Topics in Current Chemistry最新文献

Herein, recent developments for Selectfluor-mediated C–H functionalization of N-heteroarenes are described. This type of C–H bond activation is an attractive and competitive alternative to traditional methodologies, allowing the functionalization of a variety of chemical functions. In addition, Selectfluor is a more sustainable and economically accessible oxidant compared with expensive/toxic metals or hazardous peroxides. For a practical understanding, the current review classified systematically the reported strategies in four subsections as follows: (1) carbon–carbon formation, (2) carbon–nitrogen bond formation, (3) carbon–chalcogen bond, and (4) carbon–halogen bond formation. Mechanistic aspects and reaction conditions are fully discussed to provide an understanding of the aspects that govern C–H functionalization in N-heteroarenes mediated by Selectfluor.

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BODIPY (4-bora-3a,4a-diaza-s-indacene) dyes are regarded as highly useful compounds due to their rich photophysical properties, stability, and ease of functionalization. In recent years, hot topics studied with this class of compounds are targeted photodynamic therapy, photothermal therapy, fluorescent bioimaging agents, structural modification of the BODIPY core, synthesis of BODIPY analogs, and BODIPY-based supramolecular constructs. This review covers the advances in BODIPY structures substituted with additional carbon–nitrogen double bonds, namely imines, hydrazones, oximes, and related derivatives for various applications. Works based on fluorescent indicators of anions, cations, and neutral molecules are included in this review. In addition, the use of such structures for pharmaceutical applications, photodynamic therapy, fluorescent switches, and fluorescent building blocks are also investigated. In addition to covering the major literature within the mentioned subclass, design principles, working mechanisms, and outlooks are also provided to enlighten forthcoming promising efforts. With this work, we aim to provide insights about the synthesis, photophysical properties, contribution of C=N bonds to a class of dye, and possible areas of use and stimulate researchers to present new ideas and overcome the current problems using these derivatives.

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Developing new, high-performance materials is a prerequisite for technological advancement. In comparison to bulk materials, quantum dots have a number of good advantages due to their small size, high surface area, and quantum dimensions. Quantum dots, two-dimensional materials with lateral dimensions less than 100 nm, can be generated by the quantum confinement effect. Mxene quantum dots (MQDs) retain some of their two-dimensional characteristics. They also exhibit novel physicochemical properties, including enhanced dispersibility in aqueous and nonaqueous phases, modification or doping capabilities, and photoluminescence. MQDs, due to their unique and diverse properties, have been receiving a great deal of attention as new members of the Mxene group and wide use for biotechnology, bioimaging, optoelectronics, catalysis, cancer therapy, etc. This review aims to provide an overview of the synthesis of MQDs, their optical properties, and their cancer therapy applications. MQDs exhibit remarkable photothermal and photodynamic features and can be suitable for bioimaging. In addition to obtaining bioimaging, photothermal therapy (PTT) and photodynamic therapy (PDT) effects simultaneously, MQDs have high biocompatibility in vitro and in vivo, providing evidence of their potential clinical utility. Herein, recent developments and future prospects concerning MQDs biomedical applications are discussed.

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Narrow-band deep-blue organic light-emitting diodes (OLEDs) have played a key role in the field of high-quality full-color displays. However, because of the considerable challenges of inherent band gaps, unbalanced carrier injection and the lack of molecular structures, narrow-band deep-blue emitters develop slowly compared with red- and green-emitting materials. Encouragingly, with the continuous efforts of scientists in recent years, great progress has been made in the molecule design and material synthesis of highly efficient narrow-band deep-blue emitters. The typical deep-blue emitters which exhibit narrow emission with a full width at half maximum of < 50 nm are summarized in this article. They are divided into the three categories: fluorescence, phosphorescence and thermally activated delayed fluorescence. The methods of molecular design for realizing narrow-band deep-blue emission are described in detail and future research directions are also discussed in this article.

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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