【综述与专论】
自由基不对称反应研究进展
周少方*，冯勇，梁春华，吴丛瑞，张仁宝
(上海沃凯生物技术有限公司，上海 201506)
摘要：自1900年第一个稳定的三苯甲基自由基被发现后的很长一段时间内，人们普遍认为自由基很活泼、反应不可控制、产物复杂，所以自由基反应的研究和应用受到了很大的限制，发展缓慢。但近年来的研究表明，自由基反应在一定条件下是可预测、可控制并具备其他方法所没有的很多优点，如：1、自由基可以在一定的时间内稳定存在；自由基具有高活性，在一定条件下自由基反应具有很好的区域和立体选择性；2、自由基反应可以容忍很多官能团的存在；3、自由基反应条件温和，在一定的条件下产率很高。根据不同的反应策略，对近年来可控的自由基不对称反应的研究成果进行了综述，从而为新型的可控自由基反应类型的拓展和开发利用提供一定的参考。
关键词：自由基；不对称催化；过渡金属催化；对映选择性控制；路易斯酸催化
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）04-0001-10
DOI：10.13822/j.cnki.hxsj.2023.0799
Progresses on Asymmetric Radical Reactions ZHOU Shao-fang*, FENG Yong，LIANG Chun-hua, WU Cong-rui，ZHANG Ren-bao (Shanghai Our ChemBio-Technology Co., LTD., Shanghai, 201506, Shanghai, China)
Abstract： Since the discovery of the first stable radical, triphenylmethyl radical, in 1900, radicals were widely regarded as highly reactive species, leading to uncontrollable and complex reactions. Consequently, the advancement of radical reactions has been significantly impeded. However, recent research has revealed that radical reactions can be predictable and controllable, offering several advantages not found in many other reactions. These advantages include: (1) Relatively stable radicals with high reactivity and excellent regio- and stereo-selectivity; (2) Tolerance of numerous functional groups in radical reactions; (3) Conducting radical reactions under mild conditions, resulting in high yields. Here, this review focuses on recent advancements in controlled radical asymmetric reactions, categorized according to different reaction strategies. The aim is to provide valuable insights and references for the development and utilization of new types of controlled radical reactions.
Key words：free radical; asymmetric catalysis; transition metal catalysis; enantioselective control; Lewis acid catalysis
引用本文：周少方，冯勇，梁春华，等. 自由基不对称反应研究进展[J]. 化学试剂，2024，46（4）：1-10.
构建6H-1,3-噁嗪-6-酮的研究进展
周淑晶，柳召宁，洛雪，孙立娇，黄姗珊，李进京*
（佳木斯大学 药学院，黑龙江 佳木斯 154007）
摘要：6H-1,3-噁嗪-6-酮是一类重要的杂环化合物，广泛应用于有机合成、精细化工和医药领域，且在抗肿瘤、抗疟疾、抗真菌活性等方面都表现出优异的性能，故备受有机合成工作者的关注。近年来，6H-1,3-噁嗪-6-酮骨架的构筑方法和策略取得了长足发展。尤其是通过过渡金属催化机理的偶联反应得到迅速发展。因此，很有必要对其进行梳理。经查阅文献目前尚无相关专题综述对构建6H-1,3-噁嗪-6-酮的合成进行归纳总结，故对6H-1,3-噁嗪-6-酮骨架的构建方法进行详细综述，以期为类似化合物的合成方法提供新思路。
关键词：噁嗪酮；过渡金属；合成方法；反应机理；研究进展
中图分类号：O624.6 文献标识码：A 文章编号：0258-3283（2024）04-0011-10
DOI：10.13822/j.cnki.hxsj.2023.0765
Research Progress on the Construction of 6H-1,3-Oxazine-6-One ZHOU Shu-jing, LIU Zhao-ning, LUO Xue, SUN Li-jiao, HUANG Shan-shan, LI Jin-jing*(College of Pharmacy, Jiamusi University, Jiamusi 154007,China)
Abstract：6H-1,3-oxazine-6-one is a significant heterocyclic compound with wide applications in organic synthesis, the fine chemical industry, and medicine. It exhibits excellent properties in anti-tumor, anti-malaria, and anti-fungal activities, making it a subject of great interest in organic synthesis. In recent years, substantial progress has been made in the construction methods and strategies for the 6H-1,3-oxazine-6-one backbone, particularly through coupling reactions utilizing transition metal catalysis. However, there is currently no comprehensive review available that summarizes the synthesis of 6H-1,3-oxazine-6-one. Therefore, this review aims to provide a detailed overview of the construction methods employed for the 6H-1,3-oxazine-6-one backbone, with the intention of offering new insights and ideas for the synthesis of similar compounds.
Key words：oxazinone; transition metals; synthesis methods; reaction mechanism; research progress
引用本文：周淑晶，柳召宁，洛雪，等. 构建6H-1,3-噁嗪-6-酮的研究进展[J].化学试剂，2024，46（4）：11-20.
【功能材料】
染料源碳点的制备及其在光催化降解废水中的应用
吴涛，卓欢，赵孟宇，宋启军*，王婵*
（江南大学 化学与材料工程学院，江苏 无锡 214122）
摘要：罗丹明B作为工业上常用的有机染料，具有稳定性高、上色强、着色牢等特点，但其存在毒性和致癌性，且含其废水的可生化性差、降解难，故建立高效、清洁的染料废水处理技术已成为广泛研究的热点。以印染厂的含罗丹明B的染料废水为原料，通过一步水热法制备了具有光催化活性的碳点材料。通过优化制备工艺和降解条件，碳点在pH 1、光照（氙灯或日光）条件下可有效处理化学需氧量（COD）为5050 mg/L的染料废水，满足纳管排污标准。结合自由基清除实验和电子自旋共振波谱（ESR）分析可推断，光激发过程中产生了多种活性氧物种，在其共同下作用实现了对污染物高效、绿色的降解。利用阳离子交换树脂可实现碳点的回收，且回收后的碳点光催化性能稳定，具有较好的实际应用性。
关键词：罗丹明B；染料废水；荧光碳点；光催化降解；树脂回收
中图分类号：TQ579 文献标识码：A 文章编号：0258-3283（2024）04-0021-07
DOI：10.13822/j.cnki.hxsj.2023.0745
Synthesis of Dye-based Carbon Dots and their Application in the Photocatalytic Treatment of Wastewater WU Tao, ZHUO Huan, ZHAO Meng-yu, SONG Qi-jun*, WANG Chan* (School of Chemical ＆ Material Engineering, Jiangnan University, Wuxi 214122, China)
Abstract：The organic dye Rhodamine B, commonly used in the industry, exhibits notable characteristics such as high stability, intense coloring, and rapid coloration. However, it possesses potential toxicity and carcinogenicity, while its wastewater demonstrates poor biodegradability and resistance to degradation. Therefore, the development of an efficient and eco-friendly treatment technology for dye wastewater has become a key focus of extensive research. Fluorescent carbon dots with photocatalytic activity were synthesized via a one-step hydrothermal method using dye wastewater containing Rhodamine B generated in industrial facilities. Through optimization of the preparation process and degradation conditions, the wastewater sample with a COD value of 5050 mg/L can be effectively degraded by carbon dots under pH 1 and irradiation (using a xenon lamp or daylight), thereby meeting sewage discharge standards. The carbon dots can be efficiently recovered by cation exchange resin while maintaining their stable photocatalytic performance. Free radical scavenging experiments and electron spin resonance spectroscopy (ESR) analysis revealed the generation of various active oxygen species during the photoexcitation process, leading to the efficient degradation of pollutants. The practical applicability of this method is demonstrated to be excellent.
Key words：rhodamine B; dye wastewater; fluorescent carbon dots; photocatalysis degradation; ecycle
引用本文：吴涛，卓欢，赵孟宇，等. 染料源碳点的制备及其在光催化降解废水中的应用[J].化学试剂，2024，46（4）：21-27.
C6/C6+糖基碳水化合物选择性转化为糠醛的研究
谈金1，吴燕妮1，仇松柏*2
(1. 肇庆学院 a. 环境与化学工程学院，b. 广东省环境健康与资源利用重点实验室，肇庆 526061；2. 广东工业大学 轻工化工学院，广州 510006)
摘要：糠醛是一种广泛应用在食品、医药、农药和化工等领域的重要的精细化工品。通常，半纤维素解聚到五碳糖后进一步脱水可转化为糠醛，而纤维素解聚后生成的六碳糖难于转化为糠醛。基于此，实验研究了葡萄糖（C6）选择性转化糠醛的影响因素，提出了可能的反应路径；比较了几种典型的C6/C6+糖基碳水合物转化为糠醛的差异。结果表明葡萄糖在硫酸-环丁砜体系中可转化收率为32.6 %的糠醛，且糠醛在硫酸-环丁砜体系中保持6.0 h后的浓度依然较为稳定，损失率仅为4.6 %。以果糖、蔗糖与纤维素为原料时，可分别得到收率为32.4 %、46.5 %和43.5 %的糠醛。上述结果说明溶剂的性质及其对糠醛的稳定作用，糖基碳水化合物的碳链长度和结构是影响糠醛选择性生成的重要因素。
关键词：糖基碳水化合物；糠醛；溶剂；碳链结构；损失率
中图分类号：TK6 文献标识码：A 文章编号：0258-3283（2024）04-0028-06
DOI：10.13822/j.cnki.hxsj.2023.0754
Investigation on the Selective Conversion of C6/C6+ Glycosyl Carbohydrates to Furfural TAN Jin1, WU Yan-ni1, QIU Song-bai2 (1a. School of Environmental and Chemical Engineering, Zhaoqing University, 1b. Guangdong Provincial Key Laboratory of Environmental Health and Land Resource, Zhaoqing University, Zhaoqing 526061, China; 2. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China)
Abstract: Furfural is a significant fine chemical extensively utilized in the food, medicine, pesticide, and chemical industries. Typically, hemicellulose undergoes depolymerization to yield five-carbon sugars, which are subsequently dehydrated to produce furfural. However, the conversion of six-carbon sugars derived from cellulose into furfural presents challenges. In this study, an in-depth investigation was conducted on the influential factors affecting the selective conversion of glucose (C6) to furfural, along with proposed reaction pathways. A comparison was made regarding the conversion disparities of several typical C6/C6+ glycosyl carbohydrates into furfural. The results demonstrate that a furfural yield of 32.6% was obtained from glucose in the sulfuric acid-sulfolane solution. Additionally, the concentration of furfural remains stable after being retained in the sulfuric acid-sulfolane solution for 6.0 hours, with a mole loss rate of only 4.6%. When fructose, sucrose, and cellulose were employed as raw materials, the yields of furfural were 32.4%, 46.5%, and 43.5%, respectively. These findings indicate that solvent properties, the stabilizing effect of the solvent on furfural, and the length and structure of the carbon chain in glycosyl carbohydrates are influential factors that affect the selective production of furfural.
Key words: glycosyl carbohydrates; furfural; solvent; carbon chain structure; loss ratio
引用本文：谈金，吴燕妮，仇松柏. C6/C6+糖基碳水化合物选择性转化为糠醛的研究[J]. 化学试剂，2024，46（4）：28- 33.
含吲哚和喹啉的荧光探针的合成及离子识别性能
张茂风*1,2，张立光1,2，钱志程1，王江南1，吕慧敏1，陈磊1，李俊骅2
(1. 苏州卫生职业技术学院 a.苏州市检验医学重点实验室，b.药学院，江苏 苏州 215009；2. 中国科学院广州生物医药与健康研究院 化学生物学与药物研究中心，广东 广州 510530)
摘要：铜离子（Cu2+）和锰（Mn2+）在环境中分布广泛，也是生物体中重要的微量元素。目前能同时检测此两种金属离子的分子探针较少。将8-羟基喹啉-2-甲醛与吲哚-2-羧酸乙酯衍生物进行缩合，合成了两种新型的探针分子5a和5b，采用1H和13C核磁共振波谱法（NMR）、高分辨质谱（HRMS）和红外光谱（IR）对新中间体及探针分子的结构进行了表征。通过荧光和紫外光谱法研究了探针5a和5b识别Cu2+和Mn2+的性能，结果表明探针在二甲基亚砜溶液中对Cu2+和Mn2+表现出快速、灵敏的荧光淬灭响应效果，检测限低于0.5 μmol/L。通过IR、HRMS和荧光可逆性实验对结合机理进行了初步探究，提出了可能的配合方式。该方法可用于环境或工农业样品中Cu2+和Mn2+的快速识别和检测。
关键词：吲哚；喹啉；荧光探针；Cu2+；Mn2+；检测
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）04-0034-08
DOI：10.13822/j.cnki.hxsj.2023.0746
Synthesis and Ion Recognition Properties of Fluorescent Probes Containing Indole and Quinoline ZHANG Mao-feng*1,2, ZHANG Li-guang1,2, QIAN Zhi-cheng1, WANG Jiang-nan 1, LV Hui-min1, CHEN Lei1 , LI Jun-hua2 (1a.Suzhou Key Laboratory of Laboratory Medicine, 1b.School of Pharmacy, Suzhou Vocational Health College, Suzhou 215009, China; 2. Center for Chemical Biology and Drug Discovery, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, Guangzhou 510530, China)
Abstract：Both copper ions (Cu2+) and manganese ions (Mn2+) are significant trace elements present in living organisms and widely distributed in the environment. Currently, there is a limited selection of molecular probes available for the simultaneous detection of both metal ions. In this study, two new probe molecules, 5a and 5b, were synthesized by condensing ethyl indole-2-carboxylate derivatives with 8-hydroxyquinoline-2-carboxaldehyde. The structures of the new intermediates and probe molecules were characterized using various techniques, including 1H and 13C nuclear magnetic resonance spectroscopy (NMR), high-resolution mass spectrometry (HRMS), and infrared spectroscopy (IR). The performance of probes 5a and 5b in recognizing Cu2+ and Mn2+ was investigated using fluorescence and UV spectroscopy. The results demonstrated that these probes exhibited a rapid and sensitive fluorescence quenching response against Cu2+ and Mn2+ in DMSO solution, with a detection limit of less than 0.5 μmol/L. The binding mechanism was preliminarily investigated using IR, HR-MS, and fluorescence reversibility experiments, and the possible complexation modes were proposed. These methods hold the potential for rapid identification and detection of Cu2+ and Mn2+ in environmental, industrial, and agricultural samples.
Key words：indole; quinoline; fluorescence probe; Cu2+; Mn2+; detection
引用本文：张茂风，张立光，钱志程，等. 含吲哚和喹啉的荧光探针的合成及离子识别性能[J]. 化学试剂，2024, 46（4）：34-41。
基于分子模拟的功能单体筛选用于毒死蜱分子印迹聚合物制备
王斌，李玉珍，肖怀秋*，刘畅宇，王维
（湖南化工职业技术学院 制药与生物工程学院，湖南 株洲 412000）
摘要: 以毒死蜱（Chlorpyrifos，CPF）为模板，采用Materials Studio分子模拟（Molecular simulation, MS）软件及紫外光谱法分析不同功能单体与模板分子间相互作用，并通过吸附实验验证最优功能单体。在测试的5种功能单体中，4-乙烯基苯甲酸（4-Vinylbenzoic acid, VBA）与CPF相互作用能最小（-12.0633 kcal/mol），预组装所形成的复合物稳定性最好。吸附实验结果表明，以VBA为功能单体制备的MIPs相比于以甲基丙烯酸（MAA）、甲基丙烯酸甲酯（MMA）、丙烯酸（AA）及丙烯酰胺（AM）为功能单体制备的MIPs拥有更优异的吸附容量，VBA与CPF摩尔比为1:2时所制备的MIPs对CPF有高效的特异性识别能力。试验结果可为进一步研究其他类型农药分子印迹聚合物的吸附和识别机理提供理论基础。
关键词：毒死蜱；分子印迹技术；分子模拟；功能单体；筛选；吸附
中图分类号：X592； 文献标识码：A 文章编号：0258-3283（2024）04-0042-08
DOI：10.13822/j.cnki.hxsj.2023.0781
Preparation of Molecular Imprinted Polymers for Acaricide based on Functional Monomer Screening through Molecular Simulation WANG Bin, LI Yu-zhen, XIAO Huai-qiu*, LIU Chang-yu, WANG Wei (College of Pharmaceutical and bioengineering, Hunan Chemical Vocational Technology College, Zhuzhou, Hunan 412000)
Abstract: In this study, chlorpyrifos (CPF) was used as a template molecule to investigate the interactions between different functional monomers and CPF using Materials Studio molecular simulation (MS) software and ultraviolet spectroscopy. The goal was to identify the optimal functional monomer through adsorption experiments. Among the five functional monomers tested, 4-vinylbenzoic acid (VBA) exhibited the least interaction with CPF, with a calculated energy of -12.0633 kcal/mol. Additionally, the stability of the pre-assembled complex formed between VBA and CPF was the highest. Adsorption experiments were conducted to validate the findings. The results showed that molecularly imprinted polymers (MIPs) prepared using VBA as the functional monomer demonstrated superior adsorption capacity compared to MIPs prepared using other functional monomers such as methacrylic acid (MAA), methyl methacrylate (MMA), acrylic acid (AA), and acrylamide (AM). Specifically, MIPs prepared with a molar ratio of VBA to CPF of 1:2 exhibited highly efficient specific recognition capabilities for CPF. These experimental results provide a theoretical foundation for further investigation into the adsorption and recognition mechanisms of other types of pesticide molecularly imprinted polymers.
Key Words: chlorpyrifos; molecular imprinting technology; molecular simulation; functional monomer; screen; adsorption
引用本文：王斌，李玉珍，肖怀秋，等. 基于分子模拟的功能单体筛选用于毒死蜱分子印迹聚合物制备[J].化学试剂，2024，46（4）：42-49.
【分离提取技术】
响应面法优化三元低共熔溶剂提取克氏原螯虾中的甲壳素
何晓希1，杨荣玲1，朱千林1，赵祥杰1*，吴彬2，邵灿灿1
（1. 淮阴工学院 生命科学与食品工程学院，江苏 淮安 223003；2. 淮安市产品质量监督综合检验中心，江苏 淮安 223001）
摘要：以制备的三元低共熔溶剂提取克氏原螯虾中的甲壳素，分别考察甲壳素提取过程中低共熔溶剂摩尔比、反应时间和固液比对甲壳素提取率的影响，通过单因素优化确定不同因素对甲壳素提取影响的最佳参数，在单因素实验结果基础上开展响应面实验设计，确定甲壳素最优提取工艺参数，通过傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）和扫描电镜（SEM）对甲壳素进行表征，明确其性质。结果表明，以氯化胆碱、乳酸和乙酸组成的三元低共熔溶剂作为优选提取溶剂进行提取优化时，当固液比为1:10.8、反应时间为2.50 h、低共熔溶剂摩尔比为1:2.8:1，甲壳素提取率最高可达31.72%，比常规酸碱法提取率更高。通过傅里叶变换红外光谱和X射线衍射可以看出所提取甲壳素的特征峰情况和钙的脱除状况，扫描电镜照片可以清楚地看出其表面形貌特征。
关键词：三元低共熔溶剂；克氏原螯虾；甲壳素；响应面法；提取
中图分类号：TQ413 文献标识码：A 文章编号：0258-3283（2024）04-0050-09
DOI：10.13822/j.cnki.hxsj.2023.0729
Optimization of Extraction of Chitin from Crayfish (Procambarus clarkii) with Ternary Deep Eutectic Solvents by Response Surface Methodology HE Xiao-xi1, YANG Rong-ling1, ZHU Qian-lin1, ZHAO Xiang-jie1*, WU Bin2, SHAO Can-can1 (1.College of Life Sciences and Food Engineering, Huaiyin Institute of Technology, Huaian 223003, China; 2. Huaian Product Quality Supervision and Inspection Center, Huaian 223001, China)
Abstract: In this study, ternary deep eutectic solvents were prepared and used to extract chitin from crayfish (Procambarus clarkii). The effects of the molar ratio of the components in the ternary deep eutectic solvents, reaction time, and solid-liquid ratio on the extraction rate of chitin during the extraction process were investigated. Single-factor optimization was conducted to determine the optimal parameters for each factor, and then the design of response surface methodology was employed to determine the overall optimal parameters for chitin extraction from crayfish. The extracted chitin was characterized, and its properties were elucidated using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). The results indicated that the selected ternary deep eutectic solvent composed of choline chloride, lactic acid, and acetic acid was the optimal extraction solvent. The highest extraction rate of chitin, reaching 31.72%, was achieved when the solid-liquid ratio was 1:10.8, the reaction time was 2.5 hours, and the molar ratio of the deep eutectic solvent components was 1:2.8:1. This extraction rate was higher than that obtained using the conventional acid-base method. By analyzing the FTIR and XRD spectral images, characteristic peaks of the extracted chitin and the removal of calcium could be observed. The SEM photographs clearly showed the surface morphology characteristics of the extracted chitin.
Keywords: ternary deep eutectic solvents; crayfish; chitin; response surface methodology; extraction
引用本文：何晓希，杨荣玲，朱千林，等. 响应面法优化三元低共熔溶剂提取克氏原螯虾中的甲壳素[J[.化学试剂，2024，45（4）：50-58.
【化学品与环境】
食Fe(III)/2,6-吡啶二羧酸活化高碘酸盐强化染料脱色的效能与机制
陈文政，苏晗，钟欣洋，牛丽君，冯明宝*
（厦门大学 环境与生态学院，福建 厦门 361102）
摘要：有色染料是环境中非常重要的污染源之一，严重威胁着水生生态环境和人类健康。由于其难以被天然降解，且传统的污水处理工艺亦无法实现其高效去除，因此急需开发绿色、高效的水处理工艺进行有色染料污染控制。发现Fe(III)/2,6-吡啶二羧酸（2,6-PDA）可高效活化高碘酸盐（PI）实现亚甲基蓝（MB）这一典型染料的高效降解。实验结果表明，该体系在Fe(III)浓度为10 μmol/L、2,6-PDA浓度为10 μmol/L和PI浓度为200 μmol/L时，可在pH 3.0条件下使5 mg/L MB降解率在120 s内大于97%。该方法依托高级氧化原理和配位强化策略，利用PI对有色染料进行降解，为目前染料废水治理提供了新思路从而有效地修复了污染水体。
关键词：亚甲基蓝；高碘酸盐；配位活化；Fe(III)；高级氧化
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2024）04-0059-06
DOI：10.13822/j.cnki.hxsj.2023.0481
Periodate Activation by Fe(III)/2,6-pyridinedicarboxylic Acid to Enhance Dye Decolorization: Efficiency and Mechanisms CHEN Wen-zheng, SU Han, ZHONG Xin-yang, NIU Li-jun, FENG Ming-bao* (College of Environment & Ecology, Xiamen University, Xiamen, 361102, China)
Abstract: Colored dyes pose a significant environmental pollution threat, impacting both aquatic ecosystems and human health. These dyes are difficult to naturally degrade, and conventional wastewater treatment processes struggle to efficiently remove them. Therefore, there is an urgent need to develop a green and efficient water treatment method for controlling colored dye pollution. In this study, it was discovered that the combination of Fe(III) and 2,6-pyridinedicarboxylic acid (2,6-PDA) can effectively activate periodate (PI) and achieve efficient degradation of methylene blue (MB), a representative dye. Experimental results demonstrated that the removal efficiency of MB, even at a concentration of 5 mg/L, exceeded 97% within 120 seconds using 10 μmol/L Fe(III), 10 μmol/L 2,6-PDA, and 200 μmol/L PI. Based on the principles of advanced oxidation and coordination strengthening, this method employs PI to degrade colored dyes, providing a novel approach for treating dye wastewater and effectively remediating polluted water.
Key words: Methylene blue; periodate; complexed activation; Fe(III); advanced oxidation
引用本文：陈文政，苏晗，钟欣洋，等. Fe(III)/2,6-吡啶二羧酸活化高碘酸盐强化染料脱色的效能与机制[J]. 化学试剂，2024，46（4）：59- 64.
太湖水体中微塑料和纳米塑料的鉴定和定量
杨洋a，罗昊a，常婕妤a，李博文a，梁睿思a，黄彬a,b*，何欢a，李时银a
（南京师范大学 a. 环境学院，b. 江苏省水土环境生态修复工程实验室，江苏 南京 210023）
摘要：近年来，微塑料（< 5 mm）已在各种环境甚至生物体中被广泛检出。然而，人们对环境中粒径小于1 μm的纳米塑料的赋存还知之甚少。本研究以太湖竺山湾近岸带水体为研究对象，利用不同孔径滤膜通过分级过滤、H2O2消解、过滤富集等方法对水样进行处理，将样品颗粒分成3个尺寸范围（> 20 μm、1~20 μm和0.1~1 μm）。利用扫描电子显微镜（SEM）、激光红外成像光谱仪（LDIR）与热裂解-气相色谱-质谱联用（Py-GC/MS）等技术手段，综合分析太湖采样点水体中微塑料和纳米塑料的赋存情况。结果显示，水体中纳米塑料（0.1~1 μm）主要以PET、PP和PS为主，并且其含量远高于微塑料。已有研究证明纳米塑料有更高的生态健康风险，因此需要对环境中纳米塑料赋存情况的进行精准的定性及定量分析。
关键词：微塑料；纳米塑料；粒径分级；激光红外成像光谱仪；热裂解-气相色谱-质谱联用
中图分类号：X524 文献标识码：A 文章编号：0258-3283（2024）04-0065-07
DOI：10.13822/j.cnki.hxsj.2023.0806
Identification and Quantification of Microplastics and Nanoplastics in Lake Taihu YANG Yanga, LUO Haoa, CHANG Jie-yua, LI Bo-wena, LIANG Rui-sia, HUANG Bina,b*, HE Huana, LI Shi-yina (a. School of Environment, b. Jiangsu Engineering Lab of Water and Soil Eco-remediation, Nanjing Normal University, Nanjing 210023, China)
Abstract: In recent years, microplastics (MPs) with a particle size of less than 5 mm have been extensively detected in various environments, including organisms. However, there is limited knowledge about the occurrence of particles smaller than 1 μm, known as nanoparticles (NPs), in the environment. A water sample was collected from the nearshore water body of Zhushan Bay in Lake Taihu. The sample was separated using membranes with different pore sizes (20 μm, 1 μm, and 0.1 μm). The samples were then digested using an H2O2 solution, concentrated through filtration and drying processes. The particles were divided into three size ranges (>20 μm, 1~20 μm, and 0.1~1 μm) and subjected to analysis using scanning electron microscopy (SEM), dynamic light scattering (DLS), laser direct infrared (LDIR) spectroscopy, and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) for identification and quantification of MPs and NPs in the water body of Lake Taihu. The results revealed that NPs in the water, particularly those in the size range of 0.1~1 μm, mainly consisted of polyethylene terephthalate (PET), polypropylene (PP), and polystyrene (PS), with their content being significantly higher than that of MPs. It has been demonstrated that NPs pose higher ecological health risks compared to MPs. Therefore, it is crucial to enhance the accuracy of quantitative and qualitative analysis in assessing the occurrence of NPs in the environment.
Keywords: microplastics; nanoplastics; size grading; LDIR; Py-GC/MS
引用本文：杨洋，罗昊，常婕妤，等. 太湖水体中微塑料和纳米塑料的鉴定和定量[J]. 化学试剂，2024，46（4）：65-71.
Ti/SnO2-Sb/PbO2-La电极对3种新污染物的电催化氧化去除研究
杨庆，王寅骅，王冲*
（西南大学 资源环境学院，重庆 400715）
摘要：采用溶胶凝胶法和电化学沉积法制备了3种形稳态电极，并通过形貌结构和电化学性质的表征，以及降解动力学实验筛选出性能最优的Ti/SnO2-Sb/PbO2-La电极材料。新污染物的降解速率和羟基自由基表观产率与电流密度呈正相关，并且总有机碳去除率均达到89%以上。Cl-、HCO3-和腐殖酸对新污染物降解呈现不同程度的抑制作用。此外，基于恩诺沙星中间产物的鉴定和密度泛函理论计算推测了其两条降解路径，并且对中间产物的生物安全性进行了评价，结果显示污染物的可生物降解性有效提高，同时生物富集性和生物毒性显著降低。结果表明以Ti/SnO2-Sb/PbO2-La为阳极的电催化氧化技术对新污染物具有高效降解和脱毒能力。
关键词：新污染物；电催化氧化；电极；降解路径；理论计算
中图分类号：O64 文献标识码：A 文章编号：0258-3283（2024）04-0072-08
DOI：10.13822/j.cnki.hxsj.2023.0682
Electrocatalytic Oxidation Degradation of Three Emerging Contaminants by Ti/SnO2-Sb/PbO2-La Electrode YANG Qing, WANG Yin-hua, WANG Chong* (School of Resources and Environment, Southwest University, Chongqing 400715, China)
Abstract：In this study, we prepared three dimensionally stable anodes using sol-gel and electrochemical deposition methods. Among them, the Ti/SnO2-Sb/PbO2-La electrode exhibited remarkable catalytic performance, as demonstrated by the characterization of its morphological structure and electrochemical properties, as well as degradation kinetics experiments. The degradation rate constants of emerging contaminants (ECs) and the apparent yield of hydroxyl radicals in the system were found to be positively correlated with the current density range of 2~10 mA/cm2, resulting in total organic carbon removal rates exceeding 89%. It is worth noting that the presence of Cl-, HCO3-, and humic acid had varying degrees of inhibitory effects on the removal of ECs. Based on the identification of intermediate byproducts and density functional theory calculations, we proposed two degradation pathways for ENR. Furthermore, the biosafety evaluation results indicated that the biodegradability of intermediate byproducts was significantly enhanced, while their bioaccumulation and biotoxicity decreased compared to the parent compound. These findings underscore the high efficiency of the electrocatalytic oxidation technique utilizing the Ti/SnO2-Sb/PbO2-La anode for the degradation and detoxification of ECs.
Keywords：emerging contaminants; electrocatalytic oxidation; electrode; degradation paths; theoretical calculation
引用本文：杨庆，王寅骅，王冲. Ti/SnO2-Sb/PbO2-La电极对3种新污染物的电催化氧化去除研究[J]. 化学试剂，2024，46（4）：72- 79.
利用ICP-MS和LA-ICP-TOF-MS探究上海青中铅的富集与转运特征
曹敬文1,2，徐照2，刘月月2，周袁媛2,3，季涛涛2,3，李桃生2,3，程雄卫2*
（1. 安徽大学 物质科学与信息技术研究院，安徽 合肥 230601；2. 中国科学院合肥物质科学研究院核能安全技术研究所，安徽 合肥 230031；3. 中国科学技术大学，安徽 合肥 230026）
摘要：利用微波消解-电感耦合等离子体质谱(ICP-MS)和激光剥蚀电感耦合等离子体飞行时间质谱(LA-ICP-TOF-MS)进行定量测定和原位成像，对上海青(Brassica rapa var. chinensis (Linnaeus) Kitamura.)中铅(Pb)的富集与转运特征及其机制进行探究。结果表明：上海青中的Pb含量为根＞茎＞叶，对Pb的吸收效率为根＞茎＞叶，转运能力为根到茎＞茎到叶；富集系数(BCF)和转运系数(TF)受种植土壤Pb含量、pH值和大气中Pb沉降等因素影响；Pb等元素在叶片中的原位分布图表明Pb主要富集在叶脉中，与铝(Al)和铁(Fe)分布特征相似，与锌(Zn)、铜(Cu)、锰(Mn)、磷(P)、硫(S)和镁(Mg)分布特征存在差异。基于Pb的富集与转运特征及其在叶片中与其他元素原位分布特征的异同，探讨上海青对Pb的吸收、富集和转运机制，为评估Pb潜在的健康危害提供数据支撑。
关键词：Pb；上海青；转运；富集；ICP-MS；LA-ICP-TOF-MS
中图分类号：Q81 文献标识码：A 文章编号：0258-3283（2024）04-0080-08
DOI：10.13822/j.cnki.hxsj.2023.0773
The enrichment and transport characteristics of lead in Pakchoi (Brassica rapa var. chinensis (Linnaeus) Kitamura.) were studied by ICP-MS and LA-ICP-TOF-MS CAO Jing-wen1,2, XU Zhao2, LIU Yue-yue2, ZHOU Yuan-yuan2,3, JI Tao-tao2,3, LI Tao-sheng2,3, CHENG Xiong-wei2* (1. Institutes of Physical Science and Information Technology, Anhui University, He Fei 230601, China; 2. Institute of Nuclear Energy Safety Technology, He Fei Institute of Physical Sciences, Chinese Academy of Sciences, He Fei 230031, China; 3. University of Science and Technology of China, He Fei 230026, China)
Abstract: In this study, a combination of microwave digestion, inductively coupled plasma mass spectrometry (ICP-MS), and laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) was utilized to quantitatively determine and perform in situ imaging of lead (Pb) in pakchoi (Brassica rapa var. chinensis (Linnaeus) Kitamura). The objective was to investigate the enrichment, transport characteristics, and mechanisms of Pb in the plant. The results revealed a distinct distribution pattern of Pb content, with higher concentrations observed in the roots, followed by the stems and leaves of the pakchoi plant. The absorption efficiency showed a similar trend, with roots exhibiting the highest absorption capacity, followed by stems and leaves. Furthermore, the transport capacity indicated a predominant movement of Pb from roots to stems, with subsequent transfer from stems to leaves. The bioconcentration factor and transfer factor were found to be influenced by both the Pb content and the pH value of the planting soil, as well as the deposition of Pb from the atmosphere. Importantly, in situ mapping of Pb and other elements in the pakchoi leaves revealed a preferential enrichment of Pb in the leaf veins, similar to aluminum (Al) and iron (Fe), but different from zinc (Zn), copper (Cu), manganese (Mn), phosphorus (P), sulfur (S), and magnesium (Mg). By analyzing the similarities and differences in the accumulation and transport characteristics between Pb and other elements, this study provided a preliminary understanding of the absorption, enrichment, and transport mechanisms of Pb in pakchoi. These insights offer valuable data for assessing the potential health hazards associated with Pb exposure and contribute to a better understanding of Pb contamination in plants.
Key words: Pb; pakchoi; migration; enrichment; ICP-MS; LA-ICP-IOF-MS
引用本文：曹敬文, 徐照, 刘月月，等. 利用ICP-MS和LA-ICP-TOF-MS探究上海青中铅的富集与转运特征[J].化学试剂,2024，46（4）：80-87.
【分析与测试】
乙醇体系中金属离子催化转化人参皂苷Rb1的研究
曹波岩，徐丝瑜，李冠亨，王宇，鱼红闪*
（大连工业大学 生物工程学院，辽宁 大连 116000）
摘要：人参皂苷Rb1是人参中的主要皂苷之一，但人体吸收量极少，而其衍生物Rg3、Rk1、Rg5却易于人体吸收，但其制备和分离成本较高。针对以上问题将人参皂苷Rb1在50%乙醇水溶液体系和无水乙醇体系中进行催化条件的优化，并分析其产物。实验发现，通过对金属离子催化效果的筛选，选取NbCl5为反应催化剂；在50%乙醇水溶液体系中最优条件下反应，Rg3得率为18.29%；在无水乙醇体系中最优条件下反应，Rg3得率为49.45%。根据两组反应产物的对比，推测在50%乙醇水溶液体系反应时，水可能供给电子基团，并生成更多水合化合物即20(S)-25-OH-Rg3和20(R)-25-OH-Rg3；在无水乙醇体系反应时，电子基团可能无法供给，形成双键，生成其他化合物即Rk1和Rg5。该发现为金属离子催化人参皂苷以制备稀有人参皂苷的方法奠定了理论基础。
关键词：氯化铌；人参皂苷Rg3；人参皂苷Rb1；催化转化；乙醇体系
中国分类号：O65 文献标识码：A 文章编号：0258-3283（2024）04-0088-06
DOI：10.13822/j.cnki.hxsj.2023.0757
The Catalytic Effect of Metal Ions on Ginsenoside Rb1 in an Ethanol System CAO Bo-yan, XU Si-yu, LI Guan-heng, WANG Yu, YU Hong-shan (College of Biological Engineering, Dalian Polytechnic University, Dalian 116000, China)
Abstract：Ginsenoside Rb1, a major saponin found in ginseng, has limited absorption in the human body. However, its derivatives Rg3, Rk1, and Rg5 are more easily absorbed, albeit with high preparation and separation costs. To address these challenges, the catalysis of ginsenoside Rb1 was optimized in both a 50% ethanol aqueous solution and anhydrous ethanol system, followed by product analysis. NbCl5 was selected as the catalyst after screening various metal ions for their catalytic effects. Under optimal conditions using a 50% ethanol aqueous solution, the yield of Rg3 reached 18.29%. Similarly, under optimal conditions using the anhydrous ethanol system, the yield of Rg3 increased to 49.45%. A comparison of the reaction products from these two systems suggests that the presence of water in the 50% ethanol aqueous solution provides electron groups, leading to hydration compounds such as 20(S)-25-OH-Rg3 and 20(R)-25-OH-Rg3. In contrast, the anhydrous ethanol system lacks water molecules and electron groups, resulting in the formation of double bonds and other compounds like Rk1 and Rg5. This discovery establishes a theoretical foundation for the preparation of rare ginsenosides through metal ion-catalyzed reactions.
Keyword：niobium chloride; ginsenoside Rg3; gininsenoside Rb1; catalytic conversion ; ethanol system
引用本文：曹波岩，徐丝瑜，李冠亨，等. 有机醇体系中金属离子催化转化人参皂苷Rb1的研究[J]. 化学试剂，2024，46（4）：88- 93.
当归补血泡腾片的制备及质量分析
陈静1，鲁思祺2，赵永恒*2，叶志杭2，吴曦*3
(1. 十堰市人民医院中医医学中心 湖北医药学院附属人民医院，湖北 十堰 442000；2. 湖北医药学院 药学院 武当特色中药研究湖北省重点实验室 湖北省药用植物综合利用工程技术研究中心，湖北 十堰 442000；3. 湖北文理学院附属医院 襄阳市中心医院，湖北 襄阳 441000）
摘要：优选当归补血泡腾片的处方工艺，并对其质量进行分析。通过Box-Behnken响应面法优化制剂处方。通过TLC法对样品中阿魏酸、藁本内酯进行薄层鉴别。通过HPLC-CAD法对黄芪甲苷进行含量测定，通过HPLC-DAD法对样品中阿魏酸、毛蕊异黄酮葡萄糖苷进行含量测定。在当归黄芪提取物用量15%、柠檬酸用量22%、碳酸氢钠用量19%、聚乙二醇6000用量5%、可溶性淀粉用量39%时，制剂的综合评分最佳，实测值与预测值偏差为1.43%。崩解时限、重量差异、硬度、pH等检查符合药典规定。在TLC检测中，阿魏酸、藁本内酯主斑点清晰。黄芪甲苷、阿魏酸、毛蕊异黄酮葡萄糖苷的含量分别为448.38、242.31、526.02 μg/g。本实验确立的当归补血泡腾片处方科学合理，质量分析方法方便可靠。
关键词：当归补血泡腾片；处方；质量分析；黄芪甲苷；阿魏酸；毛蕊异黄酮葡萄糖苷
中图分类号：283.6 文献标识码：A 文章编号：0258-3283（2024）04-0094-08
DOI：10.13822/j.cnki.hxsj.2023.0557
Preparation and Quality Analysis of Danggui Buxue Effervescent Tablets Chen Jing1, Lu Siqi2, ZHAO Yong-heng*2, YE Zhi-hang2, WU Xi*3( 1.Department of Traditional Chinese Medicine Center , Renmin Hopital, Hubei University of Medicine. Shiyan City, Hubei Prowince , Shiyan 442000，China; 2. School of Pharmaceutical Sciences, Hubei Key Laboratory of Wudang Local Chinese Medicine Research, Hubei University of Medicine, Hubei Provincial Technology and Research Center for Comprehensive Development of Medicinal Herbs, Hubei, Shiyan 442000, China; 3. Xiangyang Central Hospital, Affiliated Hospital of Hubei University of Arts and Science, Hubei, Xiangyang 441000, China )
Abstract：The formulation process of Danggui Buxue effervescent tablets was optimized, and the quality of the tablets was analyzed. The Box-Behnken response surface method was utilized to optimize the formulation. The identification of ferulic acid and ligustilide was conducted using Thin-Layer Chromatography (TLC) method. The content of astragaloside IV in the samples was determined using the High-Performance Liquid Chromatography with Charged Aerosol Detection (HPLC-CAD) method. The content of ferulic acid and calycosin-7-glucoside was determined using the HPLC-DAD (High-Performance Liquid Chromatography with Diode Array Detection) method. The optimal formulation was determined to be: Radix angelica and astragalus extract dosage of 15%, citric acid dosage of 22%, sodium bicarbonate dosage of 19%, PEG 6000 dosage of 5%, and soluble starch dosage of 39%, resulting in the best comprehensive score for the preparation. The deviation between the measured values and the predicted values was found to be 1.43%. The disintegration time, weight difference, hardness, pH, and other tests complied with the provisions of the pharmacopoeia. In the TLC test, the main spots of ferulic acid and ligustilide were clearly visible, and the spread distance was moderate. The contents of astragaloside IV, ferulic acid, and calycosin-7-glucoside were measured as 448.38 μg/g, 242.31 μg/g, and 526.02 μg/g, respectively. The preparation technology of Danggui Buxue effervescent tablets was found to be scientific and reasonable, and the quality analysis method was convenient and reliable.
Keywords: Danggui Buxue effervescent tablets; formulation process; quality analysis; astragaloside IV; ferulic acid; calycosin-7-glucoside
引用本文：陈静，鲁思祺，赵永恒，等. 当归补血泡腾片的制备及质量分析[J].化学试剂，2024，46（4）：94-101.
柱前衍生化液质联用法测定氯乙酰氯试剂中的乙酰氯和二氯乙酰氯
邵方娴1,3，何燕琳1,2，芦丽1,3，黄朝瑜1，王晨1,3，严菲1,3*
（1. 江苏省食品药品监督检验研究院，江苏 南京 210019；2. 中国药科大学药物分析教研室，江苏 南京 210009；3. 国家药品监督管理局化学药杂质谱重点实验室，江苏 南京 210019）
摘要：建立了柱前衍生化超高效液相色谱-三重四级杆联用（UPLC-MS/MS）法同时测定酰化试剂氯乙酰氯中的杂质乙酰氯和二氯乙酰氯的含量。以苯胺作衍生化试剂，采用Poroshell 120 Aq-C18（150 mm×2.1 mm，2.7 µm）为色谱柱，0.1%(V/V)甲酸水和乙腈为流动相，梯度洗脱，流速为0.3 mL/min。在电喷雾离子源（ESI），正离子监测下，采用多反应监测扫描（MRM）模式。乙酰氯和二氯乙酰氯分别在0.5 ~ 50 ng/mL和5 ~ 500 ng/mL范围内线性关系良好（R2≥0.9986），定量限为0.5 ng/mL和5 ng/mL，检出限为0.2 ng/mL和2 ng/mL；回收率（n=3）为90.8% ~ 93.5%和92.5% ~ 108.7%，RSD为1.4% ~ 6.6%和0.9% ~ 3.8%。衍生化产物室温放置24 h内稳定。本方法准确可靠，简便高效，可用于氯乙酰氯中乙酰氯和二氯乙酰氯的同时检测。
关键词：氯乙酰氯杂质检测；乙酰氯；二氯乙酰氯；柱前衍生化；超高效液相色谱-串联质谱法（UPLC-MS/MS）
中图分类号： 文献标识码：A 文章编号：0258-3283（2024）04-0102-06
DOI：10.13822/j.cnki.hxsj.2023.0761
Determination of Acetyl chloride and Dichloroacetyl Chloride in Chloroacetyl Chloride by Pre-column Derivatization Ultra Performance Liquid Chromatography-tandem Mass Spectrometry SHAO Fang-xian1,3, HE Yan-lin1,2, LU Li1,3, HUANG Chao-yu1, WANG Chen1,3, YAN Fei1,3(1. Jiangsu Institute for Food and Drug Control, Nanjing 210019, China; 2. Department of Pharmaceutical Analysis, China Pharmaceutical University, Nanjing 210009, China; 3. Key Laboratory of Chemical Impurity Spectrometry, National Medical Products Administration, Nanjing, 210019)
Abstract：A pre-column derivatization ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was developed for the simultaneous determination of acetyl chloride and dichloroacetyl chloride in the acylating agent chloroacetyl chloride. The target compounds were derivatized with aniline. Separation was carried out using an Agilent Poroshell 120 Aq-C18 column (150mm×2.1mm, 2.7µm). The mobile phase consisted of a gradient elution of 0.1% (V/V) formic acid aqueous solution and acetonitrile. The flow rate was set at 0.3 mL/min. Detection of the target compounds was performed using electrospray ionization (ESI) in positive ionization mode under multiple reaction monitoring (MRM) mode. The established method exhibited good linearity within the concentration ranges of 0.5 to 50 ng/mL for acetyl chloride and 5 to 500 ng/mL for dichloroacetyl chloride, with correlation coefficients (R2) equal to or greater than 0.9986. The lower limits of quantitation were determined to be 0.5 ng/mL and 5 ng/mL for acetyl chloride and dichloroacetyl chloride, respectively, while the lower limits of detection were found to be 0.2 ng/mL and 2 ng/mL. The method demonstrated satisfactory accuracy, with ranges of 90.8% to 93.5% and 92.5% to 108.7%, and precision, with ranges of 1.4% to 6.6% and 0.9% to 3.8%, for acetyl chloride and dichloroacetyl chloride, respectively. The stability of the derivatives was confirmed for a period of 24 hours. The established pre-column derivatization UPLC-MS/MS method in this study is accurate and suitable for the determination of acetyl chloride and dichloroacetyl chloride in chloroacetyl chloride.
Keywords: impurities test of chloroacetyl chloride ; acetyl chloride; dichloroacetyl chloride; pre-column-derivatization; UPLC-MS/MS
引用本文：邵方娴，何燕琳，芦丽，等. 柱前衍生化液质联用法测定酰化试剂氯乙酰氯中的杂质[J]. 化学试剂，2024，46（4）：102-107.
基于Pt-PDDA/还原石墨烯纳米电极材料的构建及电化学检测4-氨基苯酚
智晋峰1，郝玺龙*2,白雅蓉1，梁文婷*1
(1. 山西大学 环境科学研究所，山西 太原 030006；2. 山西省科技情报与战略研究中心，山西 太原 030024)
摘要：通过Hummer法将天然石墨粉氧化得到氧化石墨，再将其超声分散于去离子水中形成稳定的氧化石墨分散液。为了引入铂粒子并使之与氧化石墨烯片牢固锚定，将氧化石墨分散液与氯铂酸溶液混，合成Pt-PDDA/还原石墨烯（Pt NPs-PDDA/rGO）纳米电极材料。通过红外、紫外光谱分析以及扫描循环伏安曲线、交流阻抗曲线对该复合电极材料进行了表征。由于铂优良的催化性能，聚二烯丙基二甲基氯化铵（PDDA）的防聚合功能，石墨烯巨大的表面积、优异的电子传导性能及对4-氨基苯酚（4-AP）强大的吸附作用，将制备得到的Pt-PDDA/还原石墨烯纳米电极材料构建电化学传感器，用于对4-AP超灵敏的检测。结果表明，在0.5 mol/L的磷酸盐缓冲液（PBS）中对不同浓度的4-AP进行测定，Pt NPs-PDDA/rGO复合膜修饰的GCE与裸露的GCE和功能化石墨烯（PDDA-rGO）修饰的GCE相比，4-AP的氧化还原峰电流显著增加，表明Pt NPs-PDDA/rGO具有对4-AP的电催化活性。然后对实验条件进行了优化，研究了不同实验条件对电化学传感器性能的影响。结果表明，在最理想的条件下，4-AP浓度在1.00×10-5～1.00×10-3 mol/L范围内时，氧化峰电流与浓度呈良好的线性关系，相关系数为0.9922。最后将其应用于河水和自来水中的4-AP检测，获得令人满意的结果，回收率为98.0%～106.0%。
关键词：电化学；4-氨基苯酚；玻碳电极；铂催化剂
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）04-0108-06
DOI：10.13822/j.cnki.hxsj.2024.0082
Construction and Electrochemical Detection of 4-Aminophenol Based on Pt-PDDA/Reduced Graphene Nano-Electrode Materials ZHI Jin-feng1, HAO Xi-long*2, BAI Ya-rong1, LIANG Wen-ting*1 (1. Institute of Environmental Science, Shanxi University, Taiyuan 030006, China; 2. Science & Technology Information and Strategy Research Center of Shanxi, Taiyuan 030024, China)
Abstract：In this paper, graphite oxide was obtained by oxidizing natural graphite powder by Hummer's method, and then ultrasonically dispersed in deionized water to form a stable graphite oxide dispersion. In order to introduce platinum particles and anchor them firmly to graphene oxide sheets, Pt-PDDA/reduced graphene (Pt NPs-PDDA/rGO) nanoelectrode materials were synthesized by mixing graphite oxide dispersion with chloroplatinic acid solution. The composite electrode material was characterized by infrared, ultraviolet spectral analysis, scanning cyclic voltammetry curves and AC impedance curves. Due to the excellent catalytic properties of platinum, the anti-polymerization function of Poly Diallyl Dimethyl Ammonium chloride (PDDA), the huge surface area of graphene, the excellent electron-conducting properties, and the strong adsorption of 4-aminophenol (4-AP), the electrochemical sensor constructed from Pt-PDDA/reduced graphene nanoelectrode materials were used for the ultra-sensitive detection of 4-AP. The results showed that the redox peak current of 4-AP was significantly increased in Pt NPs-PDDA/rGO composite membrane-modified GCE compared with bare GCE and functionalized graphene (PDDA-rGO)-modified GCE at different concentrations of 4-AP in 0.5 mol/L phosphate buffer solution (PBS), suggesting that Pt NPs-PDDA/rGO possesses the ability to electrocatalytic activity of 4-AP. Then the experimental conditions were optimized and the effects of different experimental conditions on the performance of electrochemical sensors were investigated. The results showed that under the optimal conditions, the oxidation peak current showed a good linear relationship with the concentration with a correlation coefficient of 0.9922 when the concentration of 4-AP was in the range of 1.00×10-5 to 1.00×10-3 mol/L. Finally, it was applied to the detection of 4-AP in the river water and tap water, and the satisfactory results were obtained with the recoveries ranging from 98.0% to 106.0%.
Key words：electrochemical; 4-aminophenol; glassy carbon electrode; platinum catalyst
引用本文：智晋峰，郝玺龙,白雅蓉，等. 基于Pt-PDDA/还原石墨烯纳米电极材料的构建及电化学检测4-氨基苯酚[J],化学试剂，2024，46（4）：108-113.
【合成与工艺技术】
抗NO生成的JAK3抑制剂的合成及其抗炎活性研究
张洁1，凌珍1，覃廷胜1，谢鑫1，曾宪霞1，谯艳妮2*，何林洪1*
（1. 广西医科大学 药学院，广西 南宁 530021；2. 重庆三峡医药高等专科学校附属人民医院，重庆 404000）
摘要：为了探索抗一氧化氮（NO）生成的两面神激酶3（JAK3）抑制剂的抗炎效果，采用药效团拼接原理设计并合成5个7H-吡咯并[2,3-d]嘧啶衍生物D1-D5。体外活性评价表明，化合物D3和D4不仅能有效地抑制NO的合成（D3: IC50 =(5.13±0.48) μmol/L，D4: IC50 =(4.67±0.98) μmol/L），对RAW264.7细胞毒性较低（IC50 >60 μmol/L），而且可以微弱抑制JAK3激酶活性（D3: IC50 =272 nmol/L，D4: IC50 =849 nmol/L）。其中，化合物D4对角叉菜胶诱导小鼠模型的急性抗炎能力优于D3，可作为抗NO生成的JAK3抑制剂的先导化合物继续研发。
关键字：一氧化氮（NO）；两面神激酶3（JAK3）；细胞毒性；抗炎活性
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2024）04-0114-06
DOI：10.13822/j.cnki.hxsj.2023.0725
Synthesis and Anti-inflammatory Activity Evaluation for JAK3 Inhibitors with the Potency of Inhibiting Nitric Oxide Production ZHANG Jie1, LING Zhen1, Qin Tingsheng1, Xie Xin1, ZENG Xian-xia1, Qiao Yanni2*, HE Lin-hong1 * ( 1．Pharmaceutical College, Guangxi Medical University, Nanning 530021, China; 2. Affiliated People’s Hospital of Chongqing Three Gorges Medical College , Chongqing, 404000, China)
Abstract: In this study, the anti-inflammatory activity of Janus kinase 3 (JAK3) inhibitors that also have the ability to inhibit nitric oxide (NO) production was investigated. Five derivatives of 7H-pyrrolo[2,3-d]pyrimidine (D1-D5) were designed and synthesized based on the pharmacophore splicing principle. In vitro testing revealed that compounds D3 and D4 demonstrated inhibitory effects on NO production in RAW264.7 cells. The IC50 values for D3 and D4 were (5.13±0.48) μmol/L and (4.67±0.98) μmol/L, respectively. Importantly, these compounds showed low cytotoxicity with IC50 values greater than 60 μmol/L. Furthermore, D3 and D4 exhibited weak inhibition of JAK3. The IC50 values for D3 and D4 against JAK3 were 272 nmol/L and 849 nmol/L, respectively. Among the tested compounds, D4 displayed better acute anti-inflammatory activity in a mouse model of carrageenan-induced paw edema. Based on these findings, compound D4 can be considered as a lead compound for the development of JAK3 inhibitors with the ability to inhibit nitric oxide production and potential anti-inflammatory activity.
Key words: Nitric oxide (NO); Janus kinase 3 (JAK3); cytotoxicity; anti-inflammatory activity
引用本文：张洁，凌珍，覃廷胜，等. 抗NO生成的JAK3抑制剂的合成及其抗炎活性研究[J].化学试剂，2024，46（4）：114-121.
化学试剂2024年第4期.pdf
