Topics in Current Chemistry最新文献

Third-generation organic light-emitting diodes (OLEDs) based on metal-free thermally activated delayed fluorescent (TADF) materials have sparked tremendous interest in the last decade due to their nearly 100% exciton utilization efficiency, which can address the low-efficiency issue of the first-generation fluorescent emitters and the high-cost issue of the second-generation organometallic phosphorescent emitters. Construction of efficient and stable TADF-OLEDs requires utilizing TADF materials with a narrow singlet–triplet energy gap (ΔE_ST), high photoluminescence quantum yield (PLQY) and short TADF lifetime. A small ΔE_ST is necessary for an efficient reverse intersystem crossing (RISC) process, which can be achieved through the effective spatial separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). TADF emitters have been generally designed as intramolecular charge transfer (ICT) molecules with highly twisted donor–acceptor (D–A) molecular architectures. A wide variety of combinations of electron donors and acceptors have been explored. In this review, we shall focus on recent progress in organic TADF molecules incorporating strong electron-donor phenoxazine moiety and their application as emitting layer (EML) in OLEDs.

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Pyrimidine is a pharmacologically important moiety that exhibits diverse biological activities. This review reflects the growing significance of transition metal-catalyzed reactions for the synthesis of pyrimidines (with no discussion being made on the transition metal-catalyzed functionalization of pyrimidines). The effect of different catalysts on the selectivity/yields of pyrimidines and catalyst recyclability (wherever applicable) are described, together with attempts to illustrate the role of the catalyst through mechanisms. Although several methods have been researched for synthesizing this privileged scaffold, there has been a considerable push to expand transition metal-catalyzed, sustainable, efficient and selective synthetic strategies leading to pyrimidines. The aim of the authors with this update (2017–2023) is to drive the designing of new transition metal-mediated protocols for pyrimidine synthesis.

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Amination reactions play a pivotal role in synthetic organic chemistry, facilitating the generation of nitrogen-containing scaffolds with broad applications in drug synthesis, material production, polymer formation, and the generation of amino acids and peptides. Amination offers the potential to fine tune the properties of natural products and produce functional materials for various applications. Palladium N-heterocyclic carbene (Pd–NHC) emerges as an innovative and highly effective catalyst in this context. Under favorable reaction conditions, this robust and simple catalyst efficiently facilitates the synthesis of a diverse range of compounds with varying complexity and utility. Pd–NHC complexes exhibit significant σ-electron donating potential, enhancing the ease of the oxidative addition process in their mechanistic pathway. Their steric topography further contributes to a rapid reductive elimination. These complexes demonstrate remarkable stability, a result of the strong Pd–ligand bond. The wide variety of Pd–NHC complexes has proven highly efficient in catalyzing reactions across a spectrum of complexities, from simple to intricate. The domain of aminations catalyzed by Pd–NHC has undergone significant diversification, presenting new opportunities, particularly in the realms of material chemistry and natural product synthesis. This review outlines the advancements in Pd–NHC-catalyzed amination reactions, covering literature up to date.

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Palladium (Pd) N-heterocyclic carbenes (NHCs) have amassed high recognition recently. They are efficient complexes with tuneable complexities promoting catalysis significantly. Amination reactions have paved way toward the formation of C–N bonds and, in turn, realizing structurally relevant molecules in organic chemistry. Inspired by these facets, we have tried to encompass in this review, the developments in Pd–NHC-catalyzed amination reactions and carries reports up to date.

While bioorthogonal reactions are routinely employed in living cells and organisms, their application within individual organelles remains limited. In this review, we highlight diverse examples of bioorthogonal reactions used to investigate the roles of biomolecules and biological processes as well as advanced imaging techniques within cellular organelles. These innovations hold great promise for therapeutic interventions in personalized medicine and precision therapies. We also address existing challenges related to the selectivity and trafficking of subcellular dynamics. Organelle-targeted bioorthogonal reactions have the potential to significantly advance our understanding of cellular organization and function, provide new pathways for basic research and clinical applications, and shape the direction of cell biology and medical research.

Light-induced bioorthogonal reactions offer spatiotemporal control over selective biomolecular labeling. This review covers the recent advances in the design of photo-activatable reagents for bioorthogonal conjugation reactions in living systems. These reagents are stable in the absence of light, but transformed into reactive species upon light illumination, which then undergo rapid ligation reactions. The light wavelength has been tuned from ultraviolet to near infrared to enable efficient photo-activation in reactions in deep tissues. The most prominent photo-activatable reagents are presented, including tetrazoles, tetrazines, 9,10-phenanthrenequinone, diarylsydnones, and others. A particular focus is on the strategies for improving reaction kinetics and biocompatibility accomplished through careful molecular engineering. The utilities of these photo-activatable reagents are illustrated through a broad range of biological applications, including in vivo protein labeling, positron emission tomography (PET) imaging, responsive hydrogels, and fluorescence microscopy. The further development and optimization of these biocompatible photo-activatable reagents should lead to new chemical biology strategies for studying biomolecular structure and function in living systems.

The desire to create biomolecules modified with functionalities that go beyond nature’s toolbox has resulted in the development of biocompatible and selective methodologies and reagents, each with different scope and limitations. In this overview, we highlight recent advances in the field of bioconjugation from 2016 to 2023. First, (metal-mediated) protein functionalization by exploiting the specific reactivity of amino acids will be discussed, followed by novel bioorthogonal reagents for bioconjugation of modified biomolecules.

Metal nanoparticles (NPs) are widely used in biomedicine, catalysis, environment, electronics, and other fields, which is closely related to its structural form. For this purpose, researchers have been looking for a simple, green, and controllable way to mass produce metal nanomaterials with desired characteristics (shape, size, stability, etc.). Due to the surface plasmon resonance (SPR) effect of metal nanoparticles, photoreduction method can control the morphology of metal nanoparticles well, which is also simple, large-scalable, and energy-saving. This review provides an overview of the photoreduction method for the synthesis of metal nanoparticles and discusses the factors such as the light source, pH value, reagents, and temperature on the morphology of the nanoparticles. Finally, the challenges and development trends in the controlled preparation of nanomaterials are proposed.

Palladium-catalyzed allylation cyclization reaction has recently emerged as an efficient and powerful synthetic platform for the construction of diverse and valuable carbo- and heterocycles. Thus the development of new allylic motifs for achieving this type of transformations in high reactivity and selectivity is of great importance. Generally, these substrates have been utilized as 1,3-, 1,4-, 1,5-, 1,6-dipoles in many reactions, which are applied to prepare highly functionalized products with complete control of chemo-, regio-, diastereo-, and enantioselectivity. In this review, we focus our attention on the development of palladium-catalyzed [4 + n] cycloaddition of allylic motifs and describe a comprehensive and impressive advances in this area. Meanwhile, the related mechanism and the application of these annulation strategies in natural product total synthesis will be highlighted in detail.

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The fascinating electrochemical properties of the redox-active compound ferrocene have inspired researchers across the globe to develop ferrocene-based electrocatalysts for a wide variety of applications. Advantages including excellent chemical and thermal stability, solubility in organic solvents, a pair of stable redox states, rapid electron transfer, and nontoxic nature improve its utility in various electrochemical applications. The use of ferrocene-based electrocatalysts enables control over the intrinsic properties and electroactive sites at the surface of the electrode to achieve specific electrochemical activities. Ferrocene and its derivatives can function as a potential redox medium that promotes electron transfer rates, thereby enhancing the reaction kinetics and electrochemical responses of the device. The outstanding electrocatalytic activity of ferrocene-based compounds at lower operating potentials enhances the specificity and sensitivity of reactions and also amplifies the response signals. Owing to their versatile redox chemistry and catalytic activities, ferrocene-based electrocatalysts are widely employed in various energy-related systems, molecular machines, and agricultural, biological, medicinal, and sensing applications. This review highlights the importance of ferrocene-based electrocatalysts, with emphasis on their properties, synthesis strategies for obtaining different ferrocene-based compounds, and their electrochemical applications.

Human existence and societal growth are both dependent on the availability of clean and fresh water. Photocatalysis is a type of artificial photosynthesis that uses environmentally friendly, long-lasting materials to address energy and environmental issues. There is currently a considerable demand for low-cost, high-performance wastewater treatment equipment. By changing the structure, size, and characteristics of nanomaterials, the use of nanotechnology in the field of water filtration has evolved dramatically. Semiconductor-assisted photocatalysis has recently advanced to become among the most promising techniques in the fields of sustainable energy generation and ecological cleanup. It is environmentally beneficial, cost-effective, and strictly linked to the zero waste discharge principle used in industrial effluent treatment. Owing to the reduction or removal of created unwanted byproducts, the green synthesis of photoactive nanomaterial is more beneficial than chemical synthesis approaches. Furthermore, unlike chemical synthesis methods, the green synthesis method does not require the use of expensive, dangerous, or poisonous ingredients, making it a less costly, easy, and environmental method for photocatalyst synthesis. This work focuses on distinct greener synthesis techniques utilized for the production of new photocatalysts, including metals, metal doped-metal oxides, metal oxides, and plasmonic nanostructures, including the application of artificial intelligence and machine learning to the design and selection of an innovative photocatalyst in the context of energy and environmental challenges. A brief overview of the industrial and environmental applications of photocatalysts is also presented. Finally, an overview and recommendations for future research are given to create photocatalytic systems with greatly improved stability and efficiency.