基于氟硼二吡咯亚甲基荧光探针的研究进展
朱金彪，闫力强*，吴雄志*
（桂林理工大学 化学与生物工程学院，广西 桂林 541006）
摘要：氟硼二吡咯亚甲基（BODIPY）荧光染料具有易于修饰、高摩尔消光系数、高荧光量子产率、优异的光稳定性、对溶剂的极性和pH敏感性低等许多突出特性，被广泛用于有机小分子荧光探针的构建。综述了2019年以来BODIPY荧光探针在金属阳离子、阴离子、活性氧和生物硫醇等检测方面的研究进展，梳理了这些探针的设计思路，对比了它们的检测性能，并展望和预测了该类荧光探针的发展趋势，为新型BODIPY荧光探针的设计与开发提供参考。
关键词：氟硼二吡咯；荧光探针；金属阳离子；阴离子；活性氧；研究进展
中图分类号：O621.4 文献标识码：A 文章编号：0258-3283（2022）- -
Progress of Fluorescent Probes Based on Fluoroborane Dipyrromethene ZHU Jin-biao, YAN Li-qiang*, WU Xiong-Zhi* (College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541006, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: Fluoroborondipyrromethene (BODIPY) dye hasa lot of prominent properties, such as easy modification, high molar extinction coefficient and fluorescence quantum yield, good photostability, low sensitivity to solvent polarity and pH, which has been widely used as a fluorophore in the construction of organic small molecule fluorescent probes. In this work, the progresses of BODIPY-based fluorescent probes in the detections of metal cations, anions, reactive oxygen species (ROS) and thiols since 2019 were reviewed, the design ideas and detection performances, and predict the development trend also were summarized. This review may provide an inspiration for the design and development of new BODIPY-based fluorescent probes.
Key words: fluoroboron dipyrromethene; fluorescent probe; metal cations; anions; reactive oxygen species; research progress
引用本文：朱金彪，闫力强，吴雄志. 基于氟硼二吡咯亚甲基荧光探针的研究进展[J]. 化学试剂，2022，44(5):633-642。
核取代萘二酰亚胺衍生物超分子自组装体系的研究进展
仇中选1，张娟2，辛飞飞*3
(1. 青岛职业技术学院 生物与化工学院，山东 青岛 230031；2. 中国石油大学（北京） 非常规油气科学技术研究院，北京 102249；3. 青岛科技大学 化学与分子工程学院，山东 青岛 266042)
摘要：超分子自组装是体系中各结构单元之间的一种自发的组织行为，能够形成纳米级或者微米级的微结构，可用于制备具有特定性质以及功能化的材料。核取代萘二酰亚胺衍生物（cNDIs）因其独特的结构特点与光电性能，是超分子自组装体系中一类重要的构筑基元，在超分子化学领域以及材料科学领域等表现出极大的应用价值。如何提高cNDIs超分子组装体的结构与性能调控效率，拓展其功能，促进其实际应用是现阶段的主要研究热点。综述结合国内外cNDIs自组装体系的文献报道，总结并阐述了调控cNDIs分子自组装行为的三种主要方式：设计cNDIs分子结构，改变体系环境，使用模板。最后，对该类超分子体系的研究方向与发展趋势进行了简要展望。
关键词：核取代萘二酰亚胺；超分子化学；可调控；自组装；微观结构
中图分类号：O641.3 文献标识码：A 文章编号：0258-3283（2022）
Supramolecular Self-assembly of Core Substituted Naphthalenediimides QIU Zhong-xuan1, ZHANG Juan2, XIN Fei-fei*3 (1. School of Biological and Chemical Engineering, Qingdao Technical College, Qingdao 266555, China; 2. Unconventional Petroleum Research Institute, China University of Petroleum, Beijing 102249, China; 3. College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China), Huaxue Shiji, 2022, 44(5), ～
Abstract：Supramolecular self-assembly rests on the spontaneous organization of components and forms various micro- or nanostructures to prepare functional materials with unique properties. Core-substituted naphthalenediimides (cNDIs) which possess unique molecular structures and opto-electrical properties are widely employed in supramolecular chemistry. Now, the main researches on cNDIs-based supramolecular assemblies include: increasing the modulation efficiency of microstructures and properties; extending the functionalities and promoting the applications. This work reviews the recent progress in supramolecular self-assemblies based on cNDIs. Three main modulating patterns of self-assemblies: we summarized including the design of cNDIs molecular structures, changing external environment and templated self-assembly. Finally, the development potential of this field is briefly discussed.
Key words: core-substituted naphthalenediimides; supramolecular chemistry; controllable; self-assembly; microstructures
引用本文：仇中选，张娟，辛飞飞. 核取代萘二酰亚胺衍生物超分子自组装体系的研究进展[J]. 化学试剂, 2022, 44(5):643-652。
碱土金属配合物催化丙交酯开环聚合的研究
刘娜1，由晓蕾1，王玲芳2，张金策1，魏杰*1，房大维*1
（1. 辽宁大学 稀散元素化学研究所，辽宁 沈阳 110036；2. 盐城工学院 材料科学与工程学院，江苏 盐城 224051）
摘要：良好的生物相容性和生物可降解性使得聚丙交酯在各个领域被广泛应用，而聚丙交酯的性能是由其微观结构决定的，因此开发高效的催化体系催化丙交酯开环聚合制备结构精确可控的聚丙交酯具有非常重大的意义。碱土金属（Ca/Sr/Ba）配合物因其无毒、生物相容性和环境友好性等优点被广泛应用于催化反应中，尤其在催化环酯类单体开环聚合方面表现出优良的催化活性。为了更清楚地了解碱土金属配合物的性质，对近十年来不同配体、不同中心金属组成的碱土金属催化剂的合成，以及其在丙交酯开环聚合中的催化活性、可控性和立体选择性进行了综述，并对其应用前景作出了高度展望。
关键词：钙配合物；锶配合物；钡配合物；丙交酯；开环聚合
中图分类号：O631 文献标识码：A 文章编号：0258-3283（2022）- -
Ring-opening Polymerization of Lactide Catalyzed by Alkaline Earth Metal Complexes LIU Na1, YOU Xiao-lei1, WANG Ling-fang2, ZHANG Jin-ce1, WEI Jie*1, FANG Da-wei*1 (1. Institute of Rare and Scattered Elements Chemistry, Liaoning University, Shenyang 110036, China; 2. School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: Polylactides (PLAs) have been widely used in various fields due to its good biocompatibility and biodegradability. The microstructure of PLA governs the properties of polymers. Therefore, it is of great significance to establish an efficient catalytic system to catalyze the ring-opening polymerization (ROP) of lactide to prepare PLA with a precise and controllable structure. Alkaline earth metal (Ca/Sr/Ba) complexes have attracted much attention of researchers due to their non-toxicity, biocompatibility and environmental friendliness. To understand the property of these complexes, it covers the latest research progress about the application of alkaline earth metal catalysts in the ROP of lactide since 2010 in this work. Meanwhile, a high prospect for their applications was also maken.
Key words: calcium complexes; strontium complexes; barium complexes; lactide; ring-opening polymerization
引用本文：刘娜，由晓蕾，王玲芳，等. 碱土金属配合物催化丙交酯开环聚合的研究[J]. 化学试剂，2022，44(5):563-661。
两种河南产迷迭香精油成分分析及抗氧化活性研究
叶兆伟1，李金平2，叶润1，李琪琪1，陈琼*1
（1. 信阳农林学院 制药工程学院，河南 信阳 464000；2. 河南息半夏药业有限公司，河南 信阳 464000）
摘要：为了鉴别和研究迷迭香生长习性及其精油组成特点，以生长在河南信阳的两种迷迭香绿色窄叶、宽叶为研究对象，考察其生物学性状，并利用气相-质谱仪（GC-MS）分析了精油的化学成分；以清除羟基自由基（·OH）能力为指标，考察当地迷迭香精油的抗氧化活性。结果表明，当地窄叶迷迭香精油主要成分包括桉叶素（29.826%）、(1S)-1,7,7-三甲基-双环[2.2.1]庚-2-酮（18.939%）、γ-松油烯（8.051%）、冰片（7.434%）、莰烯（5.542%）；宽叶迷迭香精油主要成分有(1R)-2,6,6-三甲基二环[3.1.1]庚-2-烯（28.141%）、桉叶素（23.076%）、(1S)-4,6,6-三甲基二环[3.1.1]庚-3-烯-2-酮（9.758%）、冰片（6.244%）、莰烯（4.833%）等。此两种迷迭香精油在1～1.8 mg/mL浓度范围内，羟基自由基清除率变化呈线性上升趋势，当精油浓度为1.8 mg/mL时，窄叶迷迭香精油对羟基自由基清除率达到90.33%，宽叶迷迭香精油羟基自由基清除率达到87.06%；窄叶、宽叶迷迭香品种不同，精油含量及成分有差别，窄叶精油对羟基自由基清除能力比相同浓度下宽叶精油的清除能力强，精油的清除能力均好于维生素C（Vc）。
关键词：迷迭香；精油；GC-MS；羟基自由基；抗氧化
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2022）--
Composition Analysis and Antioxidant Activity of Two Essential Oils from Rosemary officinalis in Henan YE Zhao-wei1, LI Jin-ping2,YE Run1, LI Qi-qi1, CHEN Qiong*1 (1. Xinyang Agriculture and Forestry University, School of biology and pharmaceutical engineering, Xinyang 464000, Henan China；2. Henan Xibanxia Co., Ltd, Xinyang 464000, Henan China) Huaxue Shiji, 2021, 44(5), ～
Abstract: To identify and obtain the growth habit and essential oil composition of rosemary officinalis, the biological characters of two kinds of green leaf between narrow and wide rosemary officinalis grown in Xinyang, Henan Province were investigated. The chemical components of the essential oil were analyzed by gas chromatography-mass spectrometry (GC-MS). The antioxidative activity of rosemary officinalis essential oil was investigated with the ability of scavenging hydroxyl free radical (·OH) as an index. The main components of essential oil from local narrow rosemary officinalis include Eucalyptus (29.826%), (1S) -1,7,7- three methyl - bicyclic [2.2.1] Geng -2- ketone (18.939%).γ- Terpinene (8.051%), borneol (7.434%), camphene (5.542%); The main components of Rosmarinus officinalis essential oil are: (1R) -2,6,6- three methyl bicyclic [3.1.1] heptane -2- (28.141%), Eucalyptus (23.076%), (1S) -4,6,6- three methyl bicyclic [3.1.1] heptane -3- ene -2- ketone (9.758%), borneol (6.244%), and borneol (4.833%). The scavenging rate of hydroxyl radical in the two kinds of rosemary officinalis essential oils increased linearly in the concentration range of 1～1.8 mg/mL. When the concentration of essential oil was 1.8 mg/mL, the scavenging rate of rosemary officinalis essential oil to hydroxyl radical reached 90.33%, and the scavenging rate of hydroxyl radical of Rosmarinus officinalis essential oil reached 87.06%. The content and composition of essential oil are different in different varieties of narrow and wide leaf rosemary officinalis. The scavenging ability of narrow leaf essential oil is stronger than that of wide leaf essential oil at the same concentration, and the scavenging ability of essential oil is better than vitamin C (VC).
Key words: rosemary officinalis; essential oil; GC-MS; Hydroxyl radical; antioxidant ability
引用本文：叶兆伟，李金平，叶润，等. 两种河南产迷迭香精油成分分析及抗氧化活性研究[J]. 化学试剂, 2022, 44(5): 662-667。
2-三氟甲基喹唑啉衍生物的合成及抗肿瘤活性研究
吴辉a,b,c，余佳a,c，余刚a,c，曾晓萍a,c，徐广灿a,c，徐必学*a,c
(贵州医科大学 a. 省部共建药用植物功效与利用国家重点实验室，b. 药学院，c. 贵州省中国科学院天然产物化学重点实验室, 贵州 贵阳 550014)
摘要：设计合成新型2-三氟甲基喹唑啉类化合物，以期发现高效低毒的抗肿瘤活性目标分子。以2-氨基-5-硝基苯甲酸为原料，经过三氟乙酰化、环化、氯代及偶联等反应，设计合成10个2-三氟甲基喹唑啉类化合物，并通过1H NMR、13C NMR、19F NMR进行结构确证。采用四氮唑蓝（MTT）法评价目标化合物的体外抗肿瘤活性，合成的大部分目标化合物对前列腺癌细胞（PC3、LNCaP）、人慢性髓系白血病细胞（K562）3种癌细胞都有一定的抑制作用，其中，N-（4-甲氧基苯基）-N-甲基-2-（三氟甲基）喹唑啉-4,6-二胺（5a）的IC50分别为25.2（PC3）、515.7（LNCaP）和248.7 nmol（K562），该结果为2-三氟甲基喹唑啉类化合物在抗肿瘤方面的进一步研究提供参考。
关键词：喹唑啉；三氟甲基；合成；MTT法；抗肿瘤活性
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2022）
Synthesis and Antitumor Activity of 2-Trifluoromethylquinazoline Derivatives WU Huia,b,c, YU Jiaa,c, YU Ganga,c, ZENG Xiao-pinga,c, XU Guang-cana,c, XU Bi-xue*a,c (a. State Key Laboratory of Functions and Applications of Medicinal Plants, b. School of Pharmaceutical Sciences, c. Key Laboratory of Chemistry for Natural Products of Guizhou and Chinese Academy of Sciences, Guizhou Medical University, Guiyang 550014, China), Huaxue Shiji, 2022, 44(5)
Abstract: To discover high efficiency and low toxicity target compounds, ten novel derivatives of 2-trifluoromethylquinazoline were designed and synthesized from 2-amino-5-nitrobenzoic acid by trifluoacylation, cyclization, chlorination and coupling reaction. The structures of all target compounds were confirmed by 1H NMR, 13C NMR, 19F NMR and their anti-tumor activities in vitro were demonstrated by MTT assays. Most of them have a certain inhibitory activity against prostate cancer cell lines (PC3, LNCaP), human chronic myeloid leukemia cell line (K562). The half maximal inhibitory concentration values of compound N-(4-Methoxyphenyl)-N-methyl-2-(trifluoromethyl)quinazoline-4,6-diamine (5a) against PC3, LNCaP and K562 cell lines are 25.2, 515.7 and 248.7 nmol, respectively. The results could provide reference for further investigation of the derivatives of 2-trifluoromethylquinazoline as antitumor agents.
Key words: quinazoline; trifluoromethyl; synthesis; MTT assays; antitumor activity
引用本文：吴辉, 余佳, 余刚, 等. 2-三氟甲基喹唑啉衍生物的合成及抗肿瘤活性研究[J]. 化学试剂, 2022, 44(5): 668-673。
红景天内生微生物代谢产物化感作用研究
刘香余，唐小渊，章煜，黄丹叶，陈愉，郑渝，齐智敏，卢轩*
(大连大学 生命科学与技术学院，辽宁 大连 116622)
摘要：研究红景天内生菌Fusarium sp. HJT-P-5代谢产物。采用薄层层析色谱（TLC）、正/反相柱色谱、凝胶柱色谱、以及高效液相色谱（HPLC）等多种现代分离技术对HJT-P-5代谢产物进行分离纯化，结合理化性质和核磁共振波谱数据进行结构鉴定。从HJT-P-5乙酸乙酯萃取物中分离得到4个单体化合物，选取模式植物拟南芥对分离得到的单体化合物进行活性评价。结果表明，高浓度的4个化合物均降低拟南芥平均根长和平均鲜重，证明植物衰败凋落后，红景天内生菌代谢产物累积达到一定程度后，进而抑制其他植物的生长，从而提高自身的生态竞争能力，具备开发成除草剂的潜力。
关键词：红景天；内生菌；活性评价；次级代谢产物；除草剂
中图分类号：S 文献标识码：A 文章编号：0258-3283（2022）--
Metabolites of Fusarium sp. HJT-P-5 LIU Xiang-yu, TANG Xiao-yuan, ZHANG yu, HUANG Dan-ye, CHEN Yu, ZHENG Yu, QI Zhi-min, LU Xuan* (School of College of Life Science and Technology, Dalian University, China) Huaxue Shiji, 2022, 44(5), ～
Abstract: Using thin layer chromatography (TLC), normal/reverse phase column chromatography, gel column chromatography, and high performance liquid chromatography (HPLC) and other modern separation techniques to separate and purify HJT-P-5 metabolites. The structure was confirmed by various techniques such as nature, ultraviolet spectroscopy, nuclear magnetic resonance, mass spectrometry, etc. Four monomer compounds were isolated from the ethyl acetate extract of HJT-P-5, and the model plant Arabidopsis thaliana was selected to evaluate the activity of the isolated monomer compounds. The four compounds at high concentrations all reduced the average root length and average fresh weight of Arabidopsis thaliana. This work proved from the side that the endophytic microbial metabolites can promote plant seed germination and biomass accumulation; after plant decay, Rhodiola rosea after the accumulation of metabolites of bacteria in the days reaches a certain level, they can inhibit the growth of other plants, thereby improving their own ecological competitiveness. This work provides new ideas and basis for solving the problem of Rhodiola rosea resources.
Key words: Rhodiola; endophytes; biological activity; secondary metabolites; heibicide
引用本文：刘香余，唐小渊，章煜，等. 红景天内生微生物代谢产物化感作用研究[J]. 化学试剂，2022，44(5):674-678。
金属-有机框架在离子电容器中的应用与研究
林玮昆，史晓艳*，孙志鹏*
（广东工业大学 材料与能源学院，广东 广州 510006）
摘要：离子电容器作为一种新型储能器件，其兼具了超级电容器的大功率密度与电池的高能量密度的特性，在便携式电子产品和混合动力电动汽车等储能领域中有着广泛的应用前景。作为离子电容器的核心组件，其电极材料的性能直接决定了整个器件的性能。因此，为进一步推动离子电容器的发展，开发出性能优异的电极材料势在必行。其中，金属-有机框架材料（MOFs）由于其具有大比表面积、高孔隙率、孔道规则且可调、结构和功能可设计性强等特点，MOFs及其衍生物被广泛应用于储能领域。本文将重点综述MOFs及其衍生物作为离子电容器电极材料的应用研究，讨论MOFs在应用于离子电容器电极材料时的电化学特性及其改性策略，为设计合成新型性能优异的MOFs基离子电容器电极材料提供理论依据和参考。
关键词：离子电容器；金属-有机框架；电极材料；复合材料；电化学
中图分类号：TM53 文献标识码：A 文章编号：0258-3283（2022）--
Research Progress on Metal-Organic Framework for Hybrid Ion CapacitorsLIN Wei-kun1, SHI Xiao-yan*1, SUN Zhi-peng*1(School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006,China) , Huaxue Shiji，2022，44(5), ～
Abstract: As a hybrid energy storage device, hybrid ion capacitors (HICs) combine the advantages such as high power density of supercapacitors and high energy density of batteries. Therefore, they are believed to have a wide application prospect in portable electronic products, hybrid electric vehicles, and many other energy storage fields. As the core component of the HICs, the electrochemical properties of electrode materials have a direct impact on the performance of the whole device. Thus, it is an urgent task to develop excellent electrode materials for improving the overall performance of HICs. Metal-organic framework materials (MOFs) are coordination polymers with ordered pore structures formed by coordination bonds between organic ligands and metal ions or clusters. The features such as possessing large specific surface area, high porosity, regular and adjustable channels, and strong designability of MOFs and their derivatives make them desirable electrode materials for energy storage areas. More recently, they are studied as electrode materials of HICs, and excellent performance is obtained. This paper reviews the applications of MOFs and their derivatives as electrode materials for HICs.
Key words: hybrid ion capacitors; metal-organic frameworks; electrode materials; composite materials; electrochemistry
引用本文：林玮昆，史晓艳，孙志鹏. 金属-有机框架在离子电容器中的应用与研究 [J]. 化学试剂, 2022, 44(5):679-690。
基于锌-MOF衍生自掺杂氮多孔炭在超级电容器中的研究
黄思赟1*，李帅1，丁万1，王一2
(1. 贵州应用技术职业学院，贵州 福泉 550500；2. 贵州大学 大数据与信息工程院，贵州 贵阳 550025)
摘要：通过简单的水热法工艺制备锌-MOF并调节炭化温度得到自掺杂氮多孔炭ZBTC-T，通过X射线衍射(XRD)、X射线光电子能谱(XPS)、氮气吸附曲线、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对自掺杂氮多孔ZBTC-T的结构进行了表征，说明了微观结构和宏观性能之间的关系。自掺杂氮多孔炭ZBTC-T结合了金属和炭的优势以及保留锌-MOF中的氮原子从而展现出优异的电化学性能，自掺杂氮多孔炭ZBTC-850具有7.98%的高含氮量和735.42 cm2/g的比表面积，在电流密度为1.0 A/g，具有212.9 F/g的优异比电容，经过5000次充放电循环中保持其原始值85.04%，突出良好的倍率性能优势并在高性能方面表现出广阔的应用前景。
关键词：锌-MOF；自掺杂氮多孔炭；电化学性能；超级电容器
中国分类号：O646 文献标识码：A 文章编号：0258-3283（2022）--
Research on the Application of Zinc-based MOF Derived from Nitrogen-doped Porous Carbon in Supercapacitors HUANG Si-yun*1, LI Shuai 1, DING Wan 1, WANG Yi 2 (1. Guizhou Vocational Institute of Applied Technology, Fuquan 550500, China; 2. College of Big Data and Information Engineering, Guizhou University, GuiYang 550025, China), Huaxue Shiji, 2022, 44(5), ～
Abstract：Self-doped nitrogen porous carbon (ZBTC-T) with high surface areas were easily synthesized from a Zn-based metal-organic framework (MOF) by hydrothermal method. Structure and performance were carefully studied by XRD, XPS, BET surface area method, scanning electron microscopy and high resolution transmission electron microscopy. Self-doped nitrogen porous carbon ZBTC-T combines the advantages of metal and carbon and retains nitrogen atoms in zinc MOF, showing excellent electrochemical properties, the surface area and nitrogen content of the ZBTC-850 was found to be 735.42 cm2/g and 7.98%. The electrochemical properties of self-doped nitrogen porous carbon (ZBTC-T) were evaluated by using cyclic voltammetry and galvanostatic charge-discharge studies and the specific capacitance as high as 212.9 F/g in 6 mol/L KOH electrolyte. The system showed excellent cyclability and broad application prospects with a efficiency of 85.04% at a high current density of 1.0 A/g for 5000 cycles.
Key words: zinc-MOF; self-doped nitrogen porous carbon; electrochemical performance; supercapacitor
引用本文：黄思赟，李帅，丁万，等. 基于锌-MOF衍生自掺杂氮多孔炭在超级电容器中的研究[J]. 化学试剂，2022，44（5）：691-696。
ZIF-8@SA对Pb(II)的吸附性能和机理研究
付秋平，张海润，石登红，娄杰，莫昌琍，罗军，严伟*
（贵阳学院 化学与材料工程学院，贵州 贵阳 550005）
摘要：以海藻酸钠（Sodium Alginate, SA）为前驱体，将沸石咪唑骨架材料ZIF-8加入SA中，制备出ZIF-8@SA复合材料，并研究了ZIF-8@SA对Pb(II)的吸附性能。探讨了接触时间、Pb(II)初始浓度、吸附剂用量、温度和吸附-脱附次数等因素对ZIF-8@SA吸附Pb(II)效果的影响。对吸附过程进行了吸附等温线、吸附动力学和吸附热力学分析。结果表明，等温吸附过程符合Langmuir模型，303.15 K时，Langmuir模型拟合得到的理论最大吸附量为330.364 mg/g。吸附动力学过程符合拟二级动力学模型。热力学分析表明，ZIF-8@SA对Pb(II)的吸附过程是自发的、吸热的。ZIF-8@SA对Pb(II)具有很好的吸附效果。
关键词：ZIF-8；海藻酸钠；吸附；Pb(II)；水处理
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2022）
Adsorption Performance and Mechanism of ZIF-8@SA for Pb(II) FU Qiu-ping, ZHANG Hai-run, SHI Deng-hong, LOU Jie, MO Chang-li, LUO Jun, YAN Wei* (College of Chemistry and Materials Engineering, Guiyang University, Guiyang 550005, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: In this work, sodium alginate, SA, was used as the precursor, ZIF-8 was added into SA to prepare ZIF-8@SA composites, and the adsorption performance of ZIF-8@SA for Pb(II) was investigated. The influences of contact time, initial concentration of Pb(II), dosage of adsorbent, temperature and adsorption-desorption times on the adsorption of Pb(II) by ZIF-8 SA were discussed. The adsorption process was analyzed by adsorption isotherm, adsorption kinetics and adsorption thermodynamics. The isothermal adsorption process was in accordance with the Langmuir model, and the theoretical maximum adsorption amount was 330.364 mg/g at 303.15 K. The adsorption kinetic process conforms to the pseudo-second-order kinetic model. Thermodynamic analysis shows that the adsorption of Pb(II) by ZIF-8@SA is a spontaneous endothermic process. The adsorption efficiency of Pb(II) by ZIF-8@SA is very high.
Key words: ZIF-8; sodium alginate; adsorption; Pb(II); water treatment
引用本文：付秋平, 张海润, 石登红, 等. ZIF-8@SA对Pb(II)的吸附性能和机理研究[J]. 化学试剂, 2022, 44(5)：697-702.
碳纳米管表面分子印迹聚合物的制备及固相萃取韭菜中呋喃丹
张文骥*1，耿广军2
（1. 中国刑事警察学院 刑事科学技术学院 ，辽宁 沈阳 110035；2. 沈阳市公安局交警支队，辽宁 沈阳 110000）
摘要：以羧基化修饰的多壁碳纳米管为分散载体、丙烯酸（MAA）为功能单体、三羟甲基丙烷三甲基丙烯酸酯（TRIM）为交联剂，采用交联法在多壁碳纳米管表面合成对呋喃丹具有特异性识别的分子印迹聚合物（MWNT-MIPs），并用扫描电镜（SEM）、透射电镜（TEM）、傅里叶变换红外（FT-IR）光谱和热重分析（TGA）等对该印迹聚合物进行表征。结果表明，所制备的呋喃丹分子印迹聚合物可接枝于碳纳米管表面。聚合物的平衡吸附量可达113.5 μg/mg，吸附效果优于其非印迹材料和普通分子印迹材料，且对呋喃丹的吸附效果具有特异性。在1～0.05 mg/kg添加水平内，韭菜中呋喃丹的回收率为89.7%～93.2%，优于相同质量的MIP柱。相对标准偏差（RSD）在3.2%～4.8%之间，检出限（LOD）为0.15 mg/kg。采用呋喃丹MWNT-MIPs为填料的SPE法是测定韭菜中呋喃丹残留是一种很好的样品的前处理方法。
关键词：呋喃丹；多壁碳纳米管；分子印迹；韭菜；残留
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2022）--
Preparation of Surface Molecularly Imprinting Polymers on Multi-Walled Carbon Nanotubes and Solid Phase Extraction of Carbofuran from Leek ZHANG Wen-ji*1, GENG Guang-jun2 (1.School of Forensic Sciences, Criminal Investigation Police University of China, Shenyang 110035,China; 2.Traffic Police Detachment of Shenyang Public Security Bureau, Shenyang 110000, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: A novel molecularly imprinted polymers (MIPs) based on multi-walled carbon nanotubes (MWNTs) was synthesized using carbofuran as template, methacrylic acid (MAA) as functional monomer, and trimethylolpropane trimethacrylate (TRIM) as cross-liking agent, and was confirmed using SEM, TEM, FT-IR and TGA. The carbofuran MIPs have been successfully grafted onto the surface of MWNTs as a thin layer with high stability. The results of absorption capacity test showed that the synthesized MWNT-MIPs displayed good selective recognition to carbofuran with equilibrium adsorption of 113.5 μg/mg. The MWNT-MIPs showed superior absorption performance to MWNT-NIPs and MIPs, and specific recognition to carbofuran. The recovery of carbofuran was within the range from 89.7% to 93.2%, when carbofuran was added to the leeks sample at the level of 1～0.05 mg/kg, higher than the MIP column. The RSD was within 3.2%～4.8% and the LOD was 0.15 mg/kg. The method using carbofuran MWNT-MIPS as SPE filler is an applicable method for the determination of carbofuran residues in leeks
Key words: carbofuran; multi-walled carbon nanotubes; molecularly imprinting; leeks; residue
引用本文：张文骥，耿广军.碳纳米管表面分子印迹聚合物的制备及固相萃取韭菜中呋喃丹[J]. 化学试剂，2022，44( 5): 703-709。
CeO2改性水热炭对厌氧发酵体系H2S减量的研究
张凯1,2，韦秀丽*1，李平1，蒋滔1，刘科1
(1. 重庆市农业科学院 农业工程研究所，重庆 401329；2. 重庆大学 环境与生态学院，重庆 400045)
摘要：以人粪渣为原料，通过微波水热法在1.8 MPa条件下制备CeO2改性水热炭，研究改性水热炭对新鲜牛粪厌氧发酵过程中H2S和CH4产量的影响。结果表明，当CeO2掺杂量为30%的水热炭投加量为0.65 g/g牛粪固体时，H2S的产量较未添加复合物时降低了88.09%，而CH4的产生量并未发生明显变化，这可能与不同活性位点的相互竞争、正负电荷相互作用以及改性水热炭对硫的吸附、氧化和沉淀有关。由此可见，CeO2/水热炭能够在不影响CH4产量的情况下实现H2S减量，对缓解厌氧发酵系统管道腐蚀，维持厌氧发酵系统的稳定运行具有积极影响。
关键词：CeO2改性；微波水热炭；厌氧发酵；H2S减量
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2022）--
CeO2 Modified Hydrochar and Application in H2S Reduction of Anaerobic Fermentation System ZHANG Kai1,2, WEI Xiu-li*1, Li Ping1, JIANG Tao1, LIU Ke1 (1. Institute of Agricultural Engineering, Chongqing Academy of Agricultural Sciences, Chongqing 401329, China; 2. College of Environment and Ecology, Chongqing University, Chongqing 400045, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: CeO2 modified hydrochar was prepared from human fecal residue by microwave hydrothermal method at 1.8 MPa. The effect of modified hydrochar on the yield of H2S and CH4 in the anaerobic fermentation of fresh cow feces was investigated. When the dosage of hydrothermal carbon with 30% CeO2 doping is 0.65g/g cow dung solid, the yield of H2S decreased by 88.09% compared with that without complex, but the yield of CH4 did not change significantly. This may be related to the competition of different active sites, the interaction of positive and negative charges, and the adsorption, oxidation and precipitation of sulfur by modified hydrochar. CeO2/ hydrochar can reduce H2S without affecting CH4 production, which has a positive impact on alleviating pipeline corrosion of anaerobic fermentation system and maintaining stable operation of anaerobic fermentation system.
Key words: CeO2 modification; microwave hydrochar; anaerobic fermentation; H2S reduction
引用本文：张凯，韦秀丽，李平，等. CeO2改性水热炭对厌氧发酵体系H2S减量的研究[J]. 化学试剂，2022，44(5): 710-714。
一种BAPTA荧光探针的合成、光谱性能与识别机制
成昭，郑蕾，徐玥*，何昊
（西安医学院 药学院，陕西 西安 710021）
摘要：以苯乙烯类发色团苯并咪唑作为荧光基团、多羧酸受体作为识别基团，基于分子内电荷转移机制定向构筑探针结构，合成得到一种对Zn2+、Cu2+、Hg2+具有响应的荧光探针。定性及定量识别实验显示，探针对目标物Zn2+、Cu2+、Hg2+表现特征响应，探针与目标物1：1定量结合，荧光性能随pH、时间变化而相对稳定、线性关系良好，能够用于μmol/L浓度范围目标离子的定性检测和定量分析。此外，通过荧光、紫外等光谱学手段与核磁分析，初步阐明了探针对Cu2+、Hg2+和Zn2+的不同识别机制，对于探针结构优化与性能筛选研究提供了依据。
关键词：荧光探针；多羧酸受体；识别机制；荧光响应；合成
中图分类号：O622.6 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis, Spectral Properties and Recognition Mechanism of A BAPTA Fluorescent Probe CHENG Zhao, ZHENG Lei, XU Yue*, HE Hao (School of Pharmacy, Xi’an Medical University, Xi’an 710021, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: Based on the recognition mechanism of intramolecular charge transfer, a fluorescent probe for the detection of aqueous Cu2+/Hg2+/Zn2+ was synthesized by incorporating polycarboxylic receptor and benzimidazole as the fluorophore. Qualitative and quantitative analyses on probe-Cu2+/Hg2+/Zn2+ indicated the probe-target systems’ steady optical properties versus pH/time and good linear relationships. It could be applied to qualitative and quantitative detections of target ions at the concentration of μmol/L, giving off characteristic fluorescence responses and demonstrating 1:1 complexation stoichiometry after the recognition process. Furthermore, polycarboxylic-metal ions interactions were furtherly explored and possible combination mechanisms were revealed via FS, UV-Vis and 1HNMR, offering some evidence for the future research concerning the probe’s structural modification and properties optimization.
Key words: fluorescent probe; polycarboxylic receptor; recognition mechanism; fluorescent response; synthesis
引用本文：成昭，郑蕾，徐玥，等. 一种BAPTA荧光探针的合成、光谱性能与识别机制[J]. 化学试剂，2022，44（5）：715-723.
色酮-3-甲醛席夫碱新型荧光探针高选择性检测CN离子
赵俊，蔡小华*
(贵州民族大学 化学工程学院，贵州 贵阳 550025)
摘要：以色酮-3-甲醛和3-氨基吡唑为原料，通过一锅法缩合反应得到新型猝灭型席夫碱荧光探针Z。在V（DMSO）:V（H2O）= 3:2的溶液中，通过选择性、灵敏度、抗干扰、稳定性及pH影响等实验，证实该探针具有较好的稳定性，能够高灵敏度和选择性地识别CN-，最低检测限为1.9 × 10-8 mol/L。进一步荧光滴定实验和机理研究，推测探针Z对CN-的识别为加成反应型，结合比为1 : 1，结合常数为0.4 × 103 L/mol。探针Z具有较好实用性，能够方便地用于苦杏仁中CN-定性检测。
关键词：色酮-3-甲醛，3-氨基吡唑；席夫碱；荧光探针；CN-识别
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2022）
A Novel Fluorescent Probe Based on Chromone-3-formaldehyde Schiff Base for Highly Selective CN Ion Detection ZHAO Jun, CAI Xiao-hua* (School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: A novel fluorescence quenching Schiff base probe Z was synthesized by one pot condensation reaction of chromone-3-formaldehyde and 3-aminopyrazole. In a solution of V(DMSO):V(H2O) = 3:2, the selectivity, sensitivity, anti-interference, stability and pH effect experiments show that the probe has good stability. It can identify CN- with high sensitivity and selectivity, and its minimum detection limit is 1.9 × 10-8 mol/L. Further fluorescence titration experiment and mechanism study speculated that probe Z for CN- recognition goes through an addition reaction type, its binding ratio and binding constant is 1:1 and 0.4 × 103 L/mol, respectively. Probe Z has good practicability and can be easily used for the qualitative determination of CN- in bitter almond.
Key words: chromone-3-formaldehyde; 3-aminopyrazole; fluorescent probe; Schiff base; CN-detection
引用本文：赵俊, 蔡小华.色酮-3-甲醛席夫碱新型荧光探针高选择性检测CN离子[J]. 化学试剂, 2022, 44(5)：724-728.
FeOOH/MoS2的制备及其活化过一硫酸盐的性能
刘欣悦，吴丹，胡婉洁，赵焕新*，张志傲
（沈阳化工大学 环境与安全工程学院，辽宁 沈阳 110142）
摘要：通过化学沉淀-水热法制备了FeOOH/MoS2复合催化剂，以苯酚为目标污染物，探究其活化过一硫酸盐（PMS）的性能。SEM和XRD结果表明，FeOOH成功负载于MoS2纳米片上。FeOOH和MoS2掺杂比为1:3的复合催化剂活化PMS性能最好，在最佳反应条件下，反应20min后，苯酚降解率为96.60%，且该反应符合准一级动力学模型。自由基捕获实验证实，SO4•-是体系中主要的活性氧物种。另外，考察了实际水体和常见的无机阴离子对催化降解反应的影响，苯酚降解率在实际水体中略有下降，无机阴离子对苯酚降解的干扰从大到小依次为HCO3->H2PO4->NO3-，Cl-的影响可忽略不计。以上研究可为高活性PMS催化剂的设计提供新思路。
关键词：FeOOH/MoS2；过一硫酸盐；活化；苯酚；硫酸根自由基
中图分类号：X703.1 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis of FeOOH/MoS2 and its Activation Performance for Peroxymonosulfate LIU Xin-yue, Wu Dan, Hu Wan-jie, ZHAO Huan-xin*, ZHANG Zhi-ao (College of Environmental and Safety Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: FeOOH/MoS2 composite catalyst was synthesized by the chemical precipitation-hydrothermal method. The phenol was used as the target pollutant to explore its performance of activating peroxymonosulfate (PMS). FeOOH was successfully loaded on MoS2nanosheets. The composite catalyst with a ratio of 1:3 had the best activation performance for PMS. Under optimal reaction conditions, phenoldegradation rate reached 96.60% after 20 minutes. And this reaction was in accordance with the pseudo first-order kinetic model. Free radical capture experiments confirms that SO4•- is the major reactive oxygen species in FeOOH/MoS2/PMS system. In addition, the effect of actual water and common inorganic anions on the catalytic degradation reaction was investigated. The degradation rate of phenol is reduced in actual water. The interference of inorganic anions on phenol degradation is in the order of HCO3->H2PO4->NO3-, and the influence of Cl- is negligible. The above research can provide new ideas for the design of high-activity PMS catalysts.
Keywords: FeOOH/MoS2; peroxymonosulfate; activated; phenol; sulfate radical
引用本文：刘欣悦，吴丹，胡婉洁，等. FeOOH/MoS2的制备及其活化过一硫酸盐的性能[J]. 化学试剂，2022，44（5）：729-735.
室温下柱层析法同时提取刺玫果肉中维生素C和花色苷及其体外活性研究
崔遥，戴鹂莹，钟方丽，王晓林*，王若男
(吉林化工学院 化学与制药工程学院，吉林 吉林 132022)
摘要：探究柱层析法提取刺玫果肉中维生素C和花色苷的工艺条件及体外活性。以提取液中维生素C质量和花色苷吸光度为指标，通过对溶剂浓度、pH、酸度调节剂、吸涨率（MV）、浸泡平衡时间等因素的考察确定最佳提取工艺。通过测定刺玫果肉维生素C、花色苷对α-葡萄糖苷酶的抑制率及对1,1-二苯基-2-三硝基苯肼（DPPH•）的清除率，考察其体外降血糖、抗氧化活性。结果表明，在最佳提取条件下，刺玫果肉维生素C和花色苷的提取率均在95%以上，浸膏中维生素C的含量达到15%以上、花色苷的色价为8.07。刺玫果肉维生素C、花色苷提取物抑制α-葡萄糖苷酶的活性均强于阳性对照阿卡波糖；其清除DPPH•的IC50值分别为0.0031、0.0221 mg/mL。柱层析法可以同时提取刺玫果肉中的维生素C和花色苷，避免因单独地提取一种活性成分而造成原料和溶剂的浪费，研究结果为刺玫果开发提供了科学依据。
关键词：刺玫果肉；维生素C；花色苷；柱层析法；体外活性
中图分类号：TS201 文献标识码：A 文章编号：0258-3283（2022）--
Simultaneous Extraction of Vitamin C and Anthocyanins from the Fruit Pulp of Rosa davurica Pall. by Column Chromatography at Room Temperature and Their Activities in Vitro CUI Yao, DAI Li-ying, ZHONG Fang-li, WANG Xiao-lin*, WANG Ruo-nan (School of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: The extraction conditions and activities in vitro of vitamin C and anthocyanins from the fruit pulp of Rosa davurica Pall. by column chromatography were investigated. Using quality of vitamin C and absorbance of anthocyanin as indexes, the optimal extraction process was determined base on the examination of factors such as solvent concentration, pH, acidity regulator, swelling-up rate. Both the α-glucosidase inhibitory rate and the DPPH• clearance rate of vitamin C and anthocyanin were determined to investigate their hypoglycemic and antioxidant activities in vitro. Under the optimal extraction conditions, the extraction rates of vitamin C and anthocyanin in the fruit pulp of Rosa davurica Pall. were above 95%, the content of vitamin C in extract was above 15%, and the color value of anthocyanin was 8.07. The α-glucosidase inhibition activity of vitamin C and anthocyanin in extract of the fruit pulp of Rosa davurica Pall. was stronger than positive control acarbose. The IC50 of DPPH• were 0.0031 mg/mL and 0.0221 mg/mL, respectively. Column chromatography can simultaneously extract vitamin C and anthocyanins which may avoid the waste of raw materials and solvents caused by extracting one active ingredient at one time. The results provided scientific basis for the R&D of Rosa davurica Pall.
Key words: fruit pulp of Rosa davurica Pall.; Vitamin C; Anthocyanins; column chromatography; vitro activity
引用本文：崔遥，戴鹂莹，钟方丽，等. 室温下柱层析法同时提取刺玫果肉中维生素C和花色苷及其体外活性研究[J]. 化学试剂，2022，44(5): 736-743。
石墨炔碳材料在新型电池中的研究进展
何珺
(扬州市职业大学医学院，江苏 扬州 225009)
摘要：石墨炔（graphdiyne，GDY）因其卓越的二维平面全碳多孔特性，在多个领域具有巨大的应用潜力。特别是GDY独特的结构特点和物理本征特性如可扩展的面内孔洞、适宜的层间距、规则的纳米结构、优良的导电性及其良好的离子传输性能，使GDY成为很有应用前景的新型储能装置如钾离子电池、金属硫电池、金属空气电池等器件中的电极材料。重点对近年来石墨炔碳材料在新型金属离子电池，金属空气电池，金属硫电池以及双离子电池等电池储能器件相关的研究成果进行了综述。此外，还对GDY在新型电池储能器件中的发展趋势进行了综合评价，并对未来石墨炔类碳材料在能源存储领域的进一步发展进行了展望。
关键词：石墨炔；新型电池；碳材料；储能；研究进展
中图分类号：O625 文献标识码：A 文章编号：0258-3283(2022)--
Progress of Graphdiyne Carbon Materials in Novel Batteries HE Jun * (Medical College of Yangzhou Vocational University, Yangzhou 225009, China) Huaxue Shiji, 2021, 44(5), ~
Abstract: Graphdiyne (GDY) has exhibited great application potential in various fields for the excellent two-dimensional full carbon planar and porous characteristics. Particularly, the unique structural characteristics and physical intrinsic characteristics, such as expandable in-plane holes, appropriate layer spacing, regular nanostructures, excellent conductivity and good ion transport performance, endowing GDY and its derivates can be used as an electrode material in many novel energy storage devices with great application prospects, such as sodium ion battery, potassium ion battery, metal air battery, metal sulfur battery and so on. This work focused on the research results of GDY based carbon materials in battery energy storage devices including novel ion battery, metal air battery, metal sulfur battery and double ion battery in recent years. In addition, the development trend of GDY in new battery energy storage devices is comprehensively evaluated, and the further development of GDY based carbon materials in energy storage is prospected.
Key words：graphdiyne; novel batteries; carbon material; energy storage; research progress
引用本文：何珺. 石墨炔碳材料在新型电池中的研究进展[J]. 化学试剂, 2022, 44(5): 744-754。
QuEChERS-分散液液微萃取结合GC-MS测定土壤中的多环芳烃残留
王传咪1, 2，谭华东*2, 3，武春媛*2,3，翟金玲1
(1. 海南大学 热带作物学院，海南 海口 570228；2. 中国热带农业科学院 环境与植物保护研究所，海南 海口 571101；3. 国家农业环境儋州观测实验站，海南 儋州 571737)
摘要：建立了分散液液微萃取（DLLME）结合气相色谱串联质谱（GC-MS）测定土壤中痕量多环芳烃（PAHs）新方法。采用QuEChERS（Quick、Easy、Cheap、Effective，Rugged和Safe）和DLLME对土壤中的15种PAHs进行了提取与富集，考察提取溶剂、净化剂用量、萃取溶剂种类及用量对提取效果的影响。结果表明，10 g土壤样品以20 mL V(甲醇)∶V(二氯甲烷)=1∶1混合溶剂为提取溶剂、150 mg W(PSA)∶W(C18)=4∶1吸附剂净化，2 mL上清液加100 μL甲苯作为分散、萃取剂时最佳。所建方法在6～500 μg/L范围内呈良好的线性关系，且R2≥0.9995；检测限（LODs）和定量限（LODs）分别为0.1～1.8和0.3～6.1 μg/kg。在1、5、25 μg/kg加标水平下，PAHs回收率为70.2%～108.5%，相对标准偏差（RSDs）为1.0%～11.6%。该方法简便、快速、易于提取和富集，适用于包括澄迈县在内土壤中PAHs灵敏测定。
关键词：多环芳烃；QuEChERS；分散液液微萃取；气相色谱串联质谱；土壤
中图分类号：O656.31 文献标识码：A 文章编号：0258-3283（2022）--
Determination of Polycyclic Aromatic Hydrocarbons in Soil by QuEChERS-dispersive Liquid-liquid Microextraction Combined with GC-MS WANG Chuan-mi1,2, TAN Hua-dong*2,3, WU Chun-yuan*2,3, ZHAI Jin-ling1 (1. College of Tropical Crops, Hainan University, Haikou 570228, China; 2. Institute of Environment and Plant Protection, Chinese Academy of Tropical Agricultural Sciences, Haikou 571101, China; 3. National Danzhou Observation and Experiment Station for Agricultural Environment, Danzhou 571737, Hainan, China), Huaxue Shiji, 2022, 44(5)，～
Abstract: A new method for the determination of trace polycyclic aromatic hydrocarbons (PAHs) in soil by dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography-tandem mass spectrometry (GC-MS) was established. Fifteen PAHs in soil were extracted and enriched by QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and DLLME. The effects of extraction solvent, decontaminant dosage, type and dosage of extraction solvent on extraction efficiency were investigated. The 10g soil samples were extracted with 20 mL V(methanol)∶V(dichloromethane)=1∶1 mixed solvent, purified with 150 mg W(PSA)∶W(C18)=4∶1 adsorbent. When 2 mL supernatant was added with 100 μL toluene as dispersing and extracting agent, the effect was the optimal. There was the good linearity for the established method in the range of 6～500 μ g/L, and R2≥0.9995; the detection limits (LODs) and quantitative limits (LODs) were 0.1～1.8 and 0.3～6.1μg/kg, respectively. The recoveries of PAHs ranged from 70.2% to 108.5% and the relative standard deviations (RSDs) ranged from 1.0% to 11.6% at the level of 1, 5 and 25μg/kg. The method is simple, rapid, easy to extract and enrich, it is suitable for sensitive determination of PAHs in soil including Chengmai County.
Keywords: Polycyclic aromatic hydrocarbons; QuEChERS; dispersive liquid-liquid microextraction; gas chromatography-mass spectrometry; soil
引用本文：王传咪，谭华东，武春媛，等. QuEChERS-分散液液微萃取结合GC-MS测定土壤中的多环芳烃残留[J]. 化学试剂，2022，44（5）：755-761。
HPLC-DAD-ELSD联用法同时测定华佗救心丸中13种成分的含量
朱雅琴1, 2, 3，赵冰4，祝宇龙1，闫富龙1，张云静1, 2, 3，吴德玲1, 2, 3，彭灿1, 2, 3，吴欢*1, 2, 3
(1. 安徽中医药大学 药学院，安徽 合肥230012；2. 药物制剂技术与应用安徽省重点实验室，安徽 合肥230012；3. 中药复方安徽省重点实验室，安徽 合肥230012；4. 华佗国药股份有限公司，安徽 亳州236800)
摘要：建立一种快速的HPLC-DAD-ELSD联用方法，同时测定华佗救心丸中皂苷类、蟾蜍甾烯类以及胆酸类13种成分的含量。采用HPLC-DAD-ELSD联用，色谱柱Caprisil C18( 250 mm×4.6 mm，5 μm)，柱温35 ℃，并以水和乙腈作为流动相进行梯度洗脱。紫外检测波长为296 nm和203nm，ELSD检测参数：漂移管温度60 ℃、气体压力241 kPa，检测时间为18 min。华佗救心丸中的13种分析成分线性r值均大于0.99，线性关系良好(r ≥ 0.99)，平均加样回收率在96.31%～103.30%范围内，RSD值为1.42%～2.75%。该方法更快速全面的同时测定华佗救心丸中13种分析成分含量，专属性强、精确度高，可为华佗救心丸质量控制和进一步的品质提升提供参考。
关键词：华佗救心丸；高效液相色谱法-全波长检测-蒸发光散射器联用；蟾蜍甾烯类；胆酸类；皂苷类
中图分类号:R284.1 文献标识码：A 文章编号：0258-3283（2022）--
Simultaneous Determination of 13 Components in HuatuoJiuxin Pills by HPLC-DAD-ELSD
ZHU Ya-qin1, 2, 3, ZHAO Bing4, ZHU Yu-long1, YAN Fu-long1, ZHANG Yun-jing1, 2, 3, WU De-ling 1, 2, 3, PENG Can 1, 2, 3, WU Huan* 1, 2, 3(1. School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012; 2. Anhui Province Key Laboratory of Pharmaceutical Preparation Technology and Application, Hefei 230012; 3 Anhui Key Laboratory of Chinese Medicinal Formula., Hefei 230012; 4. Huatuo Medicines Co., Ltd, Bozhou 236800), HuaxueShiji, 2022, 44(5), ～
Abstract: The HPLC-DAD-ELSD method was established to simultaneously determine the contents of 13 saponins, bufadienolides and bile acids in HuatuoJiuxin Pills. The established HPLC-DAD-ELSD method was adopted, in which a Caprisil C18 column (250 mm×4.6 mm, 5 μm) was used, the column temperature was 35 ℃, and water-acetonitrile was used as the mobile phase for gradient elution.In addition, the wavelength of UV detection was 296 nm and 203 nm. The temperature of the drift tube in the detection parameters of the evaporative light scattering detector (ELSD) was 60 ℃, the gas pressure was 241 kPa and the gain was 100. Finally, the total detection time was 18 min. Results: The linear r values of the 13 analytical components in HuatuoJiuxin Pills were all greater than 0.99, so that the linear relationship was well (r ≥ 0.99). The average recovery rate of sample addition was in the range of 96.31% to 103.30%, and the RSD was 1.42% to 2.75%. Conclusion: This method can simultaneously determine the content of 13 analytical components in Huatuo Jiuxin Pills more quickly and comprehensively, with strong specificity and high accuracy, which can provide references for the quality control and further quality improvement of HuatuoJiuxin Pills.
Key words:HuatuoJiuxin Pills; HPLC-DAD-ELSD; bufadienolides; cholic acids; saponins
引用本文：朱雅琴，赵冰。祝宇龙，等. HPLC-DAD-ELSD联用法同时测定华佗救心丸中13种成分的含量[J]. 化学试剂，2022，44(4): 762-766。
乙酰苯胺元素含量标准物质的研制
王海峰*，李佳，孙国华
（中国计量科学研究院，北京 100029）
摘要：有机元素分析仪用于测定有机化合物、煤炭等能源产品以及食品的碳、氢和氮元素含量，仪器需要有机纯物质元素含量标准物质来校准。研制了乙酰苯胺元素含量标准物质，编号为GBW 06203。使用区域熔融装置提纯乙酰苯胺原料，然后分装制成标物候选物。采用气相色谱—质谱法和差示扫描量热法测定其有机杂质含量，采用卡尔·费休库仑法测量其水分，采用灼烧残渣称重法测量其无机杂质含量，然后根据质量平衡原理计算主组分的含量。然后根据主组分和杂质的含量及其分子中待测元素的含量，计算得到标准物质的碳、氢和氮元素含量标准值。标准值溯源至纯物质的质量、温度和原子量上。碳、氢和氮元素含量的标准值分别为71.087%、6.712%和10.363%，不确定度（U，k=2）分别为0.003%、0.002%和0.001%。标准物质的准确度达到了国际先进的水平。标准物质可用于杜马斯法等有机元素分析仪的校准，也可用于油品氮含量标准物质的配制，保障有机元素含量的量值准确。
关键词：碳；氢；氮；元素分析；标准物质
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2022）--
Certified Reference Material of Acetanilide for Elemental Content WANG Hai-feng, LI Jia, SUN Guo-hua (National institute of metrology of China, Beijing 100029, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: Organic elemental analyzer was used to determine the content of carbon, hydrogen, and nitrogen of organic compounds, energy products, such as coal, and food. The analyzer should be calibrated by using the certified reference material (CRM) of organic pure substance for elemental content. The CRM of acetanilide for elemental content labelled as GBW 06203 was developed. The raw acetanilide was purified by zone melting and then packaged as candidates of CRM. Gas chromatography – mass spectrometry (GC-MS) and differential scanning calorimetry (DSC) were used to determine the organic impurities content. Karl Fischer coulometric titration and the residue on ignition was used to determine the water content and inorganic impurities content, respectively. Then, the main component content was calculated based on the mass balance theory. The certified value of carbon, hydrogen and nitrogen content was calculated by using the individual component content and the aimed elemental content in its molecule. The certified value is traceable to the mass of pure substance, temperature, and atomic weight. The certified content of carbon, hydrogen, and nitrogen was 71.087%, 6.712%, and 10.363%, respectively, with the uncertainty (U, k=2) of 0.003%, 0.002%, and 0.001%, respectively. The accuracy of CRM is on the advanced world level. The CRM can be used to calibrate the Dumas type organic elemental analyzer and prepare the CRM of petroleum for nitrogen content, which is helpful for the accuracy of the organic elemental content.
Keyword: carbon; hydrogen; nitrogen; elemental analysis; certified reference material
引用本文：王海峰，李佳，孙国华. 乙酰苯胺元素含量标准物质的研制[J]. 化学试剂，2022，44（5）：767-772
稳定同位素标记丹磺酰氯-D6的合成方法研究
刘家兴1，汪满江措1，张国宁2，臧清策1，王玉成2，张瑞萍*1
(1. 中国医学科学院 北京协和医学院药物研究所 天然药物活性物质与功能国家重点实验室，北京 100050；2. 中国医学科学院 北京协和医学院医药生物技术研究所，北京 100050)
摘要：本研究旨在报道一种原料易得、毒性小、产率高的丹磺酰氯-D6 (Dansyl chloride-D6，DnsCl-D6)的化学合成方法。以碘甲烷-D3为同位素标记原料，5-氨基-1-萘磺酸、三氯氧磷和五氯化磷为反应原料，经两步取代反应制备得到丹磺酰氯-D6。以投入的碘甲烷-D3的物质的量计算，丹磺酰氯-D6总产率为82%，经高分辨质谱测定丹磺酰氯-D6的同位素丰度为98.6 atom%D。该方法可以为稳定同位素标记衍生化试剂的合成提供参考。
关键词：稳定同位素标记；衍生化试剂；丹磺酰氯；碘甲烷-D3；化学合成
中图分类号：TQ421.6 文献标识码：A 文章编号：0258-3283（2022）
Synthesis of Stable Isotope Labelled Dansyl Chloride-D6 LIU Jia-xing1, WANG Man-jiang-cuo1, ZHANG Guo-ning2, ZANG Qing-ce1, WANG Yu-cheng2, ZHANG Rui-ping*1 (1. State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China; 2. Institute of Medical Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China), Huaxue Shiji, 2022, 44(5), 00 ~ 00
Abstract: A method with low cost, low toxicity and high yield for dansyl chloride-D6 was established. The synthesis process consisted of two-stage substitution reaction with 5-amino-1-naphthalenesulfonic acid and iodomethane-D3 as precursors while dansyl chloride-D6 (DnsCl-D6) as product. The yield of DnsCl-D6 was 82% based on the consumed iodomethane-D3. The targeted product was confirmed by HR-MS. Its isotopic abundance was 98.6 atom%D. This method can be used for stable isotope labeling derivation reagent synthesis.
Key words: stable isotope labeling; derivation reagent; dansyl chloride; iodomethane-D3; chemical synthesis
引用本文：刘家兴，汪满江措，张国宁，等. 稳定同位素标记丹磺酰氯-D6的合成方法研究[J]. 化学试剂, 2022, 44(5): 773-776。
苯甲酸催化的三组分[3+2]环加成反应合成六氢吡咯并[2,1-a]异喹啉化合物
蒋少栋，江多镀，马晓明，刘建武，严生虎，张跃*
（常州大学 药学院，江苏 常州 213164）
摘要：为发展六氢吡咯并[2,1-a]异喹啉化合物的合成方法，以苯甲酸为催化剂，4Å分子筛为添加剂，催化芳香醛、1,2,3,4-四氢异喹啉和N-取代马来酰亚胺经串联的醛胺缩合和[3+2]环加成反应，合成了一系列六氢吡咯并[2,1-a]异喹啉化合物。主要考察了催化剂、溶剂、反应时间及反应温度对产物产率的影响，最终确定在60 ℃下，以10 mL超干甲苯为溶剂，20 mol%苯甲酸为催化剂，加入250 mg分子筛，以n(芳香醛)∶n(1,2,3,4-四氢异喹啉)∶n(N-取代马来酰亚胺) = 1∶1.3∶1.2反应2 h。产物结构经1H NMR、13C NMR和HRMS等手段表征，产物4f空间立体结构由单晶X射线衍射确定。
关键词：苯甲酸；1,2,3,4-四氢异喹啉；[3+2]环加成反应；六氢吡咯并[2,1-a]异喹啉
中图分类号：TQ20 文献标识码：A 文章编号：0258-3283（2022）
Benzoic Acid Catalyzed Three-component [3+2] Cycloaddition for the Synthesis of Hexahydroyrrolo[2,1-a]isoquinoline Compounds JIANG Shao-dong, JIANG Duo-du, MA Xiao-ming, LIU Jian-wu, YAN Sheng-hu, ZHANG Yue* (School of Pharmacy, Changzhou University, Changzhou 213164, China), Huaxue Shiji, 2022, 44(5)
Abstract: A novel protocol for the synthesis of hexahydroyrrolo[2,1-a]isoquinoline compounds was developed, using benzoic acid as catalyst via three-component reaction with aromatic aldehydes, 1,2,3,4-tetrahydroisoquinoline and N-substituted maleimides through sequential condensation and [3+2] cycloaddition with 4Å molecular sieves as additives. The effects of catalyst, solvent, reaction time and reaction temperature on the yields of the products were investigated. The optimized conditions for the one-pot synthesis were found to conduct the reaction with aromatic aldehydes, 1,2,3,4-tetrahydroisoquinoline and N-substituted maleimides (mol ratio 1:1.3:1.2) using benzoic acid (20 mol%) as catalyst, in the presence of 250 mg 4Å molecular sieves in 10 mL ultra-dry toluene at 60 °C for 2 h. The products were confirmed by 1H NMR, 13C NMR, HRMS, the stereochemistry of compound 4f was confirmed by single crystal X-ray diffraction.
Key words: benzoic acid; 1,2,3,4-tetrahydroisoquinoline; [3+2] cycloaddition; hexahydropyrrolo[2,1-a]isoquinoline
引用本文：蒋少栋, 江多镀, 马晓明, 等.苯甲酸催化的三组分[3+2]环加成反应合成六氢吡咯并[2,1-a]异喹啉化合物[J].化学试剂, 2022, 44(5)：777-785。
Fries重排合成3-乙酰基-2-羟基苯甲醛肟
王琳a，侯家宁a，卢玺盟a，田宇a，常远a，耿佳鑫a，冯玉玲a,b，孙京国*a,b
（河北师范大学a. 化学与材料科学学院；b. 化学国家级实验教学示范中心 河北 石家庄 050024）
摘要：邻羟基苯乙酮衍生物是合成查尔酮、黄酮、萘醌、农药等生物活性化合物的重要中间体，采用传统的Lewis酸催化缺乏竞争力并存在环境压力，选用PPA做Fries重排反应的催化剂及溶剂，设计了（1）水杨醛经酯化、肟化、Fries重排和（2）水杨醛经肟化、酯化、Fries重排2条反应路线，实验结果表明，路线（2）较好，水杨醛在氧化锌催化下与羟胺反应生成水杨醛肟，再经乙酸酐与酚羟基和肟羟基反应同时引入乙酰基，两步产率均超过90.0%。再以80%PPA为催化剂，在150℃条件下反应2h，完成酚酯的选择性Fries重排合成新化合物3-乙酰基-2-羟基苯甲醛肟（AHbdO），产率22.4%，HPLC纯度99.33%。化合物分子结构经1H NMR、13C NMR、TLC-MS确证，研究为此类化合物反应提供了一种新的高效绿色合成方法。
关键词：肟化；酯化；Fries重排；合成
中图分类号：O626.6 文献标识码：A 文章编号：0258-3283（2022）-
Synthesis of 3-Acetyl-2-hydroxybenzaldehyde Oxime by Fries Rearrangement WANG Lina, HOU Jia-ninga, LU Xi-menga, TIAN yua, CHANG yuana, GENG jia-xina, FENG yu-linga,b , SUN Jing-guo*a,b (1. School of Chemistry and Materials Science; 2. National Experimental Teaching Demonstration Center of Chemistry (Hebei Normal University), Hebei Normal University, Shijiazhuang 050024, China), Huaxue Shiji, 2022, 44(5), ～
Abstract: O-Hydroxyacetophenone derivatives are important intermediates for the synthesis of bioactive compounds such as chalcone, flavonoids, naphthoquinones, pesticides, etc. Lack of competitiveness and environmental pressures with traditional Lewis acid catalysis. In this work, PPA was used as the catalyst and solvent for the Fries rearrangement reaction, and two reaction routes were designed: (1) Salicylaldehyde via esterification, oximation, Fries rearrangement and (2) Salicylaldehyde via oximation, esterification, and Fries rearrangement. The results showed that route (2) was preferable. Salicylaldehyde reacted with hydroxylamine under the catalysis of zinc oxide to form salicylaldoxime, which was then reacted with phenol hydroxyl and oxime hydroxyl by acetic anhydride to simultaneously introduce acetyl group. The yields of the two steps were more than 90.0%. Then 80%PPA was used as the catalyst to react at 150℃ for 2h to complete the selective Fries rearrangement of phenol ester to synthesize the new compound 3- acetyl -2- hydroxybenzaldehyde oxime (AHbdO) with the yield of 22.4% and the purity of 99.33% by HPLC. The structure was confirmed by 1H NMR, 13C NMR and TLC-MS. This work provides a new efficient and green synthesis method for the reaction of these compounds.
Key words: Oximation; Esterification; Fries rearrangement; Synthesis
引用本文：王琳，侯家宁，卢玺盟，等.Fries重排合成3-乙酰基-2-羟基苯甲醛肟[J]. 化学试剂，2022，44（5）：786-790.
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