Showing papers in "Chemistry: A European Journal in 2020"
TL;DR: A review of established laser‐based methodologies of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non‐equilibrium compounds, metal‐oxide core–shells and other anisotropic morphologies is presented.
Abstract: Although oxide nanoparticles are ubiquitous in science and technology, a multitude of compositions, phases, structures, and doping levels exist, each one requiring a variety of conditions for their synthesis and modification. Besides, experimental procedures are frequently dominated by high temperatures or pressures and by chemical contaminants or waste. In recent years, laser synthesis of colloids emerged as a versatile approach to access a library of clean oxide nanoparticles relying on only four main strategies running at room temperature and ambient pressure: laser ablation in liquid, laser fragmentation in liquid, laser melting in liquid and laser defect-engineering in liquid. Here, established laser-based methodologies are reviewed through the presentation of a panorama of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non-equilibrium compounds, metal-oxide core-shells and other anisotropic morphologies. So far, these materials showed several useful properties that are discussed with special emphasis on catalytic, biomedical and optical application. Yet, given the endless number of mixed compounds accessible by the laser-assisted methodologies, there is still a lot of room to expand the library of nano-crystals and to refine the control over products as well as to improve the understanding of the whole process of nanoparticle formation. To that end, this review aims to identify the perspectives and unique opportunities of laser-based synthesis and processing of colloids for future studies of oxide nanomaterial-oriented sciences.
160 citations
TL;DR: This minireview summarizes the rapid advances in this field and gives some insights into future developments, which will help this research field thrive.
Abstract: Axially chiral indole-based frameworks have been recognized as a class of important five-membered heterobiaryls and developing catalytic asymmetric approaches for constructing these frameworks in an enantioselective manner is highly desirable. In recent years, synthetic chemists have paid much attention to this research field, and rapid developments have occurred. At this point, a range of axially chiral indole-based scaffolds have been constructed via various catalytic asymmetric reactions based on different strategies. Thus, the catalytic asymmetric construction of axially chiral indole-based frameworks has become an emerging area. This minireview summarizes the rapid advances in this field and gives some insights into future developments, which will help this research field to thrive.
153 citations
TL;DR: In this review, the development of ultrathin 2D nanosheets in the field of electrochemistry is introduced, and their unique dimensional advantages are highlighted.
Abstract: Metal-organic framework (MOF) and covalent organic framework (COF) nanosheets are a new type of two-dimensional (2D) materials with unique design principles and various synthesis methods. They are considered ideal electrochemical devices due to the ultrathin thickness, easily tunable molecular structure, large porosity and other unique properties. There are two common methods to synthesize 2D MOF/COF nanosheets: bottom-up and top-down. The top-down strategy mainly includes ultrasonic assisted exfoliation, electrochemical exfoliation and mechanical exfoliation. Another strategy mainly includes interface synthesis, modulation synthesis, surfactant-assisted synthesis. In this Review, the development of ultrathin 2D nanosheets in the field of electrochemistry (supercapacitors, batteries, oxygen reduction, and hydrogen evolution) is introduced, and their unique dimensional advantages are highlighted.
139 citations
TL;DR: This review systematically summarized the development of the fluorescent probes based on BODIPYs for detection of biothiols, preferable detection of individual biothiolas, as well as simultaneous discrimination among Cys, Hcy and GSH.
Abstract: Fluorescent probes for biothiols have aroused increasing interest owing to their potential to enable better understanding of the diverse physiological and pathological processes related to the biothiol species. BODIPY fluorophores exhibit excellent optical properties, which can be readily tailored by introducing diverse functional units at various positions of the BODIPY core. In the present review, the development of fluorescent probes based on BODIPYs for the detection of biothiols are systematically summarized, with emphasis on the preferable detection of individual biothiols, as well as simultaneous discrimination among cysteine (Cys), homocysteine (Hcy), reduced glutathione (GSH). In addition, organelle-targeting probes for biothiols are also highlighted. The general design principles, various recognition mechanisms, and biological applications are elaboratively discussed, which could provide a useful reference to researchers worldwide interested in this area.
134 citations
TL;DR: This minireview summarizes and discusses the progress in these reactions according to the type of the chiral catalyst used, and the development of chiral Cp x ligands and their metal complexes, artificial metalloenzymes, chiral carboxylate-assisted enantioselective C-H activations, enantiOSElective alkylations assisted by chiral sulfonates, and chiral transient directing groups are discussed.
Abstract: Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties in achieving catalytic stereocontrol using these catalysts due to their lack of additional coordination sites for external chiral ligands and the conformational flexibility of the Cp ligand, catalytic enantioselective C-H functionalization reactions using the Group 9 metal triad with Cp-type ligands have been intensively studied since 2012. In this minireview, the progress in these reactions according to the type of the chiral catalyst used are summarized and discussed. The development of chiral Cpx ligands the metal complexes thereof, artificial metalloenzymes, chiral carboxylate-assisted enantioselective C-H activations, enantioselective alkylations assisted by chiral carboxylic acids or chiral sulfonates, and chiral transient directing groups are discussed.
126 citations
TL;DR: A diverse range of alterations and compositions derived from 2D carbon-based nanomaterials, mainly graphene and graphitic carbon nitride (g-C3N4), which have remarkably ameliorated the photocatalytic CO2 performance are presented.
Abstract: Photocatalytic CO2 reduction is a revolutionary approach to solve imminent energy and environmental issues by replicating the ingenuity of nature. The past decade has witnessed an impetus in the rise of two-dimensional (2D) structure materials as advanced nanomaterials to boost photocatalytic activities. In particular, the use of 2D carbon-based materials is deemed as highly favorable, not only as a green material choice, but also due to their exceptional physicochemical and electrical properties. This Review article presents a diverse range of alterations and compositions derived from 2D carbon-based nanomaterials, mainly graphene and graphitic carbon nitride (g-C3 N4 ), which have remarkably ameliorated the photocatalytic CO2 performance. Herein, the rational design of the photocatalyst systems with consideration of the aspect of dimensionality and the resultant heterostructures at the interface are systematically analyzed to elucidate an insightful perspective on this pacey subject. Finally, a conclusion and outlook on the limitations and prospects of the cutting-edge research field are highlighted.
116 citations
TL;DR: Examples of reactions especially over the past decade that can give higher yield in 100% water than in organic solvents are reviewed to understand the contribution of the water molecules at multifarious interfaces.
Abstract: Ever-evolving catalyst advances in synthetic protocols using water as a reaction medium have enriched the understanding of sustainable organic chemistry. Because conventional classification and definitions were ambivalent, it is proposed here that catalytic reactions using water be collectively called to be "in water", with further classification into seven types. When accelerated in water as heterogeneous mixtures, the reactions can be regarded as following an "on-water" mechanism. The original term "on water" coined by Sharpless is incongruous with catalytic reactions, whereas on-water used in this review covers all the interfaces involving water where chemical reactions are accelerated. As a result of the unconcluded dispute on the antiquated catalyst-free "on water" model, the modified model defines three water layers: water molecules that are oriented to extrude protons toward the oil phase in the inner layer, those enwrapped by a secondary layer, and finally the bulk water layer. In light of the latitudinous outlook on the role of water at the interface, selected examples of reactions, in particular those reported over the past decade, that follow an "on-water" mechanism are reviewed herein.
109 citations
107 citations
TL;DR: Special attention is given to the application of SCS to form metal oxide thin films at low temperature and their application in thin film transistors (TFTs), and how these affect the overall materials properties from nanostructures to thin films.
Abstract: Solution combustion synthesis (SCS) has been widely used to produce simple and complex oxides with a desired morphology (size and shape). SCS is valuable due to low cost, simplicity and energy efficient synthesis. To guarantee the best molecular-level mixing of reactants in an aqueous or solvent-based solution some parameters need to be controlled, such as fuel type, metal cations precursors, stoichiometry ratio (φ), pH effect, atmosphere and initiation type. These determine the final properties of the oxide materials, providing the potential to reach different morphologies, which are essential for their final applications. This Review article focuses on the crucial parameters in SCS and how these affect the overall materials properties from nanostructures to thin films. To finalize, special attention is given to the application of SCS to form metal oxide thin films at low temperature and their application in thin film transistors (TFTs).
104 citations
TL;DR: This contribution provides an overview of recent developments of COF-based medicines in cancer therapeutics, including drug delivery, photodynamic therapy (PDT), photothermal therapy (PTT), and combined therapy.
Abstract: As newly emerged crystalline porous materials, covalent organic frameworks (COFs) possess fascinating structures and some specific features such as modularity, crystallinity, porosity, stability, versatility, and biocompatibility. Besides adsorption/separation, sensing, catalysis, and energy applications, COFs have recently shown a promise in biomedical applications. This contribution provides an overview of the recent developments of COF-based medicines in cancer therapeutics, including drug delivery, photodynamic therapy (PDT), photothermal therapy (PTT), and combined therapy. Furthermore, the major challenges and developing trends in this field are also discussed. These recent developments are summarized and discussed to help encourage further contributions in this emerging and promising field.
104 citations
TL;DR: An overview of the past studies, current trends, and future directions in the field of gold catalyzed coupling reactions, including theoretical and computational studies of Au(I)/Au(III) chemistry, is presented.
Abstract: Transition-metal-catalyzed cross-coupling reactions are central to many organic synthesis methodologies. Traditionally, Pd, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently, many studies have showed that both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions. Here, an overview of the past studies, current trends, and future directions in the field of gold-catalyzed coupling reactions is presented. Design strategies to accomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and experimental mechanistic studies, and their applications in diverse fields are critically reviewed. Specific topics covered are: oxidant-assisted and oxidant-free reactions; strain-assisted reactions; dual Au and photoredox catalysis; bimetallic synergistic reactions; mechanisms of reductive elimination processes; enzyme-mimicking Au chemistry; cluster and surface reactions; and plasmonic catalysis. In the relevant sections, theoretical and computational studies of AuI /AuIII chemistry are discussed and the predictions from the calculations are compared with the experimental observations to derive useful design strategies.
TL;DR: The present review is focused on recent advances and findings of new antimicrobial strategies based on metal complexes, indicating that some metal ions cause different types of damages to microbial cells as a result of membrane degradation, protein dysfunction and oxidative stress.
Abstract: Traditional organic antimicrobials mainly act on specific biochemical processes such as replication, transcription and translation. However, the emergence and wide spread of microbial resistance is a growing threat for human beings. Therefore, it is highly necessary to design strategies for the development of new drugs in order to target multiple cellular processes that should improve their efficiency against several microorganisms, including bacteria, viruses or fungi. The present review is focused on recent advances and findings of new antimicrobial strategies based on metal complexes. Recent studies indicate that some metal ions cause different types of damages to microbial cells as a result of membrane degradation, protein dysfunction and oxidative stress. These unique modes of action, combined with the wide range of three-dimensional geometries that metal complexes can adopt, make them suitable for the development of new antimicrobial drugs.
TL;DR: Ueff not only has a linear correlation to the axial Dy-X bond lengths, but also to the TH for these pentagonal-bipyramidal PB SMMs, the first magnetostructural correlation in Dy SMMs.
Abstract: Although the development of single-molecule magnets (SMMs) is rapid, there are only two families of high energy barrier (Ueff ) dysprosium(III) SMMs known so far: the cyclopentadienyl (Cp) family with a sandwich structure and the pentagonal-bipyramidal (PB) family with D5h symmetry. These high-barrier SMMs, which usually possess Ueff >500 cm-1 allow the separate study of the four magnetic relaxation paths, namely, direct, quantum tunnelling, Raman and Orbach processes, in detail. Whereas the first family is chemically more challenging to modify the Cp rings, it is shown herein that the latter family, with the common formulae [DyX1 X2 (Leq )5 ]+ , such as X1 /X2 =- OCMe3 , - OSiMe3 , - OPh, Cl- or Br- ; Leq =THF/pyridine/4-methylpyridine, can be readily fine-tuned with a range of axial and equatorial ligands by simple substitution reactions. This allows unambiguous confirmation that the Ueff mainly depends on the identity of X1 and X2 , rather than on Leq . More importantly, the fitted parameters are barrier dependent. If X1 is an O donor and X2 is a halide, 500
TL;DR: Criteria for a high-quality compound library design enabling efficient virtual navigation of chemical space, as well as rise and fall of concepts for its synthetic exploration (such as combinatorial chemistry, diversity-, biology-, lead-, or fragment-oriented syntheses, DNA-encoded libraries etc.) are critically surveyed.
Abstract: All pharmaceutical products contain organic molecules; the source may be a natural product or a fully synthetic molecule, or a combination of both. Thus, it follows that organic chemistry underpins both existing and upcoming pharmaceutical products. The reverse relationship has also affected organic synthesis, changing its landscape towards increasingly complex targets. This Review article sets out to give a concise appraisal of this symbiotic relationship between organic chemistry and drug discovery, along with a discussion of the design concepts and highlighting key milestones along the journey. In particular, criteria for a high-quality compound library design enabling efficient virtual navigation of chemical space, as well as rise and fall of concepts for its synthetic exploration (such as combinatorial chemistry; diversity-, biology-, lead-, or fragment-oriented syntheses; and DNA-encoded libraries) are critically surveyed.
TL;DR: Electrophotochemistry has enabled arene C−H trifluoromethylation with the Langlois reagent CF3SO2Na under mild reaction conditions and provided a chemical oxidant‐free approach for the generation of the CF3 radical.
Abstract: Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF3 SO2 Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for the generation of the CF3 radical. The electrophotochemistry was carried out in an operationally simple manner, setting the stage for challenging C-H trifluoromethylations of unactivated arenes and heteroarenes. The robust nature of the electrophotochemical manifold was reflected by a wide scope, including electron-rich and electron-deficient benzenes, as well as naturally occurring heteroarenes. Electrophotochemical C-H trifluoromethylation was further achieved in flow with a modular electro-flow-cell equipped with an in-operando monitoring unit for on-line flow-NMR spectroscopy, providing support for the single electron transfer processes.
TL;DR: An overview of synergistic Pd/Cu catalysis in organic synthesis and the reaction mechanisms involved in this research area is provided.
Abstract: Synergistic Pd/Cu catalysis has been utilized in the Sonogashira reaction since 1975. However, this strategy has not received much attention from the organic chemist community until recently. Synergistic Pd/Cu catalysis is becoming a proficient method for the development of catalytic reactions, including several new and efficient cross-coupling reactions. Additionally, several challenging asymmetric reactions, including stereodivergent synthesis, have been discovered by the combined use of a chiral metal catalyst and a second achiral metal catalyst or two chiral metal catalysts. This review provides an overview of this field, with the aims of highlighting both the development of synergistic Pd/Cu catalysis in organic synthesis and the reaction mechanisms involved in this research area.
TL;DR: This review article presents the white light emission obtained from small organic molecules to supramolecular assemblies including polymers, micelles and also employing covalent organic frameworks and the key aspect of tuning the molecular fluorescence under the influence of pH, heat, and host-guest interactions is discussed.
Abstract: White light emitting (WLE) materials are of increasing interest owing to their promising applications in artificial lighting, display devices, molecular sensors, and switches. In this context, organic WLE materials cater to the interest of the scientific community owing to their promising features like color purity, long-term stability, solution processability, cost-effectiveness, and low toxicity. The typical method for the generation of white light is to combine three primary (red, green, and blue) or the two complementary (e.g., yellow and blue or red and cyan) emissive units covering the whole visible spectral window (400-800 nm). The judicious choice of molecular building blocks and connecting them through either strong covalent bonds or assembling through weak noncovalent interactions are the key to achieve enhanced emission spanning the entire visible region. In the present review article, molecular engineering approaches for the development of all-organic WLE materials are analyzed in view of different photophysical processes like fluorescence resonance energy transfer (FRET), excited-state intramolecular proton transfer (ESIPT), charge transfer (CT), monomer-excimer emission, triplet-state harvesting, etc. The key aspect of tuning the molecular fluorescence under the influence of pH, heat, and host-guest interactions is also discussed. The white light emission obtained from small organic molecules to supramolecular assemblies is presented, including polymers, micelles, and also employing covalent organic frameworks. The state-of-the-art knowledge in the field of organic WLE materials, challenges, and future scope are delineated.
TL;DR: In this paper, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctionsal catalyst with low overpotentials. But, the problem is that a good ORR catalyst is not necessarily efficient for OER, and vice versa.
Abstract: Metal-air batteries (MABs) and reversible fuel cells (RFCs) rely on the bifunctional oxygen catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Finding efficient bifunctional oxygen catalysts is the ultimate goal and it has attracted a great deal of attention. The dilemma is that a good ORR catalyst is not necessarily efficient for OER, and vice versa. Thus, the development of a new type of bifunctional oxygen catalysts should ensure that the catalysts exhibit high activity for both OER and ORR. Composites with multicomponents for active centers supported on highly conductive matrices could be able to meet the challenges and offering new opportunities. In this Review, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctional catalysts with low overpotentials.
TL;DR: In this mini-review, the recent progress of organic-inorganic CESs has been summarized in terms of the inorganic component, electrochemical performance, effects of theInorganic ceramic nanostructure, and ionic conducting mechanism.
Abstract: Conventional lithium-ion batteries, with flammable organic liquid electrolytes, have serious safety problems, which greatly limit their application. All-solid-state batteries (ASSBs) have received extensive attention from large-scale energy-storage fields, such as electric vehicles (EVs) and intelligent power grids, due to their benefits in safety, energy density, and thermostability. As the key component of ASSBs, solid electrolytes determine the properties of ASSBs. In past decades, various kinds of solid electrolytes, such as polymers and inorganic electrolytes, have been explored. Among these candidates, organic-inorganic composite solid electrolytes (CSEs) that integrate the advantages of these two different electrolytes have been regarded as promising electrolytes for high-performance ASSBs, and extensive studies have been carried out. Herein, recent progress in organic-inorganic CSEs is summarized in terms of the inorganic component, electrochemical performance, effects of the inorganic ceramic nanostructure, and ionic conducting mechanism. Finally, the main challenges and perspectives of organic-inorganic CSEs are highlighted for future development.
TL;DR: Both the practical methods for synthesizing sulfilimines and the versatility of these ylidic species in gold‐catalyzed preparation of structural diversity, for both heterocycles and carbocycles, will be outlined in this Concept article.
Abstract: Catalytic approaches to pharmaceutically important bioactive skeletons through gold carbene intermediates have experienced a dramatic development in the last decade. Although various carbene precursors continue to play an important role in heterocyclic syntheses, these reagents are associated with some drawbacks in terms of functional group tolerance, synthetic methods and safety limitations. A new generation of nitrene transfer reagents was established in 2019: the sulfilimines. These are safe, inexpensive and readily available. They can conveniently be stored and handled, and thus represent ideal reagents for the fast and modular modification of scaffolds and the preparation of libraries by intermolecular reactions of two components. Both the practical methods for synthesizing sulfilimines and the versatility of these ylidic species in gold-catalyzed preparation of structural diversity, for both heterocycles and carbocycles, will be outlined in this Concept article.
TL;DR: The present method exhibits high efficiency, good functional group tolerance, easy scalability and remarkable catalyst reusability, and provides an alternative way that allows rapid access to various C3 arylated or alkylated quinoxalin-2(1H)-ones in a greener and sustainable manner.
Abstract: A practical and scalable protocol for visible-light-accelerated arylation and alkylation of quinoxalin-2(1H)-ones with hydrazines is reported. In this protocol, a hydrazone-based two-dimensional covalent organic frameworks (2D-COF-1) was employed as the heterogeneous photocatalyst (PC). Due to its excellent photocatalytic properties, good chemical stability and heterogeneous nature, the present method exhibits high efficiency, good functional group tolerance, easy scalability and remarkable catalyst reusability. More importantly, it provides an alternative way that allows rapid access to various C3 arylated or alkylated quinoxalin-2(1H)-ones in a greener and sustainable manner.
TL;DR: A few important advances in metal-mediated stereoselective ROP of cyclic esters towards the synthesis of (functional) stereoregular poly(hydroxy acid)s that have recently been disclosed are highlighted, emphasizing on ( functional) β- and γ-lactones, diolide and O -carboxyanhydride (OCA) monomers and yttrium-based catalysis.
Abstract: Poly(hydroxy acid)s are a family of biocompatible and (bio)degradable polyesters with various outcomes in different domains of application. To date, poly(hydroxy acid)s are best prepared by ring-opening polymerization (ROP) of the corresponding cyclic esters. Using racemic chiral monomers featuring side-chain groups enables to access, providing a stereoselective catalyst/initiator system is implemented, stereoregular functional polymers, thereby improving their physico-chemical properties and ultimately widening their range of uses. Here, we highlight a few important advances in metal-mediated stereoselective ROP of cyclic esters towards the synthesis of (functional) stereoregular poly(hydroxy acid)s that have recently been disclosed, emphasizing on (functional) β- and γ-lactones, diolide and O -carboxyanhydride (OCA) monomers and yttrium-based catalysis. Fine-tuning of the substituents flanked on the catalyst ligand enables reaching poly(hydroxy acid)s with syndiotactic and also isotactic microstructures. The stereocontrol mechanisms at work and their probable origin, relying on steric but also electronic factors imparted in particular by the ligand substituents, are discussed. Taking advantages of such stereoselective ROPs, original copoly(hydroxy acid)s with gradient or alternated patterns then become accessible from the use of mixtures of chemically different, oppositely configurated enantiopure monomers.
TL;DR: This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities and remarkable examples of utilizing exfoliated 2D materials in energy and environmental applications are introduced.
Abstract: The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.
TL;DR: The impact of flow chemistry for exploiting highly reactive organometallic reagents and how, alongside the well-known advantages concerning safety, scalability, and productivity, flow chemistry makes possible processes that are impossible to control by using traditional batch approach are highlighted.
Abstract: In the field of organic synthesis, the advent of flow chemistry and flow microreactor technology represented a tremendous novelty in the way of thinking and performing chemical reactions, opening the doors to poorly explored or even impossible transformations using batch methods. In this Concept article, we would like to highlight the impact of flow chemistry for exploiting highly reactive organometallic reagents, and how, alongside the well-known advantages concerning safety, scalability, and productivity, flow chemistry makes possible processes that are impossible to control by using the traditional batch approach.
TL;DR: The synthetic strategy of fabricating singular coordination polymer exhibiting multiple emissions presents a promising strategy to develop facile and effective ratiometric sensors.
Abstract: As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 μm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors.
TL;DR: This work presents the first use of tellurium‐based catalysts for the activation of a carbonyl compound (and only the second such activation by chalcogen bonding in general) and concludes that organotellurium derivatives were markedly more active than their selenium and sulphur analogues and non‐coordinating counterions like BArF 4 provide the strongest dicationic catalysts.
Abstract: In the last years the use of chalcogen bonding-the noncovalent interaction involving electrophilic chalcogen centers-in noncovalent organocatalysis has received increased interest, particularly regarding the use of intermolecular Lewis acids. Herein, we present the first use of tellurium-based catalysts for the activation of a carbonyl compound (and only the second such activation by chalcogen bonding in general). As benchmark reaction, the Michael-type addition between trans-crotonophenone and 1-methylindole (and its derivatives) was investigated in the presence of various catalyst candidates. Whereas non-chalcogen-bonding reference compounds were inactive, strong rate accelerations of up to 1000 could be achieved by bidentate triazolium-based chalcogen bond donors, with product yields of >90 % within 2 h of reaction time. Organotellurium derivatives were markedly more active than their selenium and sulphur analogues and non-coordinating counterions like BArF 4 provide the strongest dicationic catalysts.
TL;DR: This review profiles 39 selected compounds featuring both of these traits in the same molecule, the total synthesis, source of the corresponding amino acids and fluorinated residues, and the medicinal chemistry aspects and biological properties of the molecules.
Abstract: Structural analysis of modern pharmaceutical practices allows for the identification of two rapidly growing trends: the introduction of tailor-made amino acids and the exploitation of fluorinated motifs. Curiously, the former represents one of the most ubiquitous classes of naturally occurring compounds, whereas the latter is the most xenobiotic and comprised virtually entirely of man-made derivatives. Herein, 39 selected compounds, featuring both of these traits in the same molecule, are profiled. The total synthesis, source of the corresponding amino acids and fluorinated residues, and medicinal chemistry aspects and biological properties of the molecules are discussed.
TL;DR: A series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC applications were prepared, and their applications were outlined as a new generation of potent PDT reagents.
Abstract: Spin-orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield phi(T)=60 %) was observed, with a triplet state lifetime (tau(T)=436 mu s) much longer than that accessed with the conventional heavy atom effect (tau(T)=62 mu s). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the (CT)-C-1/(LE)-L-3 states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC50=75 nm), with a negligible dark toxicity (EC50=78.1 mu m) compared with the conventional heavy atom PSs (dark toxicity, EC50=6.0 mu m, light toxicity, EC50=4.0 nm). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.
TL;DR: This novel type of catalysis features no solubility challenges of the catalysts nor the substrate and on top offering most facile way of separation.
Abstract: Direct mechanocatalysis describes catalytic reactions under the involvement of mechanical energy with the distinct feature of milling equipment itself being the catalyst. This novel type of catalysis features no solubility challenges of the catalysts nor the substrate and on top offering most facile way of separation.
TL;DR: In present work, the structure evolution, anionic redox, some challenges, and recent progress of NaxTMO2 cathode for SIBs are reviewed and summarized and a detailed understanding of the relationship of chemical component, structure, phase composition, and the electrochemical performance is presented.
Abstract: Sodium-ion batteries (SIBs) have attracted much attention due to their abundance, easy accessibility, and low cost. All of these advantages make them potential candidates for large-scale energy storage. The P2-type layered transition-metal oxides (Nax TMO2 ; TM=Mn, Co, Ni, Ti, Fe, V, Cr, and a mixture of multiple elements) exhibit good Na+ ion conductivity and structural stability, which make them an excellent choice for the cathode materials of SIBs. Herein, the structural evolution, anionic redox reaction, some challenges, and recent progress of Nax TMO2 cathodes for SIBs are reviewed and summarized. Moreover, a detailed understanding of the relationship of chemical components, structures, phase compositions, and electrochemical performance is presented. This Review aims to provide a reference for the development of P2-type layered transition-metal oxide cathode materials for SIBs.