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Recent Advances in Light-Induced CeCl3-Catalyzed C—C Bond Construction
ZHUANG Yuan-kai;AN Jiang-zhen;LI Hao-cong;SUN Kai;LI Xiang-fei;HOU Li-fen;YU Bing;Visible light-induced cerium(Ⅲ) chloride(CeCl3) catalysis has emerged as a green synthetic strategy,attracting significant attention in carbon-carbon bond formation due to its mild reaction conditions,high atom economy,and environmental friendliness.Unlike typical metal-to-ligand charge transfer(MLCT)-type catalysts,CeCl3 undergoes ligand-to-metal charge transfer(LMCT),in which electrons are transferred from a ligand's π orbital to the metal's d orbital,or from the metal-ligand σ orbital to the metal' s d orbital. This LMCT process plays a crucial role in redox photoreactions: ligand-derived radical species such as chlorine radicals(Cl·) exhibit extremely high reactivity and can activate C—H bonds through hydrogen atom transfer(HAT),expanding the scope of photocatalysis transformation in organic synthesis. The unique LMCT properties of the Ce element arises from its 4f electron configuration([Xe]4f~15d~16s2).The 4f orbital is located in the inner shell and shielded by the outer 5s and 5p orbitals,giving the 4f electron high localization. This configuration facilitates facile Ce3+/Ce4+redox cycling,providing an ideal pathway for LMCT processes.Leveraging its excellent photoreactivity and unique ligand-to-metal charge transfer properties,CeCl3 offers a novel approach to activating inert chemical bonds.This review summarized recent advances in visible-light-driven CeCl3-catalyzed carbon-carbon bond construction,focusing on three representative reaction types: Direct C—H functionalization,dehydroxylative transformations of alcohols,and decarboxylative coupling of carboxylic acids. In C—H functionalization,CeCl3 activates inert C—H bonds via LMCT processes,eliminating the need for pre-functionalization.In dehydroxylative transformations,photocatalytic β-scission of alkoxy radicals generates corresponding alkyl radicals. In decarboxylative coupling,visible-lightinduced CeCl3-catalyzed decarboxylation,followed by subsequent coupling. These reaction systems exhibit broad substrate scope and excellent functional group compatibility,providing new strategies for the synthesis of complex organic molecules. As an inexpensive and abundant rare-earth catalyst,CeCl3 demonstrates promising potential in photocatalytic organic synthesis.Its unique LMCT activation mechanism offers valuable insights for developing green and efficient synthetic methodologies,with significant applications in pharmaceutical synthesis and materials science.
Research Progress on Natural Active Small Molecules in the Treatment of Pancreatic Cancer
LI Hao-yang;ZHAO Run-li;LIU Meng-xiang;MENG Lin;ZHAO Yu;HAN Chao;Pancreatic cancer is characterized by an insidious onset,rapid progression,early metastasis,and pronounced chemoresistance,resulting in an extremely poor prognosis. Current therapeutic strategies,mainly based on gemcitabine,provide limited clinical benefit,highlighting the urgent need for novel treatment approaches. Natural product-derived bioactive small molecules,with their structural diversity and multi-target properties,have attracted increasing attention in pancreatic cancer research. In this review,recent studies were systematically retrieved and summarized. According to chemical structure and biological origin,natural bioactive small molecules are classified into alkaloids,flavonoids,terpenoids,saponins,as well as compounds derived from microorganisms and marine organisms. Their pharmacological activities and underlying mechanisms against pancreatic cancer in vitro and in vivo are comprehensively discussed. Accumulating evidence indicates that these compounds exert anti-pancreatic cancer effects through multiple pathways:(1) inhibiting cell proliferation and inducing apoptosis by blocking the PI3K/AKT,MAPK,NF-κB,and related signaling pathways;(2) suppressing migration and invasion by regulating epithelial-mesenchymal transition(EMT) and FAK/ERK signaling;(3) reversing chemoresistance and attenuating cancer stemness by downregulating stem cell-associated markers such as CD44 and ALDH1,thereby enhancing sensitivity to gemcitabine;and(4) inhibiting angiogenesis and modulating the tumor microenvironment. Furthermore,structural modification and nanodelivery systems have been shown to significantly improve the in vivo efficacy and bioavailability of certain compounds. Overall,natural bioactive small molecules exhibit great potential as multi-pathway therapeutic agents against pancreatic cancer. Future studies integrating multiomics,network pharmacology,and advanced delivery technologies are warranted to identify key targets and promote clinical translation.
Recent Advances in Organocatalytic Asymmetric Aldol Reactions
WANG Yu;LUO Qian-ting;HE Hua-feng;QIN Xu-long;Asymmetric catalysis has become a highly impactful strategy in organic synthesis,providing efficient and versatile tools for the construction of complex chiral molecules. According to catalyst origin and characteristics,asymmetric catalysis can be categorized into three major categories: Enzymatic catalysis,transition-metal catalysis,and small-molecule organocatalysis.Among them,organocatalysts based on small organic molecules have attracted substantial attention due to their low molecular weight,high structural tunability,excellent stability,and environmentally friendly nature. They were particularly powerful for enabling the efficient formation of challenging chiral C—C bonds under mild conditions,thereby playing a key role in sustainable synthesis.The asymmetric Aldol reaction,a classical transformation for the synthesis of β-hydroxy carbonyl compounds,has become a powerful platform for the preparation of natural products,pharmaceuticals,and functional materials. In this review,we summarized recent advances(primarily from 2022 to the present) in small-molecule organocatalytic asymmetric Aldol reactions,organized by catalyst structural classes.Emphasis was placed on amino acids and their derivatives,thiourea-based hydrogen-bonding organocatalysts,and other small organic catalysts including macrocycles,porous organic cages,covalent organic frameworks,and nanostructured systems.Representative studies were discussed with respect to catalyst design concepts,reaction efficiency and stereocontrol(yields,enantioselectivity,and diastereoselectivity),green reaction media,and catalyst recyclability. Challenges and future perspectives were also highlighted,aiming to offer insights and guidance for continued progress in organocatalytic asymmetric Aldol chemistry.
Recent Progress on the Synthesis and Function of Macrocyclic Compounds Based on Anthracene
CHEN Nan-ying;LUO Jin-rong;HUANG Chun-you;CHEN Zhi-lin;LU Yuan-hui;TAO Ping-fang;HUANG Guo-bao;Supramolecular chemistry,as an emerging and interdisciplinary field of great interest,has always advanced in tandem with the synthesis and application of novel macrocycles. Anthracene-incorporated macrocyclic compounds,which combine the excellent photophysical properties of anthracene with tunable macrocyclic cavities,have become a frontier in supramolecular chemistry and materials science. Through sophisticated molecular design,researchers have developed diverse synthetic strategies and explored their broad applications in molecular recognition,stimuli-responsive materials,optoelectronic devices,and complex assemblies. Anthracene,a classic aromatic hydrocarbon,possesses a large,rigid,hydrophobic plane and a strong electron-rich conjugated system.These features endow it with a high fluorescence quantum yield,a nanosecond-scale fluorescence lifetime,wellresolved absorption spectra,and good chemical stability,making it highly promising for applications in organic synthesis,pharmaceutical analysis,and cellular imaging. Introducing anthracene units into macrocyclic frameworks effectively merges the host-guest chemistry of macrocycles with the functional characteristics of anthracene,leading to the creation of novel functional materials with unique optical,electronic,and recognition properties.This review summarized the synthetic methods developed over the past decade for anthracene-based macrocycles and recent advances in molecular recognition and supramolecular catalysis.By treating anthracene as a fundamental building block,we delved into its irreplaceable role in macrocyclic architectures,emphasizing its unique contribution to dynamic macrocyclic chemistry and the key function of its rigid plane in stabilizing specific host-guest complexes,thereby providing valuable insights for the future synthesis and application of such macrocyclic compounds.
Preparation and Electrochemical Properties of Graphene/Si/SiOx Nanocomposites
HE Fang-fang;MAO Yan-hua;Henan Technician College of Medical and Health;A new strategy for preparing graphene/Si/SiOx(G/Si/SiOx) nanocomposites is explored. A graphene oxide(GO)suspension was prepared using an improved Hummers method; an HSQ/GO precursor was prepared via an in situ sol-gel method,with triethoxysilane as the silicon source reacting with GO under acidic conditions,and was subsequently thermally reduced in an H2/Ar mixed gas environment.The research team conducted a detailed analysis of the synthesis mechanism,crystal structure,and electrochemical properties of this nanocomposite material. The prepared composite material had a unique nanoscale structure,which not only effectively addresses the volume expansion problem of Si nanoparticles during charge-discharge cycles,but also provided fast electron transmission path.Cyclic voltammetry tests showed that the oxidation-reduction peak spacing and polarization degree of the G/Si/SiOx-2 electrode were smaller,and the peak shape was more stable during the cycling process,demonstrating good electrochemical reversibility. When this composite material was used as the negative electrode material for lithium-ion batteries,it exhibited high initial reversible capacity,excellent rate performance,and long-term cycling stability,all of which reflect its outstanding lithium storage capacity. A G/Si/SiOx nanocomposite material with synergistically optimized structure and performance was successfully prepared.Its core advantage lies in the synergistic effect of its component.Graphene,as a conductive skeleton and volume buffer layer,not only provides a continuous electron transfer channel,but also effectively alleviates the volume expansion of Si during charge-discharge processes.This study not only provides a solid theoretical and experimental foundation for the application of graphene reinforced nanometal materials in the field of energy storage,but also opens up new research avenues and perspectives for the development of a next-generation of high-performance lithium-ion battery negative electrode materials.
Journal Information
Journal Name: Chemical Reagents
First Published: April 1979 • Monthly
Governed by: China Petroleum and Chemical Industry Federation
Sponsored by:
China Association for Analysis and Testing
Sinopharm Chemical Reagents Co., Ltd.
Beijing Guohua Jingshi Consulting Co., Ltd.
Edited and Published by: Editorial Office of Chemical Reagents
Editor-in-Chief: Qing Fengling
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Serial Publication Number: ISSN 0258-3283 CN 11-2135/TQ
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