几种常用还原剂在铬污染土壤中的应用探讨
白俊宾，江晓玲,杨红健*
（河北工业大学 化工学院，天津 300130）
摘要：以化学还原法修复铬污染土壤为基础，介绍了土壤中铬的来源、存在形态及其转化方式，重点分析了纳米零价铁、硫化亚铁、硫酸亚铁、焦亚硫酸钠、硫代硫酸钠、硫化钠、多硫化钙以及有机酸在铬污染土壤修复中的应用及其研究进展，对所列还原剂的优缺点及应用现状进行了总结和评价。工程应用应综合考虑还原效率、经济成本以及操作安全等因素，选择合适的修复方法，以达到土壤修复的目的。针对土壤原位修复易造成二次污染、土壤结构破坏、生物活性降低的特点，对铬污染土壤修复的未来发展提出展望与方向。
关键词：铬污染；六价铬；土壤修复；化学还原
中图分类号：X53 文献标识码：A
Application of Several Common Reducing Agents in Chromium Contaminated Soil BAI Jun-bin, JIANG Xiao-ling, YANG Hong-jian*(Institute of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China), Huaxue Shiji, 2021, 43(2), ～
Abstract：Based on the remediation of chrome-polluted soil by chemical reduction method, the sources, existing forms and transformation modes of chromium in soil were introduced. The application and research progress of nano zero valence iron, ferrous sulfide, ferrous sulfate, sodium metabisulfite, sodium thiosulfate, sodium sulfide, calcium polysulfide and organic acids in the remediation of chromium contaminated soil were emphatically analyzed. The advantages, disadvantages and application status of reducing agent are summarized and evaluated. In engineering application, factors such as reduction efficiency, economic cost and operation safety should be considered comprehensively, and appropriate remediation methods should be selected to achieve the purpose of soil remediation. In view of the characteristics of soil in-situ remediation, which is easy to cause secondary pollution, soil structure damage and biological activity reduction, the prospect and direction of soil remediation were put forward.
Key words：Chromium pollution; hexavalent chromium; contaminated soil; chemical reduction
引用本文：白俊宾，江晓玲，杨红健. 几种常用还原剂在铬污染土壤中的应用探讨[J].化学试剂，2021，43（2）：127-135.
一种噻菁染料的合成及其在HSA检测中应用
赵晗，张颖琳，师晓栋，丁春光，于丽佳*
（国家卫生健康委职业安全卫生研究中心，北京 102308）
摘要：研究设计合成一种新型噻菁染料（Dye1），在PBS缓冲溶液中实现对人血清白蛋白（HSA）高选择性检测。向Dye1-PBS体系中加入HSA后，通过检测荧光，发现Dye1在444 nm处的荧光强度显著增加，说明此体系可应用于HSA检测。优化检测条件后，在HSA浓度为3 ~ 30 mg/L时，HSA与Dye1有良好的线性关系（R2=0.9886），检出限为1.8 mg/L，且反应迅速达到平衡，可以实现快速、高选择性检测HSA。
关键词：噻菁染料；人血清白蛋白；荧光光谱；高选择性；检测
中图分类号: O657.31 文献标识码: A
The Synthesis of One Thiacyanine Dye and the Application in Detection of HAS ZHAO Han, ZHANG Ying-lin, SHI Xiao-dong, DING Chun-guang, YU Li-jia*(National Center for Occupational Safety and Health, NHC, Beijing 102308, China)
Abstract: A thiacyanine dye (Dye1) was synthesized to realize high selectivity detection of human serum albumin(HSA) in PBS buffer. The fluorescence intensity of Dye1 at 444 nm could be increased significantly with increasing concentrations of HSA in PBS. This system could be used to detect of HSA. The detection conditions were optimized. The linear relationship of Dye1 with HSA was from 0 mg/L to 30 mg/L (R2=0.9886), the detection limit was 1.8 mg/L, and response time was short, that could achieve rapid and high selectivity detection of HSA.
Keywords: thiacyanine dye; human serum albumin(HSA); fluorescence spectroscopy; high selectivity; detection
引用本文：赵晗，张颖琳，师晓栋，等.一种噻菁染料的合成及其在HSA检测中应用[J]. 化学试剂，2020, 43（2）：136-140.
基于L-半胱氨酸的手性硅胶球固定相研究
苏鹏，彭博，艾萍*，袁黎明
（云南师范大学 化学化工学院，云南 昆明 650500）
摘要：硅胶是目前使用最广泛的高效液相色谱固定相之一，以L-半胱氨酸为手性源，利用堆砌硅珠法制备手性硅胶球，且手性来源于硅胶球自身的孔结构和骨架。由于这是一种手性的全无机硅胶球，其流动相使用宽泛，机械强度高。将其用作HPLC手性固定相，成功拆分了12种外消旋体，其中有3种外消旋体达到基线分离，此种手性硅胶球对11种苯系位置异构体有不同的分离效果，其中达到基线分离的苯系位置异构体有7种。该固定相在手性拆分领域能发挥其独特优势。
关键词：L-半胱氨酸手性硅胶球；手性固定相；高效液相色谱；手性分离
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2021）
Chiral Stationary Phase of Silica Gel Sphere Based on L-cysteine SU Peng, PENG Bo, AI Ping*, YUAN Li-ming (School of Chemistry and Chemical Engineering, Yunnan Normal University，Kunming 650500, China), Huaxue Shiji, 2021, 43(2)
Abstract: Silica gel is one of the most widely used stationary phases for high performance liquid chromatography (HPLC). The chiral silica gel spheres were prepared by stacking silica beads method with L-cysteine as the chiral source. Its chirality comes from the pore structure and skeleton of the silica gel ball itself. As it is a kind of inorganic silicone ball, many mobile phases can be used with good mechanical strength. When it was used as chiral stationary phase in HPLC, twelve racemes were successfully separated, among which three achieved baseline separation. This chiral silica gel ball had different separation effects for eleven benzene position isomers, among which seven reached baseline separation. The stationary phase can exert its unique advantages in the field of chiral resolution.
Key words: L-Cys chiral silica gel; chiral stationary phase; high performance liquid chromatography; enantioseparation
引用本文：苏鹏, 彭博, 艾萍, 等. 基于L-半胱氨酸的手性硅胶球固定相研究[J]. 化学试剂, 2021, 43(2): 141-146.
冬凌草甲素衍生物的合成及其抗肿瘤活性研究
杨宏静1 方应权1 沈庆坤2 尚凡凡2 全哲山2 张训浩*1
(1. 重庆三峡医药高等专科学校 药学院 重庆 404120)
(2. 延边大学 药学院 吉林 延吉133002)
摘要：以冬凌草甲素为原料，丁二酸为连接臂在其C-14位引入氨基磷酸酯及含氮化合物，设计并合成了6个未见文献报道的目标化合物。所有衍生物均经过氢谱、碳谱以及高分辨质谱进行结构确认，并采用噻唑
蓝比色（MTT）法对目标化合物使用人结肠癌HCT-116、人肝癌BEL-7402、人乳腺癌MCF-7细胞系进行抗癌活性筛选。结果表明，绝大多数化合物表现出较强的抗增殖作用，其中（1S，4aR，5S，6S，6aR，9S，11aS，11bS，14R）-1,5,6-三羟基-4,4-二甲基-8-亚甲基-7-氧代十二氢-1H-6,11b-（环氧甲酰基 ）-6a，9-甲基环庚[a]萘-14-基4-（（（（二乙氧基磷酰基）（苯基）甲基）氨基）-4-氧代丁酸酯表现出最强的抗增殖作用，尤其对人乳腺癌MCF-7细胞系的抗增殖活性最好，其IC50值仅为2.73 µmol/L，活性提高约4.61倍，具有进一步开发的价值。
关键词：冬凌草甲素；合成；抗肿瘤；氨基磷酸酯
中图分类号：R914.5 文献标志码：A 文章编号：0258-3283（2021）--
Study on Synthesis and Anti-tumor Activity of Oridonin Derivatives YANG Hong-Jing1, FANG Ying-Quan1, SHEN Qing-Kun2, SHANG Fan-Fan2, QUAN Zhe-Shan2, ZHANG Xun-Hao*1 (1. School of Pharmacy, Chongqing Three Gorges Medical College, Chongqing 404120, China; 2. School of Pharmacy, Yanbian University, Yanji, Jilin 133002, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: Six unreported compounds were designed and synthesized by introducing aminophosphate and nitrogenous compounds into the C-14 position of rugosin a and succinic acid as the connecting arm.The structures of all derivatives were confirmed by HNMR, CNMR and high resolution mass spectrometry, and the anticancer activities of human colon cancer HCT-116, human liver cancer BEL-7402 and human breast cancer MCF-7 cell lines were screened by MTT assay. The most of the compounds showed strong anti-proliferative effect, among which compound 1 showed the strongest anti-proliferative effect, especially for human colon cancer MCF-7 cell line, the anti-proliferative activity was the best, its IC50 value was only 2.73 µM, the activity was increased by about 4.28 times, and it had the value of further development.
Keywords: Oridonin; Synthetic; Antitumor; Phosphoramidate
引用本文：杨宏静, 方应权, 沈庆坤, 等. 冬凌草甲素衍生物的合成及其抗肿瘤活性研究[J]. 化学试剂, 2021, 43(2):147-151。
具有特定官能团化合物的手性传感研究进展
张军瑶，李莉*
（中国医学科学院 北京协和医学院药物研究所，北京 100050）
摘要：手性化合物在生命活动中起着重要作用，在医药学领域倍受关注，建立快速高效的手性分析方法刻不容缓。手性传感方法具有专属性强、灵敏性高、操作简便、样品用量少等优点，能够快速确定对映体的绝对构型及对映体过量值。氨基、羟基和羧基是手性化合物中常出现的基团，也是手性传感器研究的重要对象。聚焦于纳米粒、量子点类手性传感材料和可用于手性传感的小分子化合物，综述了手性化合物在不同类型小分子的手性识别中的应用，并对手性传感器的发展进行了展望。
关键词：手性传感器；手性识别；绝对构型；对映体过量；纳米粒；量子点
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2021）--
Progress in Chiral Sensing of Chiral Compounds with Special Functional Groups ZHANG Jun-yao, LI Li* (Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: Chiral compounds take an important role in life activities and have attracted much attention in the field of medicine. It is urgent to establish a fast and efficient chiral analysis method. The chiral sensing method has the advantages of high specificity, high sensitivity, easy operation and less sample consumption, which can quickly determine the absolute configuration and enantiomeric excess of enantiomers. Amino, hydroxyl and carboxyl groups are commonly found in chiral molecules, which are important objects of chiral sensor research. Herein, we summarized the applications of nanoparticles, quantum dots and compounds in chiral recognition of different chiral substrates, and prospected the future development of chiral sensors.
Key words: chiral sensors; absolute configuration; enantiomeric excess; nanoparticles; quantum dots
引用本文：张军瑶，李莉. 具有特定官能团化合物的手性传感研究进展[J]. 化学试剂, 2021, 43(2):152-162。
辣椒碱的合成研究进展
邹帅*，王金玉，于艳杰，闫增元，薛田
（中国人民解放军61699部队，湖北 枝江 443200）
摘要：辣椒碱（反式8-甲基-N-香草基-6-壬烯酰胺）是辣椒中产生辛辣及刺激性味道的主要生物活性物质，是一种含香草酰胺的生物碱，具有重要的生理、药理活性，被广泛应用于医药、食品、农业、涂料及军事领域，具有巨大的市场需求。然而从天然辣椒中提取分离的辣椒碱纯度低、产率低，难以实现规模化制备。因此，化学家们致力于发展化学合成法制备高纯度、高收率的辣椒碱。系统总结了现有辣椒碱的合成方法，并简单介绍了反应特点，以期为发展辣椒碱规模化制备工艺提供参考。
关键词：辣椒碱；合成；研究进展
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283(2021) -
Progress in Synthesis of Capsaicin ZOU Shuai*, Wang Jin-yu, YU Yan-jie, Yan Zeng-yuan, Xue Tian (Chinese People’s Liberation Army 61699 Troops, Zhijiang 443200, China), Huaxue Shiji, 2021, 43(2),～
Abstract: Capsaicin (CAP, trans-8-methyl-N-vanillyl-6-nonenamide), is the primary bioactive substance in chili peppers that produces the spicy and irritating. It is an alkaloid containing vanillamide and has important physiological and pharmacological activities and is widely used in medicine, food, agriculture, coatings and military fields. It also has huge market demand. However, the capsaicin extracted and separated from natural peppers has low purity and low yield, making it difficult to achieve large-scale production. Therefore, chemists are committed to the development of chemical synthesis to prepare high-purity and high-yield capsaicin. This article systematically summarizes the existing synthesis methods of capsaicin and briefly introduces the reaction characteristics, with a view to developing a large-scale production process of capsaicin for reference.
Key words: Capsaicin; synthesis; research progress
引用本文：邹帅，王金玉，于艳杰，等. 辣椒碱的合成研究进展[J]. 化学试剂, 2021, 43(2): 163-167.
瓜环试剂的发展及应用研究
余诗雨，刘智敏，杨怡，时开存，唐思静，李娇，蔡晓丽，张雪花，许志刚*
（昆明理工大学 理学院，云南 昆明 650500）
摘要：瓜环是超分子领域中的一类备受关注的新兴大环化合物，但由于其溶解度小、活性基团少、难于衍生化等因素，一定程度上限制其发展和广泛应用。简要介绍了瓜环的发展历程，全面介绍了常见瓜环化合物的合成、分离与表征，进一步介绍了各种衍生化瓜环，重点介绍了各种瓜环在分子包结与识别和分子催化等方面的应用，讨论了瓜环类试剂发展中存在的问题及发展趋势。将对从事功能材料、吸附分离方法和超分子化学等方面的研究人员提供有益的参考。
关键词：瓜环；超分子；分子包结；分子催化
中图分类号：O601；O656.4 文献标识码：A 文章编号：0258-3283（2021）
Development of Cucurbit[n]urils and Its Applications YU Shi-yu, LIU Zhi-min, YANG Yi, SHI Kai-cun, TANG Si-jing, LI Jiao, CAI Xiao-li, ZHANG Xue-hua, XU Zhi-gang* (Faculty of Science, Kunming University of Science and Technology, Kunming 650500, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: Cucurbit[n]urils are a kind of emerging macrocyclic compounds that has attracted much attention in the field of supramolecular. However, the development and application of cucurbit[n]urils are limited to a certain extent due to its low solubility, few active groups, and difficulty in derivatization. The development history of cucurbit[n]urils was briefly presented firstly. Then, the synthesis, separation and characterization of common cucurbit[n]urils were comprehensively introduced. And some derivatized cucurbit[n]urils were further introduced. The recent applications of cucurbit[n]urils in molecular inclusion and recognition, and molecular catalysis, were introduced. Finally, the urgently problems in the development of cucurbit[n]urils reagents and its development trends were also discussed. This work will provide a useful reference for researchers engaged in functional materials, adsorption and separation methods, and supramolecular chemistry.
Key words: Cucurbit[n]urils; supramolecular; molecular inclusion; molecular catalysis
引用本文：余诗雨，刘智敏，杨怡，等. 瓜环试剂的发展及应用研究[J]. 化学试剂, 2021, 43(2): 168-173.
危险化学品重大危险源辨识研究进展
宋金链，张键鑫＊，刘岩，李润喜
（天津市康科德科技有限公司，天津 301701）
摘要：简述了国内外重大危险源辨识的更新和进展。欧盟《塞维索法令》对重大危险源辨识发展具有重要意义，它根据恶性事故的发生及生产应用的需要不断完善和更新，目前已更新至第三版。我国重大危险源辨识标准起步较晚，与《塞维索法令》密切相关，随着化工行业的快速发展，重大危险源辨识标准也更新至第三版。重大危险源辨识理论仍然需要不断地完善，以适应快速发展的工业化形势，目前存在临界量不全、重大危险源分级理论中的特殊情况未做规定、非重大危险源分级管理空白等现实问题需要解决。
关键词：临界量；危险化学品；重大危险源；危险源辨识；塞维索法令；危险源分级
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283（2021）--
Progress on Identification of Major Hazard Installations for Dangerous Chemicals Song Jin-lian, Zhang Jian-xin*, Liu Yan, Li Run-xi (Tianjin Concord Technology Co., Ltd, Tianjin 300402, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: This paper briefly describes the current progress of the identification of major hazard installations in China and abroad. The European Union’s Seveso Directive is of great significance to the identification and development of major hazard installations. Now at its third edition, the Seveso Directive has been continuously improved and updated according to the occurrence of serious accidents and the needs of production and applications. The identification standards for major hazard installations in China were developed based on the Seveso Directive. With the rapid development of the chemical industry, the identification standards for major hazards installations in China have also been updated to a third edition. The identification theory of major hazard installations still needs continuous improvement to adapt to the rapidly developing industrialization situations. At present major problems need to be resolved: the values of critical quantities need to be completely defined, special circumstances should be considered in the major hazard classification theory, and guidelines should be provided for classification management of non-major hazard installations, among other issues.
Key words: critical quantity；dangerous chemicals；major hazard installations；hazard identification；Seveso Directive；classification of hazard identifications
引用本文：宋金链，张键鑫，刘岩，等. 危险化学品重大危险源辨识研究进展[J].化学试剂，2020,43（2）：174-179.
危险化学品危险源细化分级安全管理研究
宋金链，刘岩＊，郭培，李润喜，杜文玲
（天津市康科德科技有限公司，天津 301701）
摘要：按照《危险化学品重大危险源辨识》（GB 18218-2018）规定，危险化学品重大危险源实行分级管理，当辨识指标S≥1时，重大危险源按分级指标分为4级。实际发生的特别重大恶性事故危险源分级指标远远高于一级重大危险源规定的下限值，有必要在一级重大危险源之上设立特别重大危险源分级。非重大危险源涉及到中小型生产企业、研发和分析实验室及单个包装单元等众多不同应用场景，目前没有分级。不同应用中危险化学品危险源分级指标的差别非常大，中小企业的危险源分级指标一般在10-2～100，而单一常用化学试剂在10-7～10-5。将危险源分为10级，其中将重大危险源扩充到5级，将非重大危险源分为5级。危险化学品危险源细化分级对科学管理、分类管理、分级施策意义重大。
关键词：危险化学品；危险源；分级；安全管理
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283（2021）--
Research on safety management of dangerous chemicals by classification SONG Jin-lian, LIU Yan*, GUO Pei, LI Run-xi, DU Wen-ling(Tianjin Concord Technology Co., Ltd, Tianjin 301701, China), Huaxue Shiji, 2021, 43(2), ～
Abstract:According to the "Identification of Major Hazard InstallationsforDangerous Chemicals" (GB 18218-2018), when the identification index S is at least 1, the major hazard installations are divided into four levels according to the value of the grading index R. The R values in particularly serious malignant accidents are far above the lower limit of the first-level major hazard installations, therefore it is necessary to establish a more specific major hazard grade above the first-level major hazards. In addition, there is no clear classification for non-major hazard installations, which include many different applications such as small and medium-sized production enterprises, R&D and analysis laboratories, and single packaging units.The value of the grading index for hazard installations in different applications varies greatly: the hazard grading index of small and medium-sized enterprises is generally 10-2～100, while the hazard grading index of single common chemical reagent is 10-7～10-5. In this article we divide hazard installations into 10 levels, among which the major hazards are expanded to 5 levels, and the non-major hazards are divided into 5 levels. The detailed classification of hazard installations for dangerous chemicals is of great significance to scientific management, classification management and gradepolicies.
Key words: dangerous chemicals；hazard installations；classification；safety management
引用本文：宋金链，刘岩，郭培，等. 危险化学品危险源细化分级安全管理研究[J]. 化学试剂, 2021, 43(2): 180-184.
分子模拟和光谱法研究华法林与人血清白蛋白的结合机制
侯利杰，李梦媛，申炳俊，金丽虹*
(长春理工大学 生命科学技术学院，吉林 长春 130022)
摘要：华法林(WF)是临床常用口服抗凝药物，有关它与人血清白蛋白(HSA)结合位点处的热点残基、作用力类型以及对HSA构象影响报道较少。通过在模拟人体生理条件下，利用分子模拟、内源荧光光谱、三维荧光光谱和同步荧光光谱，研究了WF与HSA之间作用机理。三维荧光和同步荧光结果表明，WF能使HSA构象发生改变，导致Tyr残基微环境极性降低、Trp残基周围亲水性增强。荧光光谱显示，WF能有效猝灭HSA内源荧光，猝灭机制属静态猝灭，通过Lineweaver-Burk方程求得两者间结合常数(KA) 为3.55×105 L/mol(310 K)、结合位点数(n)约为1。Van't Hoff定律计算得到的热力学参数(ΔH=169.56 kJ/mol和ΔS = 653.23 J/(mol·K))，说明WF与HSA之间的主要作用力为疏水作用力。根据Förster’s能量转移定律确定，WF与HSA结合距离为2.87 nm。分子对接结果显示，WF通过氢键和疏水作用力与HSA的亚域ⅡA中氨基酸残基进行作用，WF周围4.0 Å区域还存在ⅠB、ⅡB、ⅢA亚结构域的30个氨基酸残基。
关键词：华法林；人血清白蛋白；分子对接；荧光光谱；相互作用
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2021）--
Binding Mechanism of Warfarin with Human Serum Albumin via Molecular simulation and spectroscopy HOU Li-jie, LI Meng-yuan, SHEN Bing-jun, JIN Li-hong *(School of Life Science and Technology, Changchun University of Science and Technology, Changchun 130022, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: Warfarin (WF) is a commonly used oral anticoagulant drug in clinic. There are few reports about the hot residues at the binding site of WF with human serum albumin (HSA), the type of acting force and the effect on the conformation of HSA. Molecular simulation, endogenous fluorescence spectra, three-dimensional fluorescence spectra and synchronous fluorescence spectra were used to investigate the interaction mechanism between WF and human serum albumin (HSA). WF could change the conformation of HSA, resulting in the decrease of the polarity of Tyr residue microenvironment and the enhancement of hydrophilicity around Trp residue. WF could effectively quench the intrinsic fluorescence of HSA, and the quenching mechanism was static quenching. According to Lineweaver-Burk equation, the binding constant (KA) is 3.55×105 L/mol (310 K) and the number of binding sites (n) is about 1. The thermodynamic parameters calculated by Van't Hoff 's law (ΔH=169.56 kJ/mol and ΔS=653.23 J/(mol·K)), indicate the main hydrophobic force between WF and HSA. According to Förster’s law of energy transfer, the binding distance between WF and HSA is 2.87 nm. WF interacted with the amino acid residues in subdomain IIA of HSA through hydrogen bonding and hydrophobic forces. There were 30 amino acid residues in subdomains IB, IIB and IIIA around WF.
Keywords: warfarin; human serum albumin; molecular docking simulation; fluorescence spectrum; interaction
引用本文：侯利杰，李梦媛，申炳俊，等.分子模拟和光谱法研究华法林与人血清白蛋白的结合机制[J]. 化学试剂, 2021, 43(2):185-190。
银杏叶提取物中组分定性检测及含量测定
罗祥敏a,b，雷芳a,b，陈伟b，何珺b*
（贵州大学 a. 药学院;b.贵州省生化工程中心，贵州 贵阳 550025）
摘要：通过显色反应实验和泡沫实验对银杏叶提取物中组成成分类别进行定性测试，并采用ΜV法和高效液相色谱法测定银杏叶提取物中成分含量。银杏叶提取物均含有黄酮、有机酸、多糖、蒽醌、鞣质、萜类化合物，无皂苷和生物碱类化合物（去掉了各成分含量范围）。两种银杏叶提取物中黄酮、有机酸、多糖、蒽醌、萜类化合物含量相差不大，鞣质含量在2015年版药典银杏叶提取物中高于水溶性银杏叶提取物。对银杏叶提取物质量整体评价及安全、稳定性研究提供数据参考。
关键词：银杏叶提取物；组成成分；定性试验；含量测定；HPLC
中图分类号：R284.1 文献标识码：A
Qμalitative Determination and Content Determination of Components in Ginkgo biloba Extract LUO Xiang-mina,b, LEI Fanga,b, CHEN Weib, HE Junb*( a. College of Pharmacy, b. Research Center of Biochemistry Engineering of Guizhou Province, Guizhou Μniversity, Guiyang 550025,China ), Huaxue Shiji, 2021, 43(2), ～
Abstract: The constitμents of ginkgo biloba extract were determined by qμalitative color development and foam test, and the content of active components of ginkgo biloba extract were determined by ΜV and HPLC. Resμlts:Ginkgo biloba extractcontains flavonoids, organic acids, polysaccharides, anthraqμinones, tannins, terpenoid lactones, no saponins and alkaloids. The content of flavonoids, organic acids, polysaccharides, anthraqμinones, terpenoid lactones in two kinds of ginkgo biloba extract did not differ significantly, tannins content was higher than water-solμble ginkgo biloba extract in the 2015 edition. This work provided data reference for the overall qμality evalμation, safety and stability study of ginkgo biloba extract.
Key words:Ginkgo biloba extract; constitμent analysis; qμalitative test; content determination; HPLC
引用本文：罗祥敏，雷芳，陈伟，等.银杏叶提取物中组分定性检测及含量测定[J]. 化学试剂，2021，43（2）：191-195.
改进QuEChERS /超高效液相色谱-串联质谱法同时测定当归中86种农药残留
谢楠1，张明童2，刘志荣*2，张平2，李冬华2，马潇2, 3，郭朝晖2, 3，杨平荣*2, 3
（1. 甘肃省药品监督管理局审评认证中心，甘肃 兰州 730070；2. 甘肃省药品检验研究院 甘肃省中藏药检验检测技术工程实验室，甘肃 兰州 730070；3. 中药材及饮片质量控制重点实验室，甘肃 兰州 730070）
摘要：建立了QuEChERS结合超高效液相色谱-串联质谱（UPLC-MS/MS）法同时测定当归中86种农药残留，比较了9种不同的QuEChERS方法的净化效率和回收率，结果表明，无石墨化碳黑（NGCB）QuEChERS方法效果最佳。在依赖保留时间的多反应监测模式（scheduled MRM）下，采用UPLC-MS/MS对农药进行定量。86种农药的线性相关系数（r）均大于0.99，检出限为0.2～4 μg/kg。3个添加水平（20、50、80 μg/kg）下，86种农药的回收率为63.0%～130.9%，相对标准偏差（RSDs，n=6）为1.0％～18.1%。采用该方法对市场上收集的20批当归样品进行了测定，检出17种农药。该方法可为准确、高效、经济地检测当归中目标物提供参考。
关键词：超高效液相色谱-串联质谱（UPLC-MS/MS）；QuEChERS；农药残留；当归
中图分类号：O65.06 文献标识码：A 文章编号：0258-3283（2021）
Simultaneous Determination of 86 Pesticide Residues in Angelica Sinensis by Improved QuEChERS/Ultra High Performance Liquid Chromatography-tandem Mass Spectrometry XIE Nan1, ZHANG Ming-tong2, LIU Zhi-rong*2, ZHANG Ping2, LI Dong-hua2, MA Xiao2, 3, GUO Zhao-hui2, 3, YANG Ping-rong*2, 3 (1. Gansu Drug Administration Review and Certification Center, Lanzhou 730070, China; 2. Gansu Tibetan Medicine Examination Engineering Laboratory, Gansu Provincial Institute of Drug Control, Lanzhou 730070, China; 3. NMPA Key Laboratory for Quality Control of Traditional Chinese Medicine (Chinese Materia Medica and prepared slices), Lanzhou 730070, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: To establish a method for the simultaneous determination of 86 pesticides residue in Angelica sinensis by ultra-high performance liquid chromatography/tandem mass spectrometric (UPLC-MS/MS). 9 kinds of QuEChERS have been compared in terms of purification efficiency and recovery, the best results were achieved with no graphitized carbon black (NGCB). The pesticides were quantified on a UPLC-MS/MS system in scheduled multiple reaction monitoring mode, and identified on the basis of product ion abundance ratios as well as characteristic fragments in enhanced product ion spectra UPLC-MS/MS system in scheduled multiple reaction monitoring mode. Calibration curves for 86 analysts showed correlation coefficients better than 0.99. Detection limits ranged from 0.2 μg/kg to 4 μg/kg. The average recoveries of 86 pesticides at the spiked levels of 20, 50, 80 μg/kg ranged from 63.0%～130.9% with RSDs of 1.0%～18.1%. The proposed method has been applied to Angelica sinensis samples from the Chinese market. The established method has advantages of good recovery, economical and a rapid clean-up procedure, showing enhanced product ion scan assisted confirmation to be a useful tool for obtaining reliable results.
Key words: ultra-high performance liquid chromatography/tandem mass spectrometric (UPLC-MS/MS); QuEChERS；pesticide residues; Angelica sinensis
引用本文：谢楠，张明童，刘志荣，等. 改进QuEChERS /超高效液相色谱-串联质谱法同时测定当归中86种农药残留[J]. 化学试剂，2021, 43(2):196-203。
鄂东某白茶园土壤特征分析和安全性评价
王泽亚1a,1b，张家泉2，柳山2，胡宏元1a,2，张喜皓1a,1b,2，龚香宜*1a,2
（1. 武汉科技大学 a. 资源与环境工程学院, b. 冶金矿产资源高效利用与造块湖北省重点实验室, 湖北 武汉 430081；2. 湖北理工学院 矿区环境污染控制与修复湖北省重点实验室，湖北 黄石 435003）
摘 要：于2018年12月采集鄂东某白茶园表层土壤并开展土壤重金属和PAHs含量分析，以有机茶产地环境条件、茶叶产地环境技术条件和湖北土壤背景值为标准，探讨茶园土壤污染特征并作污染风险安全评价。结果表明，茶园土壤中不同的重金属含量差异显著，6个茶园土壤采样点中的重金属Zn、Pb、Cr、As的平均含量低于茶叶产地环境技术条件的要求，均不超标，Cu的平均含量为52.41 mg/kg，略高于有机茶产地环境条件50 mg/kg的要求，Ni、Mn、Co、V的平均含量为0.114～0.793mg/kg，综合潜在生态风险评价结果显示该茶园属轻微生态污染；该茶园土壤中的PAHs总量、单个含量均未超过荷兰土壤中PAHs含量（10种）总量和加拿大制定的单个PAHs含量标准，这表明该茶园土壤未受到PAHs污染。通过风险评价可知，该茶场土壤整体质量总体良好，仅Cu的平均含量超标4.8%，需注意Cu潜在风险。
关键词：茶园，土壤，重金属，多环芳烃，生态风险
中图分类号：X53 文献标识码：A 文章编号：0258-3283（2021）--
Analysis of Soil Characteristics and Safety Evaluation of a White Tea Garden in East Hubei WANG Ze-ya1a,1b, ZHANG Jia-quan2, LIU Shan2, HU Hong-yuan 1a,2, ZHANG Xi-hao1a,1b,2, GONG Xiang-yi*1a,2 (1. School of Resources and Environmental Engineering, 1b. Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, China；2. Hubei Key Laboratory of Mine Environmental Pollution Control & Remediation, Hubei Polytechnic University, Huangshi 435003，China), Huaxue Shiji, 2021, 43(2), ～
Abstract: In December 2018, the surface soil of a white tea garden in the eastern Hubei was collected and analyzed for heavy metal and PAHs content. Based on the environmental conditions of the organic tea producing area, the environmental technical conditions of the tea producing area, and the Hubei soil background, the characteristics of the soil pollution in the tea garden were discussed and polluted risk safety assessment. The contents of different heavy metals in the tea garden soil were significantly different. The average contents of heavy metals Zn, Pb, Cr, and As in the six tea garden soil sampling points were lower than the environmental technical requirements of the place of origin of the tea. The average Cu content is 52.41 mg/kg, which is slightly higher than the requirement of 50 mg /kg for the environmental conditions of the organic tea producing area. The average contents of Ni, Mn, Co and V were in the range of 0.114 and 0.793mg/kg. Comprehensive potential ecological risk assessment results show slight ecological pollution in tea plantations; The total amount and individual content of PAHs in the tea plantation soil did not exceed the total amount of PAHs (10 species) in the soil in the Netherlands and the single PAHs content formulated by Canada, which indicated that the tea plantation soil was not polluted by PAHs. The average content of Cu in the tea plantation soil exceeds the standard by 4.8%.
Key words: tea garden, soil, heavy metals, polycyclic aromatic hydrocarbons, ecological risk
引用本文：王泽亚, 张家泉, 柳山, 等. 鄂东某白茶园土壤特征分析和安全性评价[J]. 化学试剂，2021，43（2）：204-209.
不同产地桔梗的红外光谱整体成分鉴别研究
司雨柔，高韵，解玫莹，李欢欢，程旺兴*
(安徽中医药大学 安徽省工程技术研究中心, 安徽 合肥 230012 )
摘要：运用傅里叶变换红外光谱法和显微红外光谱技术对多个产地的桔梗所含化学成分的红外光谱图整体变化规律进行研究，从而对不同产地桔梗进行鉴别。采用傅里叶变换红外光谱法和显微红外光谱技术，对不同产地桔梗所含成分进行分析鉴别。结果表明，不同产地桔梗的一阶红外光谱图整体上差别并不明显，二阶导数处理后，各产地的特征峰差异得以显现，显微红外光谱图则进一步直观清晰地显现出桔梗皂苷d的含量多少与分布区域，进一步佐证了不同产地桔梗间桔梗皂苷d的含量差异的结果。根据不同产地地理远近来分析，不同省之间的桔梗的物质含量与分布的差距比较明显；同省不同市之间几乎没有太大的差距，可能原因是同省不同市的地理距离太小。由此可见，红外光谱法和显微红外光谱技术提供了大量桔梗的整体化学成分信息，递进式地验证了不同产地桔梗之间的所含物质的量及分布有差异，可以初步鉴别不同产地桔梗，为今后系统完整的选择桔梗入药产地提供依据。
关键词：桔梗；傅里叶红外光谱技术；二阶导数谱；显微红外光谱技术
中图分类号：O657.33 文献标识码：A 文章编号：
Analysis and Discrimination of Platycodon Grandiflorum from Different Origins by Infrared Spectroscopy SI Yu-rou, GAO Yun, XIE Mei-ying, LI Huan-huan, Cheng Wang-xing*（School of Pharmacy and Anhui Engineering Technology Research Center of Modern Chinese Medicine of Anhui University of Chinese Medicine, Hefei, 230012, China )
Abstract： Fourier transform infrared spectroscopy (FT-IR) and Fourier transform infrared Micro spectroscopy (Micro-FTIR) were used for the identification of Platycodon grandiflorum from different origins. FT-IR and Micro-FTIR were used. The difference in the FT-IR spectra of Platycodon grandiflorum from different origins is not obvious. After the secondary derivative infrared spectra (SD-IR), the difference of the characteristic peaks of each origin can be revealed.Moreover, micro-FTIR spectroscopy visually and clearly showed the difference of content and distribution area of platycod on from different producing areas, which further testified the differences in the content of platycodin d from different origins. Based on the analysis of the geographical distance of different origins, the difference in the content and distribution of Platycodon grandiflorum between different provinces is obvious. However, there is almost no big gap between different cities in the same province, which may be due to the close geographical distance of different cities in the same province. A lot information of Platycodon grandiflorum can be provided by FT-IR spectra method and Micro-FTIR spectroscopy which can testify that the content and structure of substance of Platycodon grandiflorum from different origins were different. This method can also be used for analysis and identification of Platycodon grandiflorum from different sources which can make a good foundation for further research.
Key words：Platycodon grandiflorum; Fourier transform infrared spectroscopy; second derivative infrared spectroscopy; Fourier transform infrared micro spectroscopy
引用本文：司雨柔，高韵，解玫莹，等. 不同产地桔梗的红外光谱整体成分鉴别研究[J]. 化学试剂，2021, 43（2）：210-215.
UPLC-Q-Trip-MS/MS法测定赤芍中4种成分的含量
孙辑凯*1，张梅娟2，张宏莲1，李宏铃1，董巍1
（1. 齐齐哈尔医学院药学院，黑龙江齐齐哈尔161006；
2. 齐齐哈尔大学生命科学院，黑龙江齐齐哈尔161000）
摘要：基于超高效液相色谱-三重四级杆串联质谱（UPLC-Q-Trip-MS/MS）技术，建立赤芍中4种化学成分含量测定方法。采用 Agilent ZORBAX SB-C18色谱柱（2.1 mm×100 mm，1.8μm），流动相为甲醇-0.1%甲酸水溶液进行梯度洗脱，柱温40 ℃，流速0.3 mL/min，进样量5μL；质谱条件为Agilent ultro-triple quad LC/MS在线系统，采用多反应监测模式（MRM）模式分别在正、负离子模式下对色谱流出物进行检测，喷雾电压3.5 kV，干燥气温度为380 ℃，干燥气流量为60 L/h，雾化器压力为60 MPa。芍药苷、没食子酸、儿茶素和苯甲酸分别在5～50、0.5～5.0、0.25～2.5、0.25～2.5 μg/mL范围内与峰面积呈良好线性关系。7批赤芍中芍药苷、没食子酸、儿茶素和苯甲酸的含量均值依次为2.13%、0.047%、0.20%、7.15%。建立的UPLC-Q-trip-MS方法具有良好的定性和定量分析能力，适用于定量分析赤芍中4种化学成分。
关键词：赤芍；芍药苷；没食子酸；儿茶素；苯甲酸；定量分析
中图分类号：R917文献标识码：A 文章编号：0258-3283（2021）
Determination of Four Components in Red Peonyby UPLC-Q-Trip-MS/MS SUN Ji-kai1, ZHANG Mei-juan2, ZHANG Hong-lian*1, LI Hong-ling1, DONG Wei1(1. College of Pharmacy, Qiqihar Medical University, Qiqihar 161006, China; 2.Academy of Life Science, Qiqihar university, Qiqihar 161000, China), Huaxue Shiji, 2020, 43(2), ～
Abstract: To establish a method for the determination of four chemical components in red peony roots based on ultra-performance liquid chromatography-triple quadrupole tandem mass spectrometry (UPLC-Q-Trip-MS/MS). Agilent ZORBAX SB-C18 column (2.1 mm×100 mm, 1.8 μm) was used as stationary phase, and methanol-0.1% formic acid aqueous solution was the mobile phase for gradient elution. The flow rate was 0.3 mL/min and the column temperature was 40 ℃.The injection volume was 5 μL. The mass spectrum conditions were that multiple reaction monitoring mode (MRM) mode was set to detect chromatographic effluent in positive and negative ion modes on the Agilent ultivo triple quad LC/MS online system. Spray voltage was set at 3.5 kV, and the drying gas temperature was 380 ℃ with gas flow was 60 L/h. The atomizer pressure was 60 MPa. The linear range of paeoniflorin, gallic acid, catechin and benzoic acid were 5～50, 0.5～5.0, 0.25～2.5, 0.25～2.5μg/mL, respectively. In 7 batches of red peony, the average contents of paeoniflorin, gallic acid, catechin and benzoic acid were 2.13%, 0.047%, 0.20%, and 7.15%, respectively. The UPLC-Q-trip-MS method had good qualitative and quantitative analysis capabilities, which was suitable for the quantitative analysis of four chemical components in red peony.
Keywords: red peony; paeoniflorin; gallic acid; catechin; benzoic acid; quantitative analysis
引用本文：孙辑凯, 张梅娟, 张宏莲, 等. UPLC-Q-Trip-MS/MS法测定赤芍中4种成分的含量[J].化学试剂，2021,43(2):216-219.
美拉德反应产物对主流烟气碱性香味成分的影响研究
李瑞丽1,2，徐达1，赵琪2，苏加坤1，张峻松2，蔡继宝*1
（1. 江西中烟工业有限责任公司 技术中心，江西 南昌 330096；
2. 郑州轻工业大学 烟草科学与工程学院，河南 郑州 450001）
摘要：为研究美拉德反应产物对主流烟气中碱性香味成分的影响，在金圣卷烟空白叶组中添加美拉德反应产物（MRPs），采用溶剂萃取法提取吸烟机捕集的卷烟主流烟气粒相物中的香味成分，对萃取液进行碱性成分分离，建立气相色谱-选择离子监测-质谱 (GC-SIM-MS)分析碱性香味成分的方法，对比分析添加MRPs前后卷烟主流烟气碱性香味成分变化。结果表明，在所测线性范围内，各碱性香味成分工作曲线相关系数均大于0.999，该方法具有较低检出限和定量限，分别为0.08～0.85 μg/mL和0.26～2.80 μg/mL，回收率在76.17%～90.36%之间，RSD均小于10%；加入MRPs后，主流烟气中的14种碱性香味成分均显著增加，随着添加量的增加，碱性香味成分释放量呈现明显上升的趋势，有利于彰显卷烟烘焙、可可香，同时可提升烟气浓度。
关键词：美拉德反应产物；主流烟气；碱性香味成分；吡嗪；吡啶
中图分类号：TS411.2 文献标识码：A 文章编号：0258-3283（2021）
Effect of Maillard Reaction Products on Alkaline Aroma Components of Mainstream Smoke LI Rui-li1,2, XU Da1, ZHAO Qi2, SU Jia-kun1, ZHANG Jun-song2, CAI Ji-bao*1 (1. Technology Center, Tobacco Jiangxi Industrial Co., Ltd., Nanchang 330096, China; 2. School of Tobacco Science and Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China), Huaxue Shiji, 2021, 43(2)
Abstract: In order to understand the effect of Maillard reaction products(MRPs) on the alkaline aroma components in mainstream smoke, MRPs were added to the blank Jinsheng cigarettes, The aroma components were extracted from the mainstream smoke particulate matters collected by smoking machine with solvent extraction method, and the alkaline aroma components were separated from the extract. The method was established to analyze the alkaline aroma components based on gas chromatography selective ion monitoring mass spectrometry (GC-SIM-MS), the alkaline aroma components in mainstream cigarette were compared between before and after adding MRPs into cigarette. The correlation coefficients of the working curves of each component were greater than 0.999 within the linear range. The detection limit was 0.08～0.85 μg/mL and the quantification limit was 0.26～2.80 μg/mL, the method had lower limit of detection and quantification. The recoveries ranged from 76.17% to 90.36%, and RSD of all alkaline aroma components were less than 10%. After adding MRPs into cigarettes, 14 kinds of alkaline aroma components in mainstream smoke increased significantly, and showed an obvious upward trend with the increase of MRPs addition amount, which was conducive to highlight cigarette baking and cocoa-like flavor and to enhance smoke concentration.
Key words: Maillard reaction products; mainstream smoke; alkaline aroma component; pyrazine; pyridine
引用本文：李瑞丽, 徐达, 赵琪, 等. 美拉德反应产物对主流烟气碱性香味成分的影响研究[J]. 化学试剂, 2021, 43(2):220-224。
气相色谱法分析检测产品中磷酸二丁酯和磷酸三丁酯
冯勇，张少文*，彭传云，赵晓洁
（洛阳理工学院 环境工程与化学学院，河南 洛阳 471023）
摘要：利用毛细管色谱法建立了磷酸二丁酯（DBP）和磷酸三丁酯（TBP）的分析检测方法。实验测得，DBP和TBP在1～100 μg/L浓度范围内线性关系良好（R2 ≥0.9995），检出限（S/N = 3）为0.04～0.06 μg/L，定量限（S/N = 10）为0.16～0.25 μg/L，日内与日间检测的相对标准偏差分别为2.1%～4.3% (n = 3)、2.5%～5.8% (n = 3)。采用新建方法检测企业的DBP/TBP实际产品，加标回收率为90.1%～108.2%，相对标准偏差2.1%～6.5% (n = 3)。本方法操作简便、快速灵敏、准确可靠，适用于DBP和TBP实际检测应用和产品质量控制。
关键词：气相色谱法；衍生化；磷酸二丁酯；磷酸三丁酯
中图分类号：O6 文献标识码：A 文章编号：0258-3283（2021）
Determination of Dibutyl Phosphate and Tributyl Phosphate in Products by Gas Chromatography FENG Yong, ZHANG Shao-wen*, PENG Chuan-yun, ZHAO Xiao-jie (College of Environmental Engineering and Chemistry, Luoyang Institute of Science and Technology, Luoyang 471023, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: A new determination was developed for dibutyl phosphate (DBP) and tributyl phosphate (TBP) with gas chromatography. The linear relationship for DBP and TBP had been observed in the range of 1～100 μg/L (R2 ≥ 0.9995), with limits of detection (LOD) and limits of quantification (LOQ) of 0.04 ～ 0.06 μg/L(S/N = 3) and 0.16 ～ 0.25 μg/L(S/N = 10), respectively. The relative standard deviations for intra-day were 2.1% ～ 4.3%(n=3) and that for inter-day were 2.5% ～ 5.8%(n=3). Applied to the real products detections, the spiked recoveries were between 90.1 % and 108.2 % with the relative standard deviations (RSDs) from 2.1 % to 6.5 % (n = 3). The results showed that this method was simple, sensitive and specific, and applicable for quality control of DBP and TBP.
Key words: gas chromatography; derivatization; DBP; TBP
引用本文：冯勇, 张少文, 彭传云, 等. 气相色谱法分析检测产品中磷酸二丁酯和磷酸三丁酯[J]. 化学试剂, 2021, 43(2):225-228。
乳粉中4种生育酚的正相高效液相色谱荧光法含量测定
刘萍*1，臧珊珊2
(1. 台州科技职业学院 农业与生物工程学院，浙江 台州 318020；
2. 中国科学院 生物物理研究所，北京 100101）
摘要：建立了反相色谱法样品前处理与正相酰胺柱色谱分离相结合的正相高效液相色谱荧光（HPLC-FLU）法，同时测定乳粉中α-、β-、γ-和δ-生育酚的含量，用于乳粉中维生素E含量的准确测定。考察了不同色谱柱类型、不同流动相比例和不同进样量对4种生育酚的色谱分离情况。2.5 g乳粉样品经氢氧化钾碱性溶液皂化后，用石油醚-乙醚混合液提取浓缩至近干，用甲醇定容至10 mL，过滤膜后进样。以V（正己烷）：V（叔丁基甲基醚）：V（四氢呋喃）：V（甲醇）=810.0:85.3:104.3:0.4的混合溶液为流动相等度洗脱，α-、β-、γ-、δ-生育酚在酰胺柱上18.5 min内达到基线分离。激发波长λx=294 nm，发射波长λm=328 nm，进样体积为2 μL。4种生育酚在2 ～ 80 mg/L范围内，相关系数R2≥0.9991；4种生育酚的定量限均为0.6 mg/kg，3水平加标平均回收率范围为88.2% ～ 103%，相对标准偏差范围为1.3% ～ 4.7%。方法色谱分离效果好、重复性好、准确度高、定量限也满足标准限量要求，具有较好的实用性，并已用于实际样品的检测，可为乳粉维生素E含量的准确测定提供技术参考。
关键词：HPLC-FLU；正相色谱；生育酚；乳粉；含量测定-
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2021）--
Simultaneous Determination of 4 Tocopherol Isomers in Milk Powder by Normal Phase High Performance Liquid Chromatography with Fluorometric Detection LIU Ping*1, ZANG Shan-shan 2(1. College of Agriculture and Biotechnology, Taizhou Vocational College of Science & Technology, Taizhou 318020, China; 2. Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101, China), Huaxue Shiji, 2020, 42(11), ～
Abstract：A normal phase high performance liquid chromatography fluorometric (HPLC-FLU) method, with the characteristics of sample pretreatment from a reversed phase chromatography combining with normal phase chromatographic separation on a amide column, was established to determine the contents of α-, β-, γ- and δ-tocopherol in milk powder, and then to determinate the content of vitamin E. The different types of chromatography column, ratios of mobile phase components and injection volumes were investigated. The milk powder sample (about 2.5 g) was firstly saponificated with potassium hydroxide solution, then extracted with mixture of petroleum ether and diethyl ether. The extracted solution was concentrated to near dryness, and then 10 mL of methanol was added. The final sample solution was filtered with a filter before injection. With the mixture solution (hexane: tert-butyl methyl ether: tetrahydro furan: methanol=810.0:85.3:104.3:0.4) as mobile phase and isocratic elution, the base line separations ofα-, β-, γ- and δ-tocopherol could be achieved within 18.5 min on an amide column. The measuring wavelengths of Ex and Em were set at 294 nm and 328 nm, respectively. The injection volume was set at 2 μL. The correlation coefficient r2 was greater than or equal 0.9991 in the range of 2-80 mg/L. The limits of quantification (LOQs) were 0.6 mg/kg. The average recoveries for α-, β-, γ- and δ-tocopherol were between 88.2%～103% with the relative standard deviation (RSD) between 1.3%～4.7% in the milk powder sample. The method has shown satisfactory chromatographic separation, good accuracy and repeatability. The LOQs of α-, β-, γ- and δtocopherol are also met the requirements of relevant standards. The method has been applied to analyze milk powder samples, and can be used as useful technical reference for accurate determination of the content of vitamin E.
Key words：HPLC-FLU; normal phase chromatography; tocopherol; milk powder; content determination
引用本文：刘萍, 臧珊珊. 乳粉中4种生育酚的正相高效液相色谱荧光法含量测定[J]. 化学试剂，2021，43（2）：229-234.
2,2ʹ-二喹啉-4,4ʹ-二羧酸构筑的锰配合物的合成、结构及性质
韦文厂，刘峥*，魏润芝，梁楚欣，唐群*
（桂林理工大学 化学与生物工程学院 电磁化学功能物质广西区重点实验室，广西 桂林 541004）
摘要：利用2,2ʹ-二喹啉-4,4ʹ-二羧酸（2,2ʹ-bca）为主配体，1,10-邻菲罗啉（1,10-phen）为辅配体，与四水合醋酸锰通过溶剂热反应得到配合物1（[Mn(2,2ʹ-bca)(1,10-phen)(H2O)2]n）和配合物2（[Mn(2,2ʹ-bca)(H2O)]n），并使用X-射线单晶衍射、傅立叶红外光谱、元素分析、紫外光谱、荧光光谱、热重分析等测试手段对其结构进行表征与性质研究。单晶结构分析表明：配合物1由一个2,2ʹ-bca配体、一个1,10-phen和两个配位水分子组成，通过主配体2,2ʹ-bca的桥联作用连接Mn2+形成一维链结构，并通过氢键相互作用与p-p堆积，进一步有序堆积形成三维网络结构；配合物2是由一个2,2ʹ-bca配体和一个配位水分子组成，通过2,2ʹ-bca配体的两个羧酸基团桥联Mn2+形成无限三维框架结构。荧光分析和热重分析结果分别表明两种配合物均有良好的荧光性能和热稳定性。
关键词：锰配合物；晶体结构；2,2ʹ-二喹啉-4,4ʹ-二羧酸；荧光性质；热稳定性
中图分类号：O614.121；O614.24+1 文献标识码：A 文章编号：0258-3283(2021)
Synthesis, Crystal Structure and Properties of Manganese Complexes Constructed by 2,2ʹ-Diquinoline-4,4ʹ-dicarboxylic Acid WEI Wen-chang, LIU Zheng*, WEI Run-zhi, LIANG Chu-xin, TANG Qun* (Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemical and Biological Engineering, Guilin University of Technology, Guilin 541004, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: Two transition metal coordination polymer materials [Mn(2,2ʹ-bca)(1,10-phen)(H2O)2]n and [Mn(2,2ʹ-bca)(H2O)]n, were successfully synthesized by solvothermal method with 2ʹ-diquinoline-4,4ʹ-dicarboxylic acid (2,2ʹ-bca), 1,10-phenanthroline (1,10-phen) and manganese(II) acetate tetrahydrate. The complexes were confirmed by X-ray single crystal diffraction, Fourier infrared spectroscopy (FTIR), elemental analysis, UV-Vis spectrum, fluorescence spectroscopy (FL) and thermogravimetric analysis (TG/DTG). The single crystal structure analysis showed that complex 1 is composed of a 2,2ʹ-bca ligand, a 1,10-phen, and two coordination water molecules. The 2,2ʹ-bca ligands bridge Mn2+ to form a one-dimensional (1D) chain structure, and through hydrogen bonding interaction and π···π stacking, further form a three-dimensional (3D) network structure. Complex 2 is composed of a 2,2ʹ-bca ligand and a coordinated water molecule, through two carboxylic acid groups of 2,2ʹ-bca ligand bridge Mn2+ to form 3D framework structure. The [Mn(2,2ʹ-bca)(1,10-phen)(H2O)2]n and [Mn(2,2ʹ-bca)(H2O)]n show that both complexes have good fluorescence properties and thermal stability.
Key words: manganese complex; crystal structure; 2,2ʹ-diquinoline-4,4ʹ-dicarboxylic acid; fluorescence; thermal stability
引用本文：韦文厂, 刘峥, 魏润芝, 等. 2, 2ʹ-二喹啉-4, 4ʹ-二羧酸构筑的锰配合物的合成、结构及性质[J].化学试剂，2021，43（2）：235-242.
葡萄糖修饰罗丹明B的荧光探针的合成及其性质研究
张钰绮，陈永虎，刘华丽，张斌，黄婉婷，刘翔元，董树国*
（吉林医药学院 药学院，吉林 吉林 132013）
摘要：设计合成一种用于pH值测定的荧光探针，以罗丹明B、1-O-丙炔基-2,3,4,6-四-O-乙酰基-β-D-葡萄糖苷等为原料，利用Click反应，合成葡萄糖修饰罗丹明B荧光探针，并利用核磁共振波谱对其结构进行表征。进一步研究了该探针的荧光性质，并利用MTT法评价了所制备荧光探针的细胞毒性。实验结果表明，弱酸性条件下，在578 nm处有强荧光发射峰。在pH值4.0～6.5范围内，荧光强度与pH值呈线性关系，并具有良好的可逆性。细胞毒性试验中，当浓度大于40 μmol/L时，细胞的生存能力开始降低，通过拟合计算半抑制浓度IC50为36.56 μmol/L。所合成的荧光探针有望用于细胞微环境的pH值检测。
关键词：罗丹明B；葡萄糖；荧光探针；Click反应；应用
中图分类号： O657.3 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis and Application of Fluorescent Probes of Rhodamine B Modified with Glucose ZHANGYu-qi, CHEN Yong-hu, LIU Hua-li, ZHANG Bin, HUANG Wan-ting, LIU Xing-yuan, DONG Shu-guo*(College of Pharmacy, Jilin Medical University, Jilin 132013, china), Huaxue Shiji, 2021, 43(2), ～
Abstract: A fluorescent probe for pH measurement was designed and synthesized. Rhodamine B was modified with glucose by click reaction using rhodamine B, and 1,2,3,4,6-Penta-O-acetyl- beta-D-glucose as raw materials. The structure of the fluorescent probe was confirmed by NMR. Its fluorescence properties was investigated, and cytotoxicity was evaluated by MTT. There was a strong fluorescence emission peak at 578 nm under weakly acidic conditions. The fluorescence intensity had an excellent linear relationship with pH when pH ranged from 4.0～6.5. The fluorescent probe had a good reversibility. The results of cytotoxicity test showed that the viability of cells began to decrease when the concentration was more than 40 μmol/L. The semi-inhibitory concentration IC50 was 36.56 μmol/L by fitting calculation. The synthesized fluorescent probes are expected to be used for the pH detection of the cellular microenvironment.
Key words: rhodamine B; glucose; fluorescent probe; Click reaction；application
引用本文：张钰绮，陈永虎，刘华丽, 等. 葡萄糖修饰罗丹明B的荧光探针的合成及其性质研究[J].化学试剂，2021，43（2）：243-246.
无溶剂微波辅助一锅法合成吡喃并[2,3-c]吡唑衍生物
吴璐璐，岳阳，曹占奇，姜松，高萌璐，樊小改，潘振良*
（河南农业大学 理学院，河南 郑州 450002）
摘要：绿色、高效、简便的催化多组分一锅法反应符合当前所倡导的“绿色”化学理念，是当今有机化学的研究热点。通过在无溶剂微波辅助条件下，使用廉价易得的KF/Al2O3催化吡唑啉酮、芳香醛和丙二腈的多组分“一锅法”反应，合成了一系列吡喃并[2,3-c]吡唑衍生物，反应时间为5 ~ 10 min，产率为85% ~ 98%。标题化合物的结构经核磁共振波谱（NMR）和高分辨质谱（HRMS）确证。该方法克服了传统合成方法中溶剂对环境造成的污染及分步合成的不便，具有无溶剂参与、反应时间短且收率高的优点。催化剂回收重复使用3次，其催化活性不受影响。
关键词：无溶剂合成；微波辅助合成；一锅法；吡喃并吡唑衍生物
中图分类号：0626.32 文献标志码：A 文章编号：
Solvent-free One-pot Synthesis of Pyrano[2,3-c]pyrazoleDerivatives under Microwave Irradiation WU Lu-lu, YUE Yang, CAO Zhan-qi, JIANG Song, GAO Meng-lu, FAN Xiao-gai, PAN Zhen-liang* ( College of Science, Henan Agricultural University, Zhengzhou 450002, China)
Abstract:The green, efficient and simple catalytic reaction with multi-component one-pot is in line with the current "green" chemical concept. KF/Al2O3 as a cheap and readily accessible catalyst for the solvent-free synthesis of pyrano[2,3-c]pyrazole derivatives by multi-component one-pot reaction of pyrazolone, aryl aldehydes, malononitrile was described. The reaction time was 5 ~ 10 min, the yield ranged from 86% to 97%. The target products were confirmed by nuclear magnetic resonance spectroscopy (NMR) and high resolution mass spectrometry data (HR-MS). Compared with the traditional synthetic methods, the work overcomes the environmental pollution caused by the use of solvent and the inconvenience of stepwise reaction and has the advantages of solvent-free, short reaction time and high yield.The catalyst can be recovered and reused for five cycles without loss of activity.
Key words: solvent-free synthesis; microwave-assisted synthesis; one-pot; pyrano[2,3-c]pyrazole derivatives
引用本文：吴璐璐，岳阳，曹占奇, 等. 无溶剂微波辅助一锅法合成吡喃并[2,3-c]吡唑衍生物[J].化学试剂，2021，43（2）：247-252.
磺酰甘脲的合成工艺研究
朱超*，桂艳，黄遥，周明善，陈晓春，朱丽
（云南开放大学 化学工程学院，云南 昆明 650500）
摘要：为开发活性更强的甘脲类似物，进而扩大葫芦脲家族化合物的应用范围。以4,5-二羟基咪唑啉-2-酮、磺酰胺为原料合成了四氢-1H-咪唑并[4,5-c] [1,2,5]噻二唑-5（3H）-酮-2,2-二氧化物（磺酰甘脲），考察了不同反应条件对产物产率的影响。并通过1HNMR、MS、IR对目标产物的结构进行了表征。研究表明，最佳合成工艺为：n(4,5-二羟基咪唑啉-2-酮)∶n(磺酰胺) = 1.1∶1，pH 5.5，反应温度为65 ℃，反应时间1.5 h，产率可达63.9%，与文献数据相比提高近10%，可为进一步设计和合成具有磺酰苷脲单元的葫芦脲类似物提供重要依据。
关键词：磺酰甘脲；合成；表征；葫芦脲
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2021）
Synthesis Process of Sulfonyl Glycoluril ZHU Chao*, GUI Yan, HUAGN Yao, CHEN Xiao-chun, ZHU Li (School of Chemical Engineering, Yunnan Open University, Kunming 650500, China), Huaxue Shiji, 2021, 43(2), ～
Abstract: In order to develop more active glycoluril analogs, and further expand the application range of cucurbituril family compounds. Tetrahydro-1H-imidazo[4,5-c][1,2,5]thiadiazol-5(3H)-one 2,2-dioxide was synthesized by the reaction of 4,5-dihydroxyimidazolin-2-one and sulfonamide -2,2-dioxide, and optimized the reaction process conditions. The structure of the target product was confirmed by 1 HNMR, MS and IR. The optimal synthesis process is: the ratio of the amount of 4,5-dihydroxyimidazolin-2-one to sulfonamide is 1.1:1, the pH is 5.5, the reaction temperature is 65 ℃, and the reaction time is 1.5 h. The yield was increased to 63.9%, which is nearly 10% higher than the literature data, which can provide an important basis for the further design and synthesis of cucurbituril analogs with sulfonylurea units.
Key words: sulfonyl glycoluril; synthesis; characterization; cucurbituril
引用本文：朱超，桂艳，黄遥，等. 磺酰甘脲的合成工艺研究[J]. 化学试剂，2021，43（2）：253-255。
3-[(2,3-二氢噻吩并[3,4-b]-1,4-二噁英-2-基)甲氧基]-丙酸的合成工艺改进
马晓莉*，刘春晖，江志波，郭鑫
（北方民族大学化学与化学工程学院，宁夏银川750021）
摘要：报道了一种合成标题化合物的新工艺。以噻吩并[3,4-b]-1,4-二噁英-2-甲醇为起始原料，与丙烯酸叔丁酯发生迈克尔加成反应得到中间体化合物3-[(2,3-二氢噻吩并[3,4-b]-1,4-二噁英-2-基)甲氧基]丙酸叔丁酯。将得到的中间体化合物在碱性条件下进行水解反应，然后采用盐酸进行酸化，最终经过干燥、减压浓缩、洗脱等后处理得到合格的标题化合物，总产率为71.2%，标题化合物及中间体经1HNMR确认结构。路线操作简便，反应条件温和，产品质量可控，具有一定的工业应用意义。
关键词：3-[(2,3-二氢噻吩并[3,4-b]-1,4-二噁英-2-基)甲氧基]-丙酸；丙烯酸叔丁酯；合成；工艺；改进
中图分类号：TQ463文献标识码：A文章编码：0258-3283（2021）--
Improved Synthesis of 3-[(2,3-Dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]propanoic Acid MA Xiao-li*, LIU Chun-hui, JIANG Zhi-bo, GUO Xin(School of Chemistry and Chemical engineering, North Minzu University, Yinchuan750021, China), Huaxue Shiji, 2021, 43(2), ～
Abstract：A new process for the synthesis of 3-[(2,3-dihydrothieno [3,4-b] -1,4-dioxin-2-yl) methoxy] -propionic acid was reported. Using[3,4-b] -1,4-dioxin-2-methanol as the starting material, it was reacted with tert-butyl acrylate to give 3-[(2,3-dihydrothiophene[3,4-b] -1,4-dioxin-2-yl) methoxy] propionic acid tert-butyl ester. The ester was hydrolyzed under alkaline conditions, then was acidified with hydrochloric acid. The final sample was undergo post-treatments such as drying, vacuum distillation and elution to obtain a high purity title compound, the yield was 71.2%. The title compound and intermediate compound were confirmed by 1HNMR. The route has the advantages of simplified operation, mild reaction conditions and controllable product quality, and has certain industrial value.
Keywords：3-[(2,3-dihydrothieno [3,4-b] -1,4-dioxin-2-yl) methoxy] -propionic acid; tert-Butyl acrylate; synthesis; process; improvement
引用本文：马晓莉，刘春晖，江志波，等.3-[(2,3-二氢噻吩并[3,4-b]-1,4-二噁英-2-基)甲氧基]-丙酸的合成工艺改进[J].化学试剂，2021，43（2）：256-258.
（编辑：MCM）
