Chemical record最新文献

In recent decades, N-heterocycles have emerged as a crucial class of organic compounds with wide-ranging applications in pharmaceuticals and agrochemicals. Among them, benzodiazines, containing a benzene ring fused with a six-membered diazine containing both nitrogen atoms in the same ring, are of particular significance. Their structural compactness, synthetic versatility, and favorable physicochemical characteristics render them valuable as drug candidates, chemical probes, and intermediates in organic synthesis. Representative members of this class are cinnoline, phthalazine, quinazoline, and quinoxaline that exhibit numerous pharmacological properties, namely anticancer, antimicrobial, anti-inflammatory, anticonvulsant, antimalarial, antioxidant, antihypertensive, and other activities. Although the synthesis of each scaffold has been reviewed individually in the literature, benzodiazines as a broader class remain comparatively underexplored. The present work summarizes recent developments in the synthesis of benzodiazines, with emphasis on methodologies utilizing diverse catalysts such as solid acid catalysts, nanocatalysts, transition-metal catalysts, and ionic liquid-based catalysts. These strategies commonly employ precursors including 2-nitrobenzyl alcohols, 2-alkynylanilines, o-phenylenediamines, and o-alkyl benzophenones, which react with benzylamines, nitrosoarenes, 1,2-dicarbonyls, and di-tert-butyl azodicarboxylate, respectively. This overview aims to stimulate further exploration in the synthesis and applications of benzodiazines.

Ethylene and propylene serve as the basic platform chemicals in the chemical industry. Research on their production has garnered significant interest. One of them is the dehydrogenation of light alkanes with the oxidative promotion of CO₂. This process can simultaneously produce light olefins and achieve resource utilization of CO₂. Pt-based catalysts, extensively used in the direct dehydrogenation of light alkanes, are expected to show activity potential in the CO₂ oxidative dehydrogenation (CO₂-ODH) of light alkanes. However, research on Pt-based catalysts for CO₂-ODH of light alkanes remains limited, and no systematic review has been reported yet. Here, the advancements in Pt-based catalysts for the CO₂-ODH of ethane and propane are reviewed, including (i) reaction mechanisms, (ii) rational design strategies for efficient and stable Pt-based catalysts, and (iii) emerging reaction processes and optimization methods. Perspectives on fundamental challenges and future research are proposed. Among them, machine learning-guided design of Pt-based catalysts will be an important research direction in the future.

The growing global demand for eco-friendly and innovative biomaterials has led to the extensive use of natural polymers, such as natural gums and mucilage, in diverse industrial applications, including food, agriculture, biomedical, and cosmetics. These natural polymers are carbohydrate biomolecules derived from various natural sources, including plants, animals, microbes, and marine organisms, that exhibit a broad spectrum of physicochemical characteristics, such as biocompatibility, biodegradability, and nontoxicity. This review critically examines the chemical composition and elucidates the hydrophilic nature that leads to the formation of hydrogels, which are next-generation biomaterials for the innovation and development of advanced polymeric materials. The unique structural diversity, availability, and functionality make them highly suitable for various applications. This review provides a comprehensive overview of various natural gums and mucilage that are widely available, including their chemical constituents, structures, possible modifications, properties, crosslinking strategies for hydrogel synthesis, and recent advancements in their applications. The functional properties of natural gums and mucilage-based hydrogels highlight their potential for developing stronger, more natural, and innovative hydrogel products and also suggest future research directions, such as advanced modification techniques, hybrid hydrogel systems, and improvements in stability to support innovative applications and environmental sustainability.

Over the past 30 years, I have pursued research on the precise control of doping levels (DLs) and molecular structure in conjugated organic materials for understanding their molecular properties and applying them to photo- and electroactive materials. In this personal account, an overview of studies analyzing the molecular characteristics of conjugated oligomers-including their optical, electrochemical, thermal, and electrical properties-is provided in relation to the main-chain π-conjugated length, the electron-donating and -accepting nature of side chains, and the DLs. Furthermore, the development of dye molecules and polymeric materials based on these oligomers and their applications in energy-related devices, such as electrochromic smart windows, dye-sensitized solar cells, organic photovoltaics, and organic thermoelectrics, are described. By integrating molecular design with doping control, these efforts bridge the gap between property design and device-level functionality, offering valuable guidelines for the future development of high-performance organic materials.

Nitric oxide (NO) is one of the most extensively studied small inorganic molecules involved in biological signaling processes related to both health and disease. Many biological transformations that depend on NO rely on bioinorganic chemistry, where both redox-active and nonredox-active inorganic centers and processes play crucial roles. This review covers several key topics, including the role of heme centers in NO biosynthesis and metabolism, the function of non-heme iron in NO bioactivity, and the interplay between calcium-dependent proteins and NO signaling pathways. It also discusses the involvement of free and bound copper ions, zinc ions, and zinc proteins in NO biosynthesis and its signaling pathways is discussed. The review also examines the role of molybdenum proteins in maintaining NO homeostasis and explores the biological activities associated with the interactions between NO and other reactive nitrogen species (RNS) with bioactive molecules containing cobalt. Furthermore, the regulation of NO signaling by selenoproteins is addressed. Additionally, we focus on NO signaling through S-nitrosation and nitration, highlighting the impact of both bound and free metal ions on the formation and fate of S-nitrosothiols.

Silicon quantum dots (SiQDs) are an emerging class of high-performing, sustainable, environmentally safe luminescent nanomaterial. They offer opportunities for next-generation displays, solid-state lighting, medical applications, and quantum technologies. Here, we highlight recent breakthroughs in colloidal SiQD synthesis and photophysics, comparing eight synthetic strategies. Among these, we focus on the hydrogen silsesquioxane (HSQ) polymer route, a simple and cost-effective hot-injection-free method that yields highly crystalline, ultrabright, and stable SiQDs with photoluminescence quantum yields approaching 80%. We also describe how solvent engineering realizes SiQD light-emitting diodes (LEDs) with record external quantum efficiencies (EQEs, >16%), >700-fold-increased lifetimes, and far-red emissions to rival state-of-the-art perovskite QD LEDs. Moreover, rice husk-derived SiQD LEDs illustrate the potential for low-waste circular material cycles. Thus, SiQDs are a sustainable platform for plant growth technologies, photodynamic therapy, and beyond.

Alkyne is one of the simplest yet important functional group in organic synthesis. The richness of this entity renders it as an extremely versatile synthon for developing a diverse array of modern strategies for assembly of different heterocycles. This account describes the research efforts of more than a decade on the usage of alkynes as nucleophiles, electrophiles, and radical precursors for the synthesis of diverse set of heterocycles and the utilization in the total synthesis of structurally simple to complex bioactive natural products.

Propargylic alcohol is a shining star in the chemical space. These congeners have garnered significant attention from the synthetic chemistry community due to their dual functionality and three-centered reactivity. In this realm, the electrophilic cyclization of propargylic alcohols with a tethered nucleophile functional group is a key strategy for synthesizing hetero- and carbocycles. In these transformations, the position of the nucleophilic reactive handle can influence the reaction outcome. Consequently, these derivatives open up numerous opportunities to create complex cyclic adducts through various reaction pathways. Among all nucleophile tethers, the hydroxy group has been increasingly used in the production of oxy-heterocyclics. The hydroxy dialing on the core propargylic alcohol would lead to oxy-heterocyclics, such as benzofuran, furan, chromene, coumarin, chromone, pyrane, etc., which have numerous applications in various fields of biology and other scientific fields. In this review, we focused on uncovered hydroxy-tethered propargylic alcohol cyclization reactions. We categorized these transformations based on the structural features of hydroxy propargylic alcohols. With this review, we aim to pave the way for further efforts in discovering new reaction pathways.

The bioconjugation of aromatic amino acids has emerged as a powerful strategy in chemical biology, drug discovery, and biomolecular research. Beyond the classical targeting of cysteine and lysine, aromatic amino acids residues offer higher selectivity owing to their lower abundance and critical roles in intermolecular interactions. Current synthetic approaches include substitution reactions, addition reactions, free-radical reactions, metal-catalyzed transformations, and biocatalytic approaches, enabling precise and versatile modifications in cells, tissues, and at the proteome level. In recent years, transition-metal catalysis and radical processes have dominated the field, with particular emphasis on tyrosine and tryptophan. This review provides a critical analysis of advances from the past 3 years, categorizing methodologies by reaction mechanism and highlighting how the intrinsic reactivity of aromatic amino acids can be harnessed for site-selective functionalization, ultimately expanding the accessible chemical space across all these residues.

The rapid progression of industrialization has generated substantial environmental deterioration, posing significant threats to public health. Developing efficient and cost-effective strategies to combat environmental pollution is of paramount importance. Metal-organic frameworks (MOFs) have recently emerged as a versatile photocatalytic platform, distinguished by their structurally tunable porosity, exceptional light-harvesting capacity, and superior charge separation efficiency. In particular, the intrinsically crystalline 3D structures of MOFs, characterized by highly ordered coordination networks and well-defined pore architectures, provide stable channels for molecular transport and endow the spatial organization of catalytically active sites. This review systematically summarizes the fundamental mechanisms and recent progress in MOF-based photocatalysis for environmental remediation, focusing on the degradation of organic pollutants, decomposition of antibiotics, and reduction of toxic heavy metal ions. Finally, current challenges and prospects in the field are critically discussed, providing a perspective for the rational design of high-performance MOF photocatalysts.