in catalytic reactions are meticulously summarized. The scientific interest in the synthesis and applications of Ag NMs lies in the integrated benefits of their catalytic activity, selectivity, stability, and recovery. Therefore, the rise and journey of Ag NM-based catalysts will inspire a new generation of chemists to tailor and design robust catalysts that can effectively tackle major environmental challenges and help to replace noble metals in advanced catalytic applications. This overview concludes by providing future perspectives on the research into Ag NMs in the arena of electrocatalysis and photocatalysis. [ABSTRACT FROM AUTHOR]