【特约专稿】

光诱导三氯化铈催化构建碳-碳键的研究进展

庄元凯，安江振，李昊聪，孙凯，李祥飞，侯立芬^*，於兵^*

（郑州大学化学学院，河南郑州  450001）

摘要：可见光诱导的三氯化铈（CeCl₃）催化作为一种绿色合成策略，因其反应条件温和、原子经济性高，且环境友好，近年来在碳‑碳键构筑领域受到广泛关注。CeCl₃凭借其优异的光反应活性与独特的配体‑金属电荷转移（LMCT）特性，为惰性化学键的活化提供了新途径。综述了近年来可见光驱动下CeCl₃催化构建碳‑碳键的研究进展，总结了C?H键直接官能团化、醇的脱羟基转化以及羧酸的脱羧偶联3类代表性反应。在C?H键官能团化中，CeCl₃通过LMCT过程实现惰性C?H键的活化，避免了预官能团化步骤；醇的脱羟基转化，利用光催化下烷氧自由基的β切断，生成相应的烷基自由基；羧酸的脱羧偶联则通过可见光诱导CeCl₃催化脱羧反应，进而发生后续偶联。这些反应体系均表现出良好的底物普适性和官能团兼容性，为复杂有机分子的合成提供了新策略。CeCl₃作为一种廉价、储量丰富的稀土催化剂，在光催化有机合成领域展现出广阔的应用前景，其独特的LMCT活化机制为发展绿色、高效的合成方法提供了重要思路，在药物合成和材料科学等领域具有重要应用价值。

关键词：可见光诱导；三氯化铈；碳碳键；官能团化；烷基化；配体到金属电荷转移

中图分类号：O65              文献标识码：A              文章编号：0258-3283（2026）02-0001-08

DOI: 10.13822/j.cnki.hxsj.2025.0305

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* (College of Chemistry, Zhengzhou University, Zhengzhou 450001, China)

Abstract: 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]4f¹5d¹6s²). 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 summarizes 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-light-induced 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.

Key words: visible-light-induced; cerium(III) chloride; carbon-carbon bond; functionalization; alkylation; ligand-to-metal charge transfer

天然活性小分子在胰腺癌治疗中的研究进展

李昊洋，赵润丽，刘梦祥，孟麟，赵雨，韩超^*

（中国药科大学中药学院，江苏南京  210000）

摘要：胰腺癌起病隐匿、进展迅速、转移早且耐药性显著，患者总体预后极差，现有以吉西他滨为基础的治疗方案疗效有限，亟需开发新的治疗策略。天然产物来源的活性小分子因结构多样、作用靶点广泛，在胰腺癌防治研究中展现出重要潜力。系统检索并整理近年来国内外相关文献，按化学结构及来源将天然活性小分子分为生物碱、黄酮、萜类、皂苷以及微生物和海洋来源化合物，重点综述其在胰腺癌中的体内外药理活性及作用机制。研究表明，天然活性小分子可通过多途径、多靶点协同发挥抗肿瘤作用：一是抑制肿瘤细胞增殖并诱导凋亡，主要通过阻断 PI3K/AKT、MAPK、NF-κB 等信号通路；二是抑制迁移和侵袭，调控 EMT 进程及 FAK/ERK 等信号轴；三是逆转化疗耐药并抑制癌干性，下调 CD44、ALDH1 等干细胞相关标志物，提高吉西他滨等药物的敏感性；四是抑制血管生成并改善肿瘤免疫微环境。此外，部分天然活性小分子通过结构修饰或纳米递送体系显著改善了体内稳定性与生物利用度。综上，天然活性小分子具有多通路协同抗胰腺癌的独特优势，未来应结合多组学分析、网络药理学及先进递送技术，进一步明确关键作用靶点，推动其向临床转化应用。

关键词：胰腺癌；天然活性小分子；抗肿瘤机制；肿瘤转移；耐药性；肿瘤微环境

中图分类号：O629      文献标识码：A      文章编号：0258-3283（2026）02-0009-09

DOI：10.13822/j.cnki.hxsj.2025.0276

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^* (School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing 210000, China)

Abstract: 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 nano-delivery 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 multi-omics, network pharmacology, and advanced delivery technologies are warranted to identify key targets and promote clinical translation.

Keywords: pancreatic cancer; natural bioactive small molecules; antitumor mechanisms; metastasis; chemoresistance; tumor microenvironment

有机小分子催化不对称Aldol反应的研究进展

王宇^1,2，罗倩婷^1,2，何华锋^*1,2，秦绪隆^*1,2

（1. 山东第一医科大学（山东省科学院） 药学院（药物研究所），山东 济南  271016；

2. 济宁医学院 药学院，山东 日照  276826）

摘要：不对称催化已发展成为有机合成中一种极具影响力的手段，为构建复杂手性分子提供了多样而高效的转化路径。按照催化剂来源和特征，可将不对称催化大致分为酶催化、过渡金属催化和有机小分子催化3大类。其中，有机小分子催化剂具有分子量小、结构可设计性强、稳定性高以及环境友好等优势，能够在温和条件下高效构建具有挑战性的手性碳?碳键，在可持续合成领域展现出独特价值。不对称Aldol反应作为构建β-羟基羰基化合物的经典方法，广泛用于天然产物、药物分子及功能材料前体的合成。按照有机小分子催化剂骨架类型对近几年（主要集中于2022年至今）有机小分子催化不对称Aldol反应的研究进展进行系统梳理，重点归纳了氨基酸及其衍生物、含硫脲结构有机催化剂以及其他类型有机小分子催化剂在不对称Aldol反应中的应用。针对代表性工作，从催化剂设计理念、反应性能（收率、对映选择性及底物适用性）、反应介质绿色化以及催化剂可回收利用等方面进行总结与评述，并对存在的挑战与发展方向进行展望，以期为相关领域的深入研究提供参考与启示。

关键字：不对称催化；不对称Aldol反应；有机小分子催化剂；氨基酸；硫脲

中图分类号: O62              文献标识码：A            文章编号：0258-3283（2026）02-0018-12

DOI：10.13822/j.cnki.hxsj.2025.0235

Recent Advances in Organocatalytic Asymmetric Aldol Reactions WANG Yu^1,2, LUO Qian-Ting^1,2, HE Hua-Feng^*1,2, Qin Xu-Long^*1,2(1. School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 271016, China; 2. School of Pharmacy, Jining Medical University, Rizhao 276826, China)

Abstract: 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 are 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 summarize recent advances (primarily from 2022 to the present) in small-molecule organocatalytic asymmetric aldol reactions, organized by catalyst structural classes. Emphasis is 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 are 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 are also highlighted, aiming to offer insights and guidance for continued progress in organocatalytic asymmetric Aldol chemistry.

Keywords: asymmetric catalysis; aldol reaction; organocatalysts; amino acids; thiourea

【综述与专论】

含蒽大环化合物的合成及其功能研究进展

陈南英¹，罗金荣²，黄春游¹，陈志林¹，卢远辉¹，陶萍芳^*1，黄国保^*1

(1.玉林师范学院 a, 化学与食品科学学院, b. 广西农产资源化学与生物技术重点实验室, c 广西高校桂东南特色农产资源高效利用重点实验室, d. 电功能材料广西高校工程研究中心，广西 玉林  537000;  

2. 玉林市检验检测研究院，广西 玉林  537000)

摘要：超分子化学作为一门新兴的热点交叉学科，其发展总是伴随着新型大环化合物的合成和应用而前进。含蒽大环化合物因其结合了蒽的优异光物理性质和可调的大环空腔，已成为超分子化学和材料科学的前沿领域。通过精妙的分子设计，研究人员已经开发出多种合成策略，并探索了其在分子识别、刺激响应材料、光电器件和复杂组装体等方面的广泛应用。蒽是一种经典的芳香烃，因其具有较大的疏水刚性平面和较强的富电子共轭体系，使其较高的荧光量子产率，纳秒水平的荧光寿命，高分辨的吸收以及良好的化学稳定性。使其在有机合成，药物分析以及细胞成像领域中展现出优越的应用前景。将蒽单元引入到大环化合物的骨架中，可以结合大环的主客体化学和蒽的功能特性，创造出具有独特光学、电子和识别性能的新型功能材料。综述了最近十年含蒽大环化合物的合成方法及其在分子识别和超分子催化中的最新研究进展。以蒽为“砌块”，深入挖掘蒽在大环结构中所扮演的不可替代的角色，重点强调蒽在大环动态化学中的独特性，及其刚性平面在稳定特定主客体复合物中的关键作用，为今后此类大环化合物的合成及应用提供参考。

关键词：蒽; 大环化合物; 合成; 功能性; 分子识别

中图分类号：O626      文献标识码：A      文章编号：0258-3283（2026）02-0030-11

DOI：10.13822/j.cnki.hxsj.2025.0248

Recent Progress on the Synthesis and Function of Macrocyclic Compounds Based on Anthracene CHEN Nan-ying ¹, LUO Jin-rong ², HUANG Chun-you¹, CHEN Zhi-lin¹, LU Yuan-hui¹, TAO Ping-fang*¹, HUANG Guo-bao* ¹(1a. Yulin Normal University, 1b. Guangxi Key Laboratory of Agricultural Resources Chemistry and Biotechnology, 1c. Guangxi Colleges and Universities Key Laboratory of Efficient Utilization of Special Resources in Southeast Guangxi, 1d. University Engineering Research Center of Electrical Functional Materials, Yulin 537000, China;2. Yulin Municipal Inspection and Testing Research Institute, Yulin 537000, China)

Abstract：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, well-resolved 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 summarizes the synthetic methods developed over the past decade (2015-2025) for anthracene-based macrocycles and recent advances in molecular recognition and supramolecular catalysis. By treating anthracene as a fundamental building block, we delve 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.

Key words：anthracene; macrocyclic compounds; synthesis; functional properties; molecular recognition

【电化学与新能源】

石墨烯/Si/SiO_x纳米复合材料的制备与电化学性能研究

何方方¹，毛艳华^*2

（1. 河南应用技术职业学院 河南开封  475000；2. 河南医药健康技师学院 河南 开封  475000）

摘要：研究探索了一种新的制备石墨烯/Si/SiO_x（G/Si/SiO_x）纳米复合材料的策略。采用改进的Hummers法制备氧化石墨烯（GO）悬浮液；通过原位溶胶-凝胶法，以三乙氧基硅烷为硅源，在酸性条件下与GO反应制备HSQ/GO前驱体，随后在H₂/Ar的混合气体环境下进行热还原处理。研究团队对这种纳米复合材料的合成机制、晶体结构与电化学性质进行了详细的分析。所制备的复合材料拥有特殊的纳米级结构，不仅能够有效应对Si纳米粒子在充放电循环中的体积膨胀问题，而且还为电子提供了快速的传输路径。循环伏安测试显示，G/Si/SiO_x-2电极的氧化还原峰间距更小，极化程度更低，且循环过程中峰形更稳定，体现出良好的电化学可逆性。当这种复合材料被用作锂离子电池的负极材料时，它表现出了高首次可逆容量、出色的倍率性能以及持久的循环稳定性的特点，这些都是其卓越的储锂能力的体现。研究成功制备了结构与性能协同优化的G/Si/SiO_x纳米复合材料，其核心优势源于各组分的协同作用，石墨烯作为导电骨架与体积缓冲层，不仅提供了连续的电子传输通道，还有效缓解了 Si 充放电过程中的体积膨胀。此项研究不仅为石墨烯增强的纳米金属材料在能源存储领域的运用提供了坚实的理论与实验基础，同时也为开发新一代具有高性能的锂离子电池负极材料开辟了新的研究途径和视角。

关键词：石墨烯；纳米复合材料；制备；电化学性能；锂离子电池

中图分类号：O69      文献标识码：A      文章编号：0258-3283（2026）02-0041-08

DOI: 10.13822/j.cnki.hxsj.2025.0237 

Preparation and Electrochemical Properties of Graphene/Si/SiO_x Nanocomposites He Fang-fang¹, Mao Yan-hua^*2（1. Henan Technical Institute , Kaifeng 475000, China; 2. Henan Technician College of Medical and Health, Kaifeng 475000）

Abstract：A new strategy for preparing graphene/Si/SiO_x (G/Si/SiO_x) 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 has a unique nanoscale structure, which not only effectively addresses the volume expansion problem of Si nanoparticles during charge-discharge cycles, but also provides fast electron transmission path. Cyclic voltammetry tests showed that the oxidation-reduction peak spacing and polarization degree of the G/Si/SiO_x^-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/SiO_x 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.

Key words: graphene; nanocomposite materials; preparation; electrochemical performance; lithium-ion battery

【化学品与环境】

固相萃取-高效液相色谱-串联质谱联用法测定饮用水中17种氟喹诺酮类抗生素

李胜生^*，高绪安，林庆文

(安徽省地质实验研究所，安徽 合肥  230001)

摘要：建立了固相萃取-高效液相色谱-串联质谱联用法（SPE-HPLC-MS/MS）同时测定饮用水中17种氟喹诺酮类抗生素的分析方法。水样经0.45 μm滤膜过滤后，采用HLB固相萃取柱富集，V（甲酸）：V（甲醇）=1:1000溶液洗脱，氮吹浓缩后进行HPLC-MS/MS分析。色谱分离采用BEH C18柱（100 mm×2.1 mm，2.7 μm），以0.1%甲酸水溶液-甲醇为流动相进行梯度洗脱，质谱采用电喷雾正离子源（ESI+）和多反应监测（MRM）模式。通过系统优化色谱条件和质谱参数，获得了最佳的分离效果和检测灵敏度。结果表明，17种目标化合物在0.5~200 μg/L范围内线性关系良好（r²>0.995），检出限为0.08~0.35 ng/L，定量限为0.25~1.15 ng/L。在低、中、高 3个加标水平下，方法回收率为82.3%~108.5%，日内和日间相对标准偏差（RSD）分别小于6.2%和8.7%。方法成功应用于50份实际饮用水样品的检测，检出率为18%，为饮用水中氟喹诺酮类抗生素的监测和风险评估提供了可靠的技术支撑。

关键词： 氟喹诺酮类抗生素；固相萃取；高效液相色谱-串联质谱；饮用水；痕量检测

中图分类号：O657      文献标识码：A      文章编号：0258-3283（2026）02-0049-09

DOI：10.13822/j.cnki.hxsj.2025.0242

Determination of 17 Fluoroquinolone Antibiotics in Drinking Water by Solid Phase Extraction-High Performance Liquid Chromatography-Tandem Mass Spectrometry LI Sheng-sheng*, GAO Xu-an, Lin Qing-wen (Anhui Institute of Geological Experiment, Hefei 230001, China)

Abstract: A solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/ MS) method was developed for simultaneous determination of 17 fluoroquinolone antibiotics in drinking water. Water samples were filtered through 0.45 μm membrane, enriched using an HLB solid phase extraction cartridge, eluted with V(formic acid):V(methanol)=1:1000 solution, concentrated by nitrogen, and analyzed by HPLC-MS/MS. Chromatographic separation was performed on a BEH C18 column (100 mm×2.1 mm, 2.7 μm) with gradient elution with 0.1% formic acid aqueous solution and methanol as mobile phases. Mass spectrometry detection employed electrospray positive ionization (ESI+) and multiple reaction monitoring (MRM) mode. Systematic optimization of chromatographic conditions (mobile phase composition, column temperature, flow rate) and mass spectrometry parameters (desolvation temperature, capillary voltage, cone voltage) achieved optimal separation and detection sensitivity. The results showed that all 17 target compounds exhibited good linearity in the range of 0.5-200 μg/L (r²>0.995), with detection limits of 0.08-0.35 ng/L and quantification limits of 0.25-1.15 ng/L. Method recoveries at low, medium and high spiking levels ranged from 82.3% to 108.5%, with intra-day and inter-day relative standard deviations (RSDs) below 6.2% and 8.7%, respectively. The method was applied to 50 actual drinking water samples with a detection rate of 18%, primarily detecting norfloxacin, ciprofloxacin and enrofloxacin. This method provides reliable technical support for monitoring and risk assessment of fluoroquinolone antibiotics in drinking water.

Keywords: fluoroquinolone antibiotics; solid phase extraction; HPLC-MS/MS; drinking water; trace detection

QuEChERS-超高相液相色谱-串联质谱法测定果蔬中38种农药残留

李增明，马春光^*，李玉环^*，甘瑛琳，杨增亮

（西宁市疾病预防控制中心 青海西宁  810000）

摘要：建立了一种同时快速测定果蔬中38种农药残留的分析方法，即基于QuEChERS的分散固相萃取结合超高效液相色谱-串联质谱（UPLC-MS/MS）测定。该方法以氨基化多壁碳纳米管作为核心净化材料。蔬菜水果样品经过均质用10 mL乙腈震荡提取10 min，离心提取上清液后用改进的QuEChERS（氨基化多壁碳纳米管为净化试剂）净化方法净化，经浓缩定容后的提取液，采用 Waters ACQUITY UPLC BEH C18 色谱柱进行分离，在电喷雾正离子 (ESI+) 模式与多反应监测 (MRM) 条件下进行电离与信号采集，并基于基质匹配标准曲线外标法进行定量。结果表明：38种农药残留在1~300 μg/kg的线性范围内有良好线性关系（R²>0.991）。方法的检出限为0.001~0.003 mg/kg，定量限为0.003~0.009 mg/kg。空白加标样品在20、50 和100 μg/ kg 3个浓度水平时，38种农药残留平均回收率为63.3%~108.1%，相对标准偏差为1.20%~14.0%（n=8）。该方法快捷、重现性好、准确度高，适合对果蔬中的多种农药痕量残留进行高效富集与灵敏检测。

关键词：农药残留；QuEChERS；超高效液相色谱质谱联用；氨基化多壁碳纳米管；果蔬

中图分类号：O65      文献标识码：A      文章编号：0258-3283(2026)02-0058-08

DOI：10.13822/j.cnki.hxsj.2025.0240

Determination of 38 Pesticide Residues in Fruits and Vegetables by QuEChERS-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry LI Zeng-Ming, MA Chun-guang^*, LI Yu-huan^*, GAN Ying-ling, YANG Zeng-liang (Xining Center for Disease Control and Prevention, Xining 810000, China)

Abstract: This study established a rapid analytical method for the simultaneous determination of 38 pesticide residues in fruits and vegetables. The method is based on a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) dispersive solid-phase extraction (d-SPE) cleanup procedure coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Aminated multi-walled carbon nanotubes (NH₂-MWCNTs) were employed as the primary purification material. Homogenized samples were extracted with 10 mL of acetonitrile by vortexing for 10 min. The supernatant, obtained after centrifugation, was purified using the improved QuEChERS method with NH₂-MWCNTs. The purified extract was concentrated and reconstituted before separation on a Waters ACQUITY UPLC BEH C18 column. Detection was performed under electrospray ionization positive mode (ESI+) with multiple reaction monitoring (MRM). Quantification was achieved using a matrix-matched standard calibration curve with external standard method. The results demonstrated good linearity for all 38 pesticides in the range of 1-300 μg/kg (R² > 0.991). The limits of detection (LOD) and quantification (LOQ) ranged from 0.001 to 0.003 mg/kg and 0.003 to 0.009 mg/kg, respectively. For blank samples spiked at three concentration levels (20, 50, and 100 μg/kg), the average recoveries for the 38 pesticides ranged from 63.3% to 108.1%, with relative standard deviations (RSD, n=8) between 1.20% and 14.0%. In conclusion, the developed method is rapid, reproducible, and accurate, suitable for the efficient enrichment and sensitive detection of multiple trace pesticide residues in fruits and vegetables.

Key words: pesticide residue; QuEChERS; ultra-performance liquid chromatography-mass spectrometry; aminated multi-walled carbon nanotubes; fruits and vegetables

【分析与测试】

衍生-HPLC法同时检测反应液中丙酮酸和丙酮酸乙酯的含量

董明燕，王艳，赵磊，冯棋?，高爱红，岳涛^*

（青岛科技大学山东化工研究院，山东济南  250014）

摘要：建立了衍生-高效液相色谱（HPLC）法同时测定丙酮酸反应液中丙酮酸和丙酮酸乙酯含量的分析方法。用抗坏血酸（VC）淬灭样品溶液中过氧化氢，用2,4-二硝基苯肼（DNPH）衍生丙酮酸和丙酮酸乙酯，并考察了淬灭剂（VC）、盐酸溶液、衍生溶液、衍生温度与时间等因素对衍生试验的影响。优化后的色谱条件为：以C18柱为分析柱，以0.1%磷酸溶液和乙腈为流动相，梯度洗脱方式，检测波长为360 nm，以外标法定量。结果表明：丙酮酸和丙酮酸乙酯衍生物的色谱峰与其它色谱峰的分离度＞2.0，衍生剂、杂质与溶剂均不干扰目标物测定，方法的专属性良好；在4.50~45.00 mg/L浓度范围内，丙酮酸和丙酮酸乙酯衍生物线性关系良好，相关系数＞0.9990；检出限分别为0.00336和0.00387 mg/L，定量限分别为0.0112和0.0129 mg/L；3批次样品的精密度检测结果的相对标准偏差（RSD）值均小于1.5%（n=6），加标回收率范围分别为99.79%~101.31%与98.93%~99.45%；在室温下放置下48 h，丙酮酸与丙酮酸乙酯衍生物的峰面积的RSD＜1.0%，样品溶液稳定性良好。建立的方法前处理操作简单，检测速度快与准确度高，可用于丙酮酸制备过程中各阶段反应情况的反应监控和产率评估，为工艺优化与生产提供数据支撑。

关键词：丙酮酸乙酯；丙酮酸；2,4-二硝基苯肼（DNPH）；衍生-HPLC法；抗坏血酸

中图分类号：O65       文献标识码：A             文章编号：0258-3283（2026）02-0066-07

DOI：10.13822/j.cnki.hxsj.2025.0241

Simultaneous Detection of Pyruvate and Ethyl PyruvateContent by Derivatization -HPLC DONG Ming-yan, WANG Yan, ZHAO Lei, FENG Qi-yun, GAO Ai-hong, YUE Tao^*(Shandong Chemical Technology Academy, Qingdao University of Science & Technology, Jinan 250014, China)

Abstract：The derivatization HPLC method was established for the simultaneous detection of pyruvate and ethyl pyruvate in a pyruvate reaction solution. Hydrogen peroxide in the sample solution was quenched with ascorbic acid (VC). Pyruvate and ethyl pyruvate were derived with 2,4-dinitrophenylhydrazine (DNPH). The effects of the quenching agent (VC), hydrochloric acid concentration, derivatization reagent, derivatization temperature, and time on the derivatization reaction were investigated. The optimized chromatographic conditions were as following: a C18 column was used with 0.1% phosphoric acid solution and acetonitrile as the mobile phase under gradient elution. The detection wavelength was set at 360 nm, and quantification was performed using external standard method. The results showed that the chromatographic peaks of pyruvate and ethyl pyruvate derivatives were well separated from adjacent impurities with a resolution greater than 2.0. The derivatization reagent, impurities, and solvents did not interfere with the determination of the target compounds, indicating good specificity. Within the concentration range of 4.50~45.00 mg/L, good linear relationships were obtained for both pyruvate and ethyl pyruvate derivatives, with correlation coefficients greater than 0.9990. The detection limits were 0.00336 and 0.00387 mg/L, respectively, and the quantification limits were 0.0112 mg/L and 0.0129 mg/L, respectively. The relative standard deviation (RSD) values obtained from precision test results of three batches of samples were all less than 1.5% (n=6). The spiked recovery rates ranged from 99.79% to 101.31% for pyruvate and from 98.93% to 99.45% for ethyl pyruvate. After being placed at room temperature for 48 hours, the RSD of the peak area of pyruvate and ethyl pyruvate derivatives were less than 1.0%, indicating good stability of the sample solutions. This method features simple pretreatment, rapid analysis and high accuracy. It is suitable for reaction monitoring and yield evaluation at different stages of the pyruvate preparation process, providing reliable data support for process optimization and production.

Key words：ethyl pyruvate; pyruvic acid; 2, 4-dinitrophenylhydrazine (DNPH); derivatization -HPLC method; ascorbic acid

均一黄芪多糖APS-1a的制备与结构表征

武延慧，雷子莹，张瑜，赵生婷，王嘉蕾，韩毅丽^*，贺润丽^*

（山西中医药大学中药食品工程学院，晋中 030619）

摘要：从黄芪中制备具有潜在免疫调节活性的均一多糖组分，并系统解析其结构特征。采用透析法初步分离低分子量组分，依次利用离子交换纤维素（DEAE-52）、葡聚糖凝胶G-50（Sephadex G-50）柱分级纯化具有潜在增强免疫活性的黄芪多糖。采用凝胶渗透色谱-多角度激光光散射联用技术（GPC-MALLS）测定其分子量与溶液构象；通过离子色谱分析其单糖组成；利用傅里叶变换红外光谱（FT-IR）和核磁共振波谱（NMR）解析其糖苷键类型与官能团修饰；并借助扫描电子显微镜（SEM）观察其微观形貌。结果表明，分离纯化得到一个重均分子量为3.38 kDa、聚合物分散性指数（PDI）为1.18、纯度为99.3%的多糖组分APS-1a，核心结构为β-糖苷键连接的葡萄糖和半乳糖组成的吡喃多糖骨架，并带有O-乙酰基修饰。溶液构象分析显示其在溶液中以柔性无规线团形态存在，而固态下可观察到自组装形成的聚集体。进一步确认了具有潜在增强免疫活性黄芪多糖的结构特征，为深入研究黄芪多糖的免疫活性构效关系提供了理想的模型分子及相关制剂开发奠定了坚实的物质基础与技术支持。

关键词：黄芪；均一多糖；纯化；结构表征；自组装

中图分类号：O629      文献标识码：A      文章编号：0258-3283（2026）02-0073-08

DOI：10.13822/j.cnki.hxsj.2025.0285

Preparation and Structural Characterization of Uniform Astragalus Polysaccharide APS-1a

WU Yan-hui, LEI Zi-ying, ZHANG Yu, ZHAO Sheng-ting, WANG Jia-lei, Han Yi-li^*,HE Run-li^* (School of Traditional Chinese Medicine Food Engineering, Shanxi University of Chinese Medicine, Jinzhong 030619, China)

Abstract: This study aimed to prepare a homogeneous Astragalus membranaceus polysaccharide fraction from Astragalus membranaceus with potential immunomodulatory activity and to systematically characterize its structural properties. The crude Astragalus membranaceus polysaccharides were initially extracted and subjected to dialysis for the preliminary isolation of low-molecular-weight components. Subsequently, a sequential purification strategy was employed, involving ion-exchange chromatography on a DEAE-52 cellulose column followed by size-exclusion chromatography on a Sephadex G-50 gel column, to obtain the target Astragalus membranaceus polysaccharide fraction. The molecular weight parameters and solution conformation were precisely determined using gel permeation chromatography coupled with multi-angle laser light scattering (GPC-MALLS). The monosaccharide composition was quantified through high-performance ion chromatography. Detailed structural insights into glycosidic linkage types and functional group modifications were acquired by Fourier transform infrared spectroscopy (FT-IR) and comprehensive nuclear magnetic resonance (NMR) spectroscopy, including ¹H and ¹³C NMR. Furthermore, the morphological features in the solid state were examined using scanning electron microscopy (SEM). The results demonstrated the successful isolation of a polysaccharide fraction, designated APS-1a. It was characterized by a weight-average molecular weight (Mw) of 3.38 kDa, a narrow polymer dispersity index (PDI) of 1.18, and a high purity of 99.3%. Structural analysis revealed that APS-1a possesses a core backbone composed of β-glycosidically linked glucose and galactopyranose residues. Notably, the structure was found to be modified with O-acetyl groups. Conformational analysis in solution indicated that APS-1a adopts a flexible random coil architecture. In contrast, SEM observations revealed its tendency to form self-assembled supramolecular aggregates in the dried, solid state. In conclusion, these findings further clarify the structural features of the Astragalus membranaceus polysaccharide with potential immunoenhancing activity, providing an ideal model molecule for in-depth investigation of the structure-activity relationship of Astragalus membranaceus Polysaccharide and laying a solid material foundation and technical support for the development of related formulations.

Key words: Astragalus membranaceus; homogeneous polysaccharide; purification; structural characterization; self-assembly

【标准物质与标准品】

空气中二氧化碳同位素标准物质研制

陈欢欢^*，逯海，邢腾，任同祥，蔡玮，赵博

（中国计量科学研究院，北京 100029)

摘要：实施节能减排政策和计算碳汇需要区分不同来源的二氧化碳，碳同位素测定已成为追溯二氧化碳来源的重要手段。高准确度的二氧化碳同位素标准物质可用于校正测量仪器，是保证二氧化碳测量结果准确性和可比性的物质基础。这篇文章主要介绍了空气中二氧化碳同位素标准物质的研制过程。该气体同位素标准物质采用重量法制备，分装于380 mL的铝合金气瓶中，瓶内压力为5.0 MPa。对所研制的气体同位素标准物质进行均匀性检验，方差检验证实该标准物质均匀性良好。对该标准物质进行随时间和压力变化的稳定性检验。分别在不同的气瓶压力条件下和12个月内进行量值考察，标准物质量值在统计学上没有明显变化，稳定性良好。通过GasBench Ⅱ-连续流稳定同位素质谱仪联用分析法（GasBench Ⅱ-IRMS）进行定值，标准值的不确定度重复考虑了均匀性评估、稳定性评估、定值过程等。最终，空气中二氧化碳同位素标准物质量值为δ¹³C为-20.926 ‰，不确定度为0.256 ‰（k=2）。所研制的二氧化碳同位素标准物质可以为空气中二氧化碳中碳同位素的检测提供量值溯源标准，为“双碳”战略提供计量基础和技术支撑。

关键词：碳同位素；气体标准物质；二氧化碳；同位素质谱法；碳计量

中图分类号：TB99；O659      文献标识码：A      文章编号：0258-3283（2026）02-0081-07

DOI: 10.13822/j.cnki.hxsj.2025.0146 

Development of Carbon Dioxide Isotope Reference Material in Air CHEN Huan-huan^*, LU Hai, XING Teng, REN Tong-xiang, CAI Wei, ZHAO Bo (National Institute of Metrology, Beijing 100029, China)

Abstract: The implementation of energy conservation and emission reduction policies, as well as carbon sink calculations, necessitate the classification of carbon dioxide emissions by their respective sources. Carbon isotope analysis has emerged as a critical method for tracing carbon dioxide sources. High-accuracy carbon dioxide isotopic reference materials serve as a critical foundation for calibrating measurement instruments and for the accuracy and comparability of carbon dioxide measurements. This study describes the development of reference materials for carbon dioxide isotopes in air. A gas-isotope reference material was developed using a gravimetric method. It was then divided into 380 mL aluminum alloy cylinders pressurized to 5.0 MPa. The homogeneity of the gas-isotope materials was tested: the F-value of the variance test was lower than the critical value, indicating that the reference material exhibited satisfactory homogeneity. The stabilities of the gas isotopes were also tested by measuring the quantity of gas isotope material at different cylinder pressures over a 12 month period, during which no statistically significant change was observed, indicating that the reference material exhibited excellent stability. The GasBench II-IRMS system was used to accurately quantify the reference material. The uncertainty of the reference material value incorporates comprehensive considerations of the homogeneity assessment, stability evaluation, and quantification process. Ultimately, the carbon isotope ratio (δ¹³C) in the carbon dioxide isotope reference material was -20.926 ‰ and the expanded uncertainty was 0.256 ‰ (k = 2). Carbon dioxide isotope reference materials establish metrological traceability standards for the detection of carbon isotopes in atmospheric carbon dioxide and provide the metrological foundation and technical support for the implementation of the "dual carbon" strategy.

Key words：carbon isotopes; gas reference material; carbon dioxide; isotope mass spectrometry; carbon metering

【合成与应用】

氮杂环卡宾配合物的合成及其对芳（杂）基酯与芳（杂）硼酸Suzuki偶联反应的催化研究

罗茜佩，黄菲东，刘丰收，梁营^*

（广东药科大学医药化工学院，广东中山 528458）

摘要：设计并合成了一种新型大位阻氮杂环卡宾钯配合物C1，并将其成功应用于（杂）芳基酯与（杂）芳硼酸的 Suzuki 偶联反应。该配合物通过构建芳胺对位具有大位阻的配位环境，有效稳定了反应过程中关键的钯活性物种，从而显著提升了催化体系的反应活性与稳定性。在优化的温和反应条件下（0.5 mol% 配合物C1、2.0 mmol K₃PO₄、4 mL V(THF):V(H₂O)=1:3 混合溶剂，80 ℃，4 h），该催化体系表现出优异的反应效率和良好的操作兼容性。多种具有不同电子效应和空间位阻特征的芳基酯底物，包括电子给体和电子吸收基取代的底物，均可与多种芳基或杂芳基硼酸顺利发生交叉偶联反应，高效合成一系列二芳基酮及杂环芳基酮化合物，最高分离产率可达 98%。该体系在杂环?杂环偶联反应中同样保持较高反应活性，有效克服了传统催化体系中常见的反应效率不足和副反应较多等问题。上述结果表明，该大位阻氮杂环卡宾钯催化体系为惰性酯类底物的高效转化提供了一种切实可行的催化策略，并为结构多样、功能化酮类分子的构建提供了具有应用潜力的合成新方法。

关键词：氮杂环卡宾钯配合物；Suzuki-Miyaura偶联；芳基酯；杂环硼酸；二芳基酮

中图分类号：O62      文献标识码：A      文章编号：0258-3283（2026）02-0088-09

DOI：10.13822/j.cnki.hxsj.2025.0274

Synthesis of Nitrogen-Heterocyclic Carbene Complexes and Catalytic Study on the Suzuki Coupling Reaction of (Hetero) Aryl Esters and (Hetero) Arylboronic Acids LUO Qian-pei, Huang Fei-dong, LIU Feng-shou, LIANG Ying* (School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, ZhongShan 528458, China)

Abstract: A sterically demanding N-heterocyclic carbene palladium complex C1 was designed, synthesized and successfully applied to the Suzuki cross-coupling of (hetero)aryl esters with (hetero)aryl boronic acids. The catalyst features a highly congested coordination environment introduced by para-substituted arylamine moieties, which stabilizes key palladium species during the catalytic cycle,, thereby significantly enhancing both catalytic activity and stability. Under optimized mild reaction conditions (0.5 mol% complex C1, 2.0 mmol K₃PO₄, 4 mL V(THF):V(H₂O)=1:3, 80 °C, 4 h), the catalytic system demonstrates efficient conversion and operational compatibility.. A wide range of aryl ester substrates bearing diverse electronic properties and steric profiles, including both electron-donating and electron-withdrawing substituents, readily undergo cross-coupling with various aryl and heteroaryl boronic acids to afford a series of diaryl ketones and heteroaryl ketones in high yields, with isolated yields of up to 98%. The catalytic system also maintains high activity in heteroaryl-heteroaryl coupling, overcoming common limitations of conventional catalytic systems such as low reactivity and competitive side reactions. These results demonstrate that the sterically demanding NHC-palladium catalyst provides a practical and efficient strategy for activating inert ester substrates and offers a valuable synthetic approach for the construction of structurally diverse and functionalized ketone compounds.

Keywords: N-heterocyclic carbene palladium complex; Suzuki-Miyaura coupling; aryl ester; (hetero)aryl boronic acid; biaryl ketone

香豆素类新型三重态光敏剂的合成

马洁^*1, 李莹莹¹, 赵方铭¹, 侯玉琦², 尹彦冰¹, 何锡凤¹

（1. 齐齐哈尔大学 化学与化学工程学院，黑龙江 齐齐哈尔  161006；

2. 大连理工大学 化工学院，辽宁 大连  116024）

摘要：三重态光敏剂被广泛地应用于光催化、光动力治疗等领域而备受关注。但是现有光敏剂获得三重态的方式还存在一定的局限性，如：三重态的产生有赖于重原子效应、引入具有高效系间窜越能力的自旋转换单元或者利用电荷复合过程促进系间窜越产生机理，获得不含重原子的三重态光敏剂等。在激发态分子内质子转移过程中，能够通过系间窜越获得cis-酮式结构的三重激发态。将具有强可见光吸收能力的吸光团，与传统的具有cis-酮式三重激发态的染料结合，利用其光物理过程中产生的三重态，设计合成不含重原子的有机三重态光敏剂。通过共轭和非共轭两种连接方式，制备了香豆素和2-(2-羟基苯基)苯并噻唑（HBT）的新型染料（B-1~B-4）。B-1在甲苯中出现双发射，斯托克斯位移达到131 nm，这是激发态分子内质子转移（ESIPT）的典型特征。其中，在B-1和B-4中均观察到了三重激发态（τ_T = 20.1和50.8 μs），通过1,3-二苯基异苯并呋喃（DPBF）的光氧化反应，证明了B-1和B-4均具有光敏化能力，且B-1的敏化能力高于B-4。

关键词：香豆素；2-(2-羟基苯基)苯并噻唑；激发态分子内质子转移；三重激发态

中图分类号：O62          文献标识码：A          文章编号：0258-3283（2026）02-0097-07

DOI：10.13822/j.cnki.hxsj.2025.0297

Synthesis of Novel Triplet Photosensitizers based on Coumarin MA Jie*¹, LI Ying-ying¹, ZHAO Fang-ming¹, HOU Yu-qi², YIN Yan-bing¹, HE Xi-feng¹ ( 1.College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China; 2. College of Chemical Engineering, Dalian University of Technology, Dalian 116024, China )

Abstract: Much attention has been focused on triplet photosensitizers due to their wide applications in photocatalysis and photodynamic therapy. However, conventional photosensitizers have some limitations in obtaining triplet excited state, which usually rely on the heavy atoms or the incorporation of spin converters with highly efficient intersystem crossing ability. In addition, spin?orbit charge-transfer intersystem crossing (SOCT-ISC) is an important strategy to acquire heavy atom-free triplet photosensitizers. Previous studies has shown that cis-ketone triplet exited states can be excited in the process of excited state intramolecular proton transfer (ESIPT). Therefore, by combining chromophores with strong visible-light absorption and traditional dyes capable of forming cis-ketone triplet excited states, heavy-atom-free organic triplet photosensitizers can be designed. The dyes of coumarin conjugated or non-conjugated with 2-(2-hydroxyphenyl)benzothiazole (HBT) (B-1-B-4) were prepared. B-1 showed dual emission in toluene and its Stokes shift was up to 131 nm, which is a typical characteristics of excited state intramolecular proton transfer. The triplet excited states were observed for B-1 and B-4 (t_T = 20.1 ms and 50.8 μs, respectively). The photosensitizing abilities of B-1 and B-4 were confirmed by 1,3-diphenylisobenzofuran (DPBF) photooxidation experiments, demonstrating that B-1 exhibited higher photosensitizing efficiency compared to B-4.

Key words：coumarin; 2-(2-hydroxyphenyl)benzothiazole; excited state intramolecular proton transfer; triplet excited state