【综述与专论】

荧光硫量子点的制备及其在金属离子检测中的应用

万园媛，王思涛，刘智敏，许志刚^*

（昆明理工大学 理学院，云南 昆明  650500）

摘要：硫量子点作为一种新型的荧光纳米材料，由于具有合成简单、尺寸分布均匀、毒性低、发光性能好等优点，在生物医疗、发光材料、荧光传感等领域有着广泛的应用。以硫量子点为基础构建的荧光传感方法具有操作简单、抗干扰能力强、检测速度快、准确度高等特点，在环境、食品、日化产品等复杂样品中金属离子的检测方面具有巨大的应用潜力。综述了硫量子点的几种不同合成方法，及其在金属离子检测方面的研究进展，讨论了硫量子点在合成和应用中尚需解决的问题，展望了硫量子点在金属离子检测中的发展前景。

关键词：硫量子点；荧光；制备技术；金属离子

中图分类号：O652.6          文献标识码：A         文章编号：0258-3283（2023）--

DOI：10.13822/j.cnki.hxsj.2023.0467

Preparation of Fluorescent Sulfur Quantum Dots and Its Application in Metal Ion Detection WAN Yuan-yuan, WANG Si-tao, LIU Zhi-min, XU Zhi-gang^* (Faculty of Science, Kunming University of Science and Technology, Kunming 650500, China)

Abstract: As a new type of fluorescent nanomaterials, sulfur quantum dots have been widely used in the fields of biomedicine, luminescent materials and fluorescence sensing due to their advantages of simple synthesis, uniform size distribution, low toxicity and good luminescence performance. Fluorescence sensing method based on sulfur quantum dots has the characteristics of simple operation, strong anti-interference ability, fast detection speed, and high accuracy, which plays an important role in analysis and detection of metal ions in complex samples such as environmental, food, and daily chemical products. This review highlights several different synthetic methods of sulfur quantum dots and their research progress in detection of metal ions. Finally, the problems that need to be solved in synthesis and application of sulfur quantum dots are discussed, and the development prospect of sulfur quantum dots in metal ion detection is prospected.

Key words: sulfur quantum dots; fluorescence; preparation technology; metal ion

引用本文：万园媛，王思涛，刘智敏，等.荧光硫量子点的制备及其在金属离子检测中的应用[J]. 化学试剂, 2023, 45(11):1-8.

无机物掺杂TiO₂吸附剂用于水中污染物吸附研究进展

黄孝明^1a，陈瑶^*2，陈国力^1a，韩悦^1b

（1. 齐齐哈尔大学 a.教学实验设备管理中心，b.化学与化学工程学院， 黑龙江 齐齐哈尔  161006；

2. 黑龙江省齐齐哈尔生态环境监测中心，黑龙江 齐齐哈尔  161005）

摘要：随着人类社会的发展，对自然水体环境影响逐渐提高，尤其是部分染料和重金属通过工业废水排放到自然界，导致水体环境受到了污染。迄今为止，人们研发出了一些新型的吸附剂，可以吸附废水中污染物，达到处理废水的目的。TiO₂基吸附剂一直是研究重点，利用金属、非金属等无机物掺杂可以有效提高吸附效率或扩展吸附范围，成为近年研究热点。对此进行分析概述可以为今后设计、制备无机物掺杂TiO₂吸附剂提供参考；同时讨论了相应的改性方法对吸附性能的影响，从而达到筛选出高性能吸附剂的目的；最后总结了TiO₂基无机物改性吸附剂材料目前存在的问题，并对今后的研究重点和方向提出了展望。

关键词：无机物掺杂；TiO₂；吸附剂；水中污染物；染料；重金属；吸附

中图分类号：X52           文献标志码：A        文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0452

Research Progress on Adsorption of Pollutants in Water by Inorganic Doped TiO₂ Adsorbent HUANG Xiao-ming^1a, CHEN Yao^*2, CHEN Guo-li^1a, HAN Yue^1b (1a. Teaching and experimental equipment management center, 1b. College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China; 2. Qiqihar Ecological Environment Monitoring Center of Heilongjiang Province, Qiqihar 161005, China)

Abstract: With the development of human society, the impact on natural water environment is gradually increasing. In particular, some dyes and heavy metals are discharged into nature through industrial wastewater, which leads to the pollution of water environment. So far, people have developed some new adsorbents, which can adsorb pollutants in wastewater for the purpose of wastewater treatment. TiO₂-based adsorbent has always been the focus of research. The use of metal, non-metal, and other inorganic substances doping can effectively improve the adsorption efficiency or expand the adsorption range, which has become a research hotspot in recent years. The analysis and summary of this project can provide reference for design and preparation of inorganic doped-TiO₂ adsorbent in the future. At the same time, the influence of modification methods on adsorption properties was discussed, so as to achieve the purpose of screening high-performance adsorbent. Finally, we summarized the existing problems of TiO₂-based inorganic modified adsorbent materials and proposed the future research focus and direction.

Key words: inorganic doping; TiO₂; adsorbent; pollutants in water; dye; heavy metals; adsorption.

引用本文：黄孝明, 陈瑶, 陈国力, 等. 无机物掺杂TiO₂吸附剂用于水中污染物吸附研究进展[J]. 化学试剂, 2023，45（11）：9-17.

【生化与药用试剂】

稀有人参皂苷对CCl₄所致小鼠急性肝损伤的保护作用

张言¹，李娜¹，黄蓉²，傅容湛¹，段志广^*1,2，范代娣^*1,2

（1. 西北大学 a.化工学院，b.生物医药研究院，陕西 西安  710069；

2. 陕西巨子生物技术有限公司，陕西 西安  710077）

摘要：探究了稀有人参皂苷改善急性肝损伤（Acute liver injury，ALI）的作用。通过酸水解法制备稀有人参皂苷Rk3、Rg5、Rh4，利用HPLC分离皂苷并检验皂苷单体纯度。体内实验用C57BL/6小鼠，小鼠随机分为对照组、ALI组、稀有人参皂苷Rk3组、稀有人参皂苷Rg5组、稀有人参皂苷Rh4组，除对照组外其余小鼠在灌胃人参皂苷1周后均腹腔注射CCl₄，实验结束禁食2 h后采集小鼠肝脏组织固定后，进行石蜡包埋用于后续H&E染色；收集全血样本，离心后测量小鼠血清中丙氨酸转氨酶（ALT）和天冬氨酸转氨酶（AST）含量；使用生理盐水对肝脏组织进行匀浆，离心后检测上清液氧化应激相关指标。稀有人参皂苷Rk3、Rg5、Rh4均能有效改善ALI引起的转氨酶表达异常及氧化应激等病理进程，降低血清ALT和AST含量，降低肝脏MDA水平，提高血清SOD和肝组织GSH-Px活性，并减少CCl₄造成的小鼠肝细胞坏死灶数量。结果表明，3种稀有人参皂苷均能够有效改善CCl₄诱导的急性肝损伤。

关键词：急性肝损伤（ALI）；人参皂苷；氧化应激；丙氨酸转氨酶（ALT）；天冬氨酸转氨酶（AST）

中图分类号：R965              文献标识码：A              文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0474

Protective Effect of Rare Ginsenosides on Acute Liver Injury in CCl₄-induced Mice ZHANG Yan¹, LI Na¹, HUANG Rong², FU Rong-zhan¹, DUAN Zhi-guang^*1,2, FAN Dai-di^*1,2 (1a. School of Chemical Engineering Northwest University, 1b. Biotech & Biomed Institute of Northwest University, Xi’an 710069, China; 2. Shaanxi Giant Biotechnology Co. Ltd., Xi’an 710077, China)

Abstract：The role of rare ginsenosides in improving acute liver injury (ALI) was investigated. Rare ginsenosides Rk3, Rg5 and Rh4 were prepared by acid hydrolysis, and the saponins were separated by HPLC and the purity of saponin monomers was tested. In vivo experiments with C57BL/6 mice, mice were randomly divided into control group, ALI group, rare ginsenoside Rk3 group, rare ginsenoside Rg5 group, rare ginsenoside Rh4 group. Except for the control group, the rest of the mice were intraperitoneally injected with CCl₄ after 1 week of gavage ginsenoside, and after 2 h of fasting at the end of the experiment, the liver tissues of mice were collected and fixed, and paraffin embedding was carried out for subsequent H&E staining. Whole blood samples were collected and the contents of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) in mouse serum were measured after centrifugation. Liver tissues were homogenized using normal saline, and indicators related to oxidative stress of the supernatant were detected after centrifugation. Rare ginsenosides Rk3, Rg5 and Rh4 could effectively improve pathological processes such as abnormal expression of transaminases and oxidative stress caused by ALI, reduce serum ALT and AST content, decrease the level of MDA in liver, increase serum SOD and GSH-Px activity of liver tissue, and reduce the number of hepatocytes necrotic foci in mice caused by CCl₄. The results showed that all three rare ginsenosides could effectively improve CCl₄-induced acute liver injury.

Key words：acute liver injury (ALI); ginsenosides; oxidative stress; Alanine aminotransferase (ALT); Aspartate aminotransferase (AST)

引用本文：张言, 李娜, 黄蓉, 等. 稀有人参皂苷对CCl₄所致小鼠急性肝损伤的保护作用[J]. 化学试剂, 2023,45（11）：18-24.

气囊蛋白基脑胶质瘤靶向诊疗一体化载体构建及其评价

崔雨童，韩佳铌，唐燕琼，马香，李宏，李娟娟，刘柱^*

（海南大学 生命科学学院，海南 海口 570208）

摘要：针对目前脑胶质瘤诊断治疗中靶向性差、治疗效率低等问题，设计合成以气囊蛋白（Gas vesicles，GV）为载体，透明质酸（Hyaluronic acid，HA）靶向负载阿霉素（Doxorubicin，DOX）的纳米药物递送系统。利用EDC/NHS脱水缩合反应，制备GV@hDOX载药系统，观察其对小鼠脑胶质瘤的杀伤作用以及超声成像效果。首先，通过化学反应将HA-DOX接枝在GV的表面，得到具有靶向作用的GV@hDOX；其次，通过透射电子显微镜和荧光光谱仪等仪器对GV和GV@hDOX的形貌结构进行表征；最后，对其体外稳定性、靶向肿瘤细胞吞噬与杀伤能力进行评价。透射电子显微镜和荧光光谱图表明GV@hDOX的成功合成，负载量为66.7 µg/OD500；与GV相比，GV@hDOX具有更高的超声成像能力；与游离DOX相比，GV@hDOX显著提高了小鼠脑胶质瘤GL261细胞对DOX的吞噬效率。GV@hDOX优异的超声成像和药物递送效率为脑胶质瘤的靶向载药系统的构建提供了新的思路，为进一步实现脑胶质瘤的高效治疗奠定了基础。

关键词：气囊蛋白；脑胶质瘤；阿霉素；载药系统

中图分类号：O65              文献标识码：A         

DOI：10.13822/j.cnki.hxsj.2023.0430

Synthesis and Evaluation of a Gas Vesicle-based Glioma Targeted Theragnostic Platform CUI Yu-tong, HAN Jia-ni, TANG Yan-qiong, MA Xiang, LI Hong, LI Juan-juan, LIU Zhu^* (School of Life Sciences, Hainan University, Haikou 570208)

Abstract: The purpose of this study is to design and synthesize a new nanodrug delivery system overcoming bad targeting and low efficiency in the treatment of glioblastoma. Gas vesicles (GV) are used as carriers, hyaluronic acid (HA) serves as targeting molecules, and doxorubicin (DOX) acts as the payload. The GV@hDOX drug delivery system was prepared using EDC/NHS dehydration condensation reaction, and its killing effect on mouse glioblastoma and ultrasound imaging were observed. Firstly, HA-DOX was grafted onto the surface of GV through a chemical reaction to obtain targeted GV@hDOX. Secondly, the morphology and structure of GV and GV@hDOX were characterized by transmission electron microscopy and fluorescence spectrophotometer. Finally, the in vitro stability, targeting tumor cell phagocytosis and killing ability were evaluated. GV@hDOX was successfully synthesized with a loading capacity of 66.7 µg/OD500. Compared with GV, GV@hDOX had higher ultrasound imaging ability, and it significantly increased the phagocytic efficiency of DOX by mouse glioblastoma GL261 cells compared with free DOX. Therefore, GV@hDOX with excellent ultrasound imaging and drug delivery efficiency provides a new approach for the treatment of glioblastoma, and lays a foundation for further research in the future.

Key words：gas vesicle; glioma cells; doxorubicin; drug delivery system

引用本文：崔雨童, 韩佳铌, 唐燕琼, 等. 气囊蛋白基脑胶质瘤靶向诊疗一体化载体构建与性能评价[J]. 化学试剂, 2023, 45(11)：25-31.

多光谱法结合分子模拟分析洛索洛芬和金属离子影响三磷酸腺苷对蛋白的作用机制

刘里^*，耿来应

（曲靖师范学院 化学与环境科学学院，云南 曲靖  655011）

摘要：利用光谱法结合分子模拟分析探究在血浆中常见的5种金属元素存在下，洛索洛芬对三磷酸腺苷抑制血清白蛋白的影响。研究结果表明，在洛索洛芬钠的影响下，三磷酸腺苷以静态猝灭的模式抑制蛋白的荧光强度。ΔG < 0，ΔH < 0且ΔS > 0，表明两种药物与蛋白的结合为自发的放热反应，作用力以氢键和范德华力为主。通过希尔方程，测定出希尔系数均略大于1，表明洛索洛芬和三磷酸腺苷之间有弱的正协同效应；同步荧光数据说明结合位点更加接近于酪氨酸残基。添加的镁、钴和锰明显增强抑制作用，反而铬和铁削弱了抑制作用。分子对接法证明光谱实验的结论，为后续进一步开展探究临床实践过程中应用合并用药对疾病进行治疗奠定一定的理论基础。

关键词：洛索洛芬；三磷酸腺苷；分子间作用机制；蛋白；金属离子；分子模拟；光谱法

中图分类号：O657.3              文献标识码：A              文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0404

Multi-Spectroscopy Combined with Molecular Docking to Analyze the effect of Loxoprofen and Metal Ions on the Mechanism of Adenosine Triphosphate to Protein LIU li^*, GENG Lai-ying (College of Chemistry and Chemical Engineering, Qujing Normal University, Qujing, 655011, China)

Abstract: The effects of loxoprofen on inhibition of serum albumin by adenosine triphosphate in the presence of five common metal elements in plasma were investigated by spectrometric method combined with molecular simulation. The results showed that under the influence of loxoprofen, adenosine triphosphate inhibited the fluorescence of proteins in a static quenching mode. ΔG < 0，ΔH < 0 and ΔS > 0 showed the interaction was spontaneous exothermic reaction and mainly driven by Vander Waals forces and hydrogen. The values of Hill's coefficients obtained by Hill equation were slightly bigger than 1, which concluded that there was weak positive cooperative effect between loxoprofen and adenosine triphosphate. The synchronous fluorescence data illustrated that the binding site was close to tyrosine residue. The addition of magnesium, cobalt and manganese only significantly enhanced the inhibition, but also weakened by chromium and iron. The physical modeling method is used to further illustrate the conclusions from spectroscopic experiment. In this study, spectrometric analysis and molecular docking simulation were combined to validate the prediction of interaction of the two drugs on serum albumin without performing cell experiments. Molecular docking method proved the conclusion of spectrograph experiment. It provides theoretical basis for exploration of the application of combination drugs for treating diseases in clinical practice.

Key words: loxoprofen; adenosine triphosphate; intermolecular mechanism; albumin; metal ions; molecular simulation

引用本文：刘里, 耿来应. 多光谱法结合分子模拟分析洛索洛芬和金属离子影响三磷酸腺苷对蛋白的作用机制[J]. 化学试剂, 2023,45（11）：32-38.

薄荷醇对牛血清蛋白光谱性质的影响研究

宋吉英^a，于春娣^*b，曹淑霞^a，马子媛^a 

(青岛农业大学 a.化学与药学院, b.食品科学与工程学院，山东 青岛 266109）

摘要：探讨了薄荷醇对牛血清蛋白光谱性质的影响，并分析了牛血清蛋白的荧光猝灭类型。实验采用荧光光谱、紫外光谱、同步荧光光谱和圆二色谱等分析手段，研究了薄荷醇对牛血清蛋白光谱性质的影响因素。结果表明，薄荷醇对牛血清蛋白有荧光猝灭作用，在二元体系中，随着薄荷醇浓度的增加，猝灭作用增强，10 min左右猝灭效果最为明显，随着温度升高，荧光猝灭效果增强。从紫外光谱、同步荧光光谱和圆二色谱的扫描结果看，加入薄荷醇后，牛血清蛋白与其发生作用生成了一种复合物。结合荧光数据分析薄荷醇对牛血清蛋白的荧光猝灭类型为静态猝灭和动态猝灭共存。

关键词：牛血清蛋白；薄荷醇；荧光猝灭；光谱研究；二元体系

中图分类号：O657.3    文献标识码：A       文章编号：0258-3283（2023）--

DOI：10.13822/j.cnki.hxsj.2023.0533

Study on the effect of menthol on the spectral properties of BSA ONG Ji-ying^a, YU Chun-di^*b, CAO Shu-xia^a, MA Zi-yuan^a (a. College of Chemistry and Pharmacy Sciences, b. College of Food Science and Technology, Qingdao Agricultural University, Shandong 266109)

Abstract：This article explored the effect of menthol on the spectral properties of bovine serum proteins and analyzed the fluorescence quenching types. The experiment used analytical methods such as fluorescence spectroscopy, ultraviolet spectroscopy, synchronous fluorescence spectroscopy, and circular dichroism to study the factors affecting the spectral properties of BSA caused by menthol. The results indicated that menthol had a fluorescence quenching effect on BSA. In binary system, with the increase of menthol concentration, the quenching effect was enhanced and which was the most obvious around 10 min. With the increase of temperature, the fluorescence quenching effect was enhanced. From the scanning results of ultraviolet spectrum, synchronous fluorescence spectroscopy and circular dichroism, it was found that bovine serum albumin reacted with menthol to form a complex. Combined with fluorescence data, the fluorescence quenching types of menthol on BSA were static quenching and dynamic quenching.

Key words：Bovine serum albumin; Menthol; Fluorescence quenching; Spectral study; Binary system

引用本文：宋吉英，于春娣，曹淑霞，等. 薄荷醇对牛血清蛋白光谱性质的影响研究[J].化学试剂，2023，45（11）：39-44.

【功能材料】

过氧亚硝基传感检测的荧光探针合成与应用

叶廷秀¹，杨林¹，罗红元¹，翁艳华¹，张琳¹，蔡玉萍¹，陈曦^*2

(1. 厦门医学院 a.药学系；b. 海洋生物医药资源福建省高校工程研究中心，福建 厦门 361023；

2. 厦门大学 化学化工学院，福建 厦门  361005)

摘要：设计合成了一种基于硼酸酯为识别基团的ONOO^-荧光探针4,4,5,5-四甲基-2-（4-((4-(1,2,2-三苯乙烯基)苯氧基)甲基)苯基）-1,3,2-硼酸频哪酯（TPE-BCO），采用核磁共振氢谱（¹HNMR）、质谱（MS）表征了TPE-BCO的结构，考察了TPE-BCO进行ONOO^-检测的可行性及检测条件。结果表明：ONOO^-对TPE-BCO的荧光有猝灭作用，当加入ONOO^-的浓度在0～7.0×

10^-5 mol/L时，荧光强度的变化与ONOO^-的浓度符合指数函数关系（R² = 0.9949）；在ONOO^-浓度为7.0×10^-6～2.8 ×10^-5 mol/L的范围内呈现良好的线性相关关系，线性方程F = -54.65C ＋ 1944.45（R² = 0.9935）；最佳响应时间为25 min，检测pH 7.4，检出限为2.4×10^-8 mol/L，该检测方法简便、灵敏度高、选择性好，可用于体外ONOO^-的浓度检测。

关键词：过氧亚硝基；硼酸酯；荧光探针；活性氮

中图分类号：O65              文献标识码：A              文章编号：0258-3283（2023）

DOI: 10.13822/j.cnki.hxsj.2023.0353

Synthesis and Application of a Fluorescent Probe for the Detection of Peroxynitrite YE Ting-xiu¹，YANG Lin¹，LUO Hong-yuan¹，WENG Yan-hua¹，ZHANG Lin¹, CAI Yu-ping¹, CHEN Xi^*2 (1a. School of Pharmacy, Xiamen Medical College, 1b. Fujian Universities and Colleges Engineering Research Center of Marine Biopharmaceutical Resources, Xiamen Medical College, Xiamen 361023, China; 2. College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China)

Abstract: A fluorescence probe, 4,4,5,5-tetramethyl-2-(4-((4-(1,2,2-triphenylvinyl) phenoxy) methyl) phenyl)-1,3,2-dioxaborolane (TPE-BCO) based on borate ester was designed and synthesized for sensing ONOO^-. The structure of TPE-BCO was characterized by mass spectrometry (MS) and hydrogen nuclear magnetic resonance spectroscopy (¹H-NMR), and the feasibility and sensing conditions by using TPE-BCO for ONOO^- were investigated. The results indicate that ONOO^- had a quenching effect on the fluorescence of TPE-BCO, and the fluorescence intensity conformed to the exponential function relationship when the concentration of ONOO^- was 0～7.0 ×10^-5 mol/L (R² = 0.9949). A good linear relationship in the range of ONOO^- was found to be 7.0×10^-6～2.8 ×10^-5 mol/L with a linear equation of F = -54.65C (ONOO^-) + 1944.45 (R² = 0.9935). The reaction time was 25 min, the detection pH was 7.4, and the detection limit was 2.4×10^-8 mol/L. This detection method is simple, sensitive, and reliable for the determination of ONOO^- in vitro, which can be used for in vitro detection of ONOO^-.

Key words：peroxynitrite; borate ester; fluorescent probe; reactive nitrogen

引用本文：叶廷秀，杨林，罗红元，等. 过氧亚硝基传感检测的荧光探针合成与应用[J]. 化学试剂, 2023, 45(11): 45-50.

聚乙烯亚胺碳化聚合物点的制备及其对H₂O₂的检测

陈阳^*，丁丽丽，刘辉

(吉林建筑大学基础科学部，吉林 长春  130118)

摘要：过氧化氢（H₂O₂）作为日常生活中一种常见的物质，其细胞毒性已引起人们的高度关注，建立准确、高效的H₂O₂检测方法具有重要意义。以聚乙烯亚胺（PEI）和谷胱甘肽为碳源通过一步水热法制备了粒径均匀、水溶性良好的蓝色荧光碳化聚合物点（PEI-CPDs）。通过透射电子显微镜、荧光光谱、紫外-可见吸收光谱和红外光谱对其结构和光学性质进行了研究。磷掺杂使PEI-CPDs荧光发射强度增大，荧光量子产率增高。基于MnO₂纳米片对PEI-CPDs的荧光内滤波效应淬灭其荧光，H₂O₂使其荧光恢复，建立了测定H₂O₂浓度的荧光“开”新方法，当H₂O₂浓度范围为在0～30 μmol/L时，PEI-CPDs的荧光发射恢复强度与H₂O₂浓度呈现较好的线性关系。

关键词：碳化聚合物点；聚乙烯亚胺；荧光；H₂O₂检测；磷掺杂

中图分类号：O655                 文献标识码：A              文章编号：0258-3283（2023）--

DOI：10.13822/j.cnki.hxsj.2023.0435

Preparation of Polyethyleneimine Carbonized Polymer Dots and Their Applications in H₂O₂ Detection CHEN Yang^*, DING Li-li, LIU Hui (Basic Science Department, Jilin Jianzhu University, Changchun 130118, China)

Abstract: Hydrogen peroxide (H₂O₂) is one of the common analytes in our daily life, and its cytotoxicity has attracted high attention. Therefore, establishing an accurate and efficient H₂O₂ detection method is of great significance. In this work, blue fluorescent carbonized polymer dots (PEI-CPDs) with uniform size and water-solubility were prepared by one-step hydrothermal method using polyethyleneimine (PEI) and glutathione as carbon sources. The structure and optical properties were investigated by transmission electron microscopy, fluorescence, UV-vis and Fourier transform infrared spectra. Phosphorus doping increases the fluorescence emission intensity and quantum yield of PEI-CPDs. Based on the inner filter effect of MnO₂ nanosheets on PEI-CPDs, the fluorescence of PEI-CPDs is effectively quenched, and the quenched fluorescence can be restored by H₂O₂. A novel method with fluorescence “off-on” response to H₂O₂ is established. The emission intensity of PEI-CPDs shows a good linear relationship versus H₂O₂ at concentrations ranging from 0～30 μmol/L.

Key words：carbonized polymer dots; polyethyleneimine; fluorescence; H₂O₂ detection; phosphorus doping

引用本文：陈阳，丁丽丽，刘辉. 聚乙烯亚胺碳化聚合物点的制备及其对H₂O₂的检测[J]. 化学试剂, 2023, 45(11): 51-55.

【分离提取技术】

3种类胡萝卜素在低共熔溶剂中的溶解度、稳定性和抗氧化活性

黄慧玲^a，李骏熙^b，邹婉琳^b，冯健峰^b，程婉婷^a，高静^*b

（广东药科大学 a.公共卫生学院，广东 广州  510000; b.食品科学学院，广东 中山  528400）

摘要：与离子液体（Ionic Liquids，ILs）和有机溶剂相比，低共熔溶剂（Deep Eutectic Solvents，DESs）是一种具有成本低和可设计等优点的新型绿色溶剂，近年来受到科学界不同领域的广泛关注。测定不同温度下3种类胡萝卜素（虾青素、叶黄素和β-胡萝卜素）在乙醇、离子液体三丁基辛基氯化膦（[P₄₄₄₈]Cl）和7种DESs中的溶解性、稳定性和抗氧化活性，同时将结果相互比较。结果显示：3种类胡萝卜素在DESs中的溶解度和抗氧化活性普遍高于[P₄₄₄₈]Cl和乙醇。薄荷醇类DESs比脂肪酸类DESs具有更强的类胡萝卜素溶解能力，但是酸性太强不利于保持稳定性。溶剂本身也存在一定的抗氧化活性，但加了类胡萝卜素后抗氧化活性显著增强。因此，类胡萝卜素的特性随溶剂性质、温度、自身结构不同而具有显著差异。明确这种差异和原因有助于探索一种更为高效和绿色的类胡萝卜素萃取溶剂，为进一步利用类胡萝卜素提供数据支撑和参考价值。

关键词：类胡萝卜素；低共熔溶剂；离子液体；溶解度；稳定性；抗氧化活性

中图分类号：R154                 文献标志码：A           文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0438

Solubility, Stability, and Antioxidant Activity of Three Carotenoids in Deep Eutectic Solvents HUANG Hui-ling^a, LI Jun-xi^b, ZOU Wan-lin^b, FENG Jian-feng^b, CHENG Wan-ting^a, GAO Jing*^b (Guangdong Pharmaceutical University, a. School of Public Health, Guangzhou 510000, China; b. School of Food Science, Zhongshan 528400, China), Huaxue Shiji, 2023,

Abstract：Compared with ionic liquids (ILs) and organic solvents, deep eutectic solvents (DESs) are new green solvents with the advantages of low cost and designability, which have received extensive attention in different fields of the scientific community in recent years. The solubility, stability, and antioxidant activity of three carotenoids (astaxanthin, xanthophyll and β-carotene) in the ethanol, ionic liquids tributyl(octyl)phosphonium chloride ([P₄₄₄₈]Cl), and seven DESs were determined at different temperatures. The results showed that the solubility and antioxidant activity of three carotenoids in DESs were generally higher than that of [P₄₄₄₈]Cl and ethanol. Menthol-based DESs presented a stronger carotenoid-soluble ability than fatty acid-based DESs, while DESs with high acidity was difficult to maintain the carotenoid stability. The solvent itself also had certain antioxidant activity, but the antioxidant activity was significantly enhanced after addition of carotenoids. Therefore, the performance of carotenoids varied significantly with the solvent properties, temperatures, and self-structures. Clarifying the differences and reasons is helpful to explore more efficient and green extraction solvents for carotenoids, and will provide detailed data and guide for the application of carotenoids in the future.

Key words: carotenoids; deep eutectic solvent; ionic liquids; solubility; stability; antioxidant activity

引用本文：黄慧玲, 李骏熙, 邹婉琳, 等. 3种类胡萝卜素在低共熔溶剂中的溶解度、稳定性和抗氧化活性[J]. 化学试剂, 2023, 45(11):56-64.

【电化学和新能源】

基于多金属掺杂的氧化铈阳极的甲烷协助电解水制氢研究

冯华,章寒冰^*,叶吉超，胡鑫威,徐永海

（国网浙江省电力有限公司丽水供电公司，浙江 丽水  323000）

摘要：采用甲烷协助电解水制氢可以显著降低固体氧化物电解池制氢电耗。从甲烷氧化活性和氧离子传导性的角度出发，采用一锅水解法制备了氧化锆和氧化钐掺杂的氧化铈阳极材料（Sm_0.1Zr_0.1Ce_0.8O_2−x），并同时一锅负载Ni、Co和Fe活性金属。结果表明钐和锆的掺杂显著提高氧化铈的氧化活性，而Ni金属负载可以是甲烷完全转化温度降低75 ℃，良好的甲烷氧化活性可以实现甲烷气氛下更低的电解电压。不同负载金属的结果表明，具有良好甲烷氧化活性的Ni、Co负载Sm_0.1Zr_0.1Ce_0.8O_2−x在不同电流密度下均体现出甲烷协助电解水性能，低的欧姆阻抗和高频极化阻抗使Co负载的阳极具有更高的性能，电解电压低至0.37 V@250 mA/cm²；缺乏甲烷氧化活性的Fe负载Sm_0.1Zr_0.1Ce_0.8O_2−x具有良好的析氧性能、但缺乏甲烷辅助性能。具有甲烷氧化活性性能是实现甲烷协助电解水制氢的关键。

关键词：氧化铈；金属掺杂；甲烷氧化；电解水制氢；固体氧化物电解池

中图分类号：TK91         文献标识码：A            文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0486

Methane Assisted Hydrogen Production by Water Electrolysis Using Polymetallic Doped Cerium Oxide Anodes FENG Hua, ZHANG Han-bing^*, YE Ji-chao, HU Xin-wei, XU Yong-hai (Lishui Power Supply Company, State Grid Zhejiang Electric Power Co. Ltd., Lishui 323000, China)

Abstract: The use of methane to assist electrolysis of water to produce hydrogen can significantly reduce the electricity consumption for hydrogen production in solid oxide electrolytic cells. Herein, zirconia and samarium oxide-doped cerium oxide anode materials (Sm_0.1Zr_0.1Ce_0.8O_2−x) are prepared by one-pot hydrolysis from the perspectives of methane oxidation activity and oxygen ion conductivity. Simultaneously, nickel (Ni), cobalt (Co), and iron (Fe) catalytic metals are loaded in one pot. The results show that the doping of samarium and zirconium greatly increases the oxidation activity of cerium oxide, while Ni metal loading can reduce the complete oxidation temperature by 75°C. And high methane oxidation activity can achieve lower electrolytic voltage in methane atmosphere. The results show that Ni and Co loaded Sm_0.1Zr_0.1Ce_0.8O_2−x with good methane oxidation activity show methane-assisted water electrolysis performance at different current densities. The low ohmic impedance and high-frequency polarization impedance of the Co-loaded anode contribute to its superior performance, achieving electrolysis voltage as low as of 0.37 V@250 mA/cm². Fe-loaded Sm_0.1Zr_0.1Ce_0.8O_2−x with poorer methane oxidation activity exhibits high oxygen evolution performance, but lacks methane assisment for water electrolysis. Methane oxidation activity is the key to achieving methane-assisted electrolysis of water to hydrogen production.

Key words: cerium oxide; metal doping; methane oxidation; hydrogen production by electrolysis of water; solid oxide electrolytic cell

引用本文：冯华, 章寒冰, 叶吉超, 等. 基于多金属掺杂的氧化铈阳极的甲烷协助电解水制氢研究[J]. 化学试剂, 2023,45（11）：65-70.

碱性氢氧化电催化剂研究进展

王君^*1,杨晓丹²

(1. 天津市河北区教师发展中心，天津  300010；2. 天津师范大学 化学学院，天津  300387)

摘要：氢是一种清洁、可再生的能源载体，有望在未来促进低碳能源经济的发展。氢氧燃料电池可将氢能转为电能，大大提高了氢能源的转化效率。在碱性条件下运行的阴离子交换膜燃料电池(AEMFCs)，由于可以利用低成本的非铂电催化剂来驱动阴极氧还原反应(ORR)引起了广泛关注。然而，AEMFCs的阳极氢氧化反应(HOR)的反应动力学与酸性条件下相比低2～3个数量级，需要高活性、高稳定性的HOR催化剂来驱动，因此大量的碱性HOR催化剂被设计开发。综述了近年来碱性HOR电催化剂的研究进展，介绍了碱性HOR的反应机理、性能评价标准以及近期报道的新型HOR催化剂，重点关注了这些催化剂的设计思路、催化性能、反应机理等，并对未来碱性HOR催化剂设计的挑战和机遇进行了展望。

关键词：氢氧化反应；阴离子交换膜燃料电池；铂族催化剂；镍基催化剂；电催化

中图分类号：O646               文献标识码：A               文章编号：0258-3283（2023）--

DOI：10.13822/j.cnki.hxsj.2023.0457

Research Progress of Alkaline Hydrogen Oxidation Electrocatalysts WANG Jun*1, YANG Xiao-dan2 (1. Hebei District Teacher Development Center of Tianjin, Tianjin 300010, China; 2. College of Chemistry, Tianjin Normal University, Tianjin 300387, China)

Abstract: Hydrogen is a kind of clean and renewable energy carrier, which is promising to accelerate the development of a low-carbon energy economy in the future. Hydrogen-oxygen fuel cell can convert hydrogen energy into electricity energy, which greatly improves the efficiency of hydrogen energy conversion. Anion exchange membrane fuel cells (AEMFCs) operating in alkaline conditions have attracted much attention because of the availability of low-cost non-platinum electrocatalysts to drive cathodic oxygen reduction reaction (ORR). However, the reaction kinetics of anodic hydrogen oxidation reaction (HOR) of AEMFCs is 2～3 orders of magnitude lower than that in acidic conditions, and HOR catalysts with high activity and stability are often required. As a result, a large number of alkaline HOR catalysts have been explored and developed. In this paper, the research progress of alkaline HOR electrocatalysts in recent years has been comprehensively reviewed. The reaction mechanism and performance evaluation criteria of the basic HOR have been introduced, together with the newly reported HOR electrocatalysts. The designing ideas, catalytic performances, and reaction mechanism have been emphasized. Further, the challenges and opportunities for the design of alkaline HOR catalysts in the future are predicted.

Key words: hydrogen oxidation reaction; anion exchange membrane fuel cells; platinum-group catalysts; Ni-based catalysts; electrocatalysis

引用本文：王君，杨晓丹. 碱性氢氧化电催化剂研究进展[J]. 化学试剂, 2023, 45(11): 71-80.

基于铂@碳球@四氧化三铁/玻碳电极电化学传感器检测双酚A的研究

邵征^*1，冯奇¹，任国艳²

（1. 长垣烹饪职业技术学院 食品学院，河南 新乡  453400；2. 河南科技大学 食品与生物工程学院，河南 洛阳  471023）

摘要：制备了一种新型的铂@碳球@四氧化三铁纳米复合材料（Platinum@carbon ball@iron tetraoxide nanocomposites，Pt@Cs@Fe₃O₄），并采用玻碳电极（Glassy Carbon Electrode，GCE）为工作电极，构建了Pt@Cs@Fe₃O₄/GCE传感器对牛奶中的双酚A进行定量分析。通过对Pt@Cs@Fe₃O₄进行形貌和电化学表征对Pt@Cs@Fe₃O₄的电催化特性、导电性、吸附性等进行研究；通过对电解质种类、pH、富集时间以及富集电位的优化确定了Pt@Cs@Fe₃O₄/GCE的最佳工作条件。研究发现，Pt@Cs@Fe₃O₄对双酚A的电化学反应具有良好的催化作用，能够显著提高传感器的灵敏度。双酚A浓度与峰电流Ip在0.05 ~ 70 μmol/L范围内呈良好的线性关系，检出限（S/N = 3）为0.0184 μmol/L，对不同浓度的BPA加标回收率为96.89% ~ 101.02%，回收效果较好且Pt@Cs@Fe₃O₄/GCE对常见干扰物有良好的抗干扰能力。Pt@Cs@Fe₃O₄/GCE操作简单、成本低在快速检测双酚A方面具有较大的应用潜力。

关键词：双酚A；铂；碳球；四氧化三铁；纳米复合材料；电化学；传感器

中图分类号：O657.1;TQ64  文献标志码：A        文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0456

Study on the Detection of Bisphenol A Based on Platinum@Carbon Ball@Iron Tetraoxide/Glassy Carbon Electrode Electrochemical Sensor SHAO Zheng^*1, FENG Qi¹, REN Guo-yan² (1. Food College of Changyuan Culinary Vocational and Technical College, Xinxiang, Henan 453400, China;

2. School of Food and Bioengineering, Henan University of Science and Technology, Luoyang, China)

Abstract: A new type of platinum@carbon ball@iron tetraoxide nanocomposites (Pt@Cs@Fe₃O₄) was synthetized and Pt@Cs@Fe₃O₄/GCE was prepared using glassy carbon electrode (GCE) as the working electrode for detecting bisphenol A in milk. The electrocatalytic properties, conductivity, and adsorption of Pt@Cs@Fe₃O₄ were studied by morphology and electrochemical characterization tests. The best working conditions of Pt@Cs@Fe₃O₄/GCE were determined by optimizing the type of electrolyte, pH, enrichment time and enrichment potential. It was found that Pt@Cs@Fe₃O₄ had a good catalytic effect on the electrochemical reaction of bisphenol A and could significantly improve the sensitivity of the sensor. Bisphenol A concentration and peak current Ip were linear relationship between 0.05 and 70 μmol/L, the detection limit (S/N=3) was 0.0184 μmol/L, the recovery rate of different concentrated bisphenol A were 96.89%~101.02%, the recovery effect was good and Pt@Cs@Fe₃O₄/GCE has good anti-interference ability against common interfering substances. Pt@Cs@Fe₃O₄/GCE had great potentials in rapid detection of bisphenol A due to its simple operation and low cost.

Key words: bisphenol A; platinum; carbon spheres; iron tetroxide; nanocomposite materials; electrochemistry; sensor

引用本文:邵征, 冯奇, 任国艳. 基于铂@碳球@四氧化三铁/玻碳电极电化学传感器检测双酚A的研究[J]. 化学试剂, 2023, 45（11）：81-87.

【化学品与环境】

柴油车尾气SCR脱硝催化剂研究进展

郑乐辰，李祥如，王靖霏，訾学红^*，宋丽云，何洪

(北京工业大学 环境与生命学部，北京  100124)

摘要：柴油车尾气污染物主要有碳氢化合物（HC）、二氧化硫（SO₂）、一氧化碳（CO）、烟尘和氮氧化物（NOx），随着发动机工况的变化，尾气的组成也会发生变化。柴油车尾气中氧气含量较高，所以HC和CO的排放量较少，颗粒物和NOx是最主要的污染物。控制柴油车尾气中NO_x的排放是机动车尾气治理的重要一环，开发具有更好性能的选择性催化还原（SCR）催化剂，可以有效应对NO_x造成的大气污染。介绍了NH₃-SCR技术治理柴油车尾气的原理，归纳了目前柴油车车用NH₃-SCR催化剂的特点和主要问题。通过催化剂活性组分调配、元素掺杂、改性等方法提高催化剂的脱硝性能。研发具有较高的低温活性、高温稳定性，且成本较低的催化剂，仍是当前研究的主要方向。

关键词：柴油车；选择性催化还原；脱硝催化剂；NO_x排放；尾气治理

中图分类号：O643.3           文献标志码：A           文章编号：0258-3283（2023）--

DOI：10.13822/j.cnki.hxsj.2023.0454

Review on SCR DeNOx Catalysts for Diesel Vehicle Exhaust ZHENG Le-chen, LI Xiang-ru, WANG Jing-fei, ZI Xue-hong^*, SONG Li-yun, HE Hong （The Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China）

Abstract: The exhaust pollutants of diesel vehicles mainly include hydrocarbons (HC), sulfur dioxide (SO₂), carbon monoxide (CO), soot particles, and nitrogen oxides (NO_x). The composition of the exhaust gas varies with the engine conditions changes. The oxygen content of diesel exhaust is relatively high, so the emissions of hydrocarbons and carbon monoxide are relatively low, and soot particles and nitrogen oxides are the main components. It is important to control the emission of nitrogen oxides (NO_x) from diesel vehicles. Developing selective catalytic reduction (SCR) catalysts with better performance can effectively address atmospheric pollution caused by NO_x. This paper introduces the principle of selective catalytic reduction of NO_x by ammonia (NH₃-SCR), summarizes the characteristics and main problems of NH₃-SCR catalysts currently used in diesel vehicles. The methods are summarized to improve the denitrification performance of the catalyst through the blending of active components, element doping, and modification. Efforts are still needed to develop catalysts with high low-temperature activity, high temperature stability, and low cost.

Key words: diesel vehicle; selective catalytic reduction; denitration catalyst; NO_x emissions; vehicle emission control

引用本文：郑乐辰，李祥如，王靖霏，等. 柴油车尾气SCR脱硝催化剂研究进展[J]. 化学试剂, 2023, 45(11): 88-97.

水热处理对Cu/SSZ-39脱硝催化剂性能的影响

岳彦伟¹, 黄力^{*2, 3}，王素芹^{2, 3}，李金珂¹，王虎¹

(1. 大唐南京环保科技有限责任公司，江苏 南京  211111；2. 江苏集萃托普索先进催化技术研究所，江苏 苏州  215132；3. 江苏集萃托普索清洁能源研发有限公司，江苏 苏州  215132)

摘要：采用离子交换法制备了Cu/SSZ-39催化剂。随后，对催化剂进行不同温度下的水热处理。采用XRF、XRD、SEM、N₂-吸附脱附、H₂-TPR、XPS和NH₃-TPD表征，分析了催化剂的成分、结构、形貌等性质。随后，在固定床微型反应评价装置上测试了催化剂的脱硝活性。结果显示，水热处理对Cu/SSZ-39催化剂的成分、晶型、形貌和孔结构影响较小，但会导致催化剂上Cu物种的结构和催化剂的酸性的改变。650 ℃水热处理后，催化剂上部分Cu(OH)⁺-Z物种转变成了CuO_x物种和Cu²⁺-2Z物种。进一步提升水热处理温度至750 ℃，催化剂上更多CuO_x物种生成，同时催化剂的酸性下降。因此，经650 ℃水热处理后，催化剂的脱硝活性略低于新鲜催化剂，而在750 ℃下水热处理后的催化剂却显示了最低的脱硝活性。

关键词：脱硝；Cu/SSZ-39；水热处理；催化剂；选择性催化还原

中图分类号：TQ032.4      文献标识码：A      文章编号：0258-3283（2023）--

DOI: 10.13822/j.cnki.hxsj.2023.0428

Influence of Hydrothermal Treatment on the Catalytic Performance of Cu/SSZ-39 De-NO_x Catalyst YUE Yan-wei ¹, HUANG Li^{*2, 3}, WANG Su-qin^{2, 3}, LI Jin-ke¹, WANG Hu¹ (1. Datang Nanjing Environmental Protection Technology Co., Ltd, Nanjing 211111, China;2. Jiangsu JITRI-Topsøe Institute of Advanced Catalytic Technology, Suzhou 215132, China;3. Jiangsu JITRI-Topsøe Clean Energy R＆D Co., LTD, Suzhou 215132, China)

Abstract: Cu/SSZ-39 catalyst was prepared by ion-exchange method. Then the catalyst was hydrothermal treated at different temperatures. XRF, XRD, SEM, N₂-adsorption, H₂-TPR, XPS, and NH₃-TPD were carried out to characterize the physiochemical properties of the catalysts. The catalytic performances of the catalysts were tested via a fixed-bed micro-reactor. The results showed that the hydrothermal treatment had little impact on the composition, crystal structure, morphology, and pore structure of the catalyst. However, the hydrothermal treatment would lead to the alteration of Cu species and the acidity of the catalyst. A part of the Cu(OH)⁺-Z species would transform to CuO_x and Cu²⁺-2Z species, after hydrothermal treatment at 650℃. More CuO_x species would be generated when the hydrothermal treatment temperature was increased to 750℃. Meanwhile, the acidity of the catalyst also decreased. As a result, the catalytic activity of the catalyst hydrothermally treated at 650℃ was slightly lower than that of fresh sample, while the catalyst hydrothermally treated at 750℃ exhibited the poorest catalytic performance among the three catalysts.

Keywords: De-NO_x; Cu/SSZ-39; hydrothermal treatment; catalyst; selective catalytic reduction

引用本文：岳彦伟，黄力，王素芹，等. 水热处理对Cu/SSZ-39脱硝催化剂性能的影响[J]. 化学试剂, 2023, 45(11): 98-103.

【分析与测试】

加速溶剂同步萃取-气相色谱-串联三重四极杆质谱法测定香辛料中有机磷类农药残留

曾秋霞^1,2，黄敏兴^*1,2，刘泽槟^1,2，高裕锋^1,2，王桂华^1,2，陈晓初^1,2

（1. 广东省科学院生物与医学工程研究所， 广东 广州  510316；

2. 中国轻工业甘蔗制糖工程技术研究中心，广东 广州  510316）

摘要：采用加速溶剂同步萃取净化技术，建立了气相色谱-负化学源-串联质谱（GC-NCI-MS/MS）靶向测定香辛料中20种有机磷农药残留的方法。在萃取溶剂为80%乙腈水溶液、萃取温度为80 ℃、冲洗体积为60%萃取池体积、循环1次的加速溶剂萃取条件下，采用400 mg PSA、200 mg C₁₈、60 mg GCB在线同步净化，在负化学源多反应监测模式（MRM）下测定，外标法定量。20种有机磷农药线性良好（r²＞0.999），检出限（LOD）在0.01 ~ 0.28 μg/kg之间，定量限（LOQ）在0.03 ~ 0.93 μg/kg之间。在0.4、4.0、8.0 μg/kg 这3个加标水平下，20种有机磷回收率范围为75.63% ~ 107.42%，相对标准偏差为0.38% ~ 7.36%（n = 6）。该方法具有简单高效、灵敏度高且准确等优点，适用于香辛料中有机磷类农药残留检测。

关键词：香辛料；有机磷；加速溶剂同步萃取净化；GC-NCI-MS/MS

中图分类号：O658              文献标识码：A              文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0464

Determination of Organophosphorus Pesticide Residues in Spices by Accelerated Solvent Synchronous Extraction and Purification-GC-NCI-MS/MS ZENG Qiu-xia^1,2, HUANG Min-xing^*1,2, LIU Ze-bing^1,2, GAO Yu-feng^1,2, WANG Gui-hua^1,2, CHEN Xiao-chu^1,2 (1. Institute of Biological and Medical Engineering, Guangdong Academy of Sciences, Guangzhou 510316, China; 2. Research Center for Sugarcane Industry Engineering Technology of Light Industry of China, Guangzhou 510316, China), Huaxue Shiji

Abstract: A method was established for the determination of 20 organophosphorus pesticide residues in spices using accelerated solvent simultaneous extraction and purification coupled with gas chromatography-negative chemical source-tandem mass spectrometry (GC-NCI-MS/MS). The target compounds were extracted from spices using 80% acetonitrile aqueous solution with 60% of pool volume at 80℃ via a single cycle of accelerated solvent extraction. The extracts were synchronously purified with 400 mg primary secondary amine (PSA), 200 mg octadecylsilane (C₁₈), and 60 mg graphitized carbon black (GCB) added to the extracting. The target compounds were detected by GC-NCI-MS/MS in multiple reaction monitoring modes (MRM), and quantified by using the external standard method. Under the optimized conditions, good linearities were obtained for 20 organophosphorus pesticide residues with coefficients of determination greater than 0.999. The LOD was 0.01 ～0.28 μg/kg and the LOQ was 0.03 ～0.93 μg/kg. At three spiked levels (0.4, 4.0, 8.0 μg/kg) in spices, the recoveries of 20 organophosphorus pesticide residues were between 75.63% and 107.42%, with the relative standard deviations varying from 0.38% to 7.36% (n = 6). The method is simple, rapid, sensitive and accurate to meet requirements of organophosphorus pesticide residues analysis in spices.

Key words：spices; organophosphorus; accelerate simultaneous solvent extraction and purification; GC-NCI-MS/MS

引用本文：曾秋霞, 黄敏兴, 刘泽槟, 等. 加速溶剂同步萃取-气相色谱-串联三重四极杆质谱法测定香辛料中有机磷类农药残留[J]. 化学试剂，2023，45（11）：104-110.

基于高密度低共熔溶剂的分散液液微萃取

于洋，陈小雅，丁夕格，葛丹丹^*，王颖臻

（昆明学院 化学化工学院，云南 昆明  650214）

摘要：以六氟异丙醇为氢键供体，分别以辛胺、壬胺和癸胺氢键受体合成出一类新型高密度疏水性低共熔溶剂（DES）并作为萃取溶剂，用于涡旋辅助-分散液液微萃取-高效液相色谱法检测专利蓝V和固绿FCF。对影响萃取效率的因素进行优化，结果表明，n(辛胺) : n(六氟异丙醇)=1:2制备出的DES为萃取溶剂，萃取剂使用量为50 μL，盐浓度为1%，pH 10，旋涡萃取时间是2 min。在最优化条件下，专利蓝V和固绿FCF在浓度6 ~ 1000 ng/mL之间有良好的线性关系；方法检出限为2.0 ~ 2.6 ng/mL，定量限为6.0 ~ 8.0 ng/mL，相对标准偏差为1.0% ~ 10.0%。该方法简便、快速并且绿色环保，可用于水样和饮料样中的专利蓝V和固绿FCF分析。

关键词：分散液-液微萃取；高密度疏水性低共熔溶剂；高效液相色谱；色素；六氟异丙醇

中图分类号：O661.1              文献标识码：A         文章编码：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0422

High Density Deep Eutectic Solvents Based Dispersive Liquid-liquid Microextraction YU Yang, CHEN Xiao-ya, DING Xi-ge, GE Dan-dan^*, WANG Ying-zhen (School of Chemistry and Chemical Engineering, Kunming University, Kunming 650214, China)

Abstract: A new type of hydrophobic high density deep eutectic solvents (DESs) was prepared using hexafluoroisopropanol (HFIP, as hydrogen bond donor) and octylamine, nonylamine and decylamine (as hydrogen bond acceptor). The prepared DESs were used as extraction solvents and applied to vortex-assisted dispersive liquid-liquid microextraction of patent blue V and fast green FCF. Some parameters influencing the extraction efficiency were optimized. The obtained results show that DES prepared from octylamine and HFIP at the molar ratio of 1:2 was used as extraction solvent, the extraction solvent volume was 50 μL, the vortex time was 2 min, the salt concentration was 1%  the solution was pH 10. Under the optimized conditions, a linear range of 6 ~ 1000 ng/mL with determination coefficients of < 0.999 was obtained. The limits of detection were 2.0 ~ 2.6 ng/mL. The limits of quantification of the method were 6.0 ~ 8.0 ng/mL. Relative standard deviations were 1.0% ~ 10%. This method is easy to operat, fast and environmental friendly, and can be applied to determine patent blue V and fast green FCF in environmental water and drink samples.

Key words: dispersive liquid-liquid microextraction; high density hydrophobic deep eutectic solvent; high performance liquid chromatography; pigment; hexafluoroisopropanol

引用本文：于洋, 陈小雅, 丁夕格, 等. 基于高密度低共熔溶剂的分散液液微萃取[J]. 化学试剂, 2023,45（11）：111-116.

基于多指标定量指纹图谱和化学计量学的淫羊藿质量标准提高研究

孙礼堂¹，刘明川¹，曹健¹，宋彤彤¹，Jennifer Alfrey²，李敏杰^*1

（1.玫琳凯（中国）有限公司，浙江 杭州  310000；

2.Mary Kay Inc, Manufacturing and R&D Center, Texas Lewisville  75067）

摘要：进一步完善淫羊藿质量评价体系，提高淫羊藿质量标准。以6种8-异戊烯基黄酮苷作为指标成分，通过HPLC对4个品种、共24批次淫羊藿开展多指标定量指纹图谱的研究，并结合聚类分析（Hierarchical Clustering Analysis，HCA）、主成分分析（Principal Component Analysis，PCA）和正交偏最小二乘法判别分析（Orthogonal Partial Least Squares Discriminant Analysis，OPLS⁃DA）化学计量学方法进行质量评价。4个品种淫羊藿在相似度、指标成分含量上差异较大。发现朝藿定C、淫羊藿苷、淫羊藿次苷Ⅰ和宝藿苷Ⅰ是造成不同品种淫羊藿差异的特征性成分，淫羊藿次苷Ⅰ和宝藿苷Ⅰ可作为药材质量控制指标成分。建立的多指标定量指纹图谱分析方法稳定、可靠，结合化学计量学可更加全面、快速对淫羊藿进行质量评价，为今后提高淫羊藿的质量标准提供了科学依据。

关键词：淫羊藿；多指标定量指纹图谱；8-异戊烯基黄酮苷；化学计量学；质量标准提高

中图分类号：R284.1            文献标识码：A              文章编号：0258-3283（2023）--

DOI：10.13822/j.cnki.hxsj.2023.0410

Study on the Improvement of Quality Standard for Epimedium Based on Multi-index Quantitative Fingerprint and Stoichiometry SUN Li-tang¹, LIU Ming-chuan¹, CAO Jian¹, SONG Tong-tong¹, Jennifer Alfrey², LI Min-jie^*1 (1.Mary Kay (China) Company Ltd., Hangzhou 310000, Zhejiang, China; 2.Mary Kay Inc, Manufacturing and R&D Center, Lewisville 75067, Texas, USA)

Abstract: To improve the quality evaluation method and the quality standard of Epimedium. 24 batches of Epimedium from 4 species were studied based on six kinds of 8-isopentenyl flavonoid glycosides as index components. Multi-index quantitative fingerprint was studied by HPLC. Quality evaluation was carried out with stoichiometric methods such as hierarchical clustering analysis (HCA), principal component analysis (PCA), and orthogonal partial least squares discriminant analysis (OPLS⁃DA). The four species Epimedium have significant instructions for similarity and content of index components. Epimedium C, icariin, icariside I and baohuoside I may be the characteristic components that cause the differences between diverse Epimedium. Therefore, Icariside I and baohuoside I could be used as quality control index components. The established analysis method of multi-index quantitative fingerprint is stable and reliable. Combined with chemometrics, the quality evaluation of Epimedium can be more comprehensive and rapid, which provides a scientific basis for improving the quality standard of Epimedium in the future.

Key words: Epimedium; multi-index quantitative fingerprint; 8-isopentenyl flavonoid glycosides; stoichiometry; improvement of quality standard

引用本文：孙礼堂，刘明川，曹健，等. 基于多指标定量指纹图谱和化学计量学的淫羊藿质量标准提高研究[J]. 化学试剂, 2023, 45(11): 117-125.

【合成与工艺技术】

电催化合成1,2-二硼化合物的研究

贾智棋¹，张亚会²，宋艳玲^*1，卿光焱^*2

（1. 沈阳化工大学 制药与生物工程学院，辽宁 沈阳  110142；

2. 中国科学院大连化学物理研究所 分离分析化学重点实验室，辽宁 大连  116023）

摘要：1,2-二硼化合物是一种新型的有机硼类化合物，该化合物可构建复杂和精细的化学品。然而，用简单的烯烃为原料合成二硼化合物的方法非常有限，这是合成领域中一个具有挑战性的研究。利用绿色可持续的电力作为输出能源，提出了一种由N,N-二甲基甲酰胺（DMF）和N,N-二异丙基乙胺（DIEA）共同促进1,2-二硼化合物的电催化合成方法，其中溶剂DMF和DIEA的促进作用对整个催化体系的产率有非常重要的影响。该方法具有高收率和良好的功能相容性等优点，这种1,2-二硼化合成方法的原材料易获取，为烯烃二硼化反应提供了一种独特的方案。

关键词：有机硼类化合物；电催化；烯烃；硼化反应；1,2-二硼化合物

中图分类号：O646              文献标识码：A              文章编号：0258-3283（2023）

DOI：10.13822/j.cnki.hxsj.2023.0495

Synthesis of 1,2-Diboron Compounds by Electrocatalysis JIA Zhi-qi¹, ZHANG Ya-hui², SONG Yan-ling^*1, QING Guang-yan^*2 (1. Department of Pharmaceutical Engineering, Shenyang University of Chemical Technology, Shenyang, 110142, China; 2. CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China)

Abstract：1,2-diboron compounds are a new class of organoboron compounds, which can be used to build complex and fine chemicals. However, there are few methods to synthesize diboron compounds from simple alkenes, which is challenging in the field of synthesis. In this study, electrocatalytic synthesis of 1,2-diboron compounds co-promoted by N, N-dimethylformamide (DMF) and N, N-diisopropylethylamine (DIEA) is proposed for the first time by utilizing green and sustainable electric power as the output energy source, in which the promote of solvents DMF and DIEA has a crucial effect on the yield of whole catalytic system. This method has the advantages of high yield and good functional compatibility. The raw materials of this 1,2-diborylation synthesis method are easily accessible and provide a unique scheme for the alkene diborylation reaction.

Key words：organoboron compounds; electrocatalytic; alkene; diborylation reaction; 1, 2-diboron compounds

引用本文：贾智棋, 张亚会, 宋艳玲, 等. 电催化合成1,2-二硼化合物的研究[J]. 化学试剂, 2023, 45（11）：126-133 .

新型吡唑并[3,4-d]嘧啶-4-酮类PDE5抑制剂的合成及其活性研究

朱玉岚^a，刘玉乾^b，黄险峰^*b

（常州大学a.石油化工学院，b.药学院生物与食品工程学院，江苏常州213164）

摘要:设计并合成了一系列以吡唑并嘧啶酮为母核的PDE5抑制剂。通过放射性同位素法测定了其对PDE5的抑制活性，并计算半数有效抑制浓度（IC₅₀），随后对目标化合物进行了PDEs亚型选择性评价。化合物结构经核磁共振及质谱表征确认。活性评价结果显示，所合成的化合物对PDE5均具有一定的抑制活性，其中6-苄基-1-(4-苯基丁基)-1,5-二氢-4H-吡唑并[3,4-d]嘧啶-4-酮表现出最强的PDE5抑制活性，其IC₅₀达到90nmol/L，具有发展成为PDE5抑制剂的潜力。

关键词:PDE5；抑制剂；吡唑并[3,4-d]嘧啶-4-酮；合成；分子对接

中图分类号：O62文献标识码：A              文章编号：0258-3283

DOI：10.13822/j.cnki.hxsj.2023.0417

Synthesis and Biological Evaluation of Novel Pyrazolo[3,4-d]pyrimidin-4-one Derivatives as PDE5 InhibitorsZHU Yu-lan^a,LIU Yu-qian^b,HUANG Xian-feng^*b(a.School of Petrochemical Engineering; b. School of Pharmacy & School of Pharmacy Biological and Food Engineering, Changzhou University,Changzhou213164, China), HuaxueShiji, 2023,

Abstract：A series of pyrazolo[3,4-d]pyrimidin-4-ketone derivatives were designed and synthesizedas PDE5 inhibitors, and their inhibitory activities were evaluated by theisotopic tracer method. The PDEs selectivity of thetarget compound was also investigated. The chemical structures were characterized by ¹HNMR and ESI-MS. All of compounds showed inhibitory activities on PDE5, in which 6-benzyl-1-(4-phenylbutyl)-1,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-ketone exhibited the most potent inhibitory activity (IC₅₀ for PDE5: 90 nmol/L). Therefore, it has thepotential to develop into PDE5 inhibitor.

Keywords: PDE5; inhibitor; pyrazolo[3,4-d]pyrimidin-4-one; synthesis; molecular docking

引用本文：朱玉岚, 刘玉乾, 黄险峰.新型吡唑并[3,4-d]嘧啶-4-酮类PDE5抑制剂的合成及其活性研究[J]. 化学试剂, 2023, 45(11)：134-139.

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