纳米金电催化还原CO2的载体效应
高明洋1，朱英明*2，梁斌1, 2
（1. 四川大学 化学工程学院，四川 成都 610065；2 四川大学 新能源与低碳技术研究所，四川 成都 610207）
摘要：通过化学还原方法制备得到了不同载体（碳纳米管（CNT）、炭黑（CB）、石墨碳（GC）、介孔碳（MC））负载的纳米Au催化剂，探究了载体对纳米Au电催化还原CO2的影响。催化剂的物性表征结果显示，Au/CNT和Au/CB催化剂的载体具有较大比表面积，分别为90.1、81.5 m2/g，并且载体与纳米Au之间具有强结合能。4种催化剂电催化还原CO2的性能结果显示，Au/CB催化剂具有更好的稳定性，28 h的稳定性测试中，CO的法拉第效率（FE）仅下降5%；Au/CNT催化剂的催化活性和选择性最高，起始电压仅为-0.4 V，且此时还原产物CO的法拉第效率约为100%。相比较之下，Au/GC和Au/MC催化剂上CO2反应活性低和选择性差，在稳定性测试中对CO的选择性都降为零。
关键词：载体；纳米金；电催化还原；二氧化碳；碳纳米管；炭黑；法拉第效率
中图分类号：O611.4 文献标识码：A 文章编号：0258-3283（2020）--
Support Effect of Nano-gold Electrocatalytic Reduction of CO2 GAO Ming-yang1, ZHU Ying-ming2, LIANG Bin12 (1. School of Chemical Engineering, Sichuan University, Chengdu 610065, China; 2. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Nano Au catalysts supported on carbon nanotubes (CNT), carbon black (CB), graphite carbon (GC) and mesoporous carbon (MC) were prepared by chemical reduction method. The effect of the support on the nano-Au electrocatalytic reduction of CO2 was explored. The supports of Au/CNT and Au/CB catalysts have large specific surface areas of 90.1, 81.5 m2/g, respectively, with strong binding energy between the support and nano-Au. The performance results of four catalysts for electrocatalytic reduction of CO2 show that Au/CB catalyst has better stability. In the 28-hour stability test, the Faraday efficiency of CO decreased by only 5%. Au/CNT catalyst has the highest catalytic activity and selectivity. The initial voltage is only -0.4 V, and the Faraday efficiency of the reduction product CO is about 100%. In comparison, the Au/GC and Au/MC catalysts have low CO2 reactivity and poor selectivity, and the selectivity to CO in stability tests was reduced to zero.
Key words: support; Au nanoparticles; electrocatalytic reduction; carbon dioxide; carbon nanotubes; carbon black; faraday efficiency
引用本文：高明洋，朱英明，梁斌. 纳米金电催化还原CO2的载体效应[J]. 化学试剂，2020, 42(8): 887-892.
铁掺杂碳量子点的水热法合成及在H2O2和多巴胺检测中的应用
李䶮a，郭汉涛a，薛梅花a，卢石孔a，姚碧霞a，翁文*a,b
（闽南师范大学 a. 化学化工与环境学院，b. 福建省现代分离分析科学与技术重点实验室，福建 漳州 363000）
摘要 为了开发一种灵敏度高无标记、快速和特定的多巴胺比色检测法，通过一步水热法以β-环糊精、尿素、三氯化铁为原料制备了铁掺杂碳量子点（Fe-CDs），该Fe-CDs显示出理想的类过氧化物酶活性，可催化H2O2氧化3,3',5,5'-四甲基联苯胺（TMB）并显色，而强还原性的多巴胺抑制其催化氧化，从而使反应体系褪色。当Fe-CDs浓度为30 µg/mL、TMB浓度为500 µmol/L、H2O2浓度为0.1 mmol/L、pH 3.0、反应温度为35℃、反应时间为20 min时，多巴胺浓度在0～100 µmol/L范围内与体系吸光度呈良好的线性关系，检出限可达55.1 nmol/L。表明Fe-CDs作为类过氧化物酶具备检测多巴胺性能。
关键词 铁掺杂碳量子点；水热法；模拟过氧化物酶；过氧化氢；多巴胺
中图分类号：O655 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of Iron Doped Carbon Dots by Hydrothermal Method and Application in Detection of H2O2 and Dopamine LI Yana, GUO Han-taoa, XUE Mei-huaa, LU Shi-konga, YAO Bi-xiaa, WENG Wen*a,b(Minnan Normal University, a. College of Chemistry, Chemical Engineering and Environment, b.Fujian Provincial Key Laboratory of Modern Analytical Science and Separation Technology, Zhangzhou 363000, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: In order to develop a highly sensitive, label-free, fast and specific colorimetric detection method for dopamine, iron-doped carbon quantum dots (Fe-CDs) are prepared from β-cyclodextrin, urea and ferric chloride by a convenient one-pot hydrothermal method. The Fe-CDs show ideal peroxidase-like activity, and can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce a color change. Moreover, dopamine inhibits its catalytic oxidation, resulting in a decrease in the absorbance of the system. When the concentration of Fe-CDs, TMB, and H2O2 is 30 μg/mL, 500 μmol/L, and 0.1 mmol/L, respectively, at the optimal conditions of pH 3.0, reaction temperature 35 °C and reaction time 20 min, there exists a linear relationship between the concentration of dopamine in the range of 0 ～ 100 μmol/L and the absorbance of the system. The limit of detection is calculated to be 55.1 nmol/L based on three times the standard deviation rule. Fe-CDs have the potential application in the detection of dopamine.
Keywords: iron-doped carbon dots; hydrothermal method; peroxidase mimetic; H2O2; dopamine
引用本文：李䶮，郭汉涛，薛梅花. 铁掺杂碳量子点的水热法合成及在H2O2和多巴胺检测中的应用[J]. 化学试剂, 2020, 42(8):893-900 .
AGT介导的氯乙基亚硝基脲耐药作用机理的
密度泛函理论研究
尹方正，肖伟男，马昕艳，赵丽娇*，钟儒刚
（北京工业大学 生命科学与生物工程学院 环境与病毒肿瘤学北京市重点实验室，北京 100124）
摘要：氯乙基亚硝基脲(CENUs)是一类重要的抗癌烷化剂，通过导致DNA互补鸟嘌呤-胞嘧啶之间的共价交联(GC交联)发挥抗肿瘤作用。然而，O6-烷基鸟嘌呤-DNA烷基转移酶(AGT)对DNA烷化损伤的修复作用能够导致肿瘤细胞对CENUs产生耐药性。使用密度泛函理论(DFT)方法结合分子对接对AGT介导的CENUs耐药机制进行了研究。结果表明，AGT能够与CENUs导致GC交联的两个前体物——O6-ClEtG和N1,O6-EtG结合形成复合物，然后通过氢迁移和烷基转移两步反应，对这两个前体物进行修复，从而阻断GC交联的形成。在AGT对两个前体物的修复过程中，N1,O6-EtG的修复在动力学和热力学上比O6-ClEtG的修复均具有优势，但O6-ClEtG更有利于与AGT形成复合物。阐明了AGT介导的CENUs耐药机制，这将为开发AGT抑制剂用于与CENUs联合用药以消除耐药性提供重要的理论依据。
关键词：氯乙基亚硝基脲；O6-烷基鸟嘌呤-DNA烷基转移酶；DNA股间交联；耐药机制；密度泛函理论
中图分类号：O641 文献标识码：A 文章编号：0258-3283（2020）--
AGT-mediated Drug Resistance Mechanism of Chloroethylnitrosoureas: A DFT Investigation YIN Fang-zheng, XIAO Wei-nan, MA Xin-yan, ZHAO Li-jiao*, ZHONG Ru-gang (Beijing Key Laboratory of Environmental ＆ Viral Oncology, College of Life Science ＆ Bioengineering, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Chloroethylnitrosoureas (CENUs) are important anticancer alkylating agents, which play an anti-tumor role by causing covalent crosslink between complementary DNA base pair guanine-cytosine (GC crosslink). However, the repair of DNA alkylation damage by O6-alkylguanine-DNA alkyltransferase (AGT) can lead to the resistance of tumor cells to CENUs. Density functional theory (DFT) and molecular docking were used to investigate the mechanism of CENUs resistance mediated by AGT. The results show that AGT combines with two precursors of GC crosslink, O6-ClEtG and N1, O6-EtG, to form a complex, and then repairs these two precursors through a two-step mechanism including proton transfer and alkyl transfer, thereby blocking the formation of GC crosslinking. In the process of AGT repairing the two precursors, N1, O6-EtG is more readily to be repaired than O6-ClEtG in kinetics and thermodynamics, while O6-ClEtG is more favorable to form complex with AGT. The mechanism of drug resistance of CENUs mediated by AGT was elucidated, which will provide an important theoretical basis for the development of AGT inhibitors used in combination with CENUs to eliminate drug resistance.
Key words: chloroethylnitrosoureas (CENUs); O6-alkylguanine-DNA alkyltransferase (AGT); DNA inter strand crosslink; drug resistance mechanism; density functional theory
引用本文：尹方正，肖伟男，马昕艳，等. AGT介导的氯乙基亚硝基脲耐药作用机理的密度泛函理论研究[J].化学试剂，2020,42(8): 901-907.
β-FeOOH/PDMS超疏水涂层的制备及其性能研究
曹京宜1，张海永1，杨文静2，陈蓉蓉*2，刘婧媛2，王君2
（1. 中国人民解放军92228部队，北京100072；
2. 哈尔滨工程大学材料科学与化学工程学院，哈尔滨 150001）
摘要：通过环保的一步水热法制备了疏水性的β-FeOOH纳米粒子，将其添加到聚二甲基硅氧烷（PDMS）中，采用喷涂法在镁合金AZ31表面制备β-FeOOH/PDMS疏水涂层，利用X射线衍射（XRD）和傅里叶红外光谱分析（FTIR）对超疏水涂层进行了表征，并研究了其耐磨性、耐腐蚀性、自清洁及抗海藻粘附特性。结果表明，当m（β-FeOOH）：m（PDMS）=85:100时，涂层达到超疏水状态，水接触角为152.6°；摩擦磨损实验证明超疏水涂层的稳定性；电化学测试表明涂层在15 d内对基底能起到腐蚀防护作用；此外涂层还表现出优异的自清洁性、防污泥和抗海藻粘附性。
关键词：超疏水；β-FeOOH纳米粒子；PDMS；腐蚀防护
中图分类号：O611.6 文献标识码：A 文章编号：0258-3283(2020) –
Preparation of β-FeOOH/PDMS Super Hydrophobic Coating and Its Application Performances CAO Jing-yi1, ZHANG Hai-yong1, YANG Wen-jing2, CHEN Rong-rong*2, LIU Jing-yuan2, WANG Jun2 (1. Unit 92228, People's Liberation Army, Beijing, 100072, China; 2. College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Hydrophobic β-FeOOH nanoparticles which are prepared by environmentally friendly one-step hydrothermal method were filled into the PDMS, the β-FeOOH/PDMS composites were sprayed on the magnesium alloy AZ31 surface and formed the β-FeOOH/PDMS hydrobic surfaces. The super hydrophobic coating was characterized by X-ray diffraction (XRD) and infrared spectroscopy analysis (IR). The wear resistance, corrosion resistance, self-cleaning and anti-algae adhesion were investigated. The results showed that when m（β-FeOOH）：m（PDMS）=85:100, it reached to a super hydrophobic state and the water contact angle was 152.6°. The friction and wear test confirms the stability of the coating. The electrochemical test proved that the coating could protect the substrate from corrosion within 15 days. In addition, the coating showed excellent self-cleaning, anti-sludgeand anti-ditom properties.
Key words: super hydrophobic; β-FeOOH nanoparticles; PDMS; corrosion protection
引用本文：曹京宜, 张海永, 杨文静, 等. β-FeOOH/PDMS超疏水涂层的制备及其性能研究[J]. 化学试剂, 2020, 42(8): 908-914.
壳聚糖修饰Fe3O4纳米颗粒的制备及其磁共振造影性能
李小娟，郑维城，易夕圆，王生庚，杨增涛*
（重庆医科大学 生物医学工程学院 超声医学工程国家重点实验室 重庆市生物医学工程学重点实验室，重庆 400016）
摘要：采用碳二亚胺法将壳聚糖（CS）分子链上的-NH2和羧基化Fe3O4 （Fe3O4-COOH）纳米粒子表面的-COOH共价耦联，制备壳聚糖修饰的Fe3O4 （CS-Fe3O4）纳米颗粒。通过纳米粒度仪（Zetasizer）、透射电子显微镜（TEM）、傅里叶变换红外（FTIR）光谱仪、X-射线衍射（XRD）分析仪、低温综合物性测试系统分别对CS-Fe3O4纳米颗粒的粒径分布、表面形态、化学结构、晶体结构及磁学性质进行测试，并探究其作为T2造影剂的体外磁共振造影能力。结果表明，制备的CS-Fe3O4纳米颗粒形态圆整、大小均一，水合动力学平均粒径为109.2 nm，具有良好的分散稳定性及超顺磁性；体外磁共振显像实验表明该纳米粒子具有负性显像能力，并且其负性显像能力随Fe3O4浓度增加而增强。因此，CS-Fe3O4纳米颗粒有望成为一种新型的磁共振T2造影剂。
关键词：壳聚糖；Fe3O4纳米粒子；超顺磁性；负性显像；磁共振造影剂
中图分类号：TB383.1 文献标识码：A 文章编号：0258-3283（2020）--
Preparation of Fe3O4 Nanoparticles Modified With Chitosan and Magnetic Resonance Imaging Performance LI Xiao-juan, ZHENG Wei-cheng, YI Xi-yuan, WANG Sheng-geng, YANG Zeng-tao* (State Key Laboratory of Ultrasound in Medicine and Engineering, College of Biomedical Engineering, Chongqing Medical University, Chongqing Key Laboratory of Biomedical Engineering, Chongqing 400016, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Chitosan modified Fe3O4 (CS-Fe3O4) nanoparticles were prepared by coupling -NH2 on the molecular chains of chitosan (CS) with -COOH covalently on the surface of carboxylated Fe3O4 (Fe3O4-COOH) nanoparticles by carbon diimine method. The size distribution, surface morphology, chemical structure, crystal structure and magnetic property of CS-Fe3O4 nanoparticles were characterized by Nanometer particle size analyzer (Zetasizer), Transmission electron microscope (TEM), Fourier transform infrared (FTIR) spectrometer, X-ray diffraction (XRD), and Low temperature comprehensive physical property test system. And their vitro magnetic resonance imaging (MRI) ability as a T2 contrast agent was also explored. The results showed that the prepared CS-Fe3O4 nanoparticles with a hydrodynamic average size of 109.2 nm were round in shape and uniform in size, showing good dispersion stability and superparamagnetism. Vitro magnetic resonance imaging experiment showed that the nanoparticles had negative imaging ability, and its negative imaging ability increased with the increase of Fe3O4 concentration. Thus, CS-Fe3O4 nanoparticles are expected to be a novel magnetic resonance T2 contrast agent.
Key words: chitosan; Fe3O4 nanoparticles; superparamagnetism; negative imaging; magnetic resonance contrast agent
引用本文：李小娟，郑维城，易夕圆，等. 壳聚糖修饰Fe3O4纳米颗粒的制备及其磁共振造影性能[J]. 化学试剂，2020,42(8): 915-920.
硼改性聚硅酸铝钛的制备及絮凝性能研究
李玉莹，张浩，王希越，马捷，连丽丽*，娄大伟*
（吉林化工学院 化学与制药工程学院，吉林 吉林132022）
摘要：以硅酸钠、硫酸铝、硫酸钛、四硼酸钠为原料制备了无机高分子絮凝剂硼改性聚硅酸铝钛（B-PSATi）。以高岭土-腐植酸钠配制模拟水样，通过单因素实验确定了最佳制备条件，在pH 2.5、n（Al+Ti）：n（Si）=0.6、n（Al）：n（Ti）=8:2、n（B）：n（Si）=0.05时，B-PSATi絮凝剂对模拟水样的絮凝效果最佳，浊度去除率和色度去除率可达97.56%和98.08%。通过XRD、SEM及EDS能谱对其结构进行了表征。结果表明，B-PSATi絮凝剂是一种结构紧实的无定形聚合物。对B-PSATi的絮凝条件进行了优化，其最佳絮凝剂投加剂量为0.5 mL/L，最佳pH 7～9。
关键词：硼改性；钛盐；聚硅酸铝；无机高分子絮凝剂；去除率
中图分类号：TQ421 文献标识码：A 文章编号：0258-3283（2020）--
Preparation and Flocculation Properties of Boron Modified Polysilicate Aluminium Titanate LI Yu-ying, ZHANG Hao, WANG Xi-yue, MA Jie, LIAN Li-li*, LOU Da-wei*(School of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, China), Huaxue Shiji, 2020, 42( ), ～
Abstract：An inorganic polymer flocculant boron modified polysilicate aluminum titanate (B-PSATi) was prepared with sodium silicate, aluminum sulfate, titanium sulfate and sodium tetraborate as raw materials. Taking kaolin-sodium humate as simulated water, the optimum preparation conditions were determined by single factor experiments. When pH 2.5, n（Al+Ti）：n（Si）=0.6, n（Al）：n（Ti）=8:2, n（B）：n（Si）=0.05, the prepared B-PSATi exhibited the best flocculation performance with turbidity and color removal efficiency of 97.56% and 98.08%, respectively. The flocculant was characterized by XRD, SEM and EDS. The prepared B-PSATi was an amorphous polymer with tight structure. The flocculation conditions of B-PSATi were optimized: the dosage of flocculation was 0.5 mL/L with pH 7~9.
Key words: boron modified; titanium salt; polysilicate aluminium; inorganic polymer flocculant; removal rate
引用本文：李玉莹, 张浩, 王希越, 等. 硼改性聚硅酸铝钛的制备及絮凝性能研究[J]. 化学试剂, 2020, 42(8): 921-925.
吲哚-2-碳酰肼衍生物的合成及抗肿瘤活性评价
王宁伟，韩迎龙，张国强，黄学涛，刘明辉，杨烨鲜，王海君，卜明*
(齐齐哈尔医学院 药学院，黑龙江 齐齐哈尔 161006)
摘要：以5-氯-吲哚-2-羧酸为原料，设计合成7个全新的吲哚-2-碳酰肼衍生物，并通过1H NMR、13C NMR和MS进行结构表征。采用四甲基偶氮唑盐（MTT）染色法对化合物的抗人结肠癌细胞（HCT116）、人乳腺癌细胞（MCF-7）和人肺癌细胞（A549）增殖活性进行评价。结果表明，5-氯-N'-((5-氟-1H-吲哚)-3-亚甲基)-1H-吲哚-2-碳酰肼对HCT16细胞具有显著抑制活性，IC50值为7.72 μmol/L。另外，该化合物能够呈浓度依赖方式诱导HCT116细胞凋亡。
关键词：吲哚；碳酰肼；合成；抗肿瘤活性；凋亡
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis and Antitumor Activity Evaluation of Indole-2-carbohydrazide Derivatives WANG Ning-wei, HAN Ying-long, ZHANG Guo-qiang, HUANG Xue-tao, LIU Ming-hui, YANG Ye-xian, WANG Hai-jun, BU Ming* (School of Pharmacy, Qiqihar Medical University, Qiqihar 161006, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: Using 5-chloroindole-2-carboxylic acid as staring material, seven indole-2-carbohydrazide derivatives had been synthesized, and their structures were confirmed by MS, 1H NMR and 13C NMR. The antiproliferative activity of the compounds was evaluated against human colon cancer cells (HCT116), human breast cancer cells (MCF-7) and human lung cancer cells (A549). The results showed that 5-chloro-N'-((5-fluoro-1H-indol-3-yl)methylene) -1H-indole-2-carbohydrazide displayed significant inhibitory activity against HCT116 cell lines with IC50 value of 7.72 μmol/L. Furthermore, the compound could induce HCT116 cells apoptosis in a dose-dependent manner.
Key words: indole; carbohydrazide; synthesis; antitumor activity; apoptosis
引用本文：王宁伟，韩迎龙，张国强，等. 吲哚-2-碳酰肼衍生物的合成及抗肿瘤活性评价[J]. 化学试剂, 2020, 42(8): 926-930.
基于质量平衡法的有机物纯度测量技术进展
张庆合*1，杨吉双1, 2，焦慧1，李秀琴1
（1. 中国计量科学研究院 化学计量与分析科学研究所，北京 100029；
2. 齐齐哈尔大学 化学与化学工程学院，黑龙江 齐齐哈尔 161006）
摘要: 有机物纯度是化工、医药等行业产品质量控制的关键参数，纯度标准物质是化学测量溯源和校准标准的源头，纯度结果的准确可靠对于科技和产业至关重要。近年来，有机物纯度测量技术和不确定度水平随仪器技术同步发展，定量核磁法、质量平衡法等纯度测量方法取得很多突破。质量平衡法是通过测量样品中有机和无机杂质、水分、挥发性溶剂等杂质总量而获得纯度的1组测试方法，在纯度测量国际比对、标准物质研制、产品检测中应用很广。总结了国际计量局物质量咨询委员会-化学和生物计量有机分析工作组有机物纯度国际比对，质量平衡法测试的原理与要求，有机杂质响应因子的研究进展，水分、挥发性溶剂、无机杂质测量方法及其溯源性要求，为有机物纯度准确测量和标准物质定值提供参考。
关键词: 化学纯度；质量平衡法；响应因子；计量溯源性；标准物质
中图分类号：O652.2 文献标识码：A 文章编号：0258-3283（2020）--
Advanced in organic chemical purity measurement by mass balance method ZHANG Qing-he*1, YANG Ji-shuang1, 2, JIAO Hui1, LI Xiu-qin1 (1. Division of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, China; 2. College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Organic chemicals purity is a key parameter for product quality control in chemical industry, pharmaceutical et al. Purity certified reference materials are the source of chemical measurement traceability and calibration standards. With the development of instrument technology, organic chemicals purity measurement methods and level of uncertainty have improved rapidly. Mass balance is an indirect method via rigorous assessment of impurities in the sample. Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM) Organic Analysis Working Group (OAWG) pilot (P) studies and key (K) comparisons for organic chemical purity and Principles and requirements of Mass Balance Method validation were summarized. Progress and the traceability guarantee of organic impurity response factors, moisture, volatile solvents, and inorganic impurity measurement have been introduced. The future development and challenges are prospected.
Key words: chemical purity; mass balance method; response factor; metrological traceability; reference materials
引用本文：张庆合, 杨吉双, 焦慧, 等。基于质量平衡法的有机物纯度测量技术进展[J]. 化学试剂, 2020, 42(8): 931-939 .
碳糖苷类活性分子研究进展
周新燃，蔡津津，解瑞，涂璇，黄年玉*
（三峡大学 生物与制药学院 天然产物研究与利用湖北省重点实验室，湖北 宜昌 443002）
摘要：碳糖苷因具独特的生物活性而备受关注，但上市的碳糖苷类药物不多，为拓展碳糖苷分子的医药用途，加速其新药研发进程，有必要对其研发情况进行综述。通过查阅近十年文献，对碳糖苷活性分子的来源、获取途径、结构特点、作用机制和应用情况进行了分析整理，从降糖、抗肿瘤、心血管保护、抗菌和抗病毒活性等五方面进行了归纳总结，发现天然来源的糖苷类分子具有广泛生物活性，但其多靶点作用机制研究尚有待于深入研究。为碳糖苷分子的药物开发提供了参考。
关键词：碳糖苷；糖衍生物；天然产物；药理活性；研究进展
中图分类号：R914.4 文献标识码：A 文章编号：0258-3283（2020）--
Progress of C-glycosyl Molecules ZHOU Xin-ran, CAI Jin-jin, XIE Rui, TU Xuan, HUANG Nian-yu*(Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, 443002, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: The C-glycosides have attracted widely attention due to their unique biological activity, whereas few of them are marketed drugs. In order to explore the medical use of C-glycosides and accelerate their development of new drugs, it is necessary to review their research and development. The sources, acquiring approaches, structural features, biological mechanisms and applications of C-glycoside molecules were collected from the literatures reported on the domestic and foreign periodicals in the late decade. The research progress was summarized in five aspects from hypoglycemic, antitumor, cardiovascular protection, antibacterial and antiviral activities. Some natural C-glycosides were found to possess various activities, but their multi-target mechanisms remain to be further studied. A reference for the drug development of the C-glycosides was provided.
Key words: C-glycoside, sugar derivatives, natural products, pharmacological activities, research progress
引用本文：周新燃，蔡津津，解瑞，等. 碳糖苷类活性分子研究进展[J].化学试剂，2020，42(8):940-947.
顶空-气相色谱/质谱法检测水质中56种挥发性有机物的方法检出限筛选方法探讨
赖永忠1a,1b,2，黄意敏*3
（1. 汕头大学 a. 海洋生物研究所，b. 广东省海洋生物技术重点实验室，广东 汕头 515063；
2. 汕头市环境保护监测站，广东 汕头 515041；3. 汕头大学 医学院附属肿瘤医院内三科，广东 汕头 515041）
摘要：水质中56种挥发性有机物（VOCs）同时检测时，由于被分析物的物理、化学性质差异较大，导致他们在顶空-气相色谱/质谱法检测系统中的灵敏度和精密度参差不齐，测定方法检出限时难于严格按照HJ 168-2010进行。综合分析6个VOCs加标质量浓度水平的统计结果，把方法检出限的筛选分为六类，分类目的是得到样品结果均值与对应的计算方法检出限比值接近4，且较小的计算方法检出限作为最终的被分析物方法检出限（0.09～2.4 μg/L）；总量的方法检出限参照异构体的筛选方法，得到1,2-二氯乙烯、二甲苯、三氯苯的总量方法检出限分别为2.4、0.33、3.9 μg/L。方法检出限筛选方法，可供同行参考。
关键词：挥发性有机物；方法检出限；总量；顶空；气相色谱/质谱法；水质
中图分类号：X832 文献标识码：A 文章编号：0258-3283（2020）--
Screening Method for Detection Limits of 56 Volatile Organic Compounds in Enviromental Water by Headspace-gas Chromatography/mass Spectrometry LAI Yong-zhong1a,1b,2, HUANG Yi-min*3 (1a. Institute of Marine Sciences, Shantou University, Shantou 515063, China;1b. Guangdong Provincial Key Laboratory of Marine Biotechnology, Shantou University, Shantou 515063, China; 2. Shantou Environmental Monitoring Station, Shantou 515041, China; 3. Cancer Hospital of Medical College, Shantou University, Shantou 515041, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: The detection of method limit of analysts is difficult to follow HJ 168-2010 strictly, as the sensitivities and precisions of 56 kinds of volatile organic compounds (VOCs) in environmental water samples detected with headspace-gas chromatography/mass spectrometry were uneven due to the large differences in physical and chemical properties of the analysts. Comprehensive analysis of the statistical results of blank samples spiked with six concentration levels of VOCs, the screening of detection limits were divided into six categories, and the classification purpose was that the ratio of sample results and calculation detection limits were close to four, and the smaller calculation detection limits were used as the final detection limit (0.09～2.4 μg/L). The screening method of detection limits of total amount were based on the isomers screening method, and the detection limits of 1,2-dichloroethylene, xylene and trichlorobenzene were 2.4, 0.33, and 3.9 μg/L, respectively. Detection limit screening method discussed here is more practical and can be promoted.
Key words: volatile organic compounds; detection limit; total; Headspace; gas chromatography/mass spectrometry; environmental water
引用本文：赖永忠, 黄意敏. 顶空-气相色谱/质谱法检测水质中56种挥发性有机物的方法检出限筛选方法探讨[J]. 化学试剂, 2020, 42(8): 948-953.
基于乙二胺修饰碳点的荧光猝灭高效检测绿原酸
茅佳宁1b，岳倩1b，周雪莹2，黄敏1c，楼芯妤1c，董微*1a
（1. 沈阳医学院 a. 化学教研室，b. 2017级医学检验技术1班，c. 2017级麻醉学4班，辽宁 沈阳 110034；2. 沈阳医学院附属中心医院，辽宁 沈阳 110024）
摘要： 以葡萄糖（Glu）为碳源，乙二胺（EDA）为钝化剂，采用水热法合成量子产率为32％的荧光碳点（CDs）。基于CDs和绿原酸（CHA）之间的内滤效应和静态猝灭使得CDs的荧光猝灭，建立了以CDs为荧光探针检测CHA的传感平台。并通过TEM、紫外-可见吸收光谱、傅里叶变换红外光谱（FTIR）、荧光光谱等一系列表征研究了CDs与CHA的相互作用。在最佳实验条件下，CHA浓度为5×10-5～5×10-4 mol/L范围内，对CDs的荧光猝灭呈良好的线性关系，相关系数R2= 0.9910，线性拟合方程为ΔF=1.726×[CHA]+55.17，检出限为1.43×10-5 mol/L。利用所构建的荧光传感器用于实际样品中CHA的检测，回收率为97.50％～103.8％，相对标准偏差为1.89％（n=5）。
关键词：乙二胺修饰CDs；CHA；荧光猝灭；内滤效应；静态猝灭
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283(2020)--
Detection of Chlorogenic acid by Fluorescence Quenching of carbon spots modified via ethylenediamine MAO Jia-ning1b, Yue qian1b, Zhou xue-ying 2, Huang min1c, Lou xin-yu 1c, Dong wei *1a (a. Department of chemistry, b. Medical laboratory technology class 1, grade 2017, c. Anesthesiology Class 4, grade 2017, Shenyang medical college, Shenyang, 110034, China; 2. Affiliated central hospital of Shenyang medical college, Shenyang 110024, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: A hydrothermal method for synthesizing carbon dots (CDs) with 32% quantum yield were developed by using glucose (Glu) as carbon source and ethylenediamine (EDA) as modifier. Based on the internal filter effect and static quenching between CDs and chlorogenic acid (CHA), the fluorescence quenching of CDs was made, and a sensing platform for the detection of CHA with CDs as a fluorescent probe was established. The interaction between CDs and CHA was investigated by TEM, Uv-vis, FTIR and fluorescence spectra. Under the optimal conditions, the concentration of CHA was within the range of 5×10-5 ～5×10-4 mol/L, the fluorescence quenching of CDs presented a good linear relationship, the correlation coefficient R2 = 0.991, the linear fitting equation is ΔF=1.726×[CHA]+55.17, and the detection limit is 1.43×10-5 mol/L. The fluorescence sensor constructed is used to detect CHA in actual samples with a recovery rate of 97.5% ～103.83%, a relative standard deviation of 1.89% (n=5) and the common substances in tablets had little interference with the determination. Therefore, it is an efficient, simple and sensitive method for CHA detection.
Key words: ethylenediamine modified CDs; CHA; fluorescence quenching; internal filtration effect; static quenching
引用本文：茅佳宁, 岳倩, 周雪莹, 等. 基于乙二胺修饰碳点的荧光猝灭高效检测绿原酸[J]. 化学试剂, 2020, 42(8): 954-958.
电感耦合等离子体原子发射光谱法测定锂硼合金中
5种杂质元素
李甜，陈雄飞*,桑永珠，孙海峰，刘英，童坚
（国标（北京）检验认证有限公司，北京100088）
摘要：准确测定锂硼合金中杂质元素含量对于锂硼合金产品性能和质量控制具有重要意义。锂硼合金中锂含量较高，且其化学性质活泼、易燃，在空气中放置至充分氧化后，以水-硝酸溶解样品，采用基体匹配的方法绘制工作曲线，消除基体效应的影响，使用电感耦合等离子体原子发射光谱法（ICP-AES）测定其中的镁、钙、铁、铝、铬5种杂质元素。考察了谱线选择、介质酸度、共存元素干扰、精密度以及加标回收试验，确定了最佳实验条件。结果表明，各待测元素在测定范围内其质量浓度与发射强度呈线性，校准曲线的相关系数均大于0.9999，方法检出限为0.0047%～0.047%。按照实验方法测定锂硼合金中的5种杂质元素，相对标准偏差（RSD，n=11）在1.1%～3.1%之间，加标回收率在96.9%～105.9%之间。
关键词：锂硼合金；电感耦合等离子体原子发射光谱法；镁；钙；铁；铝；铬
中图分类号：O657.31 文献标识码：A 文章编号：0258-3283（2020）--
Determination of Five Impurities in Lithium Boron Alloy by Inductively Coupled Plasma Atomic Emission Spectrometry LI Tian1, CHEN Xiong-fei*, SANG Yong-zhu, SUN Hai-feng, LIU Ying, TONG Jian (Guobiao(Beijing) Testing & Certification Co., Ltd., Beijing 100088, China), Huaxue Shiji, 2020, 42(8), ～
Abstract：The accurate determination of impurity content in lithium-boron alloy has great significance for the performance and quality control of lithium-boron alloy products. Lithium-boron alloys have high lithium content and are chemically active and flammable. After the sample is fully oxidized in the air, the sample is dissolved in water-nitric acid, and the working curve is drawn using the matrix matching method to eliminate the effect of the matrix effect. Then, the five impurity elements of magnesium, calcium, iron, aluminum, and chromium were detected using inductively coupled plasma-atomic emission spectrometry (ICP-AES).The spectral line selection, media acidity, coexisting element interference, precision, and spike recovery experiments were investigated, the best experiment conditions are confirmed. The mass concentration of each element within the measurement range is linear with the emission intensity,the correlation coefficients of the calibration curves are all greater than 0.9995,and the detection limit of the method is 0.0047%～0.047%. Based on the experimental method, five impurity elements in lithium-boron alloys were determined, the spiked recoveries were in the range of 96.9%～105.9% with the relative standard deviation (RSD, n=11) was 1.1%～3.1%.
Key words：lithium boron alloys; inductively coupled plasma atomic emission spectrometry; magnesium; calcium; iron; aluminum; chromium
引用文本：李甜，陈雄飞，桑永珠，等. 电感耦合等离子体原子发射光谱法测定锂硼合金中5种杂质元素[J]. 化学试剂, 2020, 42(8):959 -963.
噻霉酮的高效液相色谱分析研究
陈国珍*1,2，赵锴3，党璐1，吴思拓1，苏华1，严峰1
(1. 陕西省石油化工研究设计院 陕西省危险化学品监督检验中心，陕西 西安710054；2. 西北大学 化学与材料科学学院，陕西 西安 710127；3. 西安和利时系统工程有限公司，陕西 西安 71000)
摘要：建立一种高效液相色谱-紫外-可见分光光度法对噻霉酮可湿性粉剂中的有效成分进行分析和定量。采用Eclipse XDB-C18不锈钢柱，以甲醇和水为流动相，在波长210 nm条件下对试样中噻霉酮进行分离，外标法进行定量。噻霉酮在0.008～0.040 g/L质量浓度范围内线性关系良好。5次平行测定的相对标准偏差为0.014，回收率为99.6%～101.5%。方法具有简单、快速、准确、灵敏等优点，适用于制剂中噻霉酮有效成分的定量分析。
关键词：噻霉酮；高效液相色谱；分析方法
中图分类号：TQ 450.7 文献标识码：A 文章编号： 0258-3283（2020）--
Determination of Benziothiazolinone by High Performance Liquid Chromatography CHEN Guo-zhen*1,2, ZHAO Kai3, DANG Lu1, Wu Si-tuo1 (1.Shaanxi Research Design Institute of Petroleum and Chemical Industry, Shaanxi Dangerous Chemical Supervision and Inspection Center, Xi'an 710054, China; 2. College of Chemistry & Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Provincial Key Laboratory of Electroanalytical Chemistry, Northwest University, Xi'an, 710069, China; 3. Xi'an HollySys Systems Engineering Co., Ltd., Xi'an 710000, China), Huaxue Shiji, 2020, 42( ), ～
Abstract：To establish a reversed-phase UV-vis spectrophotometry chromatographic method for the analysis and quantification of benziothiazolinone in commercial products, the determination of benziothiazolinone in the samples was conducted with Eclipse XDB-C18 column, while the mixture solution of methanol and water was used in the mobile phase, Under the wavelength of 210 nm and quantified by the external standard method. The results showed that when the content of veratrine was 0.008～0.040 g/L. The linear relationship was good. Five parallel the standard deviation of benziothiazolinone was 0.014, the recoveries of was 99.6%～101.5%. The method was simple, fast, accurate and sensitive, which can be utilized in the determination of benziothiazolinone.
Key words：High performance liquid chromatography; benziothiazolinone; analytical method
引用本文：陈国珍, 赵锴, 党璐, 等. 噻霉酮的高效液相色谱分析研究[J]. 化学试剂, 2020, 42(8): 964-966.
核磁共振定量法测定培美酸甲酯绝对含量
张海霞a，贺磊b，李善金b，徐盼b，徐静b，王艳b，程青芳*a,b
（江苏海洋大学 a.化学工程学院，b.药学院，江苏 连云港 222005）
摘要：建立核磁共振定量法测定4-[2-(2-氨基-4,7-二氢-4-氧代-1H-吡咯并[2,3-d]嘧啶-5-基)乙基]苯甲酸甲酯（培美酸甲酯）绝对含量。以盐酸吉西他滨为内标，DMSO-d6和D2O为溶剂，测定1HNMR，通过比较样品（As）与内标（Ar）的定量峰面积，分别计算3批供试品的含量。以样品与内标的峰面积比绘制线性图，结果显示，供试品与内标物质的量比在0.5053～1.9800范围内线性关系良好，线性回归方程为y = 0.7302x＋0.0323（R2 = 0.9999）。精密度、重复性和稳定性试验的相对标准偏差（RSD）分别为0.43%、0.51%、1.12%。平行配置3份样品溶液进样测定，计算3批供试品的百分含量分别为98.37%、97.54%和97.70%，RSD分别为0.12%、0.17%、0.26%，与质量平衡法测定3批结果98.75%、97.16%和97.78%基本一致。经验证，建立的qNMR法简单、快速、准确，可用于培美酸甲酯原料药的含量测定。
关键词：核磁共振定量法；培美酸甲酯；含量测定；盐酸吉西他滨；质量平衡法
中图分类号：O652.1 文献标识码：A 文章编号：0258-3283（2020）--
Determination of Methyl Pemetrexed Formate by Quantitative Nuclear Magnetic Resonance ZHANG Hai-xiaa, HE Leib, LI Shan-jinb, XU Panb, XU Jingb, WANG Yanb, CHENG Qing-fang*a,b (a. School of Chemical Engineering, b. School of Pharmacy, Jiangsu Ocean University, Lianyungang, 222005, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Quantitative nuclear magnetic resonance (qNMR) were employed to determine the content of methyl 4- [2-(2-amino-4,7-dihydro-4-oxo-1 H-pyrrolo [2,3-d] pyrimidin-5-yl)ethyl]benzoate(methyl pemetrexed formate). Gemcitabine hydrochloricde was used as an internal standard, DMSO-d6 and D2O were used as solvents in 1HNMR detection. By comparing the response peak area of sample (As) and internal standard (Ar), the contents of the 3 batches of samples were calculated. A good linear relationship was obtained between peak area ratio and molar ratio of sample to internal standard, the regression equation was y = 0.7302 x＋0.0323 (R² = 0.9999) with a molar ratio range of 0.5053 ~ 1.9800. The relative standard deviation (RSD) of precision, repeatability, and stability tests were 0.43%, 0.51%, 1.12%, respectively. Three sample solutions were tested in parallel, and the contents of three batches of samples were 98.37%, 97.54% and 97.70%, and the RSD were 0.12%, 0.17%, and 0.26%. The mass balance method determined the contents of 3 batches of samples were 98.75%, 97.16%, 97.78%, which are consistent with qNMR. The qNMR method established can simply, quickly and accurately determine the content of methyl pemetrexed formate.
Key words: quantitative nuclear magnetic resonance; methyl pemetrexed formate; determination; gemcitabine hydrochloride; mass balance method
引用本文：张海霞，贺磊，李善金, 等. 核磁共振定量法测定培美酸甲酯绝对含量[J]. 化学试剂, 2020, 42(8):967-970.
氟苯尼考纯度标准物质定值研究及不确定度评估
简凌波1,2，李鹏2，杨梦瑞2，王敏2，周剑2，王彤彤2，章程辉*1
（1. 海南大学 食品科学与工程学院，海南 海口 570100；
（2. 中国农业科学院农业质量标准与检测技术研究所 农业农村部农产品质量安全重点实验室，北京 100081）
摘要：本研究应用了质量平衡法及定量核磁法对氟苯尼考标准物质原料的纯度进行定值，并通过高效液相色谱法对氟苯尼考标准物质的均匀性进行了检验，同时完成了6个月稳定性监测，并系统评估了定制结果的不确定度。实验考察了色谱条件对于主成分及杂质分析的影响，并且比较了不同定量核磁内标。氟苯尼考标准物质（GBW（E）090959）的纯度定值结果为99.0%，扩展不确定度为0.4%（k = 2），其均匀性、稳定性符合相关国家有证标准物质技术要求。本研究填补了国内氟苯尼考纯度有证标准物质空白，为氟苯尼考药物相关检测提供了量值溯源与传递的基础，保证了检测结果的可靠性、可比性以及可溯源性。
关键词：氟苯尼考；有证标准物质；纯度；不确定度
中图分类号：TQ465.3 文献标识码：A 文章编号：0258-3283（2020）--
Purity Determination and Uncertainty Assessment of Certified Reference Material of Florfenicol JIAN Ling-bo1,2, LI Peng2, YANG Meng-rui2, WANG Ming2, ZHOU Jian2, WANG Tong-tong2, ZHANG Cheng-hui1*1 (1. College of Food Science and Technology, Hainan University, Haikou 570100, China; 2. Key Laboratory of Agri-Food Quality and Safety, Ministry of Agriculture and Rural Affairs, Institute of Quality Standard & Testing Technology for Agro-Products, Chinese Academy of Agricultural Sciences, Beijing 100081, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: Two independent approaches involving mass balance method (MB) and the quantitative nuclear magnetic resonance (qNMR) technique were employed to measure the purity of a new certified reference material (CRM) of florfenicol. The homogeneity testing and long-term stability monitoring were examined by using high performance liquid chromatography (HPLC). The uncertainty evaluation was sufficiently investigated. Chromatographic conditions were optimized for separation of main components and impurities, and several high pure substances were selected and tested as quantitative NMR internal standards. The purity of florfenicol is assigned to be 99.0% with the expanded uncertainty value 0.4% (k=2). The results indicate that the florfenicol is homogenous and stable which satisfy the requirements of CRM. The new CRM (GBW(E)090959) can be applicable to transfer and traceability of quantity value in florfenicol-related testing items. It can also assure the accuracy, comparability and traceability of results in routine monitoring.
Key words: florfenicol; CRM; purity; uncertainty
引用本文：简凌波，李鹏，杨梦瑞，等. 氟苯尼考纯度标准物质定值研究及不确定度评估[J]. 化学试剂, 2020, 42(8): 971-975.
基于萘酰亚胺的硫化氢荧光探针的合成及光谱性能研究
郭心灵1，李静2，李玄1，郭磊磊1，赵丽平1，侯旭锋＊2
（1. 信阳农林学院 生物与制药工程学院，河南 信阳 464000，2. 许昌学院 化学化工学院 河南 许昌 461000）
摘要：以6-羟基-萘酰亚胺和2-（2-吡啶基）二硫基苯甲酸为原料，并引入亲水性溶酶体靶向定位基团吗啉，设计合成一种的新型萘酰亚胺硫化氢荧光探针，合成方法简单，收率较高，产物易于提纯。通过光学活性测试，探针对硫化氢的响应速度较快（5min），在0～0.2 μmol/L的范围内，荧光强度与硫化氢浓度呈现较好的线性关系（R2=0.9933）检出限低至6.272×10-8 mol/L，其在较宽的pH（5～9）范围内光学性质稳定，并可实现可视化检测和水样检测。研究结果表明，探针对硫化氢具有高效、高灵敏度、高选择性和定位检测，在硫化氢生理活性检测和病理分析检测方面具有潜在的应用前景。
关键词：可视化检测；硫化氢；萘酰亚胺；荧光探针
中图分类号: O656.3 文章标识码：A 文章编号：0258-3283（2020）--
Synthesis and Spectral Properties of Hydrogen Sulfide Fluorescent Probe Based on Naphthalimide GUO Xin-ling, LI Jing, LI Xuan, GUO Lei-lei, ZHAO Li-ping, HOU Xu-feng＊ (1. Xinyang Agriculture and Forestry University, Xin Yang 464000. 2. College of chemistry and chemical engineering, Xu chang University, Xu Chang 461000 ), Huaxue Shiji, 2020, 42( ), ～
Abstract：A novel naphthalimide fluorescent probe was synthesized based on 6-hydroxy- naphthalimide and 2-(2-pyridyl) dithiobenzoic acid, introducing morpholine, a hydrophilic lysosome targeting group. The synthesis method is simple and the productivity was high and the product was easily to be purified. Based on the optical activity test, the response speed of the probe to hydrogen sulfide is fast (5 min). In the range of 0～0.2 μm, the detection limit of fluorescence intensity and hydrogen sulfide concentration is as low as 6.272 × 10-8 mol/L (R2 = 0.9933). Its optical property is stable in a wide range of pH (5～9), and it can realize visual detection and water sample detection. The results show that the probe has high efficiency, high sensitivity, high selectivity for hydrogen sulfide and location detection, and has potential application in the detection of physiological activity and pathological analysis of hydrogen sulfide.
Key words: visual inspection; hydrogen sulfide; naphthalimide; fluorescent probe
引用本文：郭心灵, 李静, 李玄. 一种可视化检测硫化氢的萘酰亚胺类荧光探针[J]. 化学试剂, 2020, 42(8): 976-981.
药剂复配对含铬污染土壤的稳定化效果
龚亚龙1，宋安康*1，高晓梅1，范敏1，李春全2
（1.招商局生态环保科技有限公司，重庆 400060；2.中国矿业大学（北京）化学与环境工程学院，北京100083）
摘要：工业的快速发展使得高毒性的铬（Cr）广泛存在于土壤中，给生态及人类带来了严重威胁。目前，固化/稳定化技术是铬污染土壤处置的有效手段。单一药剂的使用不仅效果及稳定性差且易造成二次污染，因而，采用将还原剂、吸附剂及固化剂进行复配的策略，通过正交试验对加药顺序及最佳药剂配方进行了研究。最终得到复合药剂的最佳组分为多硫化钙、弱碱性阴离子交换树脂和生石灰，最佳加药方式为“吸附还原-固化剂”。对处置前后铬污染土壤的红外测试进行分析，发现复合药剂成功将土壤中Cr（Ⅵ）进行了还原，有效降低了铬的毒性和迁移性，实现了在低药剂投加量的情况下对含铬污染土壤的稳定化处置，处置效果满足《生活垃圾填埋场污染控制标准》中关于总Cr和Cr（Ⅵ）浸出液的限量标准，为含铬污染土壤的处置提供了行之有效的方法。
关键词：铬；土壤修复；固化稳定化；药剂复配；加药顺序
中图分类号：X53文献标识码：A 文章编号：0258-3283（2020）--
Stabilization Effect of Composite Medicament on Soil Contaminated with Cr GONG Ya-long1, SONG An-kang*1, GAO Xiao-mei1, FAN Ming1, LI Chun-quan2 (1. China Merchants Ecological and Environmental Protection Technology Co., Ltd, Chongqing 400060, China; 2.School of Chemical and Environmental Engineering, China University of Mining and Technology(Beijing), Beijing 100083, China), Huaxue Shiji, 2020, 42(8), ～
Abstract：With the rapid development of industry, chromium (Cr) with high toxicity is widely existed in the soil, which brings serious threat to the ecology and human beings. Presently, curing/stabilization technology is an effective method for treating Cr contaminated soil. The use of single agent not only has poor effect and stability but also easily causes secondary pollution. Therefore, reducing agent, adsorbent and curing agent were compounded. Orthogonal test was used to study the dosing sequence and the optimum formulation. Ultimately, it is concluded that the best composition of the compound was calcium polysulfide, weak base anion exchange resin and quick lime, and the best dosing method was "adsorption reduction-curing agent". After evaluating the infrared test of chromium contaminated soil before and after treatment, it is found Cr (Ⅵ) in the soil was reduced successfully by the compound agents, effectively reduce the toxicity of Cr as well as the mobility. Implements in the case of low drug dosing quantity of chromium contaminated soil stabilization treatment and disposal effect meet the pollution control standards for domestic waste landfills about the standard limitation of liquor leaching for total Cr and Cr (Ⅵ). An effective method for the disposal of chromium contaminated soil was provided.
Keywords：Chromium; soil remediation; solidification and stabilization; compounding agents; dosing sequence
引用本文：龚亚龙，宋安康，高晓梅，等.药剂复配对含铬污染土壤的稳定化效果[J].化学试剂，2020，42（8）：982-986 .
二氰乙烯基咔唑荧光探针的合成及其对N2H4的检测研究
陈晓彤1，杨杨*1,2，芦宝华1，李久明*1,2,3，徐宁1,2
（1. 内蒙古自治区天然产物化学及功能分子合成重点实验室，内蒙古 通辽 028000；2. 内蒙古民族大学 化学与材料学院，内蒙古 通辽 028000；3. 内蒙古自治区高校蓖麻产业工程技术研究中心，内蒙古 通辽 028000）
摘要：以N-乙基咔唑-3-甲醛与丙二腈为原料，经Knoevenagel反应合成了一种可选择性识别N2H4的二氰乙烯基咔唑类荧光探针（DVC）。通过核磁共振波谱、红外光谱和高分辨质谱对其结构进行了表征。通过紫外-可见吸收光谱和荧光发射光谱法研究了探针对N2H4的检测能力。实验结果表明：与N2H4作用前后，探针溶液的颜色和荧光出现明显的变化，408 nm处吸收强度和425 nm处的荧光强度与N2H4浓度的呈现较好的线性回归关系。探针DVC对N2H4具有较强的定量分析能力，通过物理吸附制备的试纸也可用于N2H4蒸气浓度的分析。
关键词：二氰乙烯基咔唑；合成反应；荧光探针；N2H4；吸收光谱
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of Dicyanovinylcarbazole Fluorescent Probe and Application in Hydrazine Detection CHEN Xiaotong1, YANG Yang*1,2, LU Bao-hua1 LI Jiu-ming*1,2,3, XU Ning1,2 (1. Inner Mongolia Key Laboratory for the Natural Products Chemistry and Functional Molecular Synthesis, Tongliao 028000, China；2. College of chemistry and Material Science, Inner Mongolia University for Nationalities, Tongliao 028000,China；3. Key Laboratory for Castor Breeding of Inner Mongolia, Tongliao 028000, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: Using N-ethylcarbazole-3-carboxaldehyde and malononitrile as raw materials, a dicyanovinylcarbazole -based fluorescent probe (DVC) that can selectively recognize hydrazine was synthesized based on Knoevenagel reaction. The structure of DVC was confirmed by 1HNMR, 13CNMR, IR, and HR-MS. The detection ability of the probe for N2H4 was investigated by UV-visible absorption spectroscopy and fluorescence emission spectroscopy. The color and fluorescence of the probe solution changed significantly after reacting with N2H4. There was a good linear relationship between the fluorescence intensity at 425 nm and the absorption intensity at 408 nm with the negative logarithm of N2H4 concentration. The probe DVC has a strong ability to quantitatively analyze N2H4. The test paper prepared by physical adsorption can also be used for the quickly analysis of N2H4 concentration according to the fading speed and fluorescence changes.
Key words: dicyanovinylcarbazole; synthesis; fluorescent probe; hydrazine; absorption spectra
引用本文：陈晓彤, 杨杨, 芦宝华, 等. 二氰乙烯基咔唑荧光探针的合成及其对N2H4的检测研究[J].化学试剂, 2020, 42(8):987-991.
2-氟-5-氯-3,4-二溴硝基苯的合成及晶体结构研究
陈玉梅a,b，陈冬梅a,b，杨致松a,b，周志旭* a,b
（贵州大学 a. 药学院，b. 贵州省药物合成工程实验室，贵州 贵阳 550025）
摘要：邻二卤代苯是医药化工等领域的一类重要中间体，研究邻二卤代苯的高效合成方法具有重要的意义。采用一步反应制备目标化合物并研究其晶体结构。以2-氯-5-氟硝基苯为原料，经二溴海因溴代得到目标化合物。对合成条件进行了优化，考察了二溴海因的用量、滴加条件及反应温度对反应的影响，最终得到了较优的反应条件，反应总收率达到54.2%。其结构经1H-NMR和X-射线单晶衍射确证。该方法操作简便，能一步制得邻二卤代苯中间体，适合工业化生产。
关键词：2-氟-5-氯-3,4-二溴硝基苯；2-氯-5-氟硝基苯；合成；单晶
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis and Crystal Structure of 2,3-Dibromo-1-chloro-4-fluoro-5-nitrobenzene CHEN Yu-meia,b, CHEN Dong-meia,b, YANG Zhi-songa,b, ZHOU Zhi-xu*a,b (a. School of Pharmaceutical Sciences, b. Guizhou Engineering Laboratory for Synthetic Drugs, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: O-dihydroxybenzene is a kind of important intermediate in the field of medicine and chemical industry, and it is of great significance for the efficient synthesis method of o-dihalobenzene for the development of these fields. The target compound was prepared by one-step reaction and its crystal structure was studied. 4-Chloro-1-fluoro-2-nitrobenzene was used as raw material, and the target compound was obtained as target product by substitution reaction. The synthesis conditions were optimized, and the effect of yield was investigated such as the amount of dibromohydrin, the dropping conditions and the reaction temperature. Finally, better reaction conditions were obtained, and the total yield of the reaction reached 54.2%.Its structure was confirmed by 1HNMR and XRD. The method is simple to operate and the intermediate of o-dihalogenated benzene could be prepared in one step. It is suitable for industrial production.
Key words: 2,3-dibromo-1-chloro-4-fluoro-5-nitrobenzene; 4-chloro-1-fluoro-2-nitrobenzene; synthesis; single crystal
引用本文：陈玉梅，陈冬梅，杨致松，等. 5-氯-3,4-二溴-2-氟硝基苯的合成及晶体结构研究[J]. 化学试剂，2020，42（8）：992- 994.
响应面法优化微波辅助水蒸气蒸馏法提取汉麻叶精油工艺
田媛，孙宇峰，张旭，高宝昌，张正海，石雨，董艳*
（黑龙江省科学院大庆分院，黑龙江 大庆 163319）
摘要：以推动汉麻资源的深度开发利用，提高汉麻叶的附加价值为目的。采用微波辅助水蒸气蒸馏法（MAHD）提取汉麻叶精油。通过单因素实验和响应面法优化汉麻叶精油提取工艺，选取提取时间、料液比、微波辐射时间、微波功率为考察因素，以汉麻叶精油提取率为评价指标进行单因素实验，再进行响应面分析优化。结合提取工艺的实际可操作性和便利性，确定最佳提取工艺为提取时间8.7 h、料液比1:8(g/mL)、微波辐射时间10 min、微波功率480 W，最终实际提取率为0.210%，与理论值0.213%相接近。结果表明，MAHD法在汉麻叶精油提取方面，具有实用性和开发性。
关键词：汉麻叶；精油；微波辅助水蒸气蒸馏；响应面法
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2020）
Optimization of Microwave-assisted Steam Distillation Extraction of Essential Oil from Hemp Leaves by Response Surface Methodology TIAN Yuan, SUN Yu-feng, ZHANG Xu, GAO Bao-chang, ZHANG Zheng-hai, SHI Yu, DONG Yan* (Daqing Branch of Heilongjiang Academy of Sciences, Daqing 163319, China), Huaxue Shiji, 2020, 42(8), ～
Abstract：To promote the in-depth development and utilization of hemp resources and increase the added value of hemp leaves, the essential oil of hemp leaves was extracted by microwave assisted steam distillation (MAHD). The extraction process of essential oil from hemp leaves was optimized by single factor test and response surface methodology, the extraction time, solid-liquid ratio, microwave radiation time and microwave power were selected as the influencing factors, and the yield of essential oil from hemp leaf was taken as an evaluation index to carry out single factor test and response surface analysis and optimization. Based on the actual operability and convenience of the extraction process, the optimum extraction process was extraction time of 8.7 h, solid-liquid ratio of 1:8 (g/mL), microwave radiation time of 10 min, microwave power of 480 W. The actual extraction rate was 0.210%, which was close to the theoretical value of 0.213%. The results showed that the method was practical and exploitable in the extraction of essential oil from hemp leaves.
Key words: hemp leaf; essential oils; microwave-assisted steam distillation; response surface methodology
引用本文：田媛，孙宇峰，张旭，等. 响应面法优化微波辅助水蒸气蒸馏法提取汉麻叶精油工艺[J]. 化学试剂, 2020, 42(8): 995-999.
可见光催化条件下乙腈参与的烯烃双官能团化反应
高俊，王杨丽，周烨，许甲喆，何永辉*
（云南民族大学 民族药资源化学教育部重点实验室，云南 昆明 650500）
摘要：烯烃双官能团化反应可将烯烃转化为多种重要的化合物，是一类十分重要的有机反应。实现了室温条件下光催化活化乙腈a位碳氢键，引发分子内官能团迁移的未活化烯烃双官能团化反应。以过氧化十二酰（LPO）为氢原子转移试剂，室温下经可见光催化，实现了乙腈转变为氰自由基，通过该自由基引发苯并噻唑基团的分子内迁移，实现了烯烃的双官能团化反应，将氰基和苯并噻唑同时引入未活化的烯烃末端双键的两端。采用核磁共振和质谱等波谱技术对目标产物进行了相应的表征，并对产物的特征核磁共振谱信号及可能的反应机理进行了分析。
关键词：烯烃；光催化；双官能团化；有机合成；氰基
中图分类号：O657.36 文献标识码：A 文章编号：0258-3283（2020）--
Photocatalysis Difunctionalization Reaction of Olefins with Acetonitrile GAO Jun, WANG Yang-li, ZHOU Ye, XU Jia-zhe, HE Yong-hui * (Key Laboratory of Ethnic Medicine Resource Chemistry, State Ethnic Affairs Commission & Ministry of Education, Yunnan Minzu University, Yunnan 650500, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: The difunctionalization reactions of inactived alkenes via distal heteroaryl ipso-migration have been accomplished under room temperature conditions. Difunctionalization of alkenes via photocatalysis alkylheteroarylation between the C-C double bonds of benzothiazole-substituted tertiary alcohol and the α-C(sp3)-H bonds of acetonitrile under metal-free conditions with high functional group tolerance and a broad substrate scope. The products were confirmed by 1HNMR, 13CNMR and high resolution mass spectra (HRMS). The spectroscopic data of 4-(benzo[d]thiazol-2-yl)-7-oxo-7-phenylheptanenitrile was fully analyzed and the reaction mechanism is proposed.
Key words: alkenes; photocatalysis; difunctionalization; organic synthesis; cyanophoric
引用本文：高俊，王杨丽，周烨，等. 可见光催化条件下乙腈参与的烯烃双官能团化反应[J]. 化学试剂，2020, 42（8）：1000-1003 .
恩曲他滨的合成新工艺研究
顾继山，李苏，谢志翰，吴晓宇，熊芸，刘生鹏*
（武汉工程大学，化工与制药学院，湖北武汉430205）
摘要：研究新型核苷类逆转录酶抑制剂标题化合物合成新方法。以L-氯甲酸薄荷酯与乙二醇为起始原料，经酯化、氧化、环化、卤化、偶合、水解6步反应合成标题化合物，总收率为27.62%。并着重对乙二醇L-薄荷碳酸酯的合成进行了研究，确定了其最佳合成工艺条件为：无溶剂法以吡啶为缚酸剂，反应温度为-5 °C，反应时间为2 h。通过此工艺合成乙二醇L-薄荷碳酸酯的收率可达81%。合成的化合物均经1HNMR、13CNMR确证。本合成工艺避开了传统工艺对甲醛、浓硫酸、硼氢化钠、氢化铝锂等危险试剂的使用，具有成本低、反应条件温和、绿色环保、高规模化生产能力及可操作性等优点。
关键词：恩曲他滨；L-氯甲酸薄荷酯；抗HIV药；合成
中图分类号：O626. 2 文献标识码：A 文章编号：0258-3283（2020）--
Novel Process Research on Emtricitabine Synthesis GU Ji‐shan, LI Su, XIE Zhi-han, WU Xiao‐yu, XIONG Yun, LIU Sheng‐peng*(School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: A novel process on a novel nucleoside analogue reverse transcriptase inhibitor Emtricitabine synthesis. Emtricitabine was synthesized from L-menthylchloroformate and ethylene glycol by a six-step way including esterification, oxidation, cyclization, halogenation, coupling and hydrolysis. The overall yield was 27.62%. The synthesis of glycol L-menthol carbonate was investigated in detail, leading to an optimal process conditions: solvent-free, pyridine as acid binding agent, reaction temperature -5 °C and reaction time 2 h. The yield of glycol L-menthol carbonate synthesized by the process was 81%. The chemical structures of compounds were confirmed via 1HNMR and 13CNMR. The method obviated the use of dangerous reagents such as formaldehyde, concentrated sulfuric acid, sodium borohydride, lithium aluminum hydride by traditional processes, and has the advantages of lower cost, mild reaction condition, environmentally friendly, higher scale production capacity and maneuverability.
Key words: emtricitabine; L-menthylchloroformate; anti-HIV drug; synthesis
引用本文：顾继山, 李苏, 谢志翰, 等. 恩曲他滨的合成新工艺研究[J]. 化学试剂, 2020, 42(8):1004-1008.
金合欢素-7-O-β-糖苷的合成与表征
韩金娥，巩凯*
（江南大学 药学院，江苏 无锡 214122）
摘要：天然黄酮金合欢素具有多种生物活性，但其水溶性差，生物利用度低。对金合欢素进行糖基化修饰：以葡萄糖为原料经乙酰化、溴代得到的溴代葡萄糖，和以葡醛内酯为原料经开环、乙酰化、溴代得到的溴代葡萄糖醛酸，这两种糖基供体分别与金合欢素进行糖苷化反应，并对该反应进行了条件优化，最后进行脱保护基，合成了3个金合欢素-7-O-β-糖苷衍生物，产率为40%～71%，其中2个化合物的合成方法未见文献报道。所有化合物结构均经ESI-MS、1HNMR、13CNMR表征。
关键词：金合欢素；水溶性；葡萄糖苷；葡萄糖醛酸苷；合成
中图分类号：R914.2 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis and Characterizationof Acacetin 7-O-β-glycosides HAN Jin-E, GONG Kai*(School of Pharmaceutical Sciences, JiangNan University, Wuxi 214122, China), Huaxue Shiji, 2020, 42(8), ～
Abstract: Natural flavonoid acacetin has poor water solubility and low bioavailability, although it has a variety of biological activities. The glycosylation modificationof acacetin was reported. Two kinds of glycosyl donors were prepared. The glycoside bromide was obtained by acetylation and bromination using glucose as raw material, and the glucuronide bromide was achieved via ring opening reaction, acetylation and bromination starting from glucuronolactone. Then these glycosyl donors were respectively glycosylated with acacetin, and the reaction conditions were optimized. Finally, deprotection was performed to obtain three acacetin-7-O-β-glycoside derivatives in 40% ～ 71% yields, two of which have not been reported in literature yet. The structures of the compounds were confirmed by ESI-MS, 1HNMR, 13CNMR.
Key words: acacetin; water solubility; glucoside; glucuronide; synthesis
引用本文：韩金娥, 巩凯. 金合欢素-7-O-β-糖苷的合成与表征[J]. 化学试剂, 2020, 42(8): 1009-1013.
3-氰基-4-苯基-1,4-二氢吡啶衍生物的合成
李楠，张萌萌，杜怡婷，钟启迪*
（华北理工大学 药学院，河北 唐山 063200）
摘要：1,4-二氢吡啶衍生物具有良好的生物活性，广泛应用于医药和农药领域。以3-氰基吡啶、溴化苄或溴化烷和苯基溴化镁为原料，经亲核反应合成一系列3-氰基-4-苯基-1,4-二氢吡啶衍生物。目标产物结构通过1HNMR、13CNMR和HRMS进行确证。对提高目标产物收率进行深入探索，结果表明，反应时间1 ～ 1.5 h、温度0°C、n (3-氰基吡啶)∶n (苯基溴化镁) = 1：1.3，且避光条件下能够有效提高产品收率，总收率为52%～73%。为后续1,4-二氢吡啶衍生物生理活性及其应用的研究提供依据。
关键词：1,4-二氢吡啶衍生物；合成；亲核反应；生物活性；氰基
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of 3-Cyano-4-Phenyl-1,4-dihydropyridines LI Nan, ZHANG Meng-meng, DU Yi-ting, ZHONG Qi-di*(School of pharmacy, North China University of Science and Technology, TangShan 063200, China), Huaxue Shiji, 2020, 42( ), ～
Abstract: 1,4-Dihydropyridines have extensive biological activities, which can be widely used in the field of medicine and pesticides. 3-Cyanopyridine, benzyl bromide or methyl bromide and phenylmagnesium bromide were used as raw materials to form 3-cyano-4-phenyl-1,4-dihydropyridines with good yield (52%～73%). Necleophilicreaction was carried out in THF. The structures of the target products were confirmed by 1HNMR, 13CNMR, HRMS. In order to improve the yield of the target products, its synthetic route was optimized based on the synthesis method previously reported. The reaction time, reaction temperature, whether or not to light and ratio of material mass can increase necleophilicreaction and total yield. The preferred conditions are obtained as follows: the molar ratio of n ( 3-cyanopyridine)∶n (phenylmagnesium bromide) = 1：1.3, the reaction time of 1～1.5 h, the reaction temperature of 0°C and out of light. The experiment laid the foundation for the biological activity and application of 1,4-dihydropyridines derivatives.
Keywords:1,4-dihydropyridines derivatives; synthesis; necleophilicreaction; bioactivity; cyano
引用本文：李楠，张萌萌，杜怡婷，等.3-氰基-4-苯基-1,4-二氢吡啶衍生物的合成[J].化学试剂，2020，42(8)：1014-1018.
