Showing papers in "Chemical Society Reviews in 2022"

Electrocatalytic reduction of nitrate - a step towards a sustainable nitrogen cycle.

Abstract: Nitrate enrichment, which is mainly caused by the over-utilization of fertilisers and industrial sewage discharge, is a major global engineering challenge because of its negative influence on the environment and human health. To solve this serious problem, many technologies, such as the activated sludge method, reverse osmosis, ion exchange, adsorption, and electrodialysis, have been developed to reduce the nitrate levels in water bodies. However, the applications of these traditional techniques are limited by several drawbacks, such as a long sludge retention time, slow kinetics, and undesirable by-products. From an environmental perspective, the most promising nitrate reduction technology is enabled to convert nitrate into benign N2, and features low cost, high efficiency, and environmental friendliness. Recently, electrocatalytic nitrate reduction has been proven by satisfactory research achievements to be one of the most promising methods among these technologies. This review provides a comprehensive account of nitrate reduction using electrocatalysis methods. The fundamentals of electrocatalytic nitrate reduction, including the reaction mechanisms, reactor design principles, product detection methods, and performance evaluation methods, have been systematically summarised. A detailed introduction to electrocatalytic nitrate reduction on transition metals, especially noble metals and alloys, Cu-based electrocatalysts, and Fe-based electrocatalysts is provided, as they are essential for the accurate reporting of experimental results. The current challenges and potential opportunities in this field, including the innovation of material design systems, value-added product yields, and challenges for products beyond N2 and large-scale sewage treatment, are highlighted.

Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments

Abstract: Replacing fossil fuels with energy sources and carriers that are sustainable, environmentally benign, and affordable is amongst the most pressing challenges for future socio-economic development. To that goal, hydrogen is presumed to be the most promising energy carrier. Electrocatalytic water splitting, if driven by green electricity, would provide hydrogen with minimal CO2 footprint. The viability of water electrolysis still hinges on the availability of durable earth-abundant electrocatalyst materials and the overall process efficiency. This review spans from the fundamentals of electrocatalytically initiated water splitting to the very latest scientific findings from university and institutional research, also covering specifications and special features of the current industrial processes and those processes currently being tested in large-scale applications. Recently developed strategies are described for the optimisation and discovery of active and durable materials for electrodes that ever-increasingly harness first-principles calculations and machine learning. In addition, a technoeconomic analysis of water electrolysis is included that allows an assessment of the extent to which a large-scale implementation of water splitting can help to combat climate change. This review article is intended to cross-pollinate and strengthen efforts from fundamental understanding to technical implementation and to improve the ‘junctions’ between the field's physical chemists, materials scientists and engineers, as well as stimulate much-needed exchange among these groups on challenges encountered in the different domains.

Recent advances and perspectives for solar-driven water splitting using particulate photocatalysts.

Abstract: The conversion and storage of solar energy to chemical energy via artificial photosynthesis holds significant potential for optimizing the energy situation and mitigating the global warming effect. Photocatalytic water splitting utilizing particulate semiconductors offers great potential for the production of renewable hydrogen, while this cross-road among biology, chemistry, and physics features a topic with fascinating interdisciplinary challenges. Progress in photocatalytic water splitting has been achieved in recent years, ranging from fundamental scientific research to pioneering scalable practical applications. In this review, we focus mainly on the recent advancements in terms of the development of new light-absorption materials, insights and strategies for photogenerated charge separation, and studies towards surface catalytic reactions and mechanisms. In particular, we emphasize several efficient charge separation strategies such as surface-phase junction, spatial charge separation between facets, and polarity-induced charge separation, and also discuss their unique properties including ferroelectric and photo-Dember effects on spatial charge separation. By integrating time- and space-resolved characterization techniques, critical issues in photocatalytic water splitting including photoinduced charge generation, separation and transfer, and catalytic reactions are analyzed and reviewed. In addition, photocatalysts with state-of-art efficiencies in the laboratory stage and pioneering scalable solar water splitting systems for hydrogen production using particulate photocatalysts are presented. Finally, some perspectives and outlooks on the future development of photocatalytic water splitting using particulate photocatalysts are proposed.

Activity-based NIR fluorescent probes based on the versatile hemicyanine scaffold: design strategy, biomedical applications, and outlook.

Abstract: The discovery of a near-infrared (NIR, 650-900 nm) fluorescent chromophore hemicyanine dye with high structural tailorability is of great significance in the field of detection, bioimaging, and medical therapeutic applications. It exhibits many outstanding advantages including absorption and emission in the NIR region, tunable spectral properties, high photostability as well as a large Stokes shift. These properties are superior to those of conventional fluorogens, such as coumarin, fluorescein, naphthalimides, rhodamine, and cyanine. Researchers have made remarkable progress in developing activity-based multifunctional fluorescent probes based on hemicyanine skeletons for monitoring vital biomolecules in living systems through the output of fluorescence/photoacoustic signals, and integration of diagnosis and treatment of diseases using chemotherapy or photothermal/photodynamic therapy or combination therapy. These achievements prompted researchers to develop more smart fluorescent probes using a hemicyanine fluorogen as a template. In this review, we begin by describing the brief history of the discovery of hemicyanine dyes, synthetic approaches, and design strategies for activity-based functional fluorescent probes. Then, many selected hemicyanine-based probes that can detect ions, small biomolecules, overexpressed enzymes and diagnostic reagents for diseases are systematically highlighted. Finally, potential drawbacks and the outlook for future investigation and clinical medicine transformation of hemicyanine-based activatable functional probes are also discussed.

2D graphdiyne: an emerging carbon material

Abstract: As a new member of carbon allotropes, graphdiyne (GDY) has the characteristics of being one-atom-thick with two-dimensional layers comprising sp and sp2 hybridized carbon atoms, and represents a trend in the development of carbon materials. Its unique chemical and electronic structures give GDY many unique and fascinating properties such as rich chemical bonds, highly conjugated and super-large π structures, infinitely distributed pores and high inhomogeneity of charge distribution. GDY has entered a period of rapid development, especially with the significant emergence of fundamental research and applied research achievements over the past five years. As one of the frontiers of chemistry and materials science, graphdiyne was listed in the Top 10 research areas in the 2020 Research Frontiers report and was jointly released in the Top 10 in the world by Clarivate and the Chinese Academy of Sciences. The research results have shown the great potential of GDY in the applications of energy, catalysis, environmental science, electronic devices, detectors, biomedicine and therapy, etc. Scientists are eager to explore and fully reveal the new properties, discover new scientific concepts and phenomena, discover the new conversion modes and mechanisms of GDY in photoelectricity, energy, and catalysis, etc., and build the important scientific value of new conversion devices. This review covers research on the foundation and application of GDY, such as the controlled preparation of new methods of GDY and GDY-based materials, studies on new mechanisms and properties in chemistry and physics, and the foundation and applications in energy, catalysis, photoelectric and devices.

The fast-growing field of photo-driven theranostics based on aggregation-induced emission.

Abstract: Photo-driven theranostics, also known as phototheranostics, relying on the diverse excited-state energy conversions of theranostic agents upon photoexcitation represents a significant branch of theranostics, which ingeniously integrate diagnostic imaging and therapeutic interventions into a single formulation. The combined merits of photoexcitation and theranostics endow photo-driven theranostics with numerous superior features. The applications of aggregation-induced emission luminogens (AIEgens), a particular category of fluorophores, in the field of photo-driven theranostics have been intensively studied by virtue of their versatile advantageous merits of favorable biocompatibility, tuneable photophysical properties, unique aggregation-enhanced theranostic (AET) features, ideal AET-favored on-site activation ability and ready construction of one-for-all multimodal theranostics. This review summarised the significant achievements of photo-driven theranostics based on AIEgens, which were detailedly elaborated and classified by their diverse theranostic modalities into three groups: fluorescence imaging-guided photodynamic therapy, photoacoustic imaging-guided photothermal therapy, and multi-modality theranostics. Particularly, the tremendous advantages and individual design strategies of AIEgens in pursuit of high-performance photosensitizing output, high photothermal conversion and multimodal function capability by adjusting the excited-state energy dissipation pathways are emphasized in each section. In addition to highlighting AIEgens as promising templates for modulating energy dissipation in the application of photo-driven theranostics, current challenges and opportunities in this field are also discussed.

Adsorption of iodine in metal–organic framework materials

Abstract: Nuclear power will continue to provide energy for the foreseeable future, but it can pose significant challenges in terms of the disposal of waste and potential release of untreated radioactive substances. Iodine is a volatile product from uranium fission and is particularly problematic due to its solubility. Different isotopes of iodine present different issues for people and the environment. 129I has an extremely long half-life of 1.57 × 107 years and poses a long-term environmental risk due to bioaccumulation. In contrast, 131I has a shorter half-life of 8.02 days and poses a significant risk to human health. There is, therefore, an urgent need to develop secure, efficient and economic stores to capture and sequester ionic and neutral iodine residues. Metal–organic framework (MOF) materials are a new generation of solid sorbents that have wide potential applicability for gas adsorption and substrate binding, and recently there is emerging research on their use for the selective adsorptive removal of iodine. Herein, we review the state-of-the-art performance of MOFs for iodine adsorption and their host–guest chemistry. Various aspects are discussed, including establishing structure–property relationships between the functionality of the MOF host and iodine binding. The techniques and methodologies used for the characterisation of iodine adsorption and of iodine-loaded MOFs are also discussed together with strategies for designing new MOFs that show improved performance for iodine adsorption.

Tailored design of nanofiltration membranes for water treatment based on synthesis–property–performance relationships

Abstract: Tailored design of high-performance nanofiltration (NF) membranes is desirable because the requirements for membrane performance, particularly ion/salt rejection and selectivity, differ among the various applications of NF technology ranging from drinking water production to resource mining. However, this customization greatly relies on a comprehensive understanding of the influence of membrane fabrication methods and conditions on membrane properties and the relationships between the membrane structural and physicochemical properties and membrane performance. Since the inception of NF, much progress has been made in forming the foundation of tailored design of NF membranes and the underlying governing principles. This progress includes theories regarding NF mass transfer and solute rejection, further exploitation of the classical interfacial polymerization technique, and development of novel materials and membrane fabrication methods. In this critical review, we first summarize the progress made in controllable design of NF membrane properties in recent years from the perspective of optimizing interfacial polymerization techniques and adopting new manufacturing processes and materials. We then discuss the property-performance relationships based on solvent/solute mass transfer theories and mathematical models, and draw conclusions on membrane structural and physicochemical parameter regulation by modifying the fabrication process to improve membrane separation performance. Next, existing and potential applications of these NF membranes in water treatment processes are systematically discussed according to the different separation requirements. Finally, we point out the prospects and challenges of tailored design of NF membranes for water treatment applications. This review bridges the long-existing gaps between the pressing demand for suitable NF membranes from the industrial community and the surge of publications by the scientific community in recent years.

Is enzyme immobilization a mature discipline? Some critical considerations to capitalize on the benefits of immobilization.

Abstract: Enzyme immobilization has been developing since the 1960s and although many industrial biocatalytic processes use the technology to improve enzyme performance, still today we are far from full exploitation of the field. One clear reason is that many evaluate immobilization based on only a few experiments that are not always well-designed. In contrast to many other reviews on the subject, here we highlight the pitfalls of using incorrectly designed immobilization protocols and explain why in many cases sub-optimal results are obtained. We also describe solutions to overcome these challenges and come to the conclusion that recent developments in material science, bioprocess engineering and protein science continue to open new opportunities for the future. In this way, enzyme immobilization, far from being a mature discipline, remains as a subject of high interest and where intense research is still necessary to take full advantage of the possibilities.

Minimally invasive nanomedicine: nanotechnology in photo-/ultrasound-/radiation-/magnetism-mediated therapy and imaging.

Abstract: Traditional treatments such as chemotherapy and surgery usually cause severe side effects and excruciating pain. The emergence of nanomedicines and minimally invasive therapies (MITs) has brought hope to patients with malignant diseases. Especially, minimally invasive nanomedicines (MINs), which combine the advantages of nanomedicines and MITs, can effectively target pathological cells/tissues/organs to improve the bioavailability of drugs, minimize side effects and achieve painless treatment with a small incision or no incision, thereby acquiring good therapeutic effects. In this review, we provide a comprehensive review of the research status and challenges of MINs, which generally refers to the medical applications of nanotechnology in photo-/ultrasound-/radiation-/magnetism-mediated therapy and imaging. Additionally, we also discuss their combined application in various fields including cancers, cardiovascular diseases, tissue engineering, neuro-functional diseases, and infectious diseases. The prospects, and potential bench-to-bedside translation of MINs are also presented in this review. We expect that this review can inspire the broad interest for a wide range of readers working in the fields of interdisciplinary subjects including (but not limited to) chemistry, nanomedicine, bioengineering, nanotechnology, materials science, pharmacology, and biomedicine.

Activatable fluorescent probes for in situ imaging of enzymes.

Abstract: As the main biomarkers of most diseases, enzymes play fundamental but extremely critical roles in biosystems. High-resolution studies of enzymes using activatable in situ fluorescence imaging may help to better elucidate their dynamics in living systems. Currently, most activatable probes can realize changeable imaging of enzymes but inevitably tend to diffuse away from the original active site of the enzyme and even translocate out of cells, seriously impairing in situ high-resolution observation of the enzymes. In situ fluorescence imaging of enzymes can be realized by labelling probes or antibodies with always-on signals that fail to enable activatable imaging of enzymes. Thus, fluorescent probes with both "activatable" and "in situ" properties will enable high-resolution studies of enzymes in living systems. In this tutorial review, we summarize the existing methods ranging from design strategies to bioimaging applications that could be used to develop activatable fluorescent probes for in situ imaging of enzymes. It is expected that this tutorial review will promote the new methods generated to design such probes for better deciphering enzymes in complex biosystems and further extend the application of these methods to other fields of enzymes.

Piezoelectric nanogenerators for personalized healthcare.

Abstract: The development of flexible piezoelectric nanogenerators has experienced rapid progress in the past decade and is serving as the technological foundation of future state-of-the-art personalized healthcare. Due to their highly efficient mechanical-to-electrical energy conversion, easy implementation, and self-powering nature, these devices permit a plethora of innovative healthcare applications in the space of active sensing, electrical stimulation therapy, as well as passive human biomechanical energy harvesting to third party power on-body devices. This article gives a comprehensive review of the piezoelectric nanogenerators for personalized healthcare. After a brief introduction to the fundamental physical science of the piezoelectric effect, material engineering strategies, device structural designs, and human-body centered energy harvesting, sensing, and therapeutics applications are also systematically discussed. In addition, the challenges and opportunities of utilizing piezoelectric nanogenerators for self-powered bioelectronics and personalized healthcare are outlined in detail.

Porous organic polymers for electrocatalysis.

Abstract: Porous organic polymers (POPs) composed of organic building units linked via covalent bonds are a class of lightweight porous network materials with high surface areas, tuneable pores, and designable components and structures. Owing to their well-preserved characteristics in terms of structure and composition, POPs applied as electrocatalysts have shown promising activity and achieved considerable advances in numerous electrocatalytic reactions, including the hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, CO2 reduction reaction, N2 reduction reaction, nitrate/nitrite reduction reaction, nitrobenzene reduction reaction, hydrogen oxidation reaction, and benzyl alcohol oxidation reaction. Herein, we present a systematic overview of recent advances in the applications of POPs in these electrocatalytic reactions. The synthesis strategies, specific active sites, and catalytic mechanisms of POPs are summarized in this review. The fundamental principles of some electrocatalytic reactions are also concluded. We further discuss the current challenges of and perspectives on POPs for electrocatalytic applications. Meanwhile, the possible future directions are highlighted to afford guidelines for the development of efficient POP electrocatalysts.

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization.

Abstract: A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. This review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.

PROTACs: past, present and future.

Abstract: Proteolysis-targeting chimeras (PROTACs) are heterobifunctional molecules consisting of one ligand that binds to a protein of interest (POI) and another that can recruit an E3 ubiquitin ligase. The chemically-induced proximity between the POI and E3 ligase results in ubiquitination and subsequent degradation of the POI by the ubiquitin-proteasome system (UPS). The event-driven mechanism of action (MOA) of PROTACs offers several advantages compared to traditional occupancy-driven small molecule inhibitors, such as a catalytic nature, reduced dosing and dosing frequency, a more potent and longer-lasting effect, an added layer of selectivity to reduce potential toxicity, efficacy in the face of drug-resistance mechanisms, targeting nonenzymatic functions, and expanded target space. Here, we highlight important milestones and briefly discuss lessons learned about targeted protein degradation (TPD) in recent years and conjecture on the efforts still needed to expand the toolbox for PROTAC discovery to ultimately provide promising therapeutics.

Porous organic polymers for light-driven organic transformations.

Abstract: As a new generation of porous materials, porous organic polymers (POPs), have recently emerged as a powerful platform of heterogeneous photocatalysis. POPs are constructed using extensive organic synthesis methodologies, with various functional organic units being connected via high-energy covalent bonds. This review systematically presents the recent advances in POPs for visible-light driven organic transformations. Herein, we firstly summarize the common construction strategies for POP-based photocatalysts based on two major approaches: pre-design and post-modification; secondly, we categorize and summarize the synthesis methods and organic reaction types for constructing various types of POPs. We then classify and introduce the specific reactions of current light-driven POP-mediated organic transformations. Finally, we outline the current state of development and the problems faced in light-driven organic transformations by POPs, and we present some perspectives to motivate the reader to explore solutions to these problems and confront the present challenges in the development process.

Toxicity of metal-organic framework nanoparticles: from essential analyses to potential applications.

Abstract: In the last two decades, the field of metal-organic frameworks (MOFs) has exploded, and MOF nanoparticles in particular are being investigated with increasing interest for various applications, including gas storage and separation, water harvesting, catalysis, energy conversion and storage, sensing, diagnosis, therapy, and theranostics. To further pave their way into real-world applications, and to push the synthesis of MOF nanoparticles that are 'safe-and-sustainable-by-design', this tutorial review aims to shed light on the importance of a systematic toxicity assessment. After clarifying and working out the most important terms and aspects from the field of nanotoxicity, the current state-of-the-art of in vitro and in vivo toxicity studies of MOF nanoparticles is evaluated. Moreover, the key aspects affecting the toxicity of MOF nanoparticles such as their chemical composition, their physico-chemical properties, including their colloidal and chemical stability, are discussed. We highlight the need of more targeted synthesis of MOF nanoparticles that are 'safe-and-sustainable-by-design', and their tailored hazard assessment in the context of their potential applications in order to tap the full potential of this versatile material class in the future.

Porous organic polymers as a platform for sensing applications.

Abstract: Sensing analysis is significantly important for human health and environmental safety, and has gained increasing concern. As a promising material, porous organic polymers (POPs) have drawn widespread attention due to the availability of plentiful building blocks and their tunable structures, porosity and functions. Moreover, the permanent porous nature could provide a micro-environment to interact with guest molecules, rendering POPs attractive for application in the sensing field. In this review, we give a comprehensive overview of POPs as a platform for sensing applications. POP-based sensors are mainly divided into five categories, including fluorescence turn-on sensors, fluorescence turn-off sensors, ratiometric fluorescent sensors, colorimetric sensors and chemiresistive sensors, and their various sensing applications in detecting explosives, metal ions, anions, small molecules, biological molecules, pH changes, enantiomers, latent fingerprints and thermosensation are summarized. The different structure-based POPs and their corresponding synthetic strategies as well as the related sensing mechanisms mainly including energy transfer, donor-acceptor electron transfer, absorption competition quenching and inner filter effect are also involved in the discussion. Finally, the future outlook and perspective are addressed briefly.

Rational design of electrocatalytic carbon dioxide reduction for a zero-carbon network.

Abstract: Electrocatalytic CO2 reduction has attracted much attention for its potential application in CO2 mitigation and fuel production. During the past two decades, the electrocatalytic reduction of CO2 has made considerable progress, and it has become a promising tool to answer environmental problems. However, most research into electrocatalytic CO2 reduction focuses on catalysts at the material level instead of evaluating the performance of the entire system for practical applications, which is insufficient to promote the sound development. This review emphasizes on how to rationally design an electrocatalytic CO2 reduction system. We initially demonstrate the necessity of electrocatalytic CO2 reduction and establish its economic analysis, and at the same time provide an overview of representative breakthroughs in this field. Then, we combine with advanced characterization technologies to deeply understand the reaction pathways of electrocatalytic CO2 reduction at the molecular level. Furthermore, we point out how theoretical guidelines enable the rational design of high-throughput catalysts and the synergistic promotion of electrocatalytic CO2 reduction performance by optimizing the electrocatalytic interface and the reactor. Finally, we customize impartial recommendations and criteria for electrocatalytic CO2 reduction to promote its healthy development. We hope to stimulate high-quality research and may see the future application of electrocatalytic CO2 reduction to solve sustainable energy and environmental problems.

Organic photosensitizers for antimicrobial phototherapy.

Abstract: Microbial infectious diseases, especially those caused by new and antibiotic-resistant pathogenic microbes, have become a significant threat to global human health. As an antibiotic-free therapy, phototherapy is a promising approach to treat microbial infections due to its spatiotemporal selectivity, non-invasiveness, minimal side effects, and broad antimicrobial spectrum. Although organic photosensitizer-based antimicrobial phototherapy has been extensively studied over the last decade, there has been no specific review article on this topic yet. It is important and timely to summarize recent research progress in this field. This tutorial review highlights the concept and significance of phototherapy and summarizes innovative types of organic photosensitizers with design strategies to deal with microbial infections. In addition, examples of organic antimicrobial photosensitizers, including antibacterial photosensitizers, antiviral photosensitizers, and antifungal photosensitizers are discussed. Finally, current challenges and future directions of organic photosensitizer-based phototherapy for clinical antimicrobial applications are presented. We believe that this tutorial review will provide general guidance for the future development of efficient photosensitizers and encourage preclinical and clinical studies for phototherapy-mediated antimicrobial treatments.

Copper-catalyzed radical relay in C(sp3)-H functionalization.

Abstract: Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential in C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and the versatility of copper-catalyzed cross-coupling. More importantly, significant progress has been achieved in asymmetric C-H functionalization through judicious ligand design. This tutorial review will highlight the recent advances in this rapidly growing area, and we hope this survey will inspire future strategic developments for selective C(sp3)-H functionalization.

Ether-based electrolytes for sodium ion batteries.

Abstract: Sodium-ion batteries (SIBs) are considered to be strong candidates for large-scale energy storage with the benefits of cost-effectiveness and sodium abundance. Reliable electrolytes, as ionic conductors that regulate the electrochemical reaction behavior and the nature of the interface and electrode, are indispensable in the development of advanced SIBs with high Coulombic efficiency, stable cycling performance and high rate capability. Conventional carbonate-based electrolytes encounter numerous obstacles for their wide application in SIBs due to the formation of a dissolvable, continuous-thickening solid electrolyte interface (SEI) layer and inferior stability with electrodes. Comparatively, ether-based electrolytes (EBEs) are emerging in the secondary battery field with fascinating properties to improve the performance of batteries, especially SIBs. Their stable solvation structure enables highly reversible solvent-co-intercalation reactions and the formation of a thin and stable SEI. However, although EBEs can provide more stable cycling and rapid sodiation kinetics in electrodes, benefitting from their favorable electrolyte/electrode interactions such as chemical compatibility and good wettability, their special chemistry is still being investigated and puzzling. In this review, we provide a thorough and comprehensive overview on the developmental history, fundamental characteristics, superiorities and mechanisms of EBEs, together with their advances in other battery systems. Notably, the relation among electrolyte science, interfacial chemistry and electrochemical performance is highlighted, which is of great significance for the in-depth understanding of battery chemistry. Finally, future perspectives and potential directions are proposed to navigate the design and optimization of electrolytes and electrolyte/electrode interfaces for advanced batteries.

Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds

Abstract: C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have been devoted to transition-metal-catalyzed direct transformations of C-H bonds. Metal carbenes generated in situ from transition-metal compounds and diazo or its equivalents are usually applied as the transient reactive intermediates to furnish a catalytic cycle for new C-C and C-X bond formation. Using this strategy compounds from unactivated simple alkanes to complex molecules can be further functionalized or transformed to multi-functionalized compounds. In this area, transition-metal-catalyzed carbene insertion to C-H bonds has been paid continuous attention. Diverse catalyst design strategies, synthetic methods, and potential applications have been developed. This critical review will summarize the advance in transition-metal-catalyzed carbene insertion to C-H bonds dated up to July 2021, by the categories of C-H bonds from aliphatic C(sp3)-H, aryl (aromatic) C(sp2)-H, heteroaryl (heteroaromatic) C(sp2)-H bonds, alkenyl C(sp2)-H, and alkynyl C(sp)-H, as well as asymmetric carbene insertion to C-H bonds, and more coverage will be given to the recent work. Due to the rapid development of the C-H functionalization area, future directions in this topic are also discussed. This review will give the authors an overview of carbene insertion chemistry in C-H functionalization with focus on the catalytic systems and synthetic applications in C-C bond formation.

Construction and application of base-stable MOFs: a critical review.

Abstract: Metal-organic frameworks (MOFs) are a new class of porous crystalline materials constructed from organic ligands and metal ions/clusters. Owing to their unique advantages, they have attracted more and more attention in recent years and numerous studies have revealed their great potential in various applications. Many important applications of MOFs inevitably involve harsh alkaline operational environments. To achieve high performance and long cycling life in these applications, high stability of MOFs against bases is necessary. Therefore, the construction of base-stable MOFs has become a critical research direction in the MOF field. This review gives a historic summary of the development of base-stable MOFs in the last few years. The key factors that can determine the robustness of MOFs under basic conditions are analyzed. We also demonstrate the exciting achievements that have been made by utilizing base-stable MOFs in different applications. In the end, we discuss major challenges for the further development of base-stable MOFs. Some possible methods to address these problems are presented.

Porous organic polymers for high-performance supercapacitors.

Abstract: With the aim of addressing the global warming issue and fossil energy shortage, eco-friendly and sustainable renewable energy technologies are urgently needed. In comparison to energy conversion, studies on energy storage fall behind and remain largely to be explored. By storing energy from electrochemical processes at the electrode surface, supercapacitors (SCs) bridge the performance gap between electrostatic double-layer capacitors and batteries. Organic electrode materials have drawn extensive attention because of their special power density, good round trip efficiency and excellent cycle stability. Porous organic polymers (POPs) have drawn extensive attention as attractive electrode materials in SCs. In this review, we present and discuss recent advancements and design principles of POPs as efficient electrode materials for SCs from the perspectives of synthetic strategies and the structure-performance relationships of POPs. Finally, we put forward the outlook and prospects of POPs for SCs.

Controlling upconversion in emerging multilayer core-shell nanostructures: from fundamentals to frontier applications.

Abstract: Lanthanide-based upconversion nanomaterials have recently attracted considerable attention in both fundamental research and various frontier applications owing to their excellent photon upconversion performance and favourable physicochemical properties. In particular, the emergence of multi-layer core-shell (MLCS) nanostructures offers a versatile and powerful tool to realize well-defined matrix compositions and spatial distributions of the dopant on the nanometer length scale. In contrast to the conventional nanomaterials and commonly investigated core-shell nanoparticles, the rational design of MLCS nanostructures allows us to deliberately introduce more functional properties into an upconversion system, thus providing unprecedented opportunities for the precise manipulation of energy transfer channels, the dynamic control of upconversion processes, the fine tuning of switchable emission colours and new functional integration at a single-particle level. In this review, we present a summary and discussion on the key aspects of the recent progress in lanthanide-based MLCS nanoparticles, including the manipulation of emission and lifetime, the switchable multicolour output and the lanthanide ionic interactions on the nanoscale. Benefitting from the multifunctional and versatile luminescence properties, the MLCS nanostructures exhibit great potential in diversities of frontier applications such as three-dimensional display, upconversion laser, optical memory, anti-counterfeiting, thermometry, bioimaging, and therapy. The outlook and challenges as well as perspectives for the research in MLCS nanostructure materials are also provided. This review would be greatly helpful in exploring new structural designs of lanthanide-based materials to further manipulate the upconversion phenomenon and expand their application boundaries.

Engineering mesoporous silica nanoparticles for drug delivery: where are we after two decades?

Abstract: The present review details a chronological description of the events that took place during the development of mesoporous materials, their different synthetic routes and their use as drug delivery systems. The outstanding textural properties of these materials quickly inspired their translation to the nanoscale dimension leading to mesoporous silica nanoparticles (MSNs). The different aspects of introducing pharmaceutical agents into the pores of these nanocarriers, together with their possible biodistribution and clearance routes, would be described here. The development of smart nanocarriers that are able to release a high local concentration of the therapeutic cargo on-demand after the application of certain stimuli would be reviewed here, together with their ability to deliver the therapeutic cargo to precise locations in the body. The huge progress in the design and development of MSNs for biomedical applications, including the potential treatment of different diseases, during the last 20 years will be collated here, together with the required work that still needs to be done to achieve the clinical translation of these materials. This review was conceived to stand out from past reports since it aims to tell the story of the development of mesoporous materials and their use as drug delivery systems by some of the story makers, who could be considered to be among the pioneers in this area.

Metal-catalysed C-H bond activation and borylation.

Abstract: Transition metal-catalysed direct borylation of hydrocarbons via C-H bond activation has received a remarkable level of attention as a popular reaction in the synthesis of organoboron compounds owing to their synthetic versatility. While controlling the site-selectivity was one of the most challenging issues in these C-H borylation reactions, enormous efforts of several research groups proved instrumental in dealing with selectivity issues that presently reached an impressive level for both proximal and distal C-H bond borylation reactions. For example, in the case of ortho C-H bond borylation reactions, innovative methodologies have been developed either by the modification of the directing groups attached with the substrates or by creating new catalytic systems via the design of new ligand frameworks. Whereas meta and para selective C-H borylations remained a formidable challenge, numerous innovative concepts have been developed within a very short period of time by the development of new catalytic systems with the employment of various noncovalent interactions. Moreover, significant advancements have occurred for aliphatic C(sp3)-H borylations as well as enantioselective borylations. In this review article, we aim to discuss and summarize the different approaches and findings related to the development of directed proximal ortho, distal meta/para, aliphatic (racemic and enantioselective) borylation reactions since 2014. Additionally, considering the C-H borylation reaction as one of the most important mainstream reactions, various applications of this C-H borylation reaction toward the synthesis of natural products, therapeutics, and applications in materials chemistry will be summarized in the last part of this review article.

Biocatalysis making waves in organic chemistry

Abstract: Biocatalysis has an enormous impact on chemical synthesis. The waves in which biocatalysis has developed, and in doing so changed our perception of what organic chemistry is, were reviewed 20 and 10 years ago. Here we review the consequences of these waves of development. Nowadays, hydrolases are widely used on an industrial scale for the benign synthesis of commodity and bulk chemicals and are fully developed. In addition, further enzyme classes are gaining ever increasing interest. Particularly, enzymes catalysing selective C-C-bond formation reactions and enzymes catalysing selective oxidation and reduction reactions are solving long-standing synthetic challenges in organic chemistry. Combined efforts from molecular biology, systems biology, organic chemistry and chemical engineering will establish a whole new toolbox for chemistry. Recent developments are critically reviewed.

The mechanochemical synthesis of polymers

Abstract: Mechanochemistry – the utilization of mechanical forces to induce chemical reactions – is a rarely considered tool for polymer synthesis. It offers numerous advantages such as reduced solvent consumption, accessibility of novel structures, and the avoidance of problems posed by low monomer solubility and fast precipitation. Consequently, the development of new high-performance materials based on mechanochemically synthesised polymers has drawn much interest, particularly from the perspective of green chemistry. This review covers the constructive mechanochemical synthesis of polymers, starting from early examples and progressing to the current state of the art while emphasising linear and porous polymers as well as post-polymerisation modifications.