可见光催化构建碳氮键的研究进展
范玉兰，蔡刘欢，郭维*
（赣南师范大学 化学化工学院，江西赣州341000）
摘要：可见光是一种清洁的可再生能源，利用可见光能代替传统的热能进行化学转化具有绿色、高效优点。碳氮键是广泛存在于多种生物活性分子和药物分子中的重要化学键，光催化构筑碳氮键在有机和药物化学领域中具有重要研究意义。近年来光催化形成碳氮键研究得到了快速发展，许多新颖的合成方法不断涌现。综述了可见光催化构建C(sp2)－N键和C(sp3)－N键的研究新进展，并对部分反应机理进行了评述。
关键词：光催化反应；碳氮键形成；机理；研究进展
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2022）--
Recent Advances in Visible-Light Catalyzed Formation of Carbon-Nitrogen Bonds FAN Yu-lan, CAI Liu-huan, GUO Wei* (School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: Visible light is an efficient, clean, and renewable energy. Compared with traditional thermal conditions, visible light catalyzed chemical transformation shave huge advantages of green and high efficiency. Carbon-nitrogen bonds are important chemical bonds that exist in bioactive and medicinal molecules. Construction of carbon-nitrogen bonds is significant in organic and pharmaceuticalchemistry. Recently, various novel visible-light catalyzed synthetic carbon-nitrogen bonds formation methods have been developed rapidly. In this review, we have focused on the recent research on visible light catalyzed C(sp2)－N and C(sp3)－N bonds formation. Some possible reaction mechanisms are also reviewed.
Keywords: visible-light catalyzed reaction; carbon-nitrogen bond formation; mechanism; research progress
引用本文：范玉兰，蔡刘欢，郭维. 可见光催化构建碳氮键的研究进展[J]. 化学试剂，2022, 44(3):317-327.
pH和温度响应型介孔SiO2杂化材料的药物控释研究进展
徐小欢，孙继红*
（北京工业大学 环境化工系 绿色催化与分离北京市重点实验室，北京 100124）
摘要：基于介孔SiO2所制备的智能响应型有机-无机杂化纳米复合材料由于其优异的物化性能、可控的结构特征及其良好的生物相容性，近年来在药物缓控释领域中备受关注。针对丙烯酰胺共聚丙烯酸聚合物P(NIPAM-co-AA)和介孔SiO2纳米球，分析和归纳了具有pH和温度双重响应性能的介孔SiO2杂化材料的合成策略、物化性能及其构-效关系，重点阐述了刺激响应机制研究进展及其对药物装载和缓控释放性能的发展动态，同时对现存问题和应用前景进行了评述。为构建新型智能响应型纳米多孔复合材料具有一定的学术价值。
关键词：有机-无机杂化材料；介孔SiO2纳米颗粒；药物控释；智能响应性
中图分类号：TB33; TQ460.4 文献标识码：A 文章编号：0258-3283（2022）
Research Progress on pH- and Temperature-responsive Hybrid Materials Based on the Mesoporous Silicas for Controlled Drug Delivery XU Xiao-huan, SUN Ji-hong* (Beijing Key Laboratory of Green Catalysis and Separation, Department of Environmental and Chemical Engineering, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2022, 44(3)
Abstract: In recent years, the intelligent responsive organic-inorganic hybrid nanocomposites based on mesoporous silicas have attracted much attention in the sustained and controlled drug delivery fields due to their excellent physical and chemical properties, controllable structural characteristics and good biocompatibility. Focused on the copolymer of acrylamide and acrylic acid P(NIPAM-co-AA) and mesoporous SiO2 nanospheres, this review mainly summarized and analyzed the synthesis strategies, physic-chemical properties and structure-performance relationships of the dual pH- and temperature-sensitive mesoporous silica hybrid nanocomposites, in which the stimulus-responsive mechanism research progress and the development of drug loading, sustained and controlled drug-released properties were emphasized, and the present challenges and the developed prospects were also addressed. This contribution provided a certain academic basis for constructing novel intelligent responsive nanoporous composites.
Key words: organic-inorganic hybrid materials; mesoporous silica nanoparticles; controlled drug delivery systems; intelligent responsiveness
引用本文：徐小欢，孙继红. pH和温度响应型介孔SiO2杂化材料的药物控释研究进展[J]. 化学试剂, 2022, 44(3): 328-338。
基于TCF的荧光探针的设计与应用研究进展
李朝政，陈骏，杨金华，周莉佳，裴叔宸*
(重庆科技学院 工业发酵微生物重庆市重点实验室，重庆 401331)
摘要：2-二氰基亚甲基-3-氰基-4,5,5-三甲基-2,5-二氢呋喃（TCF）是一个强电子供体，广泛应用于光学材料和分子荧光探针。同时，TCF结构简单，活性位点少，能通过简单的反应与苯基偶联。同时，基于TCF的分子探针具有大的斯托克斯位移和较高的量子产率。根据TCF荧光探针的检测对象，将其分为阴阳离子、生物分子和其它分子，并从分子结构、性能、机理出发，综述了5年来国内外基于TCF的荧光探针在设计和检测方面的新进展。最后提出了构建新型TCF类分子荧光探针面临的挑战和发展方向。
关键词：TCF；荧光探针；响应机理；设计；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 in Design and Application of TCF-Based Fluorescent Probes LI Chao-zheng, CHEN Jun, YANG Jin-hua, ZHOU Li-jia, PEI Shu-chen* (Chongqing Key Laboratory of Industrial Fermentation Microorganism, Chongqing University of Science and Technology, Chongqing 401331, China), Huaxue Shiji, 2022, 44(3),
Abstract: 2-Dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) is a strong electron donor，which is widely used in optical materials and molecular fluorescence probes. At the same time，TCF has a simple structure, few active sites，and can be coupled to phenyl groups through a simple reaction. TCF-based molecular probes have a large Stokes shift and a high quantum yield. According to the detection object of TCF fluorescent probe, it is divided into anion and cation, biomolecule and other molecules, and starting from the molecular structure, performance and mechanism, the design and detection of TCF-based fluorescent probes at home and abroad in five years are reviewed. Finally, the challenges and development directions for constructing new TCF molecular fluorescent probes are proposed.
Key words: TCF; fluorescent probes; response mechanism; design; research progress
引用本文：李朝政，陈骏，杨金华，等.基于2-二氰基亚甲基-3-氰基-4,5,5-三甲基-2,5-二氢呋喃的荧光探针的设计与应用研究进展[J].化学试剂，2022，44（3）：339-348.
sp2-碳共价有机框架材料的研究进展
黄小莹1，张黎君1，孙淑香*1，徐元清*1,2
(1. 河南应用技术职业学院 化学工程学院，河南 郑州 450042；2. 河南大学 化学化工学院，河南 开封 475004）
摘要：共价有机框架材料是一类晶态高分子材料，通过定向的拓扑聚合将有机结构单元聚合为高度有序和延伸的二维或者三维框架材料。近5年来，合成化学的进展大大地促进了共价有机框架材料的结构设计与合成，实现了完全共轭的具有大π体系的sp2-碳共价有机框架材料的构筑。主要介绍了近年来通过不同的设计原则和合成策略来构筑基于sp2-碳共价有机框架材料的研究进展，展示了该类材料的性质、功能以及结构多样性，并就关键的科学问题和未来的发展方向进行了展望。
关键词：共价有机框架材料；共价有机框架；sp2杂化；π-共轭体系；合成方法
中图分类号：O627.32 文献标识码：A 文章编号：0258-3283(2022)--
Research Progress of sp2-C Covalent Organic Frameworks HUANG Xiao-ying1, ZHANG Li-jun1, SUN Shu-xiang*2, XU Yuan-qing*1,2 (1. School of Chemical Engineering, Henan Technical Institute, Zhengzhou 450042, China；2. Henan University, School of Chemistry and Chemical Engineering, Kaifeng 475004, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: Covalent organic frameworks (COFs) are a class of crystalline polymer material that integrate organic units into 2D or 3D skeletons to achieve ordered yet extended structures via topology-directed polymerization. Over past five years, recent progress in synthetic chemistry has greatly raised the ability of design and synthesis for the frameworks to attain fully π-conjugated all sp2-carbon-linked covalent organic frameworks. This review will summarize the chemistry to explore sp2 carbon frameworks by different design principles and synthetic strategies to demonstrate the properties, functions and structural diversity. The key scientific issues and prospects for the future of this field are also prognosticated.
Key words: covalent organic frameworks; sp2 hybridization; π-conjugate; synthetic method
引用本文：黄小莹，张黎君，孙淑香，等. 二维sp2-碳共价有机框架材料的研究进展[J]. 化学试剂，2022，44(3)：349-363.
托盘根中总多酚提取工艺及抗氧化活性研究
赵楠*，张春楠，柴军红，何婷婷
（牡丹江师范学院 生命科学与技术学院，黑龙江 牡丹江 157011）
摘要：以悬钩子属植物托盘根为研究对象，采用超声辅助乙醇提取托盘根中总多酚。通过对乙醇浓度、料液比、超声时间、超声温度4种影响因素进行考察，在单因素实验结果基础上，采用正交试验优化其最佳提取工艺，并对托盘根总多酚的抗氧化能力进行评价。结果表明，托盘活性成分的最佳提取工艺为乙醇浓度60%、超声温度80 ℃、超声时间50 min、料液比1:40 g/mL。在此条件下托盘根总多酚提取率为26.16%。托盘根总多酚清除DPPH自由基及羟基自由基的IC50值分别为0.0069和0.346 mg/mL，表明托盘根总多酚具有一定的抗氧化能力。
关键词：托盘；总多酚；超声提取；正交设计；抗氧化
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2022）
Extraction and Antioxidant Activity of Total Polyphenols from Rubus Crataegifolius Bunge Roots ZHAO Nan*, ZHANG Chun-nan, CHAI Jun-hong, HE Ting-ting (College of Life Science and Technology, Mudanjiang Normal University, Mudanjiang 157011, China), Huaxue Shiji, 2022, 44(3)
Abstract: To investigate the total polyphenols from Rubus crataegifolius Bunge roots, ultrasonic-assisted ethanol extraction was used. By investigating four influencing factors (including ethanol concentration, ultrasonic temperature and time, and solid-liquid ratio), and using orthogonal experimental design on the basis of single factor experiments, the extraction was optimized, and the antioxidant activity was evaluated. The results suggested the following optimum conditions: ethanol concentration 60%, solid-liquid ratio 1:40 g/mL, ultrasonic 50 min at 80 ℃. Under this condition, the extraction rate of total polyphenols reached 26.16%. The IC50 of total polyphenols from Rubus crataegifolius Bunge against DPPH and hydroxyl anion free radicals were 0.0069 and 0.346 mg/mL, respectively, which illustrated good antioxidant activity of the total polyphenols.
Key words: Rubus crataegifolius Bunge; total polyphenols; ultrasonic extraction; orthogonal design; antioxidant
引用本文：赵楠，张春楠，柴军红，等. 托盘根中总多酚提取工艺及抗氧化活性研究[J]. 化学试剂, 2022: 44(3), 364-368。
朝鲜淫羊藿中性多糖与酸性多糖的理化特征及抗氧化活性的比较
李波1，李珺铭1，刘富饶1，王哲*1，焦丽丽*2
(长春中医药大学a. 药学院，b. 吉林省人参科学研究院，吉林 长春 130117)
摘要：对朝鲜淫羊藿多糖(EFPC)进行分离纯化，并对其理化性质及抗氧化活性进行研究。采用水提醇沉法获得朝鲜淫羊藿粗多糖，通过除蛋白，经DEAE-52纤维素色谱柱(0.5 mol/L NaCl溶液洗脱)，得到中性多糖(EFPN)和酸性多糖(EFPA)。EFPC、EFPN和EFPA糖含量分别为79.59%、87.14%和91.43%，蛋白含量都小于1%，EFPN和EFPA的分子量分别为1.5×104～1.4×105 Da和2.5×104～9.8×104 Da；EFPN由甘露糖、鼠李糖、阿拉伯糖、半乳糖和葡萄糖组成，其物质的量比为0.6∶1.0∶1.4∶1.6∶1.7，EFPA中由甘露糖，葡萄糖，半乳糖，葡萄糖醛酸和阿拉伯糖组成，其物质的量比为1.7∶7.4∶1.4∶1.8∶1.0；EFPN在清除自由基、金属离子螯合和还原能力方面IC50值均高于EFPA，EFPN组不同程度的提高了小鼠血清与肝脏中酶活性(P<0.01或P<0.05)，降低了MDA(P<0.01或P<0.05)的水平。EFPN抗氧化活性较好，是天然抗氧化剂的良好来源，可进一步开发利用。
关键词：朝鲜淫羊藿；中性多糖；酸性多糖；理化性质；抗氧化活性
中图分类号：R965 文献标识码：A 文章编号：0258-3283（2022）--
Comparison of physicochemical properties and antioxidant activities neutral and acidic polysaccharides from Epimedium koreanum Nakai LI Bo1, LI Jun-ming1, LIU Fu-rao1, WANG Zhe*1, JIAO Li-li*2 (1a. College of Pharmacy, 1b. Jilin Ginseng Academy, Changchun University of Chinese Medicine, Changchun 130117, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: In this study, to purify polysaccharides from the Epimedium koreanum Nakai (EFPC) and then fractionated into two polysaccharides (EFPN and EFPA) by DEAE-52 with 0.5 mol/L NaCl. Then investigated for their general physicochemical properties, monosaccharide composition, molecular and their antioxidant activities. The total sugar contents of EFPC, EFPN and EFPA were 79.59%, 87.14% and 91.43%, respectively. EFPN is composed of mannose, rhamnose, arabinose galactose and glucose, with ratios of 0.6∶1.0∶1.4∶1.6∶1.7, and EFPA is composed of mannose, glucose, galactose, galacturonic acid and arabinose with ratios of 1.7∶7.4∶1.4∶1.8∶1.0. The average molecular of EFPN and EFPA were 1.5×104 Da～1.4×105 Da and 2.5×104 Da～9.8×104 Da. EFPN, showing a higher radical scavenging activities (IC50), metal chelating abilities(IC50) and reducing abilities than EFPA in vitro antioxidant assay. EFPN can significantly increase (P<0.05 and P<0.01) the content of antioxidant enzymes in serum and liver tissue of aging mice, significantly reduce (P<0.05 and P<0.01)lipid peroxide activities, and have good repair effect on oxidative stress injury.
Key words: Epimedium koreanum Nakai; neutral polysaccharides; acidic polysaccharides; physicochemical properties; antioxidant activities
引用本文：李波，李珺铭，刘富饶，等. 朝鲜淫羊藿中性多糖与酸性多糖的理化特征及抗氧化活性的比较[J]. 化学试剂，2022，44(3): 369-375。
咪唑喹啉衍生物与小牛胸腺DNA作用机理研究
王炜祺1，陈昌云*2，许小青1，鲍真真1，钟嫄1，吴洁1
（1. 江苏卫生健康职业学院 药学院，江苏 南京 211800；2. 南京晓庄学院 环境科学学院，江苏 南京 211171）
摘要：对于咪唑喹啉衍生物（IQDs）与小牛胸腺脱氧核糖核酸（CT-DNA）的相互作用机理，本文采用荧光光谱法、黏度法、热变性研究和琼脂糖凝胶电泳法等实验技术进行研究。实验结果显示，咪唑喹啉衍生物Ⅰ以嵌插模式与CT-DNA作用，衍生物Ⅱ以沟槽模式与CT-DNA作用，且衍生物Ⅰ与CT-DNA的作用强于Ⅱ，而衍生物Ⅲ几乎不与CT-DNA发生作用。利用Gaussian 98量子化学程序包构建并优化3种衍生物分子模型，在HF/6-31G基组水平上进行计算，量子化学理论计算结果表明大环C9位上的取代基对结合模式和强度起着关键作用，与实验结果一致。
关键词：咪唑喹啉衍生物；小牛胸腺DNA；荧光光谱；琼脂糖凝胶电泳；量子化学计算
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2022）--
Study on the interaction mechanism of imidazolequinoline derivatives with calf thymus DNA WANG Wei-qi1, CHEN Chang-yun*2 XU Xiao-qing1, BAO Zhen-zhen1, ZHONG Yuan1, WU Jie1 (1. School of pharmacy, Jiangsu Health Vocational College, Nanjing 211800, China; 2. School of Environmental Science, Nanjing Xiaozhuang University, Nanjing 211171, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: The mechanism of interaction between imidazoquinoline derivatives and DNA was studied by fluorescence spectroscopy, DNA viscosity determination, DNA denatured temperature and gel electrophoresis. The quantum chemistry calculation for three derivatives was performed on HF/6-31G basis set after optimizing with Gaussian 98 program. The experimental and computational results showed that the substituents at C9 position of macrocycle play a key role in the binding mode and interaction strength. The three derivatives interacted with DNA in different ways.Ⅰ interacted with CT-DNA in the mode of intercalative binding; Ⅱ interacted with CT-DNA in the mode of groove binding; Ⅲ didn’t interact with CT-DNA.
Key words: Imidazoquinoline derivatives; CT-DNA; Fluorescent spectroscopy; Gel electrophoresis; Quantum chemistry calculation
引用本文：王炜祺，陈昌云，许小青，等. 咪唑喹啉衍生物与小牛胸腺DNA作用机理研究[J]. 化学试剂，2022，44(3):376-384。
二氧化硅/聚噻吩复合吸附剂处理Pb2+和Cd2+
张丽丽*
（濮阳职业技术学院 能源与化学工程学院，河南 濮阳 457000）
摘要：绿色环保、高效等特点是吸附剂发展的趋势。以溶胶-凝胶法合成了SiO2，再与聚噻吩合成了SiO2/聚噻吩复合材料。采用扫描电镜（SEM）、傅里叶红外光谱（FT-IR）以及Zeta电位对复合材料进行了表征分析。SiO2/聚噻吩是表面粗糙的球形，且表面带有负电荷。SiO2/聚噻吩复合材料用于吸附Pb2+和Cd2+离子，改变吸附过程中的变量来研究吸附过程的影响因素，通过探讨动力学和等温线模型来研究其吸附机理。研究结果表明，pH通过改变SiO2/聚噻吩表面的电荷数来影响吸附性能，以及吸附容量与吸附剂的量不呈正相关。同时得知，SiO2/聚噻吩吸附剂吸附Pb2+和Cd2+的过程符合拟二级动力学模型及Langmuir等温线模型。以研究结果提出吸附机理：SiO2/聚噻吩表面的负电荷吸引带有正电荷的重金属离子，以单分层的化学吸附为主吸附过程。
关键词：吸附剂；复合材料；污水处理；二氧化硅；聚噻吩
中图分类号：TQ3118文献标识码：A 文章编号：008529（2021）- -
Treatment of Pb2+ and Cd2+ with silica/polythiophene composite adsorbent Zhang Li-li* (Puyang Vocational and Technical College, Puyang 457000, China), Huaxue shiji,2021, 44(3), ～
Abstract: Green environmental protection, high efficiency is characterized by the development trend of adsorbent.SiO2/polythiopheneis composites were synthesized by sol-gel method with SiO2 and polythiophene. The composites were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and zeta potential. SiO2/polythiopheneis spherical with rough surface and negative charge on the surface.SiO2/polythiopheneis composites are used to adsorb Pb2+ and Cd2+ ions. The influencing factors of the adsorption process are studied by changing the variables in the adsorption process. The adsorption mechanism is studied by discussing the kinetics and isotherm model. The results show that pH affects the adsorption performance by changing the charge number of SiO2/polythiopheneis surface, and the adsorption capacity is not positively correlated with the amount of adsorbent. It is also known that the adsorption process of Pb2+ and Cd2+ on SiO2/polythiopheneis adsorbent conforms to the pseudo second-order kinetic model and Langmuir isotherm model. Based on the research results, the adsorption mechanism is proposed: the negative charge on the SiO2/polythiopheneis surface attracts the positively charged heavy metal ions, and the single layered chemical adsorption is the main adsorption process.
Keywords: adsorbent; composite material; sewage treatment; silica
引用本文：张丽丽. 二氧化硅/聚噻吩复合吸附剂处理Pb2+和Cd2+[J]. 化学试剂，2021，44(3):385-392。
新型生物质果胶吸附材料的制备及水溶液中铜离子（II）吸附性能研究
姚元勇，何来斌，张萌，陈仕学*，吴兰艳
（铜仁学院 材料与化学工程学院 铜仁市中药民族药现代化研究与开发利用重点实验室，贵州 铜仁 554300)
摘要：为了评价生物质果胶碱化改性在重金属离子废水处理方面的吸附性能，利用水提-醇沉法提取纯化豆腐柴叶中天然果胶，并通过碱化作用，制备新型生物质果胶吸附材料，同时对水溶液中重金属铜离子进行吸附作用试验，考察其吸附率和单位吸附量。然后,通过分析新型生物质果胶吸附材料组分半乳糖醛酸含量及酯化度，探讨其吸附作用机制。实验结果表明，天然果胶在pH 9的环境中碱化作用30 min时，可制备获得具有高效吸附水体中铜离子的新型生物质果胶吸附材料，其吸附率和单位吸附量分别可达到89.6%（0.10 g）和105 mg/g（0.02 g）。另外，在果胶组分半乳糖醛酸含量和酯化度分析方面，果胶碱化作用未造成半乳糖醛酸分子的丢失，但可促使果胶中羧酸酯的水解，形成对应的羧酸钠盐，提升对水体铜离子的吸附性能。
关键词：重金属铜离子；天然果胶；豆腐柴；吸附材料；铜离子
中图分类号：X-1 文献标识码：A 文章编号：0258-3283（2022）
Preparation of Novel Biomass Pectin Adsorbing Material Modified via Alkalization And Its Adsorption Performance for Copper (II) Ion in Aqueous Solution YAO Yuan-yong, HE Lai-bing, ZHANG Meng, CHEN Shi-xue*, WU Lan-yan (Tongren Key Laboratory for Modernization Research, Development and Utilization of Traditional Chinese Medicine and National Medicine, School of Material and Chemical Engineering, Tongren university, Tongren 554300, China), Huaxue Shiji, 2022, 44(3)
Abstract: To evaluate the adsorption performance of biomass pectin modified via alkalization in the treatment of heavy-metal ion wastewater. Natural pectin isolated from Premna microphylla leaves was purified by water-alcohol precipitation. And then novel biomass pectin adsorbing material was prepared through the alkalization and applied to adsorption performance for copper ion in aqueous solution, with observing adsorption efficiency and unit adsorption quantity. Subsequently, analyzing galacturonic acid content and esterification degree of novel biomass pectin adsorbing material was utilized to propose rational mechanism of adsorption performance. The results demonstrated that novel biomass pectin adsorbing material was successfully promoted by the alkalization of natural pectin for 30 min in pH 9 aqueous solution, with good exhibitions for copper ion in adsorption efficiency and unit adsorption quantity, they are respectively 89.6% (0.10 g) and 105 mg/g (0.02 g). Furthermore, in the aspects of diagnosing galacturonic acid content and esterification degree, the alkalization for pectin is not capable to observe the loss of galacturonic acid content from the novel biomass pectin, but can promote the hydrolysis of carboxylic ester to form relative sodium salt for enhancing adsorption performance of copper ion.
Key words: heavy metal ion; natural pectin; Premna microphylla; absorbing material；Cu2+
引用本文：姚元勇, 何来斌, 张萌, 等.新型生物质果胶吸附材料的制备及水溶液中铜离子（II）吸附性能研究[J].化学试剂, 2022, 44（3）：393-400.
磁性聚苯胺纳米纤维吸附性能的探究
李大为，陶玉仑，李硕
（安徽理工大学 材料科学与工程学院，安徽 淮南 232000）
摘要：以有机酸、粉煤灰磁珠为掺杂剂，过硫酸铵为氧化剂，采用氧化聚合的方法合成了磁性聚苯胺纳米纤维，对合成的磁性聚苯胺进行扫描电子显微镜（SEM）、傅里叶变换红外光谱仪（FTIR）、紫外可见光分光光度计（UV）、振动磁强计（VSM）、X-射线衍射仪（XRD）等表征揭示了其形貌、结构、成分和磁性能，并使用磁性聚苯胺作吸附剂对铜离子溶液以及刚果红溶液进行吸附脱吸附研究，发现吸附率均在95%以上。通过吸附动力学对吸附机理进行探究，得出聚苯胺吸附铜离子及刚果红符合二级动力学模型。
关键词：磁性；有机酸；聚苯胺；吸附；动力学
中图分类号：TQ424；X703 文献标识码：A 文章编号：0258-3283（2022）
Investigation on the Adsorption Properties of Magnetic Polyaniline Nanofibers LI Da-wei, TAO Yu-lun*, LI shuo ( School of Materials Science and Engineering, Anhui University of Technology, Huainan 232000, China), Huaxue Shiji, 44(3), 00 ~ 00
Abstract: Magnetic polyaniline nanofibers were synthesized by using organic acid and fly ash beads as dopants and ammonium persulfate as oxide polymerization, and were characterized by employing scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), UV visible spectrophotometer (UV), vibrational magnetometer (VSM) and X-ray diffraction (XRD) for their morphology, structure, composition and magnetic properties. The title polyaniline was used as adsorbent to study the adsorption and desorption of copper ion solution and Congo red solution, and the adsorption rate was found to be more than 95%. Based on the investigation on the adsorption mechanism, it can be concluded that adsorption of copper ions and Congo red on the title polyaniline obey the secondary kinetic model.
Key words: magnetism; organic acid; polyaniline; adsorption; dynamics
引用本文：李大为，陶玉仑，李硕. 磁性聚苯胺纳米纤维吸附性能的探究[J]. 化学试剂, 2022, 44(3): 401-407。
Mn-P共掺杂氮化碳的制备及其光催化性能研究
艾兵*，何海南，邓璇，孙立新，杨立喜，李德刚
(山东理工大学 化学化工学院，山东 淄博 255049)
摘要：采用四水氯化锰、磷酸氢二铵和三聚氰胺为原料制备了Mn-P共掺杂的石墨相氮化碳（g-C3N4）。使用X射线衍射光谱(XRD)、扫描电子显微镜（SEM）、傅里叶变换红外光谱(FT-IR)、光致荧光光谱(PL)、紫外-可见漫反射光谱(UV⁃Vis DRS)、电化学阻抗谱（EIS）、瞬态光电流响应等分析测试手段对制备的催化剂进行了表征。结果表明，Mn-P 共掺杂改变了氮化碳的光电性质。通过可见光降解亚甲基蓝（MB）溶液证明了Mn-P共掺杂可以有效改善氮化碳的光催化性能。Mn(2.0%)-P-CN对MB的降解率在120 min 内达到62.2%，其速率常数为0.0083 min-1，是纯氮化碳的2.1倍。同时，探索了Mn-P共掺杂氮化碳的光催化反应机理和循环利用。
关键词：石墨相氮化碳；磷酸氢二铵；锰；可见光催化；共掺杂
中图分类号：O649 文献标识码：A 文章编号：0258-3283（2022）--
Preparation of Mn, P Co-doped Carbon Nitride and its photocatalytic properties AI Bing*, HE Hai-nan, DENG Xuan, SUN Li-xin, YANG Li-xi, LI De-gang (School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: Mn and P co-doped carbon nitride was prepared from manganese chloride tetrahydrate, diammonium hydrogen phosphate and melamine. The prepared catalysts were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence spectroscopy (PL), ultraviolet⁃visible diffuse reflectance spectroscopy (UV⁃Vis DRS), electrochemical impedance spectroscopy (EIS), and transient photocurrent analytical tests. The results showed that Mn and P co-doping changed the photoelectric properties of carbon nitride. It was proved that Mn and P co-doping could effectively improve the photocatalytic performance of carbon nitride by the degradation of methylene blue (MB) solution under visible light. The degradation rate of MB by Mn (2.0%)-P-CN could reach 62.2% within 120 minutes, and its degradation rate constant was 0.0083 min-1, which was about 2.1 times higher than that of pure g-C3N4. At the same time, the photocatalytic reaction mechanism and recycling of Mn and P co-doped carbon nitride were explored.
Key words: g-C3N4; diammonium hydrogen phosphate; manganese; visible-light photocatalysis; co-doping
引用本文：艾兵，何海南，邓璇，等. Mn-P共掺杂氮化碳的制备及其光催化性能研究[J]. 化学试剂，2022，44(3): 408-414。
基于三苯胺的D-A-π-A-D型化合物的合成及光物理性能
窦立薇1,2，高亚楠1,2，高宏*1,3，翟兆兰1,3
（1. 中国林业科学研究院 林产化学工业研究所 生物质化学利用国家工程实验室 国家林业和草原局林产化学工程重点实验室 江苏省生物质能源与材料重点实验室；江苏 南京 210042；2. 南京林业大学 江苏省林业资源高效加工利用协同创新中心，江苏 南京 210037；3. 中国林业科学研究院 林业新技术研究所，北京 100091）
摘要：以甲氧基三苯胺为电子供体，苯并噻二唑为电子受体，咔唑为共轭π桥，通过三步Suzuki偶联反应合成了的D-A-π-A-D型荧光化合物4, 4'-[(7, 7'-(9H-咔唑-2, 7-)-二(苯并噻二唑-7, 4-)]-二(N,N-二(4-甲氧基苯基) 苯胺（DTB-CZ），并用1HNMR、13CNMR、MALDI-TOF等手段对其结构进行表征。研究了它的光谱性能、电化学性能、轨道能级和热性能，并与D-π-D型化合物2TPA-CZ1的性能进行了比较。初步探索了DTB-CZ作为空穴传输材料在PSC中的应用性能。研究结果表明，DTB-CZ在甲苯溶液中的最大吸收波长为479 nm，最大发射波长为608 nm，在薄膜状态下最大吸收波长为495 nm，HOMO/LUMO能级为-4.91/-2.82 eV，带隙值为2.09 eV，热分解温度（T5d）为449.56 oC，玻璃化转变温度（Tg）为143.10 oC。相比2TPA-CZ1，在甲苯溶液中吸收和发射波长分别红移了104、182 nm，在薄膜状态下吸收波长红移109 nm；带隙值降低0.84 eV；T5d和Tg 分别提高了9.56、24.7 oC。结果表明，苯并噻二唑的引入，使化合物的共轭程度增大，带隙值降低，使得吸收和发射波长红移，使其具有更好的热稳定性和形态稳定性。
关键词：甲氧基三苯胺；苯并噻二唑；咔唑；D-A-π-A-D；光物理性能
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2022）
Synthesis and Photophysical Properties of D-A-π-A-D Compound Based on Triphenylamine DOU Li-wei 1,2, GAO Ya-nan 1,2, GAO Hong* 1,3, ZHAI Zhao-lan 1,3 (1. Institute of Chemical Industry of Forest Products, National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab of Biomass Energy and Material, Chinese Academy of Forestry, Nanjing 210042, China; 2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China; 3. Research Institute of Forestry New Technology, Chinese Academy of Forestry, Beijing 100091, China), Huaxue Shiji, 2022, 44(3)
Abstract: D-A-π-A-D type compound DTB-CZ was synthesized by three-step Suzuki cross coupling reaction, herein, methoxytriphenylamine acted as donor (D), benzothiadiazole acted as acceptor (A) and carbazole was selected as the middle π-bridge. The structure of DTB-CZ was characterized by 1HNMR、13CNMR and MALDI-TOF. Its spectral performance, electrochemical performance, orbital energy level and thermal performance were studied and compared with the performance of compound 2TPA-CZ1 with D-π-D structure. The application performance of DTB-CZ as a hole transport material in PSC was initially explored. The research results show that the maximum absorption wavelength of DTB-CZ in toluene solution is 479 nm, the maximum emission wavelength is 608 nm, and the maximum absorption wavelength is 495 nm in the film state. The HOMO/LUMO energy level of DTB-CZ is -4.91/-2.82 eV, and the band gap value is 2.09 eV. The thermal decomposition temperature of DTB-CZ is 449.56 oC, and the glass transition temperature is 143.10 oC. Compared with that of 2TPA-CZ1, the absorption and emission wavelengths in toluene solution red-shifted 104 nm and 182 nm, respectively, and the absorption wavelength red-shifted 109 nm in the film state; the band gap value decreased 0.84 eV; the thermal decomposition temperature and glass transition temperature increased 9.56 oC and 24.7 oC, respectively. It showed that the introduction of benzothiadiazole increased the conjugation degree of the compound and reduced the band gap value, which made the absorption and emission wavelength red shift; and it had better thermal stability and morphological stability.
Key words: methoxytriphenylamine; benzothiadiazole; carbazole; D-A-π-A-D; photophysical properties
引用本文：窦立薇，高亚楠，高宏，等.基于三苯胺的D-A-π-A-D型化合物的合成及光物理性能[J].化学试剂，2022，44（3）：415-421.
玉米芯基碳点的制备、表征及其对Cr(VI)的荧光检测研究
黎海涛1，施家威1，郭燕1，张小涛1，黎挺挺*2
（1. 浙江医药高等专科学校 食品学院，浙江 宁波 315199；2. 宁波大学 材料科学与化学工程学院，浙江 宁波 315211）
摘要：通过一步水热法制备了玉米芯基碳点（CDs），所制备的CDs粒径分布均匀，在水溶液中具有良好的分散性。通过红外光谱、紫外-可见吸收光谱以及荧光光谱对其发光性能进行了研究。基于Cr(VI)能选择性淬灭CDs的荧光，建立了以CDs为荧光探针测定Cr(VI)浓度的新方法，当Cr(VI)的浓度范围为2~80 μmol/L时，CDs荧光淬灭强度与Cr(VI)浓度呈现较好的线性关系，该方法检出限可达0.98 μmol/L。该方法应用于工业废水中Cr(VI)的测定，测得的结果与分光光度法基本一致。
关键词：碳点；荧光识别；Cr(VI)检测；淬灭机理；低检测限
中图分类号：O655.21 文献标识码：A 文章编号：
Preparation and Characterization of Corncob Carbon Dots, and Their Application in Fluorescence Detection of Cr(VI) LI Hai-tao1,SHI Jia-wei1, GUO Yan1, ZHANG Xiaotao1, LI Ting-Ting*2 (1. Faculty of Food Science, Zhejiang Pharmaceutical College, Ningbo 315100; 2. School of Material Science and Chemical Engineering, Ningbo University, Ningbo 315211)
Abstract：Carbon dots (CDs) were synthesized by one-step hydrothermal approach with corncob as the carbon source. The resultant CDs possess uniform particle size distribution and excellent dispersibility in aqueous solution. The photophysical properties of CDs were characterized by infrared spectroscopy, UV-Vis absorption spectroscopy, and fluorescence spectroscopy. The fluorescence spectra showed that the fluorescence of CDs could be quenched by Cr(VI), and thus we employed CDs as the probe to determine the Cr(VI) concentration in aqueous solution. Cr(VI) concentration displayed a good linear relationship with the intensity of fluorescence quenching in the range of 2~80 μmol/L, the corresponding detection limit was 0.98 μmol/L. Finally, this method was used to determine the Cr(VI) concentration in industrial wastewater, and the result was nearly in accordance with that obtained from spectrophotometric method.
Key words：carbon dots; fluorescence detection; Cr(VI) detection; quenching mechanism;low detection limit
引用本文：黎海涛，施家威，郭燕，等.玉米芯基碳点的制备、表征及其对Cr(VI)的荧光检测研究[J].化学试剂，44（3）：422-426.
可连续识别Cu2+和PPi的荧光探针的合成及性能研究
李生玲*1，常西亮1，孔祥鹏1，成果1，王明亚2
（1. 太原工业学院 化学与化工系，山西 太原 030008；2. 中北大学 化学工程与技术学院，山西 太原 030051）
摘要：连续识别型荧光探针能在同一测试条件下连续识别两种离子，使得离子的检测更具专一性，是在普通同类型探针检测功能方面的拓展。设计合成了以7-二乙氨基香豆素为母体、咪唑-2-甲醛为识别基团的一种高选择性的席夫碱型荧光探针CI，用于连续识别Cu2+和焦磷酸根离子（PPi）。探针CI对Cu2+表现出了明显的“开-关”荧光淬灭响应，淬灭率为100%，而形成的配合物CI-Cu2+对PPi呈现明显的“关-开”荧光增强响应。探针CI对Cu2+和PPi的检出限均为0.14 μmol/L，其与Cu2+的配位比为1∶1，而CI-Cu2+配合物与PPi以2∶1配位。在pH 5～11的范围内，探针CI和CI-Cu2+具有很好的识别能力。
关键词：香豆素；荧光探针；咪唑；Cu2+；PPi；连续识别
中图分类号：O622 文献标识码：A 文章编号：0258-3283（2022）--
A synthesis and performance study of fluorescent probe for sequential recognition of Cu2+ and PPi LI Sheng-ling*1, CHENG Xi-liang1, KONG Xiang-peng1, CHENG Guo1, WANG Ming-ya2 (1. Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China; 2. School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: Sequential recognition fluorescent chemical probe can continuously identify two kinds of ions under the same test condition, making the ion detection more specific, which is an extension of the detection function of common probes of the same type. In this study, a highly selective Schiff base fluorescent probe CI was synthesized with 7-diethylaminocoumarin as the parent and imidazole-2-carboxaldehyde as the recognition group for sequential recognition of Cu2+ and PPi. The probe CI showed an obvious "on-off" fluorescence quenching response to Cu2+ with an efficiency of 100 %, and the CI-Cu2+ complex showed an "off-on" response to PPi fluorescence enhancement. The detection limit of probe CI for Cu2+ and PPi was 0.14 μmol/L. The binding capacity of probe CI and Cu2+ was 1∶1, and the binding capacity of CI-Cu2+ complex and PPi was 2∶1. The optimum pH range of probe CI and CI-Cu2+ was 5～11.
Keywords: Coumarin; Fluorescent probe; Imidazole; Cu2+; PPi; Continuous recognition
引用本文：李生玲，常西亮，孔祥鹏，等. 可连续识别Cu2+和PPi的荧光探针的合成及性能研究[J]. 化学试剂, 2022, 44(3): 427-435。
藜麦产地的红外光谱鉴别
严伟敏1，刘刚*，田雪1，欧全宏1，车前1，时有明2
(1.云南师范大学 物理与电子信息学院，云南 昆明 650500；2.曲靖师范学院 物理与电子信息学院，云南 曲靖 655011）
摘要：种植环境差异导致不同产地的藜麦有差异，故对不同产地的藜麦进行区分鉴别对商家、消费者具有重要参考价值。将中红外光谱结合主成分分析（PCA）、线性判别分析（LDA）及混淆矩阵对不同产地藜麦进行鉴别研究。结果显示：藜麦的红外光谱主要由淀粉、蛋白质和脂质谱峰组成，且在蛋白质和糖类谱峰上有差异。用600~4000 cm-1范围的原始光谱进行PCA分析，前两个主成分（PC）取得了92%的累计方差贡献率，基于PCA分析生成的PC进行LDA分析，取得了96.25 %的分类精度。基于预测结果的混淆矩阵作为综合评价指标，得到PCA-LDA分类模型的精确度、召回率及特异性分别为96.25%、96.59%和99.48%，说明使用PCA-LDA模型可以对藜麦产地进行有效鉴别。研究表明，红外光谱结合多元统计分析方法，是鉴别藜麦产地的有效方法。
关键词：红外光谱；藜麦；产地鉴别；主成分分析；线性判别分析
中图分类号：O657.33 文献标志码：A 文章编号：0258-3283（2022）
Identification of Quinoa Origin by Infrared Spectroscopy YAN Wei-min 1, LIU Gang*1, TIAN Xue 1, OU Quan-hong 1, CHE Qian 1, SHI You-ming 2 (1. School of Physics and Electronic Information, Yunnan Normal University, Kunming 650500, China; 2. School of Physics and Electronic Engineering, Qujing Normal University, Qujing 655011, China), Huaxue Shiji, 2022, 44(3)：
Abstract: The difference of planting environment leads to the difference of quinoa in different producing areas. So, the identification of quinoa from different producing areas is of great reference value to merchants and consumers. In this paper, infrared spectroscopy combined with principal component analysis (PCA), linear discriminant analysis (LDA) and confusion matrix were used to identify quinoa from different areas. The results showed that the infrared spectra of quinoa mainly composed of starch, protein and lipid band, and there are differences in the protein and starch peaks. PCA analysis was carried out with the original spectra in the range of 600~4000 cm-1, and 92% cumulative variance contribution rate was obtained on the first two PCs. LDA analysis based on PCs generated from PCA analysis achieved 96.25% classification accuracy. Based on the confusion matrix of the predicted results as a comprehensive evaluation index, the average accuracy, recall rate and specificity of the PCA-LDA classification model were obtained as 96.25%, 96.59% and 99.48%, respectively, indicating that the PCA-LDA model can effectively discriminate the origin of quinoa. The study showed that infrared spectroscopy combined with multivariate statistical analysis method is an effective method to identify the geographical origin of quinoa.
Key words: infrared spectroscopy; quinoa; origin identification; principal component analysis; linear discriminant analysis
引用本文：严伟敏，刘刚，田雪，等. 藜麦产地的红外光谱鉴别[J].化学试剂，2022，44（3）：436-441.
不同采收期水冬瓜叶的主成分分析及抗炎镇痛谱效关系研究
韩忠耀*，张涛，黄春丽，田浩，王万乐，卢洋，王小建，罗浩
（黔南民族医学高等专科学校 药学系 ，贵州 都匀 558000）
摘要：为筛选水冬瓜叶抗炎镇痛活性成分，采用高效液相色谱（HPLC）建立不同采收期10批次水冬瓜叶药材指纹图谱，对其进行主成分分析，并基于皮尔逊相关分析法探讨不同采收期水冬瓜叶药材抗炎镇痛的谱效关系。结果显示，不同采收期水冬瓜叶药材HPLC指纹图谱中有17个共有峰，10批次药材的相似度为0.875 ~ 0.973。聚类分析将不同采收期水冬瓜叶药材分为3类。主成分分析共得到3个主成分。经皮尔逊相关分析，峰17、峰14、峰12、峰15、峰13、峰5、峰16和峰4可能为水冬瓜叶药材镇痛作用的物质基础，峰6、峰8（异槲皮苷）、峰11、峰7（金丝桃苷）、峰5、峰3、峰4、峰13、峰9和峰1可能为水冬瓜叶药材抗炎作用的物质基础。
关键词：水冬瓜叶；指纹图谱；谱效关系；皮尔逊相关分析法；化学模式识别；抗炎镇痛
中图分类号：O657.7；R285.5 文献标识码：A 文章编号： 0258-3283（2022）
Principal Component Analysis and Spectrum-effect Relationship of Anti-inflammatory and Analgesic of the Leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in Different Collecting Seasons HAN Zhong-yao, ZHANG Tao, HUANG Chun-li, TIAN Hao, LU Yang, WANG Wan-le, WANG Xiao-jian, LUO Hao(Department of Pharmacy, Qiannan Medical College for Nationalities, Duyun 558000, China), Huaxue Shiji, 2022,
Abstract: In order to screen the anti-inflammatory and analgesic active components of the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu, high performance liquid chromatography (HPLC) was used to establish the fingerprints of 10 batches of the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in different collecting seasons, and the principal component analysis was carried out. Based on Pearson correlation analysis, the spectrum-effect relationship of anti-inflammatory and analgesic effects of the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in different collecting seasons was discussed. The results showed that there were 17 common peaks in the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in different collecting seasons, and the similarity of 10 batches of medicinal materials was 0.875～0.973. Cluster analysis divided the medicinal materials of 10 batches of the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in different collecting seasons into three categories. Three principal components were obtained by principal component analysis. Pearson correlation analysis was used to calculate the correlation coefficient between each common peak and analgesic inhibition rate and anti-inflammatory swelling inhibition rate.The results showed that peak 17, peak 14, peak 12, peak 15, peak 13, peak 5, peak 16 and peak 4 may be the material basis of analgesic effect of the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in different collecting seasons, peak 6, peak 8 (isoquercitrin), peak 11, peak 7 (hyperin), peak 5, peak 3, peak 4, peak 13, peak 9 and peak 1 may be the material basis of anti-inflammatory effect of the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu in different collecting seasons.
Key words: the leaves of Toricellia Angulata Oliv.var.intermedia (Harms) Hu; fingerprint; spectrum-effect relationship; person relational analysis; chemical components; anti-inflammatory and analgesic
引用本文：韩忠耀，张涛，黄春丽，等. 不同采收期水冬瓜叶的主成分分析及抗炎镇痛谱效关系研究[J]. 化学试剂，2022，44（3）：442-449.
超声辅助悬浮固化液液微萃取-液相色谱荧光法测定血清中阿齐沙坦
龚爱琴*，姜业朝，陈娟，陈丽萍
（扬州工业职业技术学院 化学工程学院，江苏 扬州 225127 ）
摘要：建立一种悬浮固化分散液液微萃取-液相色谱荧光法测定血清中阿齐沙坦含量的新方法。在超声辅助下，乳化后的萃取剂1-十一醇高效快速萃取溶液中的阿齐沙坦，将萃取液离心后冰水浴中冷却，萃取剂凝固漂浮在水面而与溶液分离，分离后的1-十一醇用乙醇溶解后利用液相色谱荧光法测定其中阿齐沙坦的含量。实验中对液相色谱测定条件、萃取条件进行了优化，包括激发与发射波长、流动相组成、萃取剂用量、萃取溶液pH、超声时间、离心时间、冷却时间等。在优化条件下，工作曲线的线性范围为0.02～4.0 μg/mL，最低检测限为6.0 ng/mL，回收率为93.1%～100.4%。专属性实验及血清样品测定结果表明该方法可以用于人血清中阿齐沙坦含量的测定。
关键词：阿齐沙坦；1-十一醇；液液微萃取；HPLC；荧光
中图分类号：O657. 7 文献标识码：A 文章编号：0258-3283（2022）- -
Ultrasound-assisted solidification of floating organic drop micro extraction coupled to high performance liquid chromatography with fluorescence detection for the determination of azilsartan in serum GONG Ai-qin*, JIANG Ye-chao, CHEN Juan, CHEN Li-ping (Chemical Engineering Institute, Yangzhou Polytechnic Institute, Yangzhou 225127, China), Huaxue Shiji, 2022, 44(3), ～
Abstract: A new method of ultrasound-assisted solidification of floating organic drop micro extraction coupled to high performance liquid chromatography with fluorescence detection (HPLC-FLD) for the determination of azilsartan in serum was proposed. With the help of ultrasound, azilsartan could be extracted efficiently and rapidly into emulsified extractant 1-undecanol. After centrifugation, the solution was cooled at ice bath and 1-undecanol was solidified and floated on the water, which made 1-undecanol easily to separate from aqueous solution. Finally the azilsartan in 1-undecanol was dissolved in ethanol and measured by HPLC-FLD. In examination the chromatographic conditions and extraction conditions were studied and optimized, including excitation and emission wavelengths, composition of mobile phase, the volume of 1-undecanol, solution pH, ultrasonic time, centrifugation time, cooling time and so on. Under the optimized conditions, the calibration curve was linear over the range of 0.02～4.0 µg/mL, and the limit of detection (LOD) was 6.0 ng/mL. The average recoveries were between 93.1% and 100.4%. The results of specific experiment and serum sample determination indicated the studied method could be used to test azilsartan in human serum.
Key words: azilsartan; 1-undecanol; Liquid-liquid micro extraction; HPLC; Fluorescence
引用本文：龚爱琴，姜业朝，陈娟，等. 超声辅助悬浮固化液液微萃取-液相色谱荧光法测定血清中阿齐沙坦[J]. 化学试剂，2022，44(3):450-454。
UPLC-MS/MS法测定食用植物油中15种全氟化合物
张文*，闫君，陈婷，潘建忠，王行智，张新中
（兰州市食品药品检验检测研究院 国家市场监管重点实验室（食品中农药兽药残留监控） 甘肃省种植中药材外源性污染物监测工程研究中心，甘肃 兰州 730050)
摘要：建立了UPLC-MS/MS同时测定食用植物油中15种全氟化合物（包括全氟烷基羧酸类、全氟磺酸类、全氟磺酰胺、全氟调聚醇）的检测方法。采用ACQUITY UPLC BEH-C18（1.7 μm, 2.1 mm×100 mm）色谱柱，以5 mmol/L乙酸铵的5%甲醇水溶液和95%甲醇水溶液为流动相，梯度洗脱，流速为0.3 mL/min，质谱选择多反应监测模式对15种全氟化合物进行定性和定量检测。样品采用1%甲酸乙腈重复提取两次，提取液旋蒸蒸发至净干，V(甲醇)∶V(水) = 3∶2溶液复溶，14000 r/min离心除杂制得待测液，与QuEChERS方法比较，回收率高、操作简单。结果显示：15种全氟化合物在8 min内得到有效分离，线性相关性好，相关系数均大于0.9951，检出限为0.0202～0.0365 μg/kg，定量限为0.0674～0.1217 μg/kg，1.5、3.0、4.5 µg/kg 3个添加浓度的平均回收率为63.5%～101.3%，相对标准偏差为0.8%～9.4%。本方法可应用于食用植物油中全氟化合物的检测。
关键词：全氟化合物；液相色谱-质谱联用仪；食用植物油；检测；全氟羧酸；全氟磺酸；全氟磺酰胺；全氟调聚醇
中图分类号：TS207；O657 文献标识码：A 文章编号：0258-3283（2022）
Determination of 15 Perfluorinated Compounds in Edible Vegetable Oil by UPLC-MS/MS ZHANG Wen*, YAN Jun, CHEN Ting, PAN Jian-zhong, WANG Xing-zhi, ZHANG Xin-zhong (Gansu Engineering Research Center for Monitoring Exogenous Harmful Residues in Traditional Chinese Medicines, Key Laboratory of Pesticide and Veterinary Drug Monitoring for State Market Regulation, Lanzhou Institute for Food and Drug Inspection and Testing, Lanzhou 730050, China), Huaxue Shiji, 2022, 44(3)
Abstract：A UPLC-MS/MS method was established for simultaneous determination of 15 perfluorinated compounds (including perfluorinated alkyl carboxylic acids, perfluorinated sulfonic acids, perfluorinated sulfonamides and perfluorinated telomers) in edible vegetable oils. An ACQUITY UPLC BEH-C18 (1.7 μm, 2.1 mm×100 mm) column was used for gradient elution with 5 mmol/L ammonium acetate in 5% methanol solution and 95% methanol solution as mobile phases at a flow rate of 0.3 mL/min. The mass spectrometry employs the multiple reaction monitoring mode for qualitative and quantitative determination of fifteen perfluorinated compounds. The sample was extracted by 1% formic acid acetonitrile twice, and the extract was rotary-evaporated to dryness, which was then redissolved by (3+2) methanol-aqueous solution, and centrifuged to remove impurities at 14000 r/min. Compared with QuEChERS method, the present process runs simply with high recovery rate. The results showed that fifteen perfluorinated compounds were effectively separated within 8 min with good linear correlation coefficients greater than 0.9951, the detection limits over the range 0.0202-0.0365 μg/kg, and the quantification limits in the region 0.0674-0.1217 μg/kg. The average recoveries of 1.5, 3.0 and 4.5 µg/kg were 63.5% to 101.3% with relative standard deviations (RSDs) of 0.8% to 9.4%. This method can be applied to the determination of perfluorinated compounds in edible vegetable oil.
Key words: perfluorinated compound; liquid chromatograph-mass spectrometer; edible vegetable oil; detection; perfluorocarboxylic acid; perfluorinated sulfonic acid; perfluorinated sulfonamide; perfluorotelomeric alcohols
引用本文：张文，闫君，陈婷，等. UPLC-MS/MS法测定食用植物油中15种全氟化合物[J]. 化学试剂, 2022, 44(3): 455-461。
锑元素溶液标准物质的研制
孙倩芸1，吕邓义2，高捷1，张森1，王云1，郭波*1
（1.山东省计量科学研究院，山东济南250014；2.山东省食品药品检验研究院，山东济南250101）
摘要：为满足锑元素检测需求，研制了锑元素溶液标准物质。该标准物质以高纯锑和MOS级硝酸为原料，在对高纯金属纯度定值的基础上，采用重量-容量法进行配制和定值。高纯锑采用杂质扣除法测定其纯度。采用ICP-MS半定量方法对杂质进行定性分析，通过电感耦合等离子体质谱法(ICP-MS)方法对金属杂质进行准确测定，通过惰性气体熔融-红外吸收法、惰性气体熔融-热导法测定气体杂质元素C、S、O、N、H。经过标准物质的均匀性检验和稳定性检验后，将配制值作为标准值，同时评定了所研制标准物质浓度定值的不确定度。结果证明，锑元素溶液标准物质的浓度为1000μg/mL，相对扩展不确定度为1%（k=2）。
关键词：锑标准物质；金属纯度；杂质扣除法；电感耦合等离子体质谱法；不确定度
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2022）
Development of Standard Reference Material for Antimony Solution SUN Qian-yun1, LV Deng-yi2, GAO Jie1, ZHANG Sen1, WANG Yun1, GUO Bo*1（1. Shandong Institute of Metrology, Jinan250014, China; 2. Shandong Institute of Food and Drug Testing, Jinan 250101, China）Huaxue Shiji, 2022, 44(3)
Abstract：To meet the requirements of antimony detection, the standard reference material of antimony solution was developed. The standard reference material was prepared by using high-purity antimony and MOS grade acid as raw materials by weight-capacity method, and the purity of antimony was determined by impurity deduction method. The metal impurities were analyzed by ICP-MS semi-quantitative method and were accurately determined by inductively coupled plasma mass spectrometry ( ICP-MS ). The gas impurities C, S, O, N and H were determined by inert gas melting-infrared absorption method and inert gas melting-thermal conductivity method. After the verifications of homogeneity and stability, the value of standard reference material was defined, and the uncertainty was estimated. The results confirmed that the concentration of antimony solution reference material was 1000 μg/mL, while the relative expanded uncertainty was 1%( k=2 ).
Keywords：SRM of antimony; metal purity; impurity deduction; ICPMS; uncertainty
引用本文：孙倩芸，吕邓义，高捷，等.锑元素溶液标准物质的研制[J].化学试剂，2022,44(3):462-467。
芳香羧酸脱羧-偶联反应研究
钟辉a，吴聪a，文旺a，丁阳a，周旭东a,b，盛文兵*a,b
（湖南中医药大学 a. 药学院，b. 中医药民族医药创新发展国际实验室，湖南 长沙 410208）
摘要：芳香族羧酸脱羧-偶联反应能够有效构建C-C或C-杂原子键，在天然活性物质、药物中间体以及特殊材料合成等方面具有重要意义，并且该方法具有很好的区域选择性、原子经济性及环境友好性等特点。近年来以芳香羧酸为基本原料的脱羧-偶联反应得到深入研究，新颖催化剂不断涌现，反应条件不断完善，为该类反应的应用提供了理论依据。从偶联反应的类型、机理、不同过渡金属催化剂等方面展开综述，为进一步研究并开发该类反应提供参考。
关键词：芳香羧酸；脱羧-偶联反应；过渡金属催化；非金属催化；紫外光催化；低共熔溶剂
中图分类号：O621.29 文献标识码：A 文章编号：0258-3283（2022）
Study on the Decarboxylation-Coupling Reaction of Aromatic Carboxylic Acid ZHONG Huia, WU Conga, WEN Wanga, DING Yanga, ZHOU Xu-donga,b, SHENG Wen-bing*a,b (a. School of Pharmacy, b. TCM and Ethnomedicine Innovation & Development International Laboratory, Hunan University of Chinese Medicine, Hunan Changsha, 410208, China), Huaxue Shiji, 2022, 44(3),
Abstract: The decarboxylation-coupling reaction of aromatic carboxylic acid can effectively construct C-C or C-heteroatomic bonds, which is of great significance in natural active substances, drug intermediates and special material synthesis, and the method has the characteristics of good regional selectivity, atomic economy and environmental friendliness. In recent years, the decarboxylation-coupling reaction with aromatic carboxylic acid has been deeply studied, and many novel catalysts are constantly emerging, providing a theoretical basis for the application of such reactions. In order to provide a meaningful reference for further research, coupling reaction type, mechanism and the different transition metal catalysts are summarized in this mini-review.
Key words: aromatic carboxylic acids; decarboxylation-coupling reaction; catalyzed by metal
引用本文：钟辉，吴聪，文旺，等.芳香羧酸脱羧-偶联反应研究[J].化学试剂，2022，44(3)：468-476.
N-苄基吲哚类熊果酸衍生物的合成及抗肝癌活性
田宁1，刘晓娟2，张大军1，栾天*1
（1. 沈阳医学院 药学院，辽宁 沈阳 110034；2. 阜新市产业技术研究院，辽宁 阜新 123000）
摘要：为开发高效低毒的抗肝癌天然产物衍生物，依据药物拼合原理设计并合成了一系列未见文献报道的熊果酸衍生物。将熊果酸与不同取代的N-苄基吲哚片段通过Claisen-Schmidt缩合反应得到目标化合物，其化学结构均经过核磁氢谱﹑核磁碳谱以及质谱的联合确证。采用噻唑蓝（MTT）法考察其体外抗肝癌活性，结果表明，2-{[1-（2-氟苄基）-1H-吲哚基]-3-次甲基}-3-羰基熊果酸（4b）与2-{[1-（3-氟苄基）-1H-吲哚基]-3-次甲基}-3-羰基熊果酸（4c）对HepG2及BEL-7402两种肝癌细胞株的抑制活性优于熊果酸及阳性对照药氟尿嘧啶，同时对正常肝细胞L02的毒性显著降低。化合物4c的体外抗肝癌活性最为理想（针对HepG2的IC50值为3.22 μmol/L，选择性指数为6.89），分子对接实验模拟其作用靶标或为RNA聚合酶II，可对其深入研究用以开发高效低毒的抗肝癌药物。
关键词：熊果酸；吲哚；衍生物；合成；抗肝癌
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2022）
Synthesis and Anti-hepatocellular Carcinoma in Vitro of Ursolic Acid Derivatives Bearing N-benzylindole Moieties TIAN Ning1, LIU Xiao-juan2, ZHANG Da-jun1, LUAN Tian*1 (1. Department of Pharmacy, Shenyang Medical College, Shenyang 110034, China; 2. Fuxin Industrial Technology Research Institute, Fuxin 123000, China), Huaxue Shiji, 2022, 44(3)
Abstract: To develop natural derivatives with high efficiency and low toxicity for anti-hepatoma, a series of novel ursolic acid derivatives were designed and synthesized via the principle of pharmacochemical molecular combination. The target compounds were obtained by Claisen-Schmidt condensation reaction between ursolic acid and different substituted N-benzylindole, then characterized via 1H-NMR, 13C-NMR, and mass spectrometry, and investigated for anti-hepatocellular activity by MTT method. (1S,2R,4aS,6aS,6bR,12aR,E)-11-((1-(2-Fluorobenzyl)-1H-indol-3-yl)methylene)-1,2,6a,6b,9,9,12a-heptamethyl-10-oxo-1,3,4,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-octadecahydropicene-4a(2H)-carboxylic acid (4b) and (1S,2R,4aS,6aS,6bR,12aR,E)-11-((1-(3-fluorobenzyl)-1H-indol-3-yl)methylene)-1,2,6a,6b,9,9,12a-heptamethyl-10-oxo-1,3,4,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-octadecahydropicene-4a(2H)-carboxylic acid（4c） showed higher antiproliferative activity against the HepG2 and BEL-7402 cell lines in comparison with the positive-control drug 5-fluorouracil and ursolic acid, and exhibited significantly lowered cytotoxic activities against human normal liver cells (L02). Compound 4c exhibited the most potent antiproliferative activity and commendable selectivity between cancer and normal cells (IC50 = 3.22 μmol/L against the HepG2 cells, Selectivity index = 6.89). The results of a docking study that involved placing compound 4c into the RNA polymerase II binding site revealed that its mode of action was possibly as a RNA polymerase II inhibitor. In conclusion, compound 4c may be a valuable candidate for further studies aiming at the development of effective and harmless anti-hepatoma drugs.
Key words: ursolic acid; benzpyrole; derivatives; synthesis; anti-hepatoma
引用本文：田宁，刘晓娟，张大军，等. N-苄基吲哚类熊果酸衍生物的合成及抗肝癌活性[J]. 化学试剂，2022，44（3）：477-483。
