Topics in Current Chemistry最新文献

Development of nitrogen-rich energetic materials has gained much attention because of their remarkable properties including large nitrogen content and energy density, good thermal stability, low sensitivity, good energetic performance, environmental friendliness and so on. Tetrazole has the highest nitrogen and highest energy contents among the stable azoles. The incorporation of diverse explosophoric groups or substituents into the tetrazole skeleton is beneficial to obtain high-nitrogen energetic materials having excellent energetic performance and suitable sensitivity. In this review, the development of high-nitrogen energetic materials based on tetrazole skeleton is highlighted. Initially, the property and utilization of nitrogen-rich energetic materials are presented. After showing the advantage of the tetrazole skeleton, the high-nitrogen energetic materials based on tetrazole are classified and introduced in detail. Based on different types of energetic materials (EMs), the synthesis and properties of nitrogen-rich energetic materials based on mono-, di-, tri- and tetra-tetrazole are summarized in detail.

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Metal-based catalysts, encompassing both homogeneous and heterogeneous types, play a vital role in the modern chemical industry. Heterogeneous metal-based catalysts usually possess more varied catalytically active centers than homogeneous catalysts, making it challenging to regulate their catalytic performance. In contrast, homogeneous catalysts have defined active-site structures, and their performance can be easily adjusted by modifying the ligand. These characteristics lead to remarkable conceptual and technical differences between homogeneous and heterogeneous catalysts. As a recently emerging class of catalytic material, single-atom catalysts (SACs) have become one of the most active new frontiers in the catalysis field and show great potential to bridge homogeneous and heterogeneous catalytic processes. This review documents a brief introduction to SACs and their role in a range of reactions involving single-atom catalysis. To fully understand process-structure-property relationships of single-atom catalysis in chemical reactions, active sites or coordination structure and performance regulation strategies (e.g., tuning chemical and physical environment of single atoms) of SACs are comprehensively summarized. Furthermore, we discuss the application limitations, development trends and future challenges of single-atom catalysis and present a perspective on further constructing a highly efficient (e.g., activity, selectivity and stability), single-atom catalytic system for a broader scope of reactions.

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The construction of C–C and C–X (X = N, O, Si, etc.) bonds is an important field in organic synthesis and methodology. In recent decades, studies on transition metal-catalyzed functionalization of alkenes have been on the rise. The individual properties of different transition metals determine the type of reaction that can be applied. Generally, post-transition metals with a large number of electrons in the d-orbit such as Mn, Fe, Co, Ni, Cu and Zn, etc., can be applied to more reaction types than pre-transition metals with a small number of electrons (e.g., Ti, Zr, etc.). Alkyl nickel intermediates formed by oxidative addition could couple with various of nucleophiles or electrophiles. Moreover, nickel has several oxidation valence states, which can flexibly realize a variety of catalytic cycles. These characteristics make nickel favored by researchers in the field of functionalization of alkenes, especially for the hydrofunctionalization of alkenes. Both terminal and internal alkenes could be converted, and the strategies of synthesizing linear and branched compounds have been expanded. Moreover, the guiding groups in alkenes played an almost decisive role in the regional selectivity, and the ligand or temperature also had regulating effects. Herein, we will give a comprehensive and timely overview of the works about the Ni-catalyzed hydrofunctionalization of alkenes and some insights on regional selectivity.

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The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has caused a worldwide pandemic since 2019, spreading rapidly and posing a significant threat to human health and life. With over 6 billion confirmed cases of the virus, the need for effective therapeutic drugs has become more urgent than ever before. RNA-dependent RNA polymerase (RdRp) is crucial in viral replication and transcription, catalysing viral RNA synthesis and serving as a promising therapeutic target for developing antiviral drugs. In this article, we explore the inhibition of RdRp as a potential treatment for viral diseases, analysing the structural information of RdRp in virus proliferation and summarizing the reported inhibitors’ pharmacophore features and structure–activity relationship profiles. We hope that the information provided by this review will aid in structure-based drug design and aid in the global fight against SARS-CoV-2 infection.

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It has been established that pyrazolines and their analogs are pharmacologically active scaffolds. The pyrazoline moiety is present in several marketed molecules with a wide range of uses, which has established its importance in pharmaceutical and agricultural sectors, as well as in industry. Due to its broad-spectrum utility, scientists are continuously captivated by pyrazolines and their derivatives to study their chemistry. Pyrazolines or their analogs can be prepared by several synthesis strategies, and the focus will always be on new greener and more economical ways for their synthesis. Among these methods, chalcones, hydrazines, diazo compounds, and hydrazones are most commonly applied under different reaction conditions for the synthesis of pyrazoline and its analogs. However, there is scope for other molecules such as Huisgen zwitterions, different metal catalysts, and nitrile imine to be used as starting reagents. The present article consists of recently reported synthetic protocols, pharmacological activities, and the structure–activity relationship of pyrazoline and its derivatives, which will be very useful to researchers.

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Materials capable of displaying strong ratiometric fluorescence with Förster resonance energy transfer (FRET) processes have attracted much research interest because of various chemosensor and biomedical applications. This review highlights several popular strategies in designing FRET-OFF/ON mechanisms of ratiometric fluorescence systems. In particular, the developments of organic and polymeric FRET materials featuring aggregation-induced emission-based luminogens (AIEgens), supramolecular assemblies, photochromic molecular switches and surfactant-induced AIE/FRET mechanisms are presented. AIEgens have been frequently employed as FRET donor and/or acceptor fluorophores to obtain enhanced ratiometric fluorescences in solution and solid states. Since AIE effects and FRET processes rely on controllable distances between fluorophores, many interesting fluorescent properties can be designed by regulating aggregation states in polymers and supramolecular systems. Photo-switchable fluorophores, such as spiropyran and diarylethene, provide drastic changes in fluorescence spectra upon photo-induced isomerizations, leading to photo-switching mechanisms to activate/deactivate FRET processes. Supramolecular assemblies offer versatile platforms to regulate responsive FRET processes effectively. In rotaxane structures, the donor-acceptor distance and FRET efficiency can be tuned by acid/base-controlled shuttling of the macrocycle component. The tunable supramolecular interactions are strongly influenced by external factors (such as pH values, temperatures, analytes, surfactants, UV-visible lights, etc.), which induce the assembly and disassembly of host-guest systems and thus their FRET-ON/FRET-OFF behavior. In addition, the changes in donor or acceptor fluorescence profiles upon detections of analytes can also sufficiently alter the FRET behavior and result in different ratiometric fluorescence outputs. The strategies and examples provided in this review offer the insights and toolkits for future FRET-based material developments.

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The formation of semiconductor heterojunctions and Z-schemes is still a very prominent and efficient strategy of materials chemists to extend the absorption range of semiconductor combinations. Moreover, the spatial separation of photoexcited charge carriers and thereby the reduction of their recombination ultimately lead to increased photocatalytic activities. The present article reviews recent trends in semiconductor heterojunctions and Z-schemes with a focus on hydrogen generation and water splitting, exhibiting specific needs for charge carrier separation. We also included recent material trends, i.e. 2D/2D combinations, direct Z-schemes, MOFs and COFs, and combinations with upconversion materials.

In situ characterization of materials in their operational state is a highly active field of research. Investigating the structure and response of materials under stimuli that simulate real working environments for technological applications can provide new insight and unique input to the synthesis and design of novel materials. Over recent decades, experimental setups that allow different stimuli to be applied to a sample inside an electron microscope have been devised, built, and commercialized. In this review, we focus on the in situ investigation of optically active materials using transmission electron microscopy. We illustrate two different approaches for exposing samples to light inside the microscope column, explaining the importance of different aspects of their mechanical construction and choice of light source and materials. We focus on the technical challenges of the setups and provide details of the construction, providing the reader with input on deciding which setup will be more useful for a specific experiment. The use of these setups is illustrated using examples from the literature of relevance to photocatalysis and nanoparticle synthesis.

Solar-powered photocatalysis has come a long way since its humble beginnings in the 1990s, producing more than a thousand research papers per year over the past decade. In this review, immobilized photocatalysts operating under sunlight are highlighted. First, a literature review of solar-driven films is presented, along with some fundamental operational differences in relation to reactions involving suspended nanoparticles. Common strategies for achieving sunlight activity from films are then described, including doping, surface grafting, semiconductor coupling, and defect engineering. Synthetic routes to fabricate photocatalytically active films are briefly reviewed, followed by the important factors that determine solar photocatalysis efficiency, such as film thickness and structure. Finally, some important and specific characterization methods for films are described. This review shows that there are two main challenges in the study of photocatalytic materials in the form of (thin) films. First, the production of stable and efficient solar-driven films is still a challenge that requires an integrated approach from synthesis to characterization. The second is the difficulty in properly characterizing films. In any case, the research community needs to address these, as solar-driven photocatalytic films represent a viable option for sustainable air and water purification.

Organic dyes, porphyrins and inorganic complexes containing imidazole (IM) motifs have been demonstrated as a new class of sensitizers in dye-sensitized solar cells (DSSCs). Particularly, the amphoteric nature of IM-based motifs allows them to be used as donors (D), auxiliary donors (D_A), linker/branch (π), or acceptors (A) in D–π–A-based organic dyes and porphyrins and also employed as cyclometalated heteroleptic and ancillary ligands in the Ru(II) and Ir(III) complexes for DSSCs. It is noteworthy that the introduction of IM chromophores in the dyes of D–π–A configuration can improve the light-harvesting properties and prohibit the charge recombination reactions due to the extension of the π-conjugated structures and hydrophobic nature. Similarly, in the case of inorganic complexes, the presence of IM motifs as ligands can improve the light-harvesting ability, give facilely tuned HOMO and LUMO energy levels, increase the charge recombination resistance and photostability. This results in enhanced photocurrent (J_SC) and photovoltage (V_OC) and consequently solar-to-power conversion efficiency (η) of DSSC devices based on Ru(II) and Ir(III) complexes. Considering the interesting DSSC applications of IM-derived molecules, in this review, we therefore comprehensively discuss their photophysical, electrochemical and photovoltaic properties reported so far and establish their structure–activity relationship to further advance the η of DSSCs. To the best of our knowledge, there is no such a review interpreting the importance of molecules possessing IM-motifs for DSSC applications to date.

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