As an important strategic resource, rare earths (REs) constitute 17 elements in the periodic table, namely 15 lanthanides (Ln) (La–Lu, atomic numbers from 57 to 71), scandium (Sc, atomic number 21) and yttrium (Y, atomic number 39). In the field of catalysis, the localization and incomplete filling of 4f electrons endow REs with unique physical and chemical properties, including rich electronic energy level structures, variable coordination numbers, etc., making them have great potential in electrocatalysis. Among various RE catalytic materials, rare earth oxide (REO)-based electrocatalysts exhibit excellent performances in electrocatalytic reactions due to their simple preparation process and strong structural variability. At the same time, the electronic orbital structure of REs exhibits excellent electron transfer ability, which can reduce the band gap and energy barrier values of rate-determining steps, further accelerating the electron transfer in the electrocatalytic reaction process; however, there is a lack of systematic review of recent advances in REO-based electrocatalysis. This review systematically summarizes the synthesis, properties and applications of REO-based nanocatalysts and discusses their applications in electrocatalysis in detail. It includes the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), methanol oxidation reaction (MOR), nitrogen reduction reaction (NRR) and other electrocatalytic reactions and further discusses the catalytic mechanism of REs in the above reactions. This review provides a timely and comprehensive summary of the current progress in the application of RE-based nanomaterials in electrocatalytic reactions and provides reasonable prospects for future electrocatalytic applications of REO-based materials.

Synthetic dynamic helical polymers (supramolecular and covalent) and foldamers share the helix as a structural motif. Although the materials are different, these systems also share many structural properties, such as helix induction or conformational communication mechanisms. The introduction of stimuli responsive building blocks or monomer repeating units in these materials triggers conformational or structural changes, due to the presence/absence of the external stimulus, which are transmitted to the helix resulting in different effects, such as assymetry amplification, helix inversion or even changes in the helical scaffold (elongation, J/H helical aggregates). In this review, we show through selected examples how different stimuli (e.g., temperature, solvents, cations, anions, redox, chiral additives, pH or light) can alter the helical structures of dynamic helical polymers (covalent and supramolecular) and foldamers acting on the conformational composition or molecular structure of their components, which is also transmitted to the macromolecular helical structure.

The development of novel materials capable of securely storing hydrogen at high volumetric and gravimetric densities is a requirement for the wide-scale usage of hydrogen as an energy carrier. In recent years, great efforts via nanoscale tuning and designing strategies on both physisorbents and chemisorbents have been devoted to improvements in their thermodynamic and kinetic aspects. Increasing the hydrogen storage capacity/density for physisorbents and chemisorbents and improving the dehydrogenation kinetics of hydrides are still considered a challenge. The extensive and fast development of advanced nanotechnologies has fueled a surge in research that presents huge potential in designing solid-state materials to meet the ultimate U.S. Department of Energy capacity targets for onboard light-duty vehicles, material-handling equipments, and portable power applications. Different from the existing literature, in this review, particular attention is paid to the recent advances in nanoscale engineering of solid-state materials for boosting hydrogen storage, especially the nanoscale tuning and designing strategies. We first present a short overview of hydrogen storage mechanisms of nanoscale engineering for boosted hydrogen storage performance on solid-state materials, for example, hydrogen spillover, nanopump effect, nanosize effect, nanocatalysis, and other non-classical hydrogen storage mechanisms. Then, the focus is on recent advancements in nanoscale engineering strategies aimed at enhancing the gravimetric hydrogen storage capacity of porous materials, reducing dehydrogenation temperature and improving reaction kinetics and reversibility of hydrogen desorption/absorption for metal hydrides. Effective nanoscale tuning strategies for enhancing the hydrogen storage performance of porous materials include optimizing surface area and pore volume, fine-tuning nanopore sizes, introducing nanostructure doping, and crafting nanoarchitecture and nanohybrid materials. For metal hydrides, successful strategies involve nanoconfinement, nanosizing, and the incorporation of nanocatalysts. This review further addresses the points to future research directions in the hope of ushering in the practical applications of hydrogen storage materials.

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Metal–oxo clusters hold great potential in several fields such as catalysis, materials science, energy storage, medicine, and biotechnology. These nanoclusters of transition metals with oxygen-based ligands have also shown promising reactivity towards several classes of biomolecules, including proteins, nucleic acids, nucleotides, sugars, and lipids. This reactivity can be leveraged to address some of the most pressing challenges we face today, from fighting various diseases, such as cancer and viral infections, to the development of sustainable and environmentally friendly energy sources. For instance, metal–oxo clusters and related materials have been shown to be effective catalysts for biomass conversion into renewable fuels and platform chemicals. Furthermore, their reactivity towards biomolecules has also attracted interest in the development of inorganic drugs and bioanalytical tools. Additionally, the structural versatility of metal–oxo clusters allows for the efficiency and selectivity of the biomolecular reactions they promote to be readily tuned, thereby providing a pathway towards reaction optimization. The properties of the catalyst can also be improved through incorporation into solid supports or by linking metal–oxo clusters together to form Metal–Organic Frameworks (MOFs), which have been demonstrated to be powerful heterogeneous catalysts. Therefore, this review aims to provide a comprehensive and critical analysis of the state of the art on biomolecular transformations promoted by metal–oxo clusters and their applications, with a particular focus on structure–activity relationships.

Electrocatalytic high-throughput seawater electrolysis for hydrogen production is a promising green energy technology that offers possibilities for environmental and energy sustainability. However, large-scale application is limited by the complex composition of seawater, high concentration of Cl− leading to competing reaction, and severe corrosion of electrode materials. In recent years, extensive research has been conducted to address these challenges. Metal nitrides (MNs) with excellent chemical stability and catalytic properties have emerged as ideal electrocatalyst candidates. This review presents the electrode reactions and basic parameters of the seawater splitting process, and summarizes the types and selection principles of conductive substrates with critical analysis of the design principles for seawater electrocatalysts. The focus is on discussing the properties, synthesis, and design strategies of MN-based electrocatalysts. Finally, we provide an outlook for the future development of MNs in the high-throughput seawater electrolysis field and highlight key issues that require further research and optimization.

Catalysts play a major role in chemical synthesis, and catalysis is considered to be a green and economic process. Catalysis is dominated by covalent interactions between the catalyst and substrate. The design of non-covalent catalysts came into limelight only recently. Hydrogen bonding (HB) catalysts are well established among non-covalent catalysts, including asymmetric HB catalysts. Though halogen bonding (XB) catalysis and its asymmetric version are gaining admiration, non-covalent chalcogen bonding catalysis (ChB) is in the budding stage. This tutorial review will focus on the recently evolved chalcogen bonding catalysis and emphasis will be given to the chalcogen bonding of chiral molecules. Since successful enantioselective chalcogen bonding catalysis is yet to be reported, this review will focus on the basics of non-covalent bonding catalysis, chalcogen bonding catalysis, chiral chalcogenide synthesis, rigidification of transition states by ChB, stabilization of cations by chiral chalcogens, details of unsuccessful asymmetric chalcogen bonding catalysis, enantioseparation of racemic molecules using ChB, and the existence of ChB in chiral biomolecules.

Nuclear targeting of therapeutics provides a strategy for enhancing efficacy of molecules active in the nucleus and minimizing off-target effects. ‘Active’ nuclear-directed transport and efficient translocations across nuclear pore complexes provide the most effective means of maximizing nuclear localization. Nuclear-targeting systems based on nuclear localization signal (NLS) motifs have progressed significantly since the beginning of the current millennium. Here, we offer a roadmap for understanding the basic mechanisms of nuclear import in the context of actionable therapeutic design for developing NLS-therapeutics with improved treatment efficacy.

Epoxy resins (EPs), accounting for about 70% of the thermosetting resin market, have been recognized as the most widely used thermosetting resins in the world. Nowadays, 90% of the world's EPs are obtained from the bisphenol A (BPA)-based epoxide prepolymer. However, certain limitations severely impede further applications of this advanced material, such as limited fossil-based resources, skyrocketing oil prices, nondegradability, and a “seesaw” between toughness and strength. In recent years, more and more research has been devoted to the preparation of novel epoxy materials to overcome the compromise between toughness and strength and solve plastic waste problems. Among them, the development of bio-based hyperbranched epoxy resins (HERs) is unique and attractive. Bio-based HERs synthesized from bio-derived monomers can be used as a matrix resin or a toughener resulting in partially or fully bio-based epoxy thermosets. The introduction of a hyperbranched structure can balance the strength and toughness of epoxy thermosets. Here, we especially focused on the recent progress in the development of bio-based HERs, including the monomer design, synthesis approaches, mechanical properties, degradation, and recycling strategies. In addition, we advance the challenges and perspectives to engineering application of bio-based HERs in the future. Overall, this review presents an up-to-date overview of bio-based HERs and guidance for emerging research on the sustainable development of EPs in versatile high-tech fields.

Gene therapy is on its way to revolutionize the treatment of both inherited and acquired diseases, by transferring nucleic acids to correct a disease-causing gene in the target cells of patients. In the fight against infectious diseases, mRNA-based therapeutics have proven to be a viable strategy in the recent Covid-19 pandemic. Although a growing number of gene therapies have been approved, the success rate is limited when compared to the large number of preclinical and clinical trials that have been/are being performed. In this review, we highlight some of the hurdles which gene therapies encounter after administration into the human body, with a focus on nucleic acid degradation by nucleases that are extremely abundant in mammalian organs, biological fluids as well as in subcellular compartments. We overview the available strategies to reduce the biodegradation of gene therapeutics after administration, including chemical modifications of the nucleic acids, encapsulation into vectors and co-administration with nuclease inhibitors and discuss which strategies are applied for clinically approved nucleic acid therapeutics. In the final part, we discuss the currently available methods and techniques to qualify and quantify the integrity of nucleic acids, with their own strengths and limitations.

Proteins are multifunctional large organic compounds that constitute an essential component of a living system. Hence, control over their bioconjugation impacts science at the chemistry–biology–medicine interface. A chemical toolbox for their precision engineering can boost healthcare and open a gateway for directed or precision therapeutics. Such a chemical toolbox remained elusive for a long time due to the complexity presented by the large pool of functional groups. The precise single-site modification of a protein requires a method to address a combination of selectivity attributes. This review focuses on guiding principles that can segregate them to simplify the task for a chemical method. Such a disintegration systematically employs a multi-step chemical transformation to deconvolute the selectivity challenges. It constitutes a disintegrate (DIN) theory that offers additional control parameters for tuning precision in protein bioconjugation. This review outlines the selectivity hurdles faced by chemical methods. It elaborates on the developments in the perspective of DIN theory to demonstrate simultaneous regulation of reactivity, chemoselectivity, site-selectivity, modularity, residue specificity, and protein specificity. It discusses the progress of such methods to construct protein and antibody conjugates for biologics, including antibody–fluorophore and antibody–drug conjugates (AFCs and ADCs). It also briefs how this knowledge can assist in developing small molecule-based covalent inhibitors. In the process, it highlights an opportunity for hypothesis-driven routes to accelerate discoveries of selective methods and establish new targetome in the precision engineering of proteins and antibodies.

The employment of light and/or electricity – alternatively to conventional thermal energy – unlocks new reactivity paradigms as tools for chemical substrate activations. This leads to the development of new synthetic reactions and a vast expansion of chemical spaces. This review summarizes recent developments in photo- and/or electrochemical activation strategies for the functionalization of strong bonds – particularly carbon–heteroatom (C–X) bonds – via: (1) direct photoexcitation by high energy UV light; (2) activation via photoredox catalysis under irradiation with relatively lower energy UVA or blue light; (3) electrochemical reduction; (4) combination of photocatalysis and electrochemistry. Based on the types of the targeted C–X bonds, various transformations ranging from hydrodefunctionalization to cross-coupling are covered with detailed discussions of their reaction mechanisms.

Crystalline–amorphous hybrid materials (CA-HMs) possess the merits of both pure crystalline and amorphous phases. Abundant dangling bonds, unsaturated coordination atoms, and isotropic structural features in the amorphous phase, as well as relatively high electronic conductivity and thermodynamic structural stability of the crystalline phase simultaneously take effect in CA-HMs. Furthermore, the atomic and bandgap mismatch at the CA-HM interface can introduce more defects as extra active sites, reservoirs for promoted catalytic and electrochemical performance, and induce built-in electric field for facile charge carrier transport. Motivated by these intriguing features, herein, we provide a comprehensive overview of CA-HMs on various aspects—from synthetic methods to multiple applications. Typical characteristics of CA-HMs are discussed at the beginning, followed by representative synthetic strategies of CA-HMs, including hydrothermal/solvothermal methods, deposition techniques, thermal adjustment, and templating methods. Diverse applications of CA-HMs, such as electrocatalysis, batteries, supercapacitors, mechanics, optoelectronics, and thermoelectrics along with underlying structure–property mechanisms are carefully elucidated. Finally, challenges and perspectives of CA-HMs are proposed with an aim to provide insights into the future development of CA-HMs.

Low valent group 14 compounds exhibit diverse structures and reactivities. The employment of diazaborolyl anions (NHB anions), isoelectronic analogues to N-heterocyclic carbenes (NHCs), in group 14 chemistry leads to the exceptional structures and reactivity. The unique combination of σ-electron donation and pronounced steric hindrance impart distinct structural characteristics to the NHB-substituted low valent group 14 compounds. Notably, the modulation of the HOMO–LUMO gap in these compounds with the diazaborolyl substituents results in novel reaction patterns in the activation of small molecules and inert chemical bonds. This review mainly summarizes the recent advances in NHB-substituted low-valent heavy Group 14 compounds, emphasizing their synthesis, structural characteristics and application to small molecule activation.

Although they are emerging technologies for achieving high-efficiency and green and eco-friendly energy conversion, ceramic electrochemical cells (CECs), i.e. solid oxide electrolysis cells (SOECs) and fuel cells (SOFCs), are still fundamentally limited by their inferior catalytic activities at low temperature, poor thermo-mechanical stability, high material cost, etc. The materials used in electrolytes and electrodes, which are the most important components in CECs, are highly associated with the cell performances. Therefore, rational design of electrolytes and electrodes with excellent catalytic activities and high stabilities at relatively low cost is a meaningful and valuable approach for the development of CECs. Nanotechnology is a powerful tool for improving the material performances in CECs owing to the favourable effects induced by the nanocrystallization of electrolytes and electrodes. Herein, a relatively comprehensive review on the nanotechnologies implemented in CECs is conducted. The working principles of CECs and the corresponding challenges were first presented, followed by the comprehensive insights into the working mechanisms of nanocrystalline materials in CECs. Then, systematic summarization and analyses of the commonly used nano-engineering strategies in the fabrication of CEC materials, including physical and chemical methods, were provided. In addition, the frontiers in the research of advanced electrolyte and electrode materials were discussed with a special emphasis on the modified electrochemical properties derived from nanotechnologies. Finally, the bottlenecks and the promising breakthroughs in nanotechnologies were highlighted in the direction of providing useful references for rational design of nanomaterials for CECs.

Covalent organic frameworks (COFs) represent an important class of crystalline porous materials with designable structures and functions. The interconnected organic monomers, featuring pre-designed symmetries and connectivities, dictate the structures of COFs, endowing them with high thermal and chemical stability, large surface area, and tunable micropores. Furthermore, by utilizing pre-functionalization or post-synthetic functionalization strategies, COFs can acquire multifunctionalities, leading to their versatile applications in gas separation/storage, catalysis, and optoelectronic devices. Our review provides a comprehensive account of the latest advancements in the principles, methods, and techniques for structural design and determination of COFs. These cutting-edge approaches enable the rational design and precise elucidation of COF structures, addressing fundamental physicochemical challenges associated with host–guest interactions, topological transformations, network interpenetration, and defect-mediated catalysis.

Correction for ‘A tutorial on asymmetric electrocatalysis’ by Jonas Rein et al., Chem. Soc. Rev., 2023, https://doi.org/10.1039/D3CS00511A.

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On 16 June 2023, the United Nations Environment Programme highlighted the severity of nitrogen pollution faced by humans and called for joint action for sustainable nitrogen use. Excess nitrogenous waste (NW: NO, NO2, NO2−, NO3−, etc.) mainly arises from the use of synthetic fertilisers, wastewater discharge, and fossil fuel combustion. Although the amount of NW produced can be minimised by reducing the use of nitrogen fertilisers and fossil fuels, the necessity to feed seven billion people on Earth limits the utility of this approach. Compared to current industrial processes, electrocatalytic NW reduction or CO2–NW co-reduction offers a potentially greener alternative for recycling NW and producing high-value chemicals. However, upgrading this technology to connect upstream and downstream industrial chains is challenging. This viewpoint focuses on electrocatalytic NW reduction, a cutting-edge technology, and highlights the challenges in its practical application. It also discusses future directions to meet the requirements of upstream and downstream industries by optimising production processes, including the pretreatment and supply of nitrogenous raw materials (e.g. flue gas and sewage), design and macroscopic preparation of electrocatalysts, and upscaling of reactors and other auxiliary equipment.

Fullerene chemistry has come a long way since 1990, when the first bulk production of C60 was reported. In the past decade, progress in supramolecular chemistry has opened some remarkable and previously unexpected opportunities regarding the selective (multiple) functionalization of fullerenes and their (self)assembly into larger structures and frameworks. The purpose of this review article is to provide a comprehensive overview of these recent developments. We describe how macrocycles and cages that bind strongly to C60 can be used to block undesired addition patterns and thus allow the selective preparation of single-isomer addition products. We also discuss how the emergence of highly shape-persistent macrocycles has opened opportunities for the study of photoactive fullerene dyads and triads as well as the preparation of mechanically interlocked compounds. The preparation of two- or three-dimensional fullerene materials is another research area that has seen remarkable progress over the past few years. Due to the rapidly decreasing price of C60 and C70, we believe that these achievements will translate into all fields where fullerenes have traditionally (third-generation solar cells) and more recently been applied (catalysis, spintronics).