The 100 most-cited articles in Chemical Communications, 2017

The formation of highly enantioenriched boronic esters through both stoichiometric and catalytic methods has received much attention over the past decade. Accordingly, the transformations of the boronic ester moiety into other functional groups is of considerable interest in synthesis. Specifically, transformations which retain the high enantioenrichment of the starting boronic ester, either through a stereoretentive or a stereoinvertive pathway, lead to the formation of new C-C, C-O, C-N, C-X, or C-H bonds at stereogenic centres. This feature article summarises the current state of the art in stereospecific transformations of both secondary and tertiary boronic esters into other functionalities and groups, whilst considering critically the transformations that are currently unattainable and would represent future advances to the field.

A two-dimensional metal-organic framework (MOF) comprising nickel species and an organic ligand of benzenedicarboxylic acid is fabricated and explored as an electrocatalyst for urea oxidation reaction (UOR). The excellent UOR performance is found to be partially due to the high active site density of the two-dimensional MOF, and largely because of the high oxidation state of the nickel species.

), which provides a convenient single number to measure steric impact and (b) steric maps, which provide a graphical representation of the steric profile of a ligand using colour-coded contour maps. A critical discussion of the scope and limitations of these tools is presented, along with some examples of their use in organometallic chemistry and catalysis. This Article should provide all users of NHCs, from organic, organometallic, and inorganic chemistry backgrounds, with an appreciation of how these tools can be used to quantify and compare their steric properties.

ZnGa 2 O 4 /SAPO-34 catalysed the direct conversion of CO 2 into lower olefins with 86% selectivity at 13% CO 2 conversion via a methanol intermediate.

Phosphorescent materials are mostly based on metal complexes. Metal-free organic molecules usually display phosphorescence only in a rigid matrix at 77 K. In the last few years, there has been increasing interest in the design of organic molecules displaying long-lived and highly intense room-temperature phosphorescence, an extremely difficult task since these two properties are generally conflicting. This review reports the most recent and tutorial examples of molecules that are weakly or non-phosphorescent in deaerated fluid solution and whose room temperature phosphorescence is switched on upon aggregation. The examples are divided into two classes according to the mechanism responsible for switching on phosphorescence: (i) rigidification by crystallization or by encapsulation in a polymeric matrix and (ii) interaction with other molecules of the same type (self-aggregation) or a different type by taking advantage of heavy-atom effects.

We herein report a monomer-mediated in situ growth strategy for the controllable construction of porous nanospheres with a magnetic core and a tunable COF shell. The composite exhibits high stability and excellent performance for the removal of a typical class of endocrine-disrupting chemicals, bisphenol chemicals, in aqueous solution.

A Zn-doped Ni 3 S 2 nanosheet array on Ni foam (Zn-Ni 3 S 2 /NF) acts as a high-performance and durable electrocatalyst for the oxygen evolution reaction in 1.0 M KOH, driving a catalytic current density of 100 mA cm −2 at an overpotential of 330 mV, 90 mV less than that for Ni 3 S 2 /NF.

, leading to stable cycle performance. This is the first report to confirm the charge/discharge behaviours of vanadium phosphate electrodes in 4 V-class K cells.

P/NF. In addition, it also demonstrates excellent long-term electrochemical durability for at least 25 h. This work offers us a promising catalyst material for water-splitting devices for large-scale production of hydrogen fuels.

. This is one of the most characteristic galvanic replacement reactions, and it can be tuned to create a huge variety of nanoparticle morphologies. We will discuss how advanced electron microscopy characterization enables us to uncover surface-segregation behavior as a function of compositions, and relate this to the detected catalytic performance. We will also discuss how galvanic replacement can be extended to trimetallic compositions, leading to improvements in catalytic activities compared to mono or bimetallic counterparts. Furthermore, we will show how surface morphology, size, and anisotropic growth can be controlled by tuning the temperature during the synthesis and by combining galvanic replacement reaction with co-reduction. Finally, we will demonstrate how these approaches are promising for large-scale synthesis of controlled hollow nanostructures and their incorporation into supports to produce catalysts at the gram-scale. We believe the developments described herein shed important insights and may inspire the development of sophisticated and controlled nanomaterials at…

Thermo-electrochemical cells (also called thermocells) are promising devices for harvesting waste heat for the sustainable production of energy. Research into thermocells has increased significantly in recent years, driven by advantages such as their ability to continuously convert heat into electrical energy without producing emissions or consuming materials. Until relatively recently, the commercial viability of thermocells was limited by their low power output and conversion efficiency. However, there have lately been significant advances in thermocell performance as a result of improvements to the electrode materials, electrolyte and redox chemistry and various features of the cell design. This article overviews these recent developments in thermocell research, including the development of new redox couples, the optimisation of electrolytes for improved power output and high-temperature operation, the design of high surface area electrodes for increased current density and device flexibility, and the optimisation of cell design to further enhance performance.

Rational control of the interlayer space of multilayered Ti 3 C 2 T x enables the MXene to exhibit an excellent U( vi ) sorption capacity and an exceptional radionuclide encapsulation performance.

We herein report the construction of a new heteropore COF which consists of two different kinds of micropores with unprecedented shapes. It exists as hollow microspheres and exhibits an extremely high volatile iodine uptake (up to 481 wt%) by encapsulating iodine in the inner cavities and porous shells of the microspheres.

Two-photon excitation has attracted the attention of biologists, especially after the development of two-photon excited microscopy in the nineties. Since then, new applications have rapidly emerged such as the release of biologically active molecules and photodynamic therapy (PDT) using two-photon excitation. PDT, which requires a light-activated drug (photosensitiser), is a clinically approved and minimally invasive treatment for cancer and for non-malignant diseases. This feature article focuses on the engineering of molecular two-photon photosensitisers for PDT, which should bring important benefits to the treatment, increase the treatment penetration depth with near-infrared light excitation, improve the spatial selectivity and reduce the photodamage to healthy tissues. After an overview of the two-photon absorption phenomenon and the methods to evaluate two-photon induced phototoxicity on cell cultures, the different classes of photosensitisers described in the literature are discussed. The two-photon PDT performed with historical one-photon sensitisers are briefly presented,…

Herein, we compare the bulk, 2H and 3R phases of two most prevalent TMD materials: MoS 2 and WS 2 .

In this feature article, we discuss in detail developmental bottleneck issues in Raman spectroscopy in its early stages and surface-enhanced Raman spectroscopy (SERS) in the past four decades. We divide SERS research into two different directions with different targets. Fundamental research is extending the limits of SERS to single-molecule, sub-nanometer resolution and femtosecond processes. In contrast, practical research is expanding the range of applications with the aim of providing versatile analytical tools for surface, materials, life, environmental, forensic and food sciences and also commercial instruments for use in daily life. In the second direction there have continually been many complex bottlenecks to be overcome. We attempt to enumerate the key issues in detail and also describe the achievements made to overcome the bottlenecks. In the last, but not least important part, we discuss the remaining bottlenecks and possible strategies for overcoming them to enable SERS to be an even more powerful and versatile technique.

P2-/P3-K x CoO 2 electrodes deliver a reversible capacity of 60 mA h g −1 with multiple reversible phase transitions including potassium/vacancy orderings.

A fast and facile route for the optimization of covalent triazine frameworks (CTFs) for photocatalytic hydrogen production is presented.

/C nanocomposite exhibits a high-potential platform of 3.6-3.9 V and a good capacity retention of at least 100 cycles. This work may provide new insight into developing cathode materials for potassium-ion batteries.

The response electron distribution anisotropy (REDA) approximation was proposed to analyze the relationship between optical anisotropy and distribution of bonding electrons in compounds. Further, the optical anisotropy of tetrahedral chromophore compounds with common small birefringence can be enhanced and excellent nonlinear optical properties can be obtained by optimizing the distribution.

A novel N-doped MOF-based hierarchical carbon fiber (NPCF) towards supercapacitors was prepared by the pyrolysis of MOF nanofibers. Due to its unique 1D hollow structures, the NPCF exhibits better energy storage capacity than the other previously reported MOF-derived carbon materials.

Water splitting is promising for energy storage and conversion, but the sluggish oxygen evolution reaction (OER) hinders its wide application. The search for efficient and low-cost electrocatalysts for oxygen evolution has been pursued owing to their significance for green energy generation and storage. Layered Double Hydroxide (LDH) based materials are promising for the OER to improve this weakness. However, the wide application of LDHs is limited by their electronic properties and active sites. Here we report a simple and promising method to improve the OER catalytic activity via an acid-base reaction, which resulted in an exfoliation process and multiple defects including Co, Fe and O vacancies. The acid etched LDHs exhibit better oxygen evolution performance than the pristine LDHs under alkaline conditions with a small Tafel slope and good durability. The acid etching improves the electronic structure and provides more active sites, which results in significant enhancement of OER activity. This work will open up a novel and inexpensive way to improve the catalytic performance in…

The ability to selectively functionalise a specific C-H bond is a long-standing challenge due to the ubiquity of such bonds in organic molecules. One of the most common approaches to overcome this obstacle consists of installing directing groups into substrates to direct the functionalisation towards the desired C-H bond, leaving behind the directing group in the molecule. Alternatively, carboxylic acids have been employed as traceless directing groups that are easily removed after carboxylic acid-directed installation of the desired functionality. This review focuses on the development of this concept and its application to organic synthesis during the last decade.

Significant progress has been accomplished in directed C–H functionalization through the use of earth-abundant and inexpensive first-row transition metals.

) for the alkaline electrochemical water oxidation is reported. The different role of cations could be uncovered along with the detection of drastic surface-structural changes during the catalysis using spectroscopic and microscopic methods.

Cyclin-dependent kinase 9 (CDK9), a member of the cyclin-dependent protein kinase (CDK) family, is involved in transcriptional elongation of several target genes. CDK9 is ubiquitously expressed and has been shown to contribute to a variety of malignancies such as pancreatic, prostate and breast cancers. Here we report the development of a heterobifunctional small molecule proteolysis targeting chimera (PROTAC) capable of cereblon (CRBN) mediated proteasomal degradation of CDK9. In HCT116 cells, it selectively degrades CDK9 while sparing other CDK family members. This is the first example of a PROTAC that selectively degrades CDK9.

The preliminary results described here show that the adsorbability of uranyl ions by a highly stable MOF UiO-66 can be drastically enhanced by tailoring the missing-linker defects in this MOF. The combination of defect-induced functionality improvement with the acid-resistant nature of UiO-66 substantiates the applicability of this material for actinide capture from acidic media.

NSs) exhibit excellent electrochemical performance for their potential use as a promising candidate for the next generation of supercapacitors.

Coordination-driven self-assembly of metal ions and organic ligands has been extensively utilised over the past four decades to access a variety of nano-sized cage assemblies, with functions ranging from sensing and catalysis to drug delivery. Many of the reported examples, however, are highly symmetric architectures that contain one type of organic ligand carrying not more than a single functionality. This contrasts significantly with the level of structural and functional complexity encountered in biological macromolecular hosts, which are able to bind and chemically convert smaller molecules in their highly-decorated internal cavities. To address this disparity, rational approaches that facilitate heteroleptic assembly by regulating integrative self-sorting of metal ions and multiple ligand components have emerged. Among these, routes to access coordination cages from 'naked' metal cations that offer more than two coordination sites are still in early development, as the complexity of the self-sorted products in terms of composition and stereochemistry presents an entropic…

The rate capability of hard carbon has long been underestimated in prior studies that used carbon/Na two-electrode half-cells. Through a three-electrode cell setup, we discover that it is the overpotential of the sodium counter electrode that drives the half-cells to the lower cutoff potential prematurely during hard carbon sodiation, particularly at high current rates, which prevents the hard carbon anode from being fully sodiated.

A structured spinneret comprising two acentric needles nested into a third metal capillary was developed to conduct three-fluid electrospinning processes. With an exterior solvent surrounding two core fluids arranged side-by-side, high quality polyvinylpyrrolidone/shellac Janus nanofibers could be prepared, which was not possible using a standard side-by-side spinneret without this innovation.

We present a facile approach, without the need for external heating and any additional energy input, to produce fluorescent carbon dots (CDs) inexpensively and on a large scale. Fluorescence emission wavelengths from the obtained CDs shift gradually from 630 to 400 nm with reduction in their concentration in solution. This work offers a novel avenue for tuning band gaps in CDs and endowing them with potential for various applications.

MnS has the capability of storing zinc ions with high capacity and long cycle performance.

Surface-assisted Ullmann coupling is the workhorse of on-surfaces synthesis. Among the various couplings that were successfully transferred from solution to solid surfaces, Ullmann coupling is arguably the most reliable, controllable, and widespread coupling reaction. The basic reaction scheme is straightforward: halogenated precursors are deposited onto solid surfaces, normally of coinage metals. In the adsorbed state the halogen substitutents are split off by virtue of the surface's reactivity, thereby generating acitvated species that subsequently recombine by forming C-C bonds. Ullmann coupling is well suited for reticular synthesis of novel organic nanostructures: ideally, the halogen substitution pattern of the precursor - which becomes the monomer upon dehalogenation - predetermines dimensionality and topology of the covalent nanostructures. Also in many relevant systems, side-reactions do not occur. However, in reality topological defects, competing C-H activation on more reactive surfaces, and reaction intermediates render this seemingly simple coupling reaction not only…

, exceeding the capacity of graphite. These results open the door for a new class of high capacity anode materials (based on sulfide chemistry) for potassium-ion batteries.

A composite catalyst combining the partially reducible ZnCrO x with zeolite ZSM-5 enables direct conversion of syngas to aromatics, with a selectivity to aromatics reaching 73.9% at a single pass CO conversion of 16.0%.

Atropisomerism is a fundamental property of molecules featuring a hindered rotation around a chemical bond. If six-membered ring biaryl or heterobiaryl atropisomers are the most popular ones, the focus of this feature article will be put on less common and more challenging five-membered ring containing atropisomers displaying either a stereogenic C-N or C-C bond. After an historical background, a description of the latest flourishing enantioselective strategies for the construction of this attractive family of atropisomers will be presented.

Fe 3 O 4 @ZIF-8 nanoparticles with outstanding UO 2 2+ adsorption capacity and selectivity for lanthanide ions could be simply separated by magnet from a solution containing lanthanide ions.

Metal–organic framework derived carbon-confined Ni 2 P nanocrystals supported on graphene with high effective surface area, more exposed active sites, and enhanced charge transport were successfully designed.

, was investigated in detail using electrochemical galvanostatic cycling at various current densities. X-ray diffraction and X-ray photoelectron spectroscopy were used to study the potassiation mechanism and its structural changes.

compound) chemical libraries, making it an extraordinary tool for drug discovery. The current review charts the history of flexizyme technology and its use for non-canonical peptide synthesis and screening.

A new class of iodinated cyanine dyes have been prepared for use in NIR excited photodynamic therapy (PDT) and demonstrated improved efficacy in two pancreatic cell lines as well as excellent tumour control in a murine model of the disease.

One-step functionalization of alginate with boronic acid groups allowed spontaneous formation of biocompatible hydrogels under basic conditions without additional complementary molecules or crosslinking agents. The dynamic nature of boronate ester bonds formed with vicinal diols present on alginate pyranose rings provided remarkable self-healing, injectable and multi-stimuli responsive properties to the material.

An explosion approach was developed for efficiently preparing graphdiynes (GDYs) at 120 °C in air without any metal catalyst.

MoO 3−x quantum dots possessing strong photoabsorption have been used for interfacial heating for water evaporation.

. Moreover, no faster fading in capacity is observed after 500 cycles. This electrolyte could provide a new system for Al ion batteries, which can be used for large scale energy storage, owing to its cost advantages, high-rate capability and durability.

QDs with great stability and high quantum yield in phospho-silicate glass, which was fabricated by using a heat-treatment approach, for white light emitting devices. QD glasses exhibited excellent photo- and thermal stability, and significantly prolonged the lifetime of light emitters under ambient air conditions.

The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

Highly ordered 2D COF TTA–DHTA was synthesized on amino-functionalized MWCNTs with high crystallinity, regular pore structures and improved electrochemical performance.

(BPyTPE)] (1) (BPyTPE = (E)-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)phenyl)ethene) has been designed and constructed. The solvent-free 1 exhibits strong blue-green emission with an excellent fluorescence quantum yield of 99% and provides a facile and reversible method to sensitively and quantitatively detect trace pesticide of 2,6-dichloro-4-nitroaniline.

A mesoporous cationic Cr-based metal–organic framework (MOF), FJI-C10 , has been obtained and exhibited excellent performances in chemical fixation of CO 2 into cyclic carbonates under co-catalyst free and mild conditions.

at 20 °C, excellent thermal stability up to 300 °C, and a large electrochemical stability window of 3 V including stability towards sodium metal anodes, all essential prerequisites for a stable room-temperature 3 V all-solid-state sodium-ion battery.

was the dominant reactive oxygen species towards the efficient degradation of ofloxacin and phenol, demonstrating a promising application in real wastewater treatment.

In 2008, a new class of pillar-shaped supramolecular macrocyclic hosts was reported, known as "pillararenes". Their particular electron-rich cavity and the ease of their functionalization offer possibilities for the design and synthesis of novel fluorescent chemosensors. Subsequently, pillararene-based fluorescent sensors and probes have been rapidly developed. This feature article covers the most recent contributions from the pillararene-based fluorescent sensor field in terms of anion/cation sensing, small molecule recognition, biomolecule detection, fluorescent supramolecular aggregates, and biomedical imaging. Meanwhile, we hope that this feature article will inspire more effort to be devoted to this emerging field.

We herein report the design of a versatile covalent organic framework (COF)-based platform for sensing biomolecules. As a proof of concept, a highly sensitive and selective COF-based fluorescence turn-on detection of DNA and adenosine 5'-triphosphate is demonstrated.

SC with a controllable thickness of 16 μm and a size of 6 × 8 mm. Additionally, the SC solar cell achieves an intriguing efficiency of 7.11% with an impressive stability, maintaining 93% initial PCE after aging for 1000 h.

Amides are of fundamental interest in many fields of chemistry involving organic synthesis, chemical biology and biochemistry. Here, we report the first catalytic Buchwald-Hartwig coupling of both common esters and amides by highly selective C(acyl)-X (X = O, N) cleavage to rapidly access aryl amide functionality via a cross-coupling strategy. Reactions are promoted by versatile, easily prepared, well-defined Pd-PEPPSI type precatalysts, and proceed in good to excellent yields and with excellent chemoselectivity for the acyl bond cleavage. The method is user friendly because it employs commercially-available, moisture- and air-stable precatalysts. Notably, for the first time we demonstrate selective C(acyl)-N and C(acyl)-O cleavage/Buchwald-Hartwig amination under the same reaction conditions, which allows for streamlining amide synthesis by avoiding restriction to a particular acyl metal precursor. Of broad interest, this study opens the door to using a family of well-defined Pd(ii)-NHC precatalysts bearing pyridine "throw-away" ligands for the selective C(acyl)-amination of…

A photoredox approach to generate distal cyano-substituted alkyl radicals through C-C bond cleavage of cyclobutanone oximes was developed. The radicals produced by this method were applied to three-component cyanopropylation/etherification of unactivated alkenes. Their reactions with diverse radical acceptors were also demonstrated.

This feature article surveys the various ways by which a structurally simple hydrazone can be used in accessing different functional materials, mainly photo/chemically activated switches, fluorophores and sensors. The modularity of this functional group enabled us to develop new switching mechanisms, pathways, cascades and loops, while addressing challenges in the field, such as waste accumulation, how to control cross-talk between different types of switches, developing photochromic compounds with benign activation wavelengths, among others. All of these advances are expected to play, in one permutation or another, an important role in the coming decades in the field of molecular switches and machines.

@COFs can serve as an ideal absorbent for the highly efficient enrichment of peptides and the simultaneous exclusion of proteins from complex biological samples.

Herein we propose a general mechanism for the racemization of [n]helicenes up to n = 24. It is a concerted process for n = 4-7, but a multi-step mechanism is followed for n≥ 8, involving 2n- 14 intermediates. The changes in the barriers are a delicate consequence of the steric hindrance and the π-interactions.

Plasmonic nanomaterials have been widely used for photothermal therapy (PTT) of cancer, but their recognition specificity remains challenging. We prepared monosaccharide-imprinted gold nanorods (AuNRs) for targeted cancer PTT, using sialic acid (SA) as a representative monosaccharide. The SA-imprinted AuNRs exhibited good specificity, enabling the killing of cancer cells without damaging healthy cells.

, X = Br/I) are found to work as efficient triplet sensitizers for photon upconversion based on triplet-triplet annihilation (TTA-UC) at low excitation intensity.

For the first time, free base and N-methylated porphyrins have been utilized as bifunctional organocatalysts in Michael additions and it was found that distortion of the macrocycle is a vital prerequisite for their catalytic activity. Conformational design has been used to tailor the properties of nonplanar porphyrins with regards to availability of the N-H units for hydrogen bonding (distortion-dependent hydrogen bonding) and the basicity of the heterocyclic groups. NMR spectroscopic- and catalyst screening studies provided insight into the likely mode of catalyst action. This unprecedented use of free base and N-substituted porphyrins as organocatalysts opens a new functional role for porphyrins.

∼ 700 nm) with a large Stokes shift (Δλ ≈ 234 nm) is synthesized by using excited-state intramolecular proton transfer (ESIPT). The phenolic proton, which controls ESIPT, acts as a switch to give strong fluorescence at pH ≈ 5. The probe can selectively show lysosome organelles, therefore leading to a lysosome probe without exhibiting "an alkalinizing effect".

(-2J formalism). The dysprosium complexes with n = 0 and 1 are single-molecule magnets in zero applied field, whereas the complex with n = 2 does not show slow magnetic relaxation.

Heterocyclic compounds are commonly found in the core structures of several pharmaceuticals, natural products, and agrochemicals, thus spurring intensive research for conducting their synthesis in a mild and simpler way. Over the years, a host of different strategies has been introduced in an effort to synthesize these heterocyles. In this context, significant attention has been gained by methodologies that ensure both step as well as atom efficiency. Synthesis of heterocyclic moieties via multiple C-H activations was found to fulfill these expectations besides guaranteeing the use of starting materials that are easily procurable. This review is focused on the current development in the field of benzofuran and indole synthesis using multiple C-H functionalization strategies.

Herein a series of mitochondria-targeted AIE (aggregation-induced emission)-active Ir(iii) complexes were designed to selectively exert one-/two-photon photodynamic activities in mitochondria to address the issues which current PDT are confronted with (i.e., shallow penetration depth of routinely used irradiation; systematic toxicity associated with effective drug concentration; concentration-quenched photodynamic activity at the target, etc.).

Nanosheets, which are two-dimensional polymeric materials, remain among the most actively researched areas of chemistry and physics this decade. Generally, nanosheets are inorganic materials created from bulk crystalline layered materials and have fascinating properties and functionalities. An emerging alternative is molecule-based nanosheets containing organic molecular components. Molecule-based nanosheets offer great diversity because their molecular, ionic, and atomic constituents can be selected and combined to produce a wide variety of nanosheets. The present article focuses on coordination nanosheets (CONASHs), a class of molecule-based nanosheets comprising organic ligand molecules and metal ions/atoms in a framework linked with coordination bonds. Following the Introduction, Section 2 describes CONASHs, including their definition, design, synthetic procedures, and characterisation techniques. Section 3 introduces various examples of CONASHs, and Section 4 explores their functionality and possible applications. Section 5 describes an outlook for the research field of CONASHs.

in 1.0 M KOH containing AE; however, a cell volatge of 1.63 V is required to drive the same current density in the absence of AE. Fe-CoP/CC also exhibits strong long-term electrochemical durability and nearly 100% faradaic efficiency.

A facile sunlight-induced derivatization of heteroaromatics via photocatalyzed C-H functionalization in amides, ethers, alkanes and aldehydes is described. Tetrabutylammonium decatungstate (TBADT) was used as the photocatalyst and allowed to carry out the process under mild conditions.

The electronic structure of f-element compounds is complex due to a combination of relativistic effects, strong electron correlation and weak crystal field environments. However, a quantitative understanding of bonding in these compounds is becoming increasingly technologically relevant. Recently, bonding interpretations based on analyses of the physically observable electronic density have gained popularity and, in this Feature Article, the utility of such density-based approaches is demonstrated. Application of Bader's Quantum Theory of Atoms in Molecules (QTAIM) is shown to elucidate many properties including bonding trends, orbital overlap and energy degeneracy-driven covalency, oxidation state identification and bond stability, demonstrating the increasingly important role that simulation and analysis play in the area of f-element bond characterisation.

Only a few studies on the use of halogen bonding in catalysis have been published so far. Herein, (benz)imidazolium-based halogen bond donors are used as catalysts in a Michael addition reaction. The most potent catalyst, a rigid atropisomer featuring two iodobenzimidazolium moieties, provided a rate acceleration versus a reference compound of ca. 50.

We present a first direct measurement of the temperature during milling combined with in situ Raman spectroscopy monitoring. The data reveal a low temperature increase due to the mechanical impact and clear temperature increases as a consequence of the reaction heat. Based on the data, temperature rises as postulated in the magma plasma and hot spot theory can be excluded for soft matter milling syntheses.

A visible light-driven catalytic cycle for hydrocarboxylation of alkenes with CO 2 was established using a combination of a Rh( i ) complex as a carboxylation catalyst and [Ru(bpy) 3 ] 2+ (bpy = 2,2′-bipyridyl) as a photoredox catalyst.

An unusual but highly desired increase in the separation selectivity of C 3 H 6 /C 3 H 8 under high pressures was found on the PDMS-coated ZIF-8 polycrystalline membrane.

UiO-66 metal-organic frameworks (MOFs) can be endowed with greatly enhanced photocatalytic properties by introducing titanium into the frameworks. A microwave-assisted method was developed to substitute the zirconium with titanium in UiO-66, which was accomplished within a few hours compared to several days reported previously, with the crystallinity well maintained and photocatalytic activities tremendously improved.

-methyladenosine (m6A), representing the first m6A-sensitive RNA cleavage enzyme. The methyl-sensitivity of MazF allowed simple analyses of both m6A demethylase and methyltransferase activity. Furthermore, the approach could be used for inhibitor screening.

Plastics are ubiquitous in modern society. However, the reliance on fossil fuels and the environmental persistence of most polymers make them unsustainable. Scientists are facing the challenge of developing cost-effective and performance-competitive polymers from renewable resources. Carbohydrates are a renewable feedstock with tremendous potential: sugars are widely available, environmentally benign and are likely to impart biocompatibility and degradability properties to polymers due to their high oxygen content. Sugars are also a feedstock with great structurally diversity and functionalisation potential that can enable fine tuning of the resulting polymer properties. In recent years, Ring-Opening Polymerisation (ROP) has emerged as the method of choice for the controlled polymerisation of renewable cyclic monomers, in particular lactones and cyclic carbonates, to allow the precise synthesis of complex polymer architectures and address commodity and specialist applications. This feature article gives an overview of sugar-based polymers that can be made by ROP. In particular,…

H 2 O 2 -triggered release of CO: an intratumoral H 2 O 2 -responsive nanomedicine is constructed by effectively encapsulating the hydrophilic manganese carbonyl prodrug into an advanced hollow mesoporous silica nanoparticle carrier to realize selective killing of tumor cells, exhibiting high in vitro and in vivo efficacies of CO gas therapy.

For the first time, we have synthesized APbBr 3 (A = Cs + /MA + /FA + , where MA + = CH 3 NH 3 + and FA + = CH(NH 2 ) 2 + ) bulk as well as nanoparticles (NPs) by solid-state reactions at room temperature.

Fine-tuning of HUMs through pillar substitution can significantly enhance trace CO 2 sorption performance and stability.

Single-electron reduction of C[double bond, length as m-dash]O and C[double bond, length as m-dash]N bonds of aldehydes, ketones, and imines results in the formation of ketyl and α-aminoalkyl anion radicals, respectively. These reactive intermediates are characterized by an altered electronic character with respect to their parent molecules and undergo a diverse range of synthetically useful transformations, which are not available to even-electron species. This Review summarizes the reactions of ketyl and α-aminyl radicals generated from carbonyl derivatives under transition-metal photoredox-catalysed conditions. We primarily focus on recent developments in the field, as well as give a brief overview of catalytic enantioselective transformations that provide a means to achieve precise stereocontrol over the reactivity of ion radicals.

Here, the first example is reported of a new, molecularly defined SNS-cobalt(ii) catalyst for the acceptorless dehydrogenative coupling (ADC) of unprotected amino alcohols with secondary alcohols leading to pyrrole and pyridine derivatives.

Traditional textile materials can be transformed into functional electronic components upon being dyed or coated with films of intrinsically conducting polymers, such as poly(aniline), poly(pyrrole) and poly(3,4-ethylenedioxythiophene). A variety of textile electronic devices are built from the conductive fibers and fabrics thus obtained, including: physiochemical sensors, thermoelectric fibers/fabrics, heated garments, artificial muscles and textile supercapacitors. In all these cases, electrical performance and device ruggedness is determined by the morphology of the conducting polymer active layer on the fiber or fabric substrate. Tremendous variation in active layer morphology can be observed with different coating or dyeing conditions. Here, we summarize various methods used to create fiber- and fabric-based devices and highlight the influence of the coating method on active layer morphology and device stability.

A facile and one step-method was developed to enhance the water stability of CD-MOF nanoparticles through surface modification with cholesterol. CD-MOFs were able to maintain their cubic crystalline structures even after 24 h of incubation, well tolerated in vivo and could increase up to 4 times the blood half-life of DOX.

Palladium-catalyzed C-H activation/C-C cross-coupling reactions typically require stoichiometric chemical oxidants and exogenous ligands. However, there are significant disadvantages associated with the use of traditional stoichiometric oxidants. To overcome these issues, we have developed an electrochemical strategy to achieve methylation and acylation.

to CO under visible light irradiation in organic media without the assistance of a sensitizer and no competitive hydrogen evolution for several days.

Mono-biotinylated Pt IV complex with one hydroxyl ligand in the axial position shows potent inhibition against cisplatin-insensitive breast cancer cells.

We herein present a porphyrinic metal-organic framework (MOF) as a highly sensitive fluorescent probe targeting Cu(ii) ions with a fast response. The well-isolated nature of porphyrin moieties within the framework greatly enable accessible recognition sites, which leads to an outstanding detection limit performance of 67 nM among MOF-based materials.

, with good repeatability, stability, and applicability in real samples. This work will establish a new platform for biosensing and extend the application scope of MOF materials.

selectivities of membranes, resulting in performances that surpass the upper bound limit for polymer membranes.

This communication reports on the design and synthesis of mechanochromophores with a dynamic covalent system composed of a tetraarylsuccinonitrile skeleton that generate a metastable organic luminescent carbon radical. The mechanically generated radical species showed pink color and yellow light emission under UV irradiation. Unusually high stability of the luminescent carbon-centered radicals was also observed in a polymer system.

As a durable catalyst, an FeMoS 4 nanorod array on carbon cloth shows high activity for hydrogen evolution in neutral media, achieving a geometrical catalytic current density of 10 mA cm −2 at an overpotential of 204 mV.

In 2003, we successfully created the first fluorescent polymeric thermometer by combining a thermo-responsive polymer and an environment-sensitive (polarity and hydrogen bonding-sensitive) fluorophore. Its high sensitivity to temperature variation and high hydrophilicity, even under conditions of high ionic strength, enabled intracellular temperature measurements. Along with the progress of our research projects, the development of new luminescent molecular thermometers and the establishment of novel methods for measuring intracellular temperature have matured in this field. In this Feature Article, we summarize the background and history of intracellular temperature measurements using fluorescent polymeric thermometers based on studies performed in our laboratory and the relationship between our methods and those of other eminent research groups. Future research directions regarding intracellular temperature measurements are also discussed.

A two-photon fluorescent probe based on an ESIPT fluorophore bearing AIE characteristics was utilized to detect H 2 S.

The CPL of a chiral diamine can be switched between two regions under concomitant inversion of the handedness, while a strong PL intensity is maintained in the same region.

Two extremely rare β-cyclodextrin (β-CD) supported metal-organic frameworks (MOFs), CD-MOF-1 and CD-MOF-2, were induced to crystallize for the first time through a template-induced approach. The targeted CD-MOFs were employed to perform controlled drug delivery and cytotoxicity assays that confirmed their favourable biological potential of being used as drug carriers.

. The detection limit of AA reaches 7 nM, showing its potential for AA detection in the environmental industry and clinical medicine.

A Sr-MOF possessing polar tubes and open acidic sites shows outstanding performance for light hydrocarbon separation and CO 2 capture and conversion.