The 100 most-cited articles in Chemical Communications, 2022

Femtosecond transient absorption spectroscopy (fs-TAS) is a powerful technique for monitoring the electron transfer kinetics in photocatalysis. Several important works have successfully elucidated the electron transfer mechanism in heterojunction photocatalysts (HPs) using fs-TAS measurements, and thus a timely summary of recent advances is essential. This feature article starts with a thorough interpretation of the operating principle of fs-TAS equipment, and the fundamentals of the fs-TAS spectra. Subsequently, the applications of fs-TAS in analyzing the dynamics of photogenerated carriers in semiconductor/metal HPs, semiconductor/carbon HPs, semiconductor/semiconductor HPs, and multicomponent HPs are discussed in sequence. Finally, the significance of fs-TAS in revealing the ultrafast interfacial electron transfer process in HPs is summarized, and further research on the applications of fs-TAS in photocatalysis is proposed. This feature article will provide deep insight into the mechanism of the enhanced photocatalytic performance of HPs from the perspective of electron transfer…

This work reports on the proof-of-concept of a photoelectrochemical (PEC) biosensor with a horseradish peroxidase-single stranded DNA-encoded magnetic bead (MB-ssDNA-HRP) signal probe cleaved by the catalytic hairpin assembly (CHA)-mediated clustered regularly interspaced short palindromic repeats (CRISPR)-Cas12a system for the quantification of microRNA (miR-21) by using yolk-in-shell Au@CdS as a photoactive material.

). The heterogeneous and homogeneous catalysts used in the corresponding reduction processes are introduced, with emphasis on the product selectivity regulation and reaction mechanism understanding. Finally, the challenges and opportunities in this field are analyzed as well. This review can provide guidelines for designing electrochemical systems with high efficiency and specificity for nitrite reduction.

storage systems. The use of solid adsorbents as candidate materials offers a less energy-intensive way of storing hydrogen. The exceptional diversity and tunability of the chemical composition, topological structure, and surface chemistry together with large surface area position porous metal-organic frameworks as promising hydrogen storage material candidates. In this review, we first introduce several classes of important metal-organic frameworks for hydrogen storage, and then highlight the progress associated with the key challenges to be addressed, including the improvement of hydrogen-framework interaction required for enhancing room-temperature hydrogen storage capacities, and the optimization/balance of both gravimetric and volumetric storage/working capacities. In particular, the strategies used to tune and enhance hydrogen binding energies have been comprehensively reviewed. Future development prospects and related challenges of using porous metal-organic frameworks as hydrogen storage materials are also outlined. This feature review provides a wide perspective and…

the milling balls themselves are the catalyst of the reaction. In this article we follow the historical evolution of this novel concept and give a guide to this emerging, powerful synthesis tool. Within this perspective we seek to highlight the impact of the relevant milling parameters, the nature of the catalyst and potential additives, the scope of reactions that are currently accessible by this method, and the thus far raised hypotheses on the underlying mechanisms of direct mechanochemical transformations.

However, they still suffer from significant limitations in terms of the scale-up synthesis and shaping, hindering the realization of large-scale commercial applications. Despite some attempts having been devoted to addressing this, challenges remain. In this paper, we outline the advantages and drawbacks of existing synthetic routes such as electrochemistry, microwave, ultrasonic radiation, green solvent reflux, room temperature stirring, steam-assisted transformation, mechanochemistry, and fluid chemistry in terms of scale-up production. Then, the shaping methods of MOFs such as extrusion, mechanical compaction, rolling granulation, spray drying, gel technology, embedded granulation, phase inversion, 3D printing and other shaping methods for the preparation of membranes, coatings and nanoparticles are discussed. Finally, perspectives on the large-scale synthesis and shaping of MOFs are also proposed. This work helps provide in-depth insight into the scale-up production and shaping process of MOFs and boost commercial applications of MOFs.

Orbital hybridization to regulate the electronic structures and surface chemisorption properties of transition metals has been extensively investigated for searching high-performance catalysts toward various reactions. Unlike conventional d-d hybridization, the d-sp hybridization interaction between transition metals and p-block elements could result in surprising electronic properties and catalytic activities. This feature article highlights the recent progress in the development of high-performance transition metal-based catalysts through the extraordinary d-sp hybridization strategy, particularly for energy-related electrocatalytic applications. We start by giving an introduction of fundamental concepts associated with electronic structures of transition metal catalysts, including the Sabatier principle, d-band theory, electronic descriptor, as well as the comparison of d-d hybridization and d-sp hybridization strategies. Then, we summarize the theoretical and experimental advances in d-sp hybridization catalysts, including p-block element-doped metal catalysts, intermetallic…

In this review, we summarise the recent applications of pyridinium salts in the radical-mediated difunctionalization of alkenes. Pyridinium salts are a privileged class of compounds that show great utility in natural products and synthetic chemistry. Various organic transformations of pyridinium salts, especially in radical chemistry, have been developed in recent years. We prepared this review based on the two distinguished properties of pyridinium salts in radical transformation: (1) pyridinium salts can easily undergo single electron reduction to deliver X radicals. (2) Pyridinium salts are highly electrophilic so that alkyl radical intermediates can easily add to the pyridine core. Based on the role of pyridinium salts in difunctionalization of alkenes, the main body of this review is divided into three parts: (1) using pyridinium salts as X transfer reagents. (2) Using pyridinium salts as novel pyridine transfer reagents. (3) Using pyridinium salts as bifunctional reagents (X and pyridine). The C2 and C4 selectivity during pyridylation is discussed in detail. We hope that this…

efficient ICT and recent discoveries related to potentially useful live cell imaging applications of these asymmetric cyanine dyes. This article explores three interesting asymmetric benzothiazolium dye designs (D-π-A, π-A and D-π-2A) in detail while discussing their optical properties. The key advantage of these probes is the synthetic tunability of the probe's photophysical properties and cellular selectivity by simply modifying the donor (D) or the acceptor (A) group in the structure. These new asymmetric ICT fluorophore systems exhibit large Stokes' shifts, high biocompatibility, wash-free staining, red to NIR emission and facile excitation with commercially available laser wavelengths.

Photochemistry has recently attracted the interest of synthetic chemists to conduct photolysis reactions of diazoalkanes. In this feature article, we provide a concise overview on this field, starting with discoveries in physical organic chemistry and then discuss examples in organic synthesis of singlet carbene intermediates, ranging from classic reactivity towards advances in cascade reactions and unusual protonation reactions under photochemical conditions. We then commence with a discussion on the electronic control of singlet and triplet carbene intermediates and last discuss the advances that have been made with regards to the reaction of weakly colored diazoalkanes in dye-sensitized reactions to access radical or triplet carbene intermediates.

The electrocatalytic urea oxidation reaction (UOR) has attracted substantial research interests over the past few years owing to its critical role in coupled electrochemical systems for energy conversion, for example, coupling with the hydrogen evolution reaction (HER) to realize urea-assisted hydrogen production and assembling direct urea fuel cells (DUFC) by coupling with the oxygen reduction reaction (ORR). The UOR process has been proved to be a two-step process which involves an electrochemical pre-oxidation reaction of the metal sites and a subsequent chemical oxidation of the urea molecules on the as-formed high-valence metal sites. Hence, designing advanced (pre-)catalysts with a boosted pre-oxidation reaction is of great importance in improving the UOR performance and thus accelerating the coupled reactions. In this feature article, we discuss the significant role of the pre-oxidation process during the urea electro-oxidation reaction, and summarize detailed strategies and recent advances in promoting the pre-oxidation reaction, including the modulation of the…

Metal oxides, sulphides, selenides and tellurides have routinely been investigated and utilised for a wide range of applications, in particular in the areas of energy (photovoltaic, thermoelectric) and catalysis (thermocatalysis, electrocatalysis and photoelectrocatalysis). A recent development in this chemical space is high entropy and entropy-stabilised inorganic materials, which took inspiration from preceding work on high entropy metal alloys (multicomponent alloys). High entropy inorganic materials typically have many (often ≥6) different cations or anions to yield a high configurational entropy, which can give unexpected structures and properties that are conducive to a broad range of applications in energy and catalysis. More recently still, high entropy metal chalcogenides have been developed and have been investigated for thermoelectric energy generation, batteries for energy storage and electrocatalysis. This review sets out to define entropic stabilisation in high entropy materials, along with a discussion of synthetic techniques to produce these compounds, focusing on…

The introduction of organic functionalities into porous inorganic materials not only makes the resulting hybrid porous framework to be more flexible and hydrophobic, but also provides additional scope for anchoring metal binding sites, which is beneficial for different frontline applications. Furthermore, the nanoscale porosity and high surface area of these organic-inorganic hybrid materials offer a better dispersion of active sites, which greatly enhances their application potential in adsorption, sensing, drug-delivery, energy storage, optoelectronics, light harvesting and catalysis. Easy post-synthetic functionalization of these hybrid materials has widened their application potential. Herein, we highlight several important synthetic strategies to design a wide range of organic-inorganic hybrid porous materials starting from the respective molecular precursors and their task-specific applications in energy and environmental research. We also outline the recent developments in their respective application areas together with various challenges that need to be overcome.

Ionic liquids (ILs) are becoming a revolutionary synthesis medium for inorganic nanomaterials, permitting more efficient, safer and environmentally benign preparation of high quality products. A smart combination of ILs and unconventional synthesis methods allows added value to be drawn from the broad matrix of available property combinations. Mixed systems such as Deep Eutectic Solvents (DES) offer a similarly broad combinatorial playground, which is also beginning to translate into applications. Approached holistically, these liquids therefore enable new universal manufacturing techniques that provide solutions to the existing problems of nanomanufacturing, and beyond that will open completely new horizons and possibilities for controlling the growth and assembly of nanostructures. Examples that illustrate the power of ILs in the improved manufacturing of nanomaterials are explored, such as the synthesis of light phosphors with exceptional quantum yields, record-figure-of merit thermoelectrics, and efficient photocatalysts, alongside developments in DES nanostructure and deep…

The chemistry of aluminyl compounds has rapidly expanded since their discovery in 2018 and is evaluated in this summary.

The discovery of N-heterocyclic carbenes (NHCs) revolutionized organometallic chemistry due to their strong metal-ligand bonds. These strong bonds also lend enhanced stability to gold surfaces and nanoparticles. This stability and high degree of synthetic tunability has allowed NHCs to supplant thiols as the ligand of choice when functionalizing gold surfaces. This review article summarizes the basic science and applications of NHCs on gold surfaces and gold nanoparticles. Additionally, scientific questions that are unique to gold-NHC systems are discussed, such as the NHC adatom binding motif and the NHC surface mobility. Finally, new applications for NHCs on gold are covered with particular attention to biomedicine, catalysis, and microelectronics.

honeycomb lattice of molecular nanographenes allows the preparation of chiral molecules with tuned band-gaps and chiroptical properties. There are two requirements that a system must fulfill to be chiral: (i) lack of inversion elements (planes or inversion centres) and (ii) to be configurationally stable. The first condition is inherently established by the symmetry group of the structure, however, the limit between conformational and configurational isomers is not totally clear. In this feature article, the chirality and dynamics of synthetic molecular nanographenes, with special emphasis on their racemization barriers and, therefore, the stability of their chiroptical properties are discussed. The general features of nanographenes and their bottom-up synthesis, including the main defects inducing chirality in molecular nanographenes are firstly discussed. In this regard, the most common topological defects of molecular NGs as well as the main techniques used for determining their energy barriers are presented. Then, the manuscript is structured according to the dynamics of…

C-H/X bond functionalization or addition processes in both aliphatic and aromatic hydrocarbons. Diversified reagents ranging from radical and electrophilic to nucleophilic trifluoromethylating agents and their respective mechanisms have been further deliberated in this comprehensive overview. The comprehensive coverage on this topic is expected to make this review unique and beneficial for further future applications enriching the community towards further improvements in the field of trifluoromethylation reactions, in turn improving the propensity towards further development of agrochemical drugs.

OTf), has enabled the introduction of unprotected amino groups on various different feedstock compounds, such as alkenes, arenes and thiols. This strategy obviates undesired protecting-group manipulations and thus improves step efficiency and atom economy. Overall, this feature article gives a recent update on several reactions that have been unlocked by employing versatile hydroxylamine-derived aminating reagents, which facilitate the generation of unprotected primary, secondary and tertiary amino groups.

Polyethylene oxide (PEO) based polymer electrolytes have been widely used in solid-state lithium batteries (SSBs) owing to the high solubility of lithium salt, favourable ionic conductivity, flexibility for improved interfacial contact and scalable processing. In this work, we summarize the main limitations remaining to be solved before the large-scale commercialization of PEO-based SSBs, including (1) improving ionic conductivity toward high-rate performance and lower operating temperature, (2) enhancing mechanical strength for improved lithium dendrite resistance and large-scale processing, (3) strengthening electrochemical stability to match high energy density electrodes with high voltage, and (4) achieving high thermal stability toward safe operation. Meanwhile, the characterization methods to investigate the ion transportation mechanism, lithium dendrite growth and decomposition reaction are also discussed.

A NiFe layered double hydroxide nanosheet array is designed as an efficient NORR catalyst for NH 3 electrosynthesis with a maximal FE of 82% and the highest yield rate of 1586.7 μg h −1 mg cat. −1 , exceeding most recently reported results.

class of assemblies due to their relative structural simplicity and the wealth of studies reported in the literature. The core principles discussed will, however, be generalisable to other classes of MOCs, and abiotic host systems as a whole. Gaining increasing mastery over the fine tuning of MOC cavity properties, whilst retaining facile, high-fidelity self-assembly processes, will lead to ever more precise engineering of the cavities of artificial host systems with complex and highly specific functionality.

Porous organic cages (POCs) have emerged as a new sub-class of porous materials that stand out by virtue of their tunability, modularity, and processability. Similar to other porous materials such as carbons, zeolites, and MOFs, the pore network formed by the interconnected cavities of POCs makes them inherently good candidates for gas capture and gas separation. However, in this review, we focus on the emerging trends in the application of POCs in the fields of clean energy and environmental sustainability, which are a result of their unique features. The structure-property relationship we attempted to extract from the case studies will provide guidance for the design of new functional POCs in the future.

evolution campaigns include improved folding stability, catalytic activity, and/or substrate specificity. Despite significant progress in recent years in the areas of high-throughput screening and DNA sequencing, our ability to explore the vast space of functional enzyme sequences remains severely limited. Here, we review the currently available suite of modern methods for enzyme engineering, with a focus on novel readout systems based on enzyme cascades, and new approaches to reaction compartmentalization including single-cell hydrogel encapsulation techniques to achieve a genotype-phenotype link. We further summarize systematic scanning mutagenesis approaches and their merger with deep mutational scanning and massively parallel next-generation DNA sequencing technologies to generate mutability landscapes. Finally, we discuss the implementation of machine learning models for computational prediction of enzyme phenotypic fitness from sequence. This broad overview of current state-of-the-art approaches for enzyme engineering and evolution will aid newcomers and experienced…

Living and proliferating cells undergo repeated cycles of growth, replication and division, all orchestrated by complex molecular networks. How a minimal cell cycle emerged and helped primitive cells to evolve remains one of the biggest mysteries in modern science, and is an active area of research in chemistry. Protocells are cell-like compartments that recapitulate features of living cells and may be seen as the chemical ancestors of modern life. While compartmentalization is not strictly required for primitive, open-ended evolution of self-replicating systems, it gives such systems a clear identity by setting the boundaries and it can help them overcome three major obstacles of dilution, parasitism and compatibility. Compartmentalization is therefore widely considered to be a central hallmark of primitive life, and various types of protocells are actively investigated, with the ultimate goal of developing a protocell capable of autonomous proliferation by mimicking the well-known cell cycle of growth, replication and division. We and others have found that coacervates are…

optical energy transfer and reabsorbance mechanisms. There is also an urgent need to develop a suitable technique for creating geometrically and dimensionally well-defined organic crystals displaying photonic attributes. Finally, the goal should be to build a library of selected optical crystals to facilitate the construction of OPICs with a pick-and-place approach.

H labelling strategies, which traditionally require high temperatures, high pressures of deuterium gas in hydrothermal autoclave reactors, or require reagents capable of generating highly reactive species which are then quenched by a deuterium source. Such harsh conditions or reagents can consequently lower chemo- or regioselectivity in many deuteration processes. Transition metal catalysis and more recently photocatalysis have emerged as methods to access selectively deuterated compounds under significantly more mild conditions. Now, electrochemistry, which is increasingly becoming a mainstream synthetic tool, is primed to enter this space. Accordingly, this highlight will feature a selection of electrochemical deuteration methods developed in recent years, and propose where the use of electrosynthesis could access novel reactivity in the context of deuteration.

Advances in developing organic fluorescent probes and fluorescence imaging techniques have enhanced our understanding of cell biology. The endoplasmic reticulum (ER) is a dynamic structure that plays a crucial role in protein synthesis, post-translational modifications, and lipid metabolism. The malfunction of ER contributes to several physiological and pathological conditions. Therefore, the investigations on the imaging and role of ER have attracted a lot of attention. Due to their simplicity, synthetic tunability, photostability, high quantum yields, easier cellular uptake, and lower cytotoxicity, organic fluorophores offer invaluable tools for the precision targeting of various cellular organelles and probe ER dynamics. The precision staining is made possible by incorporating specific functional groups having preferential and local organelle biomolecular interactions. For instance, functional moieties such as methyl sulfonamide, sulfonylurea, and pentafluorophenyl assist in ER targeting and thus have become essential tools to probe a deeper understanding of their dynamics.…

We report a polycrystalline SnS x nanofilm deposited on carbon paper via simple vacuum evaporation for CO 2 -to-formate conversion. When paired with an IrO 2 anode in a MEA electrolyzer, it demonstrates a high faradaic efficiency (>75%).

In this work, a Bi-doped Co 3 O 4 nanosheet array grown on Ni foam was used as an efficient bifunctional catalyst, which shows high activity and good stability toward HMF oxidation and hydrogen evolution.

, which provides a new idea for the development of high-performance PBA battery materials. Meanwhile, owing to the spring-like structure, the battery has a high stretchability of 600% and maintains stable electrochemical properties during stretching.

Considering the serious damage to aquatic ecosystems and marine life caused by oil spills and oily wastewater discharge, efficient, environment-friendly and sustainable oil/water separation technology has become an inevitable trend for current development. Herein, fabrics are recognized as eco-friendly materials for water treatment due to their good degradability and low cost. Particularly, fabrics with rough structures and natural hydrophilicity/oleophilicity enable the construction of superwetting surfaces for the selective separation of oil/water mixtures and even complex emulsions. Therefore, superwetting fabrics for efficiently solving oil spills and purifying oily wastewater have received extensive attention. Especially, Janus and smart fabrics are highly anticipated to enable the on-demand and sustainable treatment of oil spills and oily wastewater due to their changeable wettability. Moreover, the fabrication of superwetting fabrics with multifunctional performances for oily wastewater purification can further promote their practical industrial applications, such as…

Herein, an electrochemical sensor was developed for sensitive detection of dopamine (DA) based on a novel COF-based nanocomposite named COF/Pt/MWCNT-COOH, which possesses large specific surface area, excellent electrical conductivity, and high catalytic activity, thus broadening the application of COFs in the electrochemical sensing area.

By introducing a reactive oxygen species (ROS) triggered leaving group (arylboronic acid) to the parent PROTACs, ROS-responsive Pre-PROTACs were designed and evaluated. Pre-PROTAC (7) efficiently degraded the target protein BRD3 according to ROS levels. Our research provides an effective approach to control PROTAC activation by the endogenous ROS-related microenvironment.

One-step electrodeposition strategy is employed to synthesis the Ni–Mn–Se electrocatalyst, exhibiting remarkable hydrogen evolution and urea oxidation reactions catalytic activity and stability at large current densities even superior to platinum.

Catalysis is central to a more sustainable future and a circular economy. If the energy required to drive catalytic processes could be harvested directly from sunlight, the possibility of replacing contemporary processes based on terrestrial fuels by the conversion of light into chemical energy could become a step closer to reality. Plasmonic catalysis is currently at the forefront of photocatalysis, enabling one to overcome the limitations of "classical" wide bandgap semiconductors for solar-driven chemistry. Plasmonic catalysis enables the acceleration and control of a variety of molecular transformations due to the localized surface plasmon resonance (LSPR) excitation. Studies in this area have often focused on the fundamental understanding of plasmonic catalysis and the demonstration of plasmonic catalytic activities towards different reactions. In this feature article, we discuss recent contributions from our group in this field by employing plasmonic nanoparticles (NPs) with controllable features as model systems to gain insights into structure-performance relationships in…

The direct synthesis of isocoumarin skeletons has been developed through Rh( iii )-catalyzed cascade C–H/C–C bond activation of enaminones and iodonium ylides under mild conditions.

Hybrid materials of metal-organic frameworks (MOFs) and nanoparticles (NPs) have attracted significant attention because of the wide variety of attractive properties derived from the two components. In the last decade, the development of synthesis techniques for NP/MOF composites was particularly significant. In the field of catalysis in particular, various synergistic effects that make the composites attractive catalysts have been reported. However, the role of MOFs in the composite catalysts is still not well understood and is being elucidated. In this feature article, we focus on recent progress in NP/MOF composite catalysts, concentrating on the analysis of the interaction between NPs and MOFs and the reaction mechanisms, together with the synthetic techniques used for NP/MOF hybrid materials.

Metal-organic frameworks (MOFs) have been a research hotspot for the last two decades, witnessing an extraordinary upsurge across various domains in materials chemistry. Ionic MOFs (both anionic and cationic MOFs) have emerged as next-generation ionic functional materials and are an important subclass of MOFs owing to their ability to generate strong electrostatic interactions between their charged framework and guest molecules. Furthermore, the presence of extra-framework counter-ions in their confined nanospaces can serve as additional functionality in these materials, which endows them a significant advantage in specific host-guest interactions and ion-exchange-based applications. In the present review, we summarize the progress and future prospects of iMOFs both in terms of fundamental developments and potential applications. Furthermore, the design principles of ionic MOFs and their state-of-the-art ion exchange performances are discussed in detail and the future perspectives of these promising ionic materials are proposed.

Indazole and pyrazole are renowned as a prodigious class of heterocycles having versatile uses in medicinal as well as industrial chemistry. Considering sustainable approaches, recently, photocatalysis has become an indispensable tool in organic chemistry due to its application for the activation of small molecules and the use of a clean energy source. In this review, we have highlighted the use of metal-based photocatalysts, organic photoredox catalysts, energy transfer photocatalysts and electron-donor-acceptor complexes in the functionalization of indazole and pyrazole. This perspective is arranged based on the types of functionalization reactions on indazole and pyrazole. A detailed discussion regarding the reaction mechanism of each reaction is given to provide a comprehensive guide to the reader. Finally, a summary of existing challenges and the future outlook towards the development of efficient photocatalytic methods for functionalization of these heterocycles is also presented.

CPs can also be prepared into nanoparticles for acquiring controllable particle size and dispersion through the common synthesis procedure. In this review, we focus on the latest developments of CPs in biotherapy, biological regulation, biological response and bioprinting applications. The major challenges and outlooks of CPs for applications in the biomedical field are also discussed.

Molecular polymer bottlebrushes are densely grafted, individual macromolecules with nanoscale proportions. The last decade has seen an increased focus on this material class, especially in nanomedicine and for biomedical applications. This Feature Article provides an overview of major developments in this area to highlight the many opportunities that these polymer architectures bring to nano-bio research. The article covers aspects of bottlebrush synthesis and summarises their use in drug and gene delivery, imaging, as theranostics and as prototype materials to correlate nanoparticle structure and composition to biological function and behaviour. Areas for future research in this area are discussed.

There is growing interest in the design of bimetallic cooperative complexes, which have emerged due to their potential for bond activation and catalysis, a feature widely exploited by nature in metalloenzymes, and also in the field of heterogeneous catalysis. Herein, we discuss the widespread opportunities derived from combining two metals in close proximity, ranging from systems containing multiple M-M bonds to others in which bimetallic cooperation occurs even in the absence of M⋯M interactions. The choice of metal pairs is crucial for the reactivity of the resulting complexes. In this context, we describe the prospects of combining not only transition metals but also those of the main group series, which offer additional avenues for cooperative pathways and reaction discovery. Emphasis is given to mechanisms by which bond activation occurs across bimetallic structures, which is ascribed to the precise synergy between the two metal atoms. The results discussed herein indicate a future landscape full of possibilities within our reach, where we anticipate that bimetallic synergism…

This feature article uncovers a tactical blueprint for the sustainable development of synthetic manifestations in the transition-metal catalyzed directing group assisted multiple annulations (L-type, Y-type, and B-type) of inert C(arene)–H bonds.

Defective H x MoO 3− y with plasmonic features is applied for photocatalysis, thermal catalysis, and photothermal catalysis, enabling energy-saving chemical processes.

The replacement of traditional incandescent, halogen and fluorescent lamps by white light emitting diodes (WLEDs) is expected to reduce the global electricity consumption by one-third by 2030, according to the US Department of Energy. The current WLED technology uses rare-earth element (REE) based phosphor materials, which, not only is cost-intensive but also constitutes an environmental concern. Hence, researchers are in a quest for a new-generation of opto-electronic materials that can replace the conventional phosphors in WLEDs and thus aim towards a cleaner and more energy efficient lighting technology for the future. Luminescent metal-organic frameworks (LMOFs) have recently emerged as a new sub-class of MOFs which have demonstrated enormous potential for applications in sensing, imaging, optoelectronics and in solid-state lighting (SSL) technology. LMOFs could be game changers as lighting phosphors due to advantages such as high luminescence quantum yield, tunable excitation and emission which can be achieved by rational design and optimization of metal centers, linkers, and…

Cobalt nanoparticle-decorated pomelo-peel-derived carbon acts as a highly active electrocatalyst for NO 3 − –to–NH 3 conversion, capable of attaining a large faradaic efficiency of 90.1% and an ultrahigh NH 3 yield of 1.1 mmol h −1 mg cat . −1 .

electrolyte (3 M) is obtained and shows higher retention due to higher Zn-nucleation overpotential and slower corrosion reactions.

molten salt etching and utilizing a KOH wash to add hydroxyl surface groups. However, little is known about the oxidation of molten salt etched MXenes compared to acid-etched MXenes. Our results indicate slower oxidation behavior for MXenes etched by molten salts, which may be due to the decreased amount of oxygen-containing terminal groups.

fuel cell performance in alkaline media. Theoretical simulations indicate that Ru clusters endow a thermodynamically favourable HOR kinetics and an optimal hydrogen adsorption affinity.

By combining the precisely sized cavity of pillar[5]arene and photodynamic properties of porphyrin derivatives, novel COMs (P5COMs) as an efficient cancer therapy platform from aldehyde-modified pillar[5]arene (P5CHO) and tetra-(4-aminophenyl)porphyrin (TAPP) were fabricated successfully.

-carboxylate complexes with different coordination geometries were synthesized and characterized by X-ray analysis, correlating their structure with their ability to initiate light-induced decarboxylations.

in alkaline solution. This monolithic catalyst also shows high durability with the maintenance of its catalytic activity for 12 h. Theoretical calculations further reveal the critical role of oxygen vacancies in nitrite electroreduction.

This review summarizes the recent progress on MoS 2 -based electrocatalysts toward the hydrogen evolution reaction (HER), nitrogen fixation (NRR) and carbon dioxide reduction reaction (CO 2 RR).

(where AzrH = aziridinium, Hal = Cl, Br or I). This highly reactive species was stabilized in 3D lead halide frameworks and was found to be a small enough organic cation to promote the formation of semiconducting organo-inorganic materials.

This review article describes the recent development in the chemistry of carbamoyl radicals generated from oxamic acids. This mild and efficient method compares well with previous methods of generation of these nucleophilic radicals. The oxidative decarboxylation of oxamic acids can be mediated through thermal, photochemical, electrochemical or photoelectrochemical means, generating carbamoyl radicals, which may further add to unsaturated systems to provide a broad range of important amides. Oxidative decarboxylation of oxamic acids also offers a straightforward entry for the preparation of urethanes, ureas, and thioureas.

Water pollutions have caused serious threats to the aquatic environment and human health, it is of great significance to monitor and control their contents in water. Compared with the traditional single treatment method, multiple treatment can simultaneously realize detection and removal of water pollutions on one material, which brings convenience and promotes comprehensive treatment for water remediation. Metal-organic frameworks (MOFs) are versatile porous materials that hold huge potential in wastewater treatments. This feature article reviews the recent advances in MOFs for multifunctional water treatment. First, strategies to design the sensing, removal and degradation functions onto MOFs are introduced. Then, the sensing, removal and degradation effects on various inorganic and organic water pollutions based on multifunctional MOF materials are summarized, and the interaction mechanisms are discussed in detail. Finally, the current challenges and the future research trends on MOF materials for wastewater treatment are discussed as well.

A hybrid ZIF-8/ZIF-62 glass membrane was first fabricated, demonstrating excellent performance for carbon capture and C 3 H 6 /C 3 H 8 separation.

A bimetallic FeCo 2 O 4 spinel nanowire array grown on carbon cloth is highly active and stable for electrocatalytic NO 3 − reduction to NH 3 , capable of attaining a large NH 3 yield of 4988 μg h −1 cm −2 with a high faradaic efficiency of 95.9%.

White-light emission in donor-acceptor systems usually requires relatively high acceptor content and/or multiple acceptors to "neutralize" the primary color of donors. Herein, a cyanostilbene-bridged ditopic ureidopyrimidinone donor (CSU) was designed and synthesized, which can self-assemble into dispersed nanoparticles in water. Fascinatingly, efficient white-light emission can be realized by co-assembling 0.1% DBT into the nanoparticles through a light-harvesting strategy. This new system is further demonstrated for use in white-light encryption materials.

This work showcases the remarkable ability of sigma profiles to function as molecular descriptors in deep learning. The sigma profiles of 1432 compounds are used to train convolutional neural networks that accurately correlate and predict a wide range of physicochemical properties. The architectures developed are then exploited to include temperature as an additional feature.

Quantum technologies have seen a rapid developmental surge over the last couple of years. Though often overshadowed by quantum computation, quantum sensors show tremendous potential for widespread applications in chemistry and biology. One system stands out in particular: the nitrogen-vacancy (NV) center in diamond, an atomic-sized sensor allowing the detection of nuclear magnetic resonance (NMR) signals at unprecedented length scales down to a single proton. In this article, we review the fundamentals of NV center-based quantum sensing and its distinct impact on nano- and microscale NMR spectroscopy. Furthermore, we highlight possible future applications of this novel technology ranging from energy research, materials science, to single-cell biology, and discuss the associated challenges of these rapidly developing NMR sensors.

Three substituents shield the reactive core of Clar’s hydrocarbon triangulene and make it persistent at room temperature in solution. Image of Erich Clar from Dr. Winfried Willicks (1926–2010) is courtesy of Glasgow University, School of Chemistry.

Metal-organic cages are macrocyclic structures that can possess an intrinsic void that can hold molecules for encapsulation, adsorption, sensing, and catalysis applications. As metal-organic cages may be comprised from nearly any combination of organic and metal-containing components, cages can form with diverse shapes and sizes, allowing for tuning toward targeted properties. Therefore, their near-infinite design space is almost impossible to explore through experimentation alone and computational design can play a crucial role in exploring new systems. Although high-throughput computational design and screening workflows have long been known as powerful tools in drug and materials discovery, their application in exploring metal-organic cages is more recent. We show examples of structure prediction and host-guest/catalytic property evaluation of metal-organic cages. These examples are facilitated by advances in methods that handle metal-containing systems with improved accuracy and are the beginning of the development of automated cage design workflows. We finally outline a scope…

Sulfonimidoyl halides have previously shown poor stability and selectivity in reaction with organometallic reagents. Here we report the preparation of enantioenriched sulfonimidoyl fluorides and their stereospecific reaction at sulfur with Grignard reagents. Notably the first enantioenriched alkyl sulfonimidoyl fluorides are prepared, including methyl. The nature of the N-group is important to the success of the stereocontrolled sequence to sulfoximines.

A novel core-shell metal organic framework (MOF), Cu-MOF@SMON/DOX-HA, was fabricated using 3-amino-1,2,4-triazole (3-AT) and organosilicon for combined chemo-chemodynamic therapy with high drug-loading capacity, pH/GSH dual-responsiveness, and good biocompatibility. The Cu-MOF@SMON/DOX-HA could not only generate reactive oxygen species, but also effectively consume glutathione (GSH) to induce cell ferroptosis. This work involves the modification of organosilicon on the surface of MOFs, which possess good performance in high drug-loading ability and pH/GSH dual-responsive degradation for combined chemo-chemodynamic therapy.

3D-printed micro-supercapacitors (MSCs) have emerged as the ideal candidates for energy storage devices owing to their unique characteristics of miniaturization, structural diversity, and integration. Exploring the 3D printing technology for various materials and architectures of MSCs is key to realizing customization and optimizing the performance of 3D-printed MSCs. In this review, we summarize the latest progress in 3D-printed MSCs with regards to general printing approaches, printable materials, and rational design considerations. Specifically, several general types of 3D printing techniques (their working principles, available materials, resolutions, advantages, and disadvantages) and their applications to fabricate electrodes with different energy storage mechanisms, and various electrolytes, are summarized. We further discuss research directions in terms of integrated systems with other electronics. Finally, future perspectives on the research and development directions in this important field are further discussed.

Research on organic cages has blossomed over the past few years into a mature field of study which can contribute to solving some of the challenging problems. In this review we aim to showcase the recent trends in synthesis of organic cages including a brief discussion on their use in catalysis, gas sorption, host-guest chemistry and energy transfer. Among the organic cages, water-soluble analogues are a special class of compounds which have gained renewed attention in recent times. Due to their advantage of being compatible with water, such cages have the potential of showing biomimetic activities and can find use in drug delivery and also as hosts for catalysis in aqueous medium. Hence, the synthetic strategies for the formation of water-soluble organic cages shall be discussed along with their potential applications.

The first example of transition metal catalyzed asymmetric transformations of the in situ generated p -QMs has been developed, avoiding using pre-synthesized p -QMs requiring bulky 2,6-substitutions.

Advancements in computer science and software engineering have greatly facilitated mass spectrometry (MS)-based untargeted metabolomics. Nowadays, gigabytes of metabolomics data are routinely generated from MS platforms, containing condensed structural and quantitative information from thousands of metabolites. Manual data processing is almost impossible due to the large data size. Therefore, in the "omics" era, we are faced with new challenges, the big data challenges of how to accurately and efficiently process the raw data, extract the biological information, and visualize the results from the gigantic amount of collected data. Although important, proposing solutions to address these big data challenges requires broad interdisciplinary knowledge, which can be challenging for many metabolomics practitioners. Our laboratory in the Department of Chemistry at the University of British Columbia is committed to combining analytical chemistry, computer science, and statistics to develop bioinformatics tools that address these big data challenges. In this Feature Article, we elaborate on…

analysis to develop effective and more competent 11β-hydroxysteroid dehydrogenase (11β-HSD1) protein inhibitors. The AAB4 molecule was shown to have stronger interactions and binding affinity than standard inhibitors (co-crystallized molecules). These results were based on conventional, steered and enhanced umbrella sampling simulations.

Carbon-supported Pt-based nanoalloys (CSPtNs) as the oxygen reduction reaction (ORR) electrocatalysts are considered state-of-the-art electrocatalysts for use in proton exchange membrane fuel cells (PEMFCs). Although their ORR activity performance is already adequate to allow lowering of the Pt loading and thus commercialisation of the fuel cell technology, their stability remains an open challenge. In this Feature Article, the recent achievements and acquired knowledge on the degradation behaviour of these electrocatalysts are overviewed and discussed.

methods. Most synthetic approaches introduced here tentatively showed that the energy barriers associated with Al incorporation in zeolites can be variable during zeolite crystallization processes, occurring in complex media with multiple chemical interactions. Although the generic interpretation of each strategy and underlying crystallization mechanism remains largely unknown (and often limited to a specific framework), this review will provide guidance on more efficient methods to prepare fine-tuned zeolites with desired chemical properties.

Gold catalysis has witnessed immense evolution in recent years, yet it still requires the use of activators to render the common [AuCl(L)] complexes catalytically active. Herein, the H-bonding donor properties of hexafluoroisopropanol (HFIP) are utilized for Au-Cl bond activation and the ancillary ligand and counteranion effects on cycloisomerization reactions are showcased in HFIP as solvent.

Expanding knowledge of low valent aluminium chemistry, rubidium and caesium aluminyls are reported to complete the group 1 (Li-Cs) set of metal aluminyls. Both compounds crystallize as a contacted dimeric pair supported by M⋯π(arene) interactions with a pronounced twist between aluminyl units. Density functional theory calculations show symmetrical bonding between the M and Al atoms, with an Al centred lone-pair donating into vacant Rb and Cs orbitals. Interestingly, despite their structural similarity the Cs aluminyl enables C-H bond activation of benzene, but not the Rb aluminyl reflecting the importance of the alkali metal in these heterobimetallic systems.

Targeting deubiquitinating enzymes (DUBs) has emerged as a promising therapeutic approach in several human cancers and other diseases. DUB inhibitors are exciting pharmacological tools but often exhibit limited cellular potency. Here we report PROTACs based on a ubiquitin-specific protease 7 (USP7) inhibitor scaffold to degrade USP7. By investigating several linker and E3 ligand types, including novel cereblon recruiters, we discovered a highly selective USP7 degrader tool compound that induced apoptosis of USP7-dependent cancer cells. This work represents one of the first DUB degraders and unlocks a new drug target class for protein degradation.

A novel cyanine-rhenium(I) tricarbonyl complex is developed as a potent sonosensitizer and sono-activatable CO-releasing agent for synergistic sonodynamic therapy and CO gas therapy of cancer. The complex induced ferroptosis as the mode of cell death.

Despite the persistent presence of medium-sized (seven- to nine-membered) scaffolds in natural products and biologically active molecules, their asymmetric syntheses have always been considered a formidable task; therefore, they have remained underdeveloped when compared to the enantioselective synthesis of five- and six-membered ring scaffolds. One important class of such medium-sized ring frameworks includes seven- to nine-membered biaryl bridged carbo- and heterocycles. These medium-ring-sized biaryl frameworks possess more configurational stability than the related smaller ring structures and are common features of valuable natural products, bioactive compounds, chiral catalysts, and molecular motors. Due to these exciting properties and broad applications, over the last few years, the catalytic enantioselective synthesis of medium-sized bridged biaryls has seen an upsurge. This highlight article describes the development of organocatalysed and transition-metal catalysed transformations for procuring seven-, eight-, and nine-membered bridged biaryls bearing a chiral axis/one or…

), respectively. To our knowledge, 1 represents the first tetrahedral supercluster containing the basket-like POM structure. Besides, macromolecule 1 exhibits high catalytic activity and reusability for the oxidation of thioethers to sulfoxides.

We developed a first-in-class proteolysis targeting chimera (PROTAC) for selective degradation of histone deacetylase 8 (HDAC8). The PROTAC induced degradation of HDAC8 without affecting the levels of other HDACs in cellular assays, and inhibited the growth of T-cell leukemia Jurkat cells more potently than a conventional HDAC8 inhibitor.

Oxide chemiresistors have mostly been used to detect reactive gases such as ethanol, acetone, formaldehyde, nitric dioxide, and carbon monoxide. However, the selective and sensitive detection of volatile aromatic compounds such as benzene, toluene, and xylene, which are extremely toxic and harmful, using oxide chemiresistors remains challenging because of the molecular stability of benzene rings containing chemicals. Moreover, the performance of the sensing materials is insufficient to detect trace concentration levels of volatile aromatic compounds, which lead to harmful effects on human beings. Here, the strategies for designing highly selective and sensitive volatile aromatic compound gas sensors using oxide chemiresistors were suggested and reviewed. Key approaches include the use of thermal activation, design of sensing materials with high catalytic activity, the utilization of catalytic microreactors and bilayer structures with catalytic overlayer, and the pretreatment of analyte gases or post analysis of sensing signals. In addition, future perspectives from the viewpoint of…

Resonant acoustic mixing (RAM) enables mechanoredox catalysis with BaTiO3 as the piezoelectric catalyst on model diazonium coupling reactions. RAM proceeds without formal grinding or impact media, is faster than the analogous ball-milling strategy, and is readily scalable to gram-scale. Combined X-ray diffraction and spectroscopy indicate that reusability of BaTiO3 as a mechanoredox catalyst might be limited by unwanted boration.

The electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furanedioic acid (FDCA) has received increasing attention. To achieve satisfactory electrooxidation of HMF, the development of an efficient electrocatalyst is particularly critical. Herein, porous Ce-CoP nanosheets integrating Ce doping and P vacancies are designed through a deep eutectic solvent approach, and they allow the excellent electrocatalytic oxidation of HMF to FDCA in 1 M KOH electrolyte with 100% HMF conversion, 98% FDCA yield, and a faradaic efficiency of 96.4% at low potential.

Light-activable spatiotemporal control of PROTAC-induced protein degradation was achieved with novel arylazopyrazole photoswitchable PROTACs (AP-PROTACs). The use of a promiscuous kinase inhibitor in the design enables this unique photoswitchable PROTAC to selectively degrade four protein kinases together with on/off optical control using different wavelengths of light.

. Taken together, we opine that microdroplet chemistry may adopt significant roles in atmospheric redox chemistry.

An amorphous NiCoFeCrMo-based high-entropy hydroxide possesses the maximum content of high-valence Ni 3+ species, boosting the oxygen evolution electrocatalytic performance.

Lm) with a simple solvothermal method. Due to the unique photoelectric response properties of the viologen units, reversible photochromic and electrochromic properties have been combined in D/L-Cd-MOF, which points to a new way of designing and constructing multifunctional photoelectric materials.

An extremely bulky xanthene bridged diamide ligand (TCHPNON = 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) has been developed and used to prepare two monomeric diamido-calcium complexes [(TCHPNON)Ca(D)n] (D = THF, n = 2, 3; D = toluene, n = 1, 4). Reduction of 4 with 5% w/w K/KI under an N2 atmosphere gave the first well-defined, anionic s-block complex of activated dinitrogen, [{K(TCHPNON)Ca}2(-2:2-N2)] 5, presumably via a transient calcium(I) intermediate.

Chirality exists in every corner of nature and is closely associated with the phenomenon of life. The unique optical properties and enhanced enantioselectivity of chiral nanomaterials mean that they excel in many applications in nanobiology and nanomedicine. Here, we comprehensively review the progress that has been made toward the use of chiral nanomaterials in biosensing, bioimaging, and disease therapies. The construction strategies for three different types of chiral nanomaterials and their chirality-generating mechanisms are first generalized. We then focus on the biological applications of these chiral nanomaterials, ranging from chirality-based ultrasensitive detection and multifunctional imaging to therapeutic purposes. Finally, we present an in-depth discussion of the current challenges and future prospects in the utilization of these exciting materials.

Electronic resonances are states that are unstable towards loss of electrons. They play critical roles in high-energy environments across chemistry, physics, and biology but are also relevant to processes under ambient conditions that involve unbound electrons. This feature article focuses on complex-variable techniques such as complex scaling and complex absorbing potentials that afford a treatment of electronic resonances in terms of discrete square-integrable eigenstates of non-Hermitian Hamiltonians with complex energy. Fundamental aspects of these techniques as well as their integration into molecular electronic-structure theory are discussed and an overview of some recent developments is given: analytic gradient theory for electronic resonances, the application of rank-reduction techniques and quantum embedding to them, as well as approaches for evaluating partial decay widths.

The application of merocyanine photoacids has been previously largely limited to neutral and acidic pH values. Here we introduce a new merocyanine photoacid with superior pH switching qualities. By increasing the pKa in the dark (pKadark) and the solubility we increased the reversible visible light induced pH jump to 3.5 units. Moreover, it is the first demonstration of a merocyanine photoacid able to generate a significant pH drop from a basic (pH 8.3) to an acidic (pH 5.2) environment.

The targeted degradation of histone deacetylase 6 (HDAC6) by heterobifunctional degraders constitutes a promising approach to treat HDAC6-driven diseases. Previous HDAC6 selective degraders utilised a hydroxamic acid as a zinc-binding group (ZBG) which features mutagenic and genotoxic potential. Here we report the development of a new class of selective HDAC6 degraders based on a difluoromethyl-1,3,4-oxadiazole warhead as ZBG.

A mild silver-catalysed oxidative C–H alkylation of N -heteroarenes is developed, utilizing aliphatic ketone-derived 2,3-dihydroquinazolinones as an alkyl radical reservoir.

CO 2 reacts with EG rather than reacting with phenolic anions in DESs consisting of phenol-based superbase ILs and EG.

, replenishing the prevailing α-deuteration of the pyridine systems. Preliminary mechanistic studies suggested that the dimsyl carbanion acts as one of the key intermediates.

The synthesis of 2-vinyl pyrroles has been achieved via copper-catalyzed cascade reactions of enaminones and alkyl propiolates. The synthesis of 2,3-dicarboxylate-functionalized products has been tuned by using internal alkynyl dicarboxylates.

Hydrogen energy is a promising energy source that is environmentally friendly due to its long-term, large-capacity storage and low greenhouse gas emissions. However, the mass production of hydrogen is still technically difficult due to limitations in efficiency, stability, and cost, even though it can satisfy all of the current energy demands. Water splitting using an electrocatalyst is an efficient method for environmentally friendly hydrogen production, and various catalyst-related studies are being conducted for this purpose. For the last decade, transition metal-based compositions have been at the center of water splitting catalyst research. Despite numerous studies and developments, studies on transition metal-based catalysts so far still have various problems to be solved. Although excellent review papers on transition metal-based catalysts have been reported, the overall scope of transition metal-based catalysts has rarely been covered in the reports. In this review, we present the research about overall transition metal-based electrocatalysts for hydrogen production from…

Amorphous CoB x nanoparticles supported on carbon paper were synthesized by a simple wet chemical reduction method, and exhibited remarkable performance toward electrochemical nitrate reduction.

and a mass activity about 24.8-fold that of commercial Pt/C. The results suggest that the Pt single atom catalyst can not only accelerate the Volmer steps in alkaline media, but also optimize the hydrogen adsorption process, improving the HER catalytic activity.

. These values are significantly superior to those of the original PANI electrode, indicating the high efficiency of the proposed strategy. This simple protonation method could be applicable for many electrochemical devices, such as supercapacitors, sensors, and batteries.