一种铀酰配合物的合成、结构分析及对染料吸附性能的研究
王超
(宁波大学 材料科学与化学工程学院，浙江 宁波 315211)
摘要：在常温下，采用UO2(Ac)2·2H2O与间甲氧基苯甲酸（HL）反应得到一例铀酰配合物 ([(UO2)(DMSO)(L)2]2) (DMSO：二甲亚砜)。通过X–射线单晶衍射分析配合物属于三斜晶系，P-1空间群，a ＝ 10.744(2) Å，b ＝ 14.467(3) Å，c ＝ 14.632(3) Å，α ＝ 91.04(3) °，β ＝ 107.87(3) °，γ ＝ 94.59(3) °，V ＝ 2155.5(8) Å3，Dc ＝ 2.004 g/cm3，Z ＝ 2。U(VI)离子均为七配位的UO7五角双锥构型。此外，研究了配合物对染料的吸附性能。结果表明，配合物对阳离子染料具有较好的吸附性能，其中对罗丹明B的最大吸附量达到249.87 mg/g，对阴离子染料的吸附几乎可以忽略，说明配合物具有选择性吸附阳离子染料的性能。
关键词：铀酰配合物；选择性染料吸附；间甲氧基苯甲酸；阳离子染料
Synthesis, Structural Analysis and Adsorption Properties of the Uranyl Complex WANG Chao (School of Material Science and Chemical Engineering, Ningbo University, Ningbo 315211, China)
Abstract: UO2(Ac)2·2H2O Reacted with m-methoxybenzoic acid (HL) at room temperature to obtain the uranyl complex ([(UO2)(DMSO)(L)2]2). The crystal structure of the complex was characterized by single-crystal X-ray diffraction analysis. The crystallographic data are as follows: ([(UO2)(DMSO)(L)2]2) belongs to the triclinic with space group P-1, a ＝ 10.744(2) Å, b ＝ 14.467(3) Å, c ＝ 14.632(3) Å, α ＝ 91.04(3)°, β ＝ 107.87(3)°, γ ＝ 94.59(3)°, V ＝ 2155.5(8) Å3, Dc ＝ 2.004 g/cm3, Z ＝ 2, in which U(VI) ions show 7-fold coordination environment, demonstrating UO7 pentagonal bipyramidal geometries. In addition, the adsorption properties of ([(UO2)(DMSO)(L)2]2) towards organic dyes are investigated. The results show that ([(UO2)(DMSO)(L)2]2) has good adsorption performance for cationic dyes, and the maximum adsorption amount of rhodamine B (RhB+) is up to 249.87 mg/g, but the adsorption capacity to anionic dyes is negligible. These findings indicate that this uranyl complex possesses the excellent absorbing property towards cationic dyes.
Key words: uranyl complex; selective dye adsorption; m-methoxybenzoic acid; cationic dye
稀土-对苯二甲酸金属有机骨架材料对刚果红的高效吸附
付秋平*，王洋，田茂文，郭燕菊，刘芳，刘渊
（贵阳学院 化学与材料工程学院，贵州 贵阳 550005）
摘要：以对苯二甲酸和硝酸铈为原料，采用溶剂热法合成Ce2(BDC)3(H2O)4。采用X-射线粉末衍射仪和紫外-可见分光光度计对样品的物相及其对刚果红的吸附性能进行了表征。探讨了刚果红初始浓度、吸附时间和背景离子对吸附量的影响。结果表明，Ce2(BDC)3(H2O)4对刚果红的吸附量随刚果红初始浓度的增加而增大。在5 min内，吸附基本达到平衡。Li+、Na+、K+等背景离子均会严重影响吸附效果，Ce2(BDC)3(H2O)4对刚果红的吸附符合Freundlich等温吸附模型，吸附动力学符合二级动力学模型。
关键词：金属有机骨架；刚果红；吸附
中图分类号：O614.6 文献标识码：A 文章编号：0258-3283（2019）
Highly Efficient Adsorption Capacity of Rare-earth 1,4-Benzenedicarboxylat Metal Organic Framework Material for Congo Red FU Qiu-ping, WANG Yang, TIAN Mao-wen, GUO Yan-ju, LIU Fang, LIU Yuan (College of Chemical and Material Engineering, Guiyang University, Guiyang 550005, China),Huaxue Shiji, 2019, 41(4),
Abstract: Terephthalic acid and cerium nitrate were used to synthesize Ce2(BDC)3(H2O)4 by using solvent heat method. The phase of the sample and the adsorption property of samples on Congo red were measured by X-ray powder diffraction and UV-visible spectrophotometer. The effects of initial concentration of Congo red, adsorption time and background ions on the adsorption capacity were investigated. The results show that, the adsorption capacity of Congo red onto Ce2(BDC)3(H2O)4 increased with increasing of initial concentration of Congo red. The adsorption basically reached the adsorption equilibrium within 5 min. The adsorption effect was seriously affected by the background ions, such as Li+, Na+, K+. The adsorption model of Ce2(BDC)3(H2O)4 for Congo red complies with Freundlich isotherm model and the adsorption kinetics complies with second-order kinetics.
Key words: metal organic frameworks; Congo red; adsorption
4-苯氨基喹啉化合物的合成及其与EGFRT790M分子对接研究
刘丹*，张昕旸，袁莹，薛艾奇
（沈阳化工大学 制药与生物工程学院，辽宁 沈阳 110142）
摘要：以6-氟(或7-氟)-4-氯-喹啉为原料与二苯胺经亲核取代反应，得到4-(4’-氨基苯氨基)喹啉化合物，再与不同的酰化试剂发生酰化反应，得到12个未见文献报道的化合物，结构经过ESI-MS确认。用Molegro Virtual Docker软件完成与EGFRT790M的分子对接，并用Discovery Studio 2016 Client软件分析化合物与EGFRT790M的作用模式。分子对接研究表明6-氟-4-{4’-[（4’’-甲氧基）-苯酰氨基]-苯氨基}-喹啉 1位的氮和4’位甲氧基上的氧分别与ARG A776和HIS A850残基形成两个氢键。为开发EGFRT790M抑制剂提供基础。
关键词：酪氨酸激酶抑制剂；6-氟(或7-氟)-4-氯-喹啉；分子对接
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2019）
Synthesis of 4-Phenylamino Quinoline Compounds and Molecular Docking Study with EGFRT790M LIU Dan*, ZHANG Xin-yang, YUAN Ying, XUE Ai-qi (College of Pharmaceutical and Biological Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China), Huaxue Shiji, 2019
Abstract: 6-Fluoro(or 7-fluoro)-4-chloro-quinoline reacted with diphenylamine to give 4-(4'-aminophenylamino) quinoline compounds by nucleophilic substitution reaction. Acylation of 4-(4'-aminophenyl amino) quinoline compounds with different acylation reagents yields twelve novel compounds. The structure of the target compunds was confirmed by ESI-MS. Molecular docking was performed with Molegro Virtual Docker software, The interaction between compounds and EGFRT790M was analyzed by Discovery Studio 2016 Client software. The Molecular docking showed that N of 1 position and O of 4’ position of compound Ⅲ1.4 give a hydrogen bond with ARG A776 and HIS A850, respectively. This work provides basis for developing EGFR T790M inhibitors.
Key words: Tyrosine Kinase Inhibitor; 6-fluorine(or 7-fluorine)-4-chlorine-quinolines; Molecular docking
金包覆的核壳结构纳米材料的制备进展
吴睿*a，刘存芳a，张强a，宋娟a，郭鸿b，熊海涛a，田光辉a
(陕西理工大学 a. 化学与环境科学学院 陕西省催化基础与应用重点实验室；
b. 土木工程与建筑学院，陕西 汉中 723000 )
摘要: 金、银等贵金属纳米材料具有独特的光学、电学和催化性能以及良好的生物兼容性，其在化学、物理、生物和医学等领域具有广泛的应用。以贵金属纳米金作为核或者作为壳，制备成核壳结构复合纳米材料，这样的核壳材料同时具有核和壳的性质以及其它优越的性能，因此受到研究者的广泛青睐。金包覆纳米颗粒制备核壳结构的方法众多，主要对金包覆所形成的核壳型纳米材料的制备方法进行综述。
关键词: 金；核壳结构；包覆；制备
中图分类号：O654.2 文献标识码：A 文章编号：0258-3283(2019)
Preparation of Core-shell Structure of Au Coating Nanocomposites WU Rui*a, LIU Cun-fang a, ZHANG Qianga, SONG Juana, GUO Hongb, XIONG Hai-taoa, TIAN Guang-huia (a. Shaanxi key laboratory of catalysis and application, College of Chemical and Environment Science, b. College of Civil Engineering and Architecture, Shaanxi University of Technology, Hanzhong 723000, China ), Huaxue Shiji, 2019
Abstract: Au, Ag and other precious metal nanomaterials(NPs) have been widely used in the fields of chemistry, physics, biology and medicine due to their unique optical, electrical, catalytic properties and good biocompatibility. Au NPs are employed as core or shell to prepare core-shell type of composite NPs, which are widely favored by researchers. Such core-shell NPs endow with both the performance of core and shell, as well as other superior properties, there are many methods for preparing core-shell structure with Au coating NPs. In this work, the methods for preparing core-shell NPs with Au coating was reviewed.
Key words: Au; shell structure; coating; preparation
腙参与的环加成反应研究进展
杜佳，闫文静，冯涛，李兴，常宏宏，高文超，魏文珑*
(太原理工大学 化学化工学院，山西 太原 030024)
摘要：环加成是两个或多个分子通过结合生成环状化合物的反应，它在有机合成中起着非常重要的作用。腙是一类重要的有机含氮化合物，作为有机合成中间体，它可与含有各种不饱和键的化合物发生不同类型的环加成反应来制备多种含氮杂环化合物；这些杂环化合物骨架广泛存在于医药、农药、材料和天然产物等分子结构中。主要对近几年腙与含有各种不饱和键化合物发生的各种环加成反应进行了综述，主要包括[3+3]、[3+2]、[3+4]、[4+2]和[4+3]等环加成反应，并对其发展方向进行了展望。
关键词：腙；环加成；不饱和键
中图分类号： 0626 文献标识码：A文章编号：0258-3283（2019）
Progress in Cycloaddition Reactions of Hydrazones DU Jia，YAN Wen-jing，FENG Tao，LI Xing，WEN Wen-long* (College of Chemistry Engineering, Taiyuan University of Technology, Taiyuan 030024, China) Huaxue Shiji, 41(5), ～
Abstract：Cycloaddition is the formation of a cyclic compound via the reaction of two or more molecules, and it plays a very important role in organic synthesis. Hydrazones are very important nitrogen-contain compounds and they could react with various compounds having diverse unsaturated bonds to synthesize different nitrogen-contain heterocyclics. And these heterocyclic skeletons are widely presented in the molecular structure of medicine, pesticides, materials and natural products. The recent progress in the cycloadditions of hydrazones with diverse compounds mainly bearing various unsaturated bonds is summarized, including [3+3], [3+2], [3+5], [4+2] and [2+3] cycloaddition. Moreover, the prospects of future development are also discussed.
Key words：hydrazone; cycloaddition; unsaturated bonds
甲醇中克伦特罗、莱克多巴胺和沙丁胺醇3种溶液标准物质的定值及不确定度评估
周剑，齐鑫，杨梦瑞，王彤彤，王敏*
(中国农业科学院农业质量标准与检测技术研究所，北京 100081)
摘要：采用有证标准物质和市售纯品为标准物质原料，经过定性和纯度核验的研究，采用重量-容量法配制了甲醇中克伦特罗、莱克多巴胺和沙丁胺醇3种溶液标准物质，经均匀性和稳定性检验合格，并进行了定值、均匀性和稳定性的不确定度评估。3种溶液以配制值为发布值，已被批准为国家二级标准物质，标准物质的研制为农产品质量安全相关项目的监测与风险评估提供了溯源保障。
关键词：克伦特罗；莱克多巴胺；沙丁胺醇；溶液标准物质
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2019）--
Determination and Uncertainty Evaluation of Clenbuterol, Ractopamine and Salbutamol in Methanol Solution ZHOU Jian, QI Xin, YANG Meng-rui, WANG Tong-tong, WANG Min* (Institute of Quality Standard and Testing Technology for Agro-Products of CAAS, Beijing 100081, China) Huaxue Shiji, 2019, 41(5), ～
Abstract：The certified reference material and pure products after qualitative and purity verification were used in this study. The clenbuterol, ractopamine and salbutamol in methanol solution were prepared by a gravity-volume method, then were investigated homogeneity study, stability study and uncertainty evaluation. Finally, 100 mg·L-1 clenbuterol, ractopamine and salbutamol in methanol have been approved as the national secondary standard materials, which could provide traceability for the program of monitoring and risk assessment of agricultural product.
Key words：clenbuterol; ractopamine; salbutamol; solution reference material
混合磷酸盐pH溶液标准物质的研制
周瑾艳1，黄彦捷*1，许俊斌1，陈玲1，王世超1，花秀兵1，尹强1，吴朝阳2
（1.广东省计量科学研究院华南国家计量测试中心，广东 广州 510405；2．湖南大学 化学化工学院, 湖南 长沙 410000）
摘要：通过遴选标准物质原材料，优化特性量值测量方法，采用溯源至美国国家标准与技术研究院（NIST）研制的标准物质的定值方法，系统介绍了混合磷酸盐pH溶液标准物质的研究工作。同时考察了标准物质的均匀性和稳定性，分析了样品的均匀性、测量的分散性及其他因素对不确定度的贡献，综合评定了整个研制体系的不确定度。稳定性考察结果表明，混合磷酸盐pH溶液标准物质在6个月内量值可靠稳定。其pH值为7.41（25 ℃），pH的扩展不确定度为0.03pH。该系列标准物质性能良好，已成功申请国家二级标准物质，编号为GBW(E)130522，可满足食品、药品、日化、环境保护及化工产品研究和检测的需要，可望用于相关仪器（pH计）的校准、分析方法评价，为统一相关量值发挥应有的作用。
关键词：标准物质、pH、混合磷酸盐、不确定度
中图分类号：TB99 文献标识码：A 文章编号：0258-3283（2019）--
Development of Certified Reference Material for Mixed Phosphate pH Solution ZHOU Jin-yan1, HUANG Yan-jie*1, XU Jun-bin1, CHEN Ling1, WANG Shi-chao1, HUA Xiu-bin1, YIN Qiang1, WU Zhao-yang2 (1.Guangdong Provincial Institute of Metrology & South China National Centre of Metrology, Guangzhou 510405；2. College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410000) Huaxue Shiji, 2019, 41(5), ～
Abstract：The research work of the certified reference material of mixed phosphate pH solution was systematically introduced by selecting the raw material, optimizing the measurement method of characteristic quantity value, and adopting the determination method of certified reference material traceable to the reference material from American National Institute of Standards and Technology (NIST). The uniformity and stability of the certified reference materialwere investigated, the uniformity of the sample, the dispersion of the measurement and the contribution of other factors to the uncertainty were analyzed, and the uncertainty of the whole system was comprehensively evaluated.The results show that the certified reference material of the mixed phosphate pH solution was reliable and stable in 6 months.The pH value is 7.41 at 25 ℃ with the expanded uncertainty of 0.02pH.Thesolution reference materialshas been successfullyidentified as the national grade II certified reference materials, which is numbered GBW(E)130522, and is expected to be used in the calibration of instruments(pH meter) and method evaluation in food and cosmetic analysis.
Key words：reference materials;b pH; mixed phosphate; uncertainty
质量控制图在标准物质稳定性评估中的应用
汪斌*，卢晓华，王茜
（中国计量科学研究院，北京 100029）
摘要：标准物质稳定性评估是标准物质研制的一个重要环节，目的是评估标准物质量值在一定时间内的波动情况，并据此给出标准物质有效期。常用的方法是线性回归趋势分析和方差分析法。根据质量控制图的特点及标准物质稳定性评估的实际需要，探索将质量控制图应用于标准物质量值的稳定性监测与评估工作中。通过对比发现，质量控制图具有灵敏直观的特点，可以作为标准物质稳定性评估的一个有效手段。
关键词：质量控制图；稳定性评估；标准物质
中图分类号：TB9x 文献标识码：A 文章编号：0258-3283（2019）--
The application of control chart for assessment of stability of reference materials WANG Bin*，LU Xiao-hua, WANG Qian (National Institute of Metrology, Beijing 100029, China) huaxue shiji, 2019, 41(5), ～
Abstract: The assessment of stability of reference materials is an important stage of the development. The aim of assessment of stability is to demonstrate the changes of the values, and give the period of validity for reference materials. The common methods are trend analysis by least squares regression and variance analysis. Control chart will be used in the assessment of stability. By the comparison, it can be found that control chart is very sensitive and intuitive. Control chart can be a useful method for the assessment of stability.
Key words: control chart, assessment of stability, reference materials metrology
质量平衡法测定金属银纯度的不确定度评定
田衎，岳亚萍，杨永*，张覃，郭伟臣，邢书才，房丽萍
(环境保护部标准样品研究所 国家环境保护污染物计量和标准样品研究重点实验室，北京 100029)
摘要：采用质量平衡法对金属银纯度定值。选择电感耦合等离子体质谱法（ICP-MS）测定了金属银中9种痕量金属杂质含量，按照《CNAS-GL006：2018化学分析中不确定度的评估指南》中有关规定分别评定了9种金属杂质的不确定度，不确定度主要来源于样品称量、标准溶液和样品稀释制备、工作曲线拟合及测量重复性等，以9种杂质的合成不确定度分量作为金属银纯度的不确定度。金属银纯度定值结果为99.637%，扩展不确定度为 0.025% (k ＝ 2 )。
关键词：质量平衡法；金属银；不确定度评定
中图分类号：O655.1 文献标识码：A 文章编号：0258-3283(2019)
Uncertainty Evaluating of Metallic Silver by Mass Balance Method TIAN Kan, YUE ya-ping, YANG yong*, ZHANG qin, GUO Wei-chen, XING Shu-cai, FANG Li-ping (Institute for Environmental Reference Materials of Ministry of Environmental Protection, State Key Laboratory of Environmental Pollutant Metrology and Reference Materials of Environmental Protection, Beijing 100029, China) Huaxue Shiji, 41(5),～
Abstract: The purities of metallic silver were analysis by mass balance method. The 9 trace impurities in metallic silver were determined by inductively coupled plasma mass spectrometry (ICP-MS) and the uncertainty evaluation for the results were carried out according to CNAS-GL006：2018 Guidance on Evaluating the Uncertainty in Chemical Analysis. The main sources of measurement uncertainties were analyzed, including sample weighing，diluting standard solution，standard curve fitting and measurement repeatability, etc. The standard uncertainty of 9 elements and the combined extending uncertainty of silver were evaluated respectively. The certified result with the mass balance method was 99.637% and the expanded uncertainty was 0.025% ( k ＝ 2 ).
Key words: mass balance method; metallic silver; uncertainty evaluation
12种氯苯类化合物纯度定值色谱方法研究
纪洁*，张伟，何雅娟
（中国计量科学研究院 化学所，北京 100029）
摘要：对用于溶液标准物质制备的12种氯苯类纯品原料进行了高效液相色谱法(HPLC-DAD)和气相色谱法(GC-FID)两种纯度定值方法的研究。在优化的色谱条件下，甲醇基体混合溶液中的12个目标物组分包含一氯代苯、1,2-二氯苯、1,4-二氯苯、1,3-二氯苯、1,2,3-三氯苯、1,2,4-三氯苯、1,3,5-三氯苯、1,2,3,4-四氯苯、1,2,4,5-四氯苯、1,2,3,5-四氯苯、五氯苯、六氯苯均能良好分离。避免了氯苯类原料中存在的同分异构体及同系物杂质与主体成分没有良好分离而导致的对纯度定值结果的影响。
关键词：氯苯类；纯度；高效液相色谱；气相色谱；标准物质
中图分类号：O625.2 文献标识码：A 文章编号：0258-3283 (2019)--
Purity Measurement for 12 Kinds of Chlorobenzenes via Chromatography JI Jie*, ZHANG Wei, HE Ya-juan (Chemical Metrology & Analytical Science Division, National Institute of Metrology, Beijing 100029, China), Huaxue Shiji, 2019, 41(5), ～
Abstract:The research of purity chromatography measurement method （HPLC-DAD and GC-FID）for 12 kinds of chlorobenzenes raw materials which were used to prepare chlorobenzenes solution reference material was introduced. It contains monochlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,3-dichlorobenzene 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,4, 5-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, pentachlorobenzene and hexachlorobenzene. Under optimized chromatographic conditions, good chromatographic separation result was gotten for 12 chlorobenzenes target compounds which were in methanol matrix mixed solution. It avoided the influence of the impurities of isomers and homologues in the raw materials on the results of purity determination due to the poor separation between the impurities and the target compounds.
Key words: chlorobenzenes; purity; high performance liquid chromatography; gas chromatography; reference material
模拟汽油馏程标准物质的研制
裴从莹1，王海峰*2，叶青1，李佳2，宋小平2
(1.北京工业大学 环境与能源工程学院，北京 100022；2.中国计量科学研究院 环境计量中心，北京 100029)
摘要：馏程反映了液体的蒸发性能，是有机溶剂、原油及石油产品的重要的技术指标之一。针对国内外对馏程标准物质的迫切需求，研制了模拟汽油馏程标准物质。采用十氢化萘等8种有机物混合物为基体，在剧烈搅拌条件下连续分装，制备了标准物质。基于《GB/T 6536 石油产品常压蒸馏特性测定法》系统研究了方法的影响因素。基于纯物质的沸点，采用比较法将自动馏程测定仪的铂电阻温度计溯源到了水银温度计，实现了温度的量值溯源。联合多家权威实验室，采用国家标准方法为标准物质合作定值。标准物质的蒸发温度不确定度在1.3 ～ 3.4 ℃范围内。该标准物质可用于馏程测定仪的检定和校准以及汽油馏程测定方法的验证。
关键词：馏程；标准物质；不确定度；汽油
中图分类号：O657.99 文献标识码：A 文章编号：0258-3283（2019）--
Development of Certified Reference Material of Synthetic Gasoline for Distillation PEI Cong-Ying1, WANG Hai-Feng*2, YE Qing1, LI Jia2, SONG Xiao-Ping2 (1.college of environmental and energy engineering, Beijing University of Technology 100022, China; 2.centre of environmental metrology, National institute of metrology of China, Beijing 100029) Huaxue Shiji, 2019, 41(5), ～
Abstract：Distillation is one of important properties of organic solvent, crude oil and its products which reveals the evaporating performance of samples. The present study developed the certified reference material (CRM) of synthetic gasoline for distillation in order to satisfy the urgent need of CRM. The mixture of 8 organic solvent including naphthene was employed as the matrix of CRM which is dispensed continuously under vigorous stirring for the preparation of CRM. Based on the national standard method for distillation of petroleum products and liquid fuels at atmospheric pressure (GB/T 6536), various effects upon the distillation were investigated. The platinum resistance thermometer of distillation analyzer was calibrated by the mercury thermometer through the boiling point of toluene, which realized the traceability of temperature of distillation to SI unit. The collaborative-study was used to certify the CRM using the national standard method above. The uncertainty of the certified temperature of evaporated volume of CRM ranged from 1.3 ℃ to 3.4 ℃. This CRM can be employed in the verification and calibration of distillation analyzer, and the validation of measurement method of distillation.
Key words：distillation; reference material; uncertainty; gasoline
水中3种苯胺类混合标准样品的研究初探
刘海萍，黄林艳，赵亚娴，房丽萍*
(环境保护部标准样品研究所 国家环境保护污染物计量和标准样品研究重点实验室，北京 100029)
摘要：探索了水中苯胺、对硝基苯胺和间硝基苯胺多组份混合标准样品的制备技术。本实验从制备介质、参比波长、流动相、稳定剂、保存条件等方面进行探索，结果表明，采用“重组法”制备水中3种苯胺类混合标准样品在SDB-C18型液相色谱柱、甲醇-水混合溶液为流动相的液相色谱仪上分离度良好；分层随机抽取10瓶样品进行瓶间均匀性检验，经单因素方差分析法统计，证明样品均匀性良好；将室温避光和4 ℃冷藏避光保存的样品进行稳定性检验，经趋势分析法计算，其线性直线的斜率均不显著，表明在180 d的监测期内，室温避光和4 ℃冷藏避光保存条件下的样品稳定性均良好。本方法为后续开展水中有机物标准样品的研制提供了参考和借鉴价值。
关键词：水；苯胺类；标准样品；初探
中图分类号：N023 文献标识码：A 文章编号：0258-3283(2019)--
Anilines in Water Reference Material LIU Hai-ping1, HUANG Lin-yan1, ZHAO Ya-xian1, FANG Li-ping*1 (State Environmental Protection Key Laboratory of Measurement and Reference Material, Institute for Environmental Reference Materials, Beijing 100029, China), Huaxue Shiji, 2019, 41(5), ～ Abstract: The preparation method of anilines in water reference material was introduced, including aniline, p-nitroaniline and m-nitroaniline. It was prepared by the method of a spiking solution added to water, and factors in the process of preparation were investigated, such as preparation medium, reference wavelength, mobile phase, stabilizer, preservation conditions, et.al. The result showed that anilines in water had a good resolution on the liquid chromatograph with SDB-C18 column, using methanol and water as mobile phase. 10 units selected by random stratified sampling coving the whole batch were obtained for homogeneity, and indicated good homogeneity using one-way analysis of variance. At ambient and 4℃ refrigeration storage conditions, the concentration of anilines did not change during monitoring period of 180 d. At the same time, trend analysis method was used for the stability data, and its linear slope was not significant, indicating good stability. This method provides reference for the subsequent development of organic compounds in water reference material.
Key words: water; Anilines; reference material; preliminary research
荧光光谱仪的校准方法研究及不确定度评定
黄彦捷1，李成辉2，周瑾艳1，黄振宇1，陈玲1，王鑫3，关妍*3
(1.广东省计量科学研究院，广东 广州 510405；2.四川大学 分析测试中心，四川 成都 610064；3.北京大学 化学与分子工程学院，北京 100871)
摘要：荧光光谱仪是一种常用的分析仪器，适用于食品、卫生、农业、环境等方面的样品分析，能提供被测样品的激发光谱、发射光谱、荧光强度、量子产率、荧光寿命及荧光偏振等一种或多种信息。介绍适用于检测波长范围为200 ～ 1700 nm的荧光光谱仪的校准方法，针对波长示值误差和重复性、检出限、测量线性及峰值强度重复性给出了校准实例和不确定度评价方法。其中波长示值误差的扩展不确定度为0.20 nm (k ＝ 2)；检出限为8.09×10-11 g/mL，其扩展不确定度为3.60×10-11 g/mL (k ＝ 2)；测量线性的相对扩展不确定度为3.1% (k ＝ 2)；峰值强度重复性的相对扩展不确定度为2.0% (k ＝ 2)。荧光光谱仪的校准过程及结果评价的描述将为相关仪器的校准提供一个良好的范例。
关键词：荧光光谱仪；不确定度；波长；检出限；测量线性；峰值强度；校准
中图分类号：TB99 文献标识码：A 文章编号：0258-3283（2019）--
Study on Calibration Method of Fluorescence Spectrometer and Evaluation of Uncertainty HUANG Yan-jie1, LI Cheng-hui2, ZHOU Jin-yan1, HUANG Zhen-yu1, CHEN Ling1, WANG Xin3, GUAN Yan*3 (1.Guangdong Provincial Institute of Metrology, Guangzhou 510405, China; 2.Analytical Instrumentation Center, Sichuan University, Chengdu 610064, China; 3.College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China) Huaxue Shiji, 2019, 41(5), ～
Abstract：Fluorescence spectrometer is a common analytical instrument, which is suitable for the analysis in food, health, agriculture and environment areas. It can provide one or more information such as excitation spectrum, emission spectrum, fluorescence intensity, quantum yield, fluorescence lifetime, and fluorescence polarization. The calibration methods and uncertainty evaluation methods for fluorescence spectrometer with detection wavelength ranging from 200 nm to 1700 nm are introduced, which containing wavelength indication error and repeatability, detection limit, measurement linearity and peak intensity repeatability. The expanded uncertainty of wavelength indication error is 0.20 nm (k ＝ 2); the limit of detection is 8.09×10-11 g·mL-1 with an expanded uncertainty to be 3.60×10-11 g·mL-1 (k ＝ 2); the relative expanded uncertainty of measurement linearity is 3.1% (k ＝ 2); the relative expanded uncertainty of peak intensity repeatability is 2.0% (k ＝ 2). The calibration process and result evaluation of fluorescence spectrometer described in this paper will provide a good example for calibration of related instruments.
Key words：fluorescence spectrometer; uncertainty; wavelength; limit of detection; measurement linearity; peak intensity; calibration
新型进样瓶-气相色谱质谱法测定烟叶中的24种有机酸
刘欣1，梁梦洁2，李银科1，王燕梅1，米其利1，孔维松1，许永1，李晶*1
(1.云南中烟工业有限责任公司 技术中心，云南 昆明 650106；2.昆明医科大学 药学院，云南 昆明 650504)
摘要：研发建立了一个新型进样瓶，结合气相色谱质谱法（GC-MS）可以测定烟叶中的24种有机酸。结果表明：新型进样瓶可以集提取、过滤、干燥、衍生化反应和进样功能为一体，在一定程度上减少操作步骤，缩短前处理时间，可以保障样品检测的平行性和稳定性；利用新型进样瓶，以二氯甲烷为提取剂，N,O-双(三甲基硅烷基)三氟乙酰胺（BSTFA）为衍生化试剂，将提取液在40 ℃下反应60 min，衍生化后的样品利用气相色谱质谱法，选择离子模式进行检测。该方法在0.5 ～ 50 mg/L范围内，线性关系较好（R > 0.99），检出限为0.1 ～ 6.8 µg/g，加标回收率在85% ～ 104%之间，相对标准偏差在1.1% ～ 5.1%之间；利用该方法对不同生长期的烟叶进行检测，发现有机酸物质具有差异性。该方法操作简易、重复性好、准确度高，可以满足烟草及相关样品中有机酸的检测要求。
关键词：烟叶；有机酸；气相色谱质谱法（GC-MS）；新型进样瓶
中图分类号：O657.61 文献标识码：A 文章编号：0258-3283（2019）--
Determination of 24 Organic Acids in Tobacco Leaf via Novel Sampling Bottle-gas Chromatography-mass Spectrometer (GC-MS) for the LIU Xin1, LIANG Meng-jie2, LI Yin-ke1, WANG Yan-mei1, MI Qi-li1, KONG Wei-song1, XU Yong1, LI Jing*1 (1. Technology Center, China Tobacco Yunnan Industrial Co., Ltd, Kunming 650106, China; 2. School of Pharmacy, Kunming Medical University, Kunming 650504, China), Huaxue Shiji, 2019, 41(5), ～
Abstract：A novel sampling bottle was developed to couple with gas chromatography-mass spectrometer (GC-MS) for the determination of 24 organic acids in tobacco leaf. The results show that: the pretreatment including extraction, filtering, removing the water, derivation and sampling could be finished in one step by the novel sampling bottle, which can make the procedure simpler, timesaving and having good repeatability; based on the pretreatment device, the tobacco leaf sample was extracted by dichloromethane, then derivatized with N,O-bis(trimethylsilyl) trifluoroacetamide under 40℃ for 60 min. The separation of 24 organic acids including formic acid, acetic acid, etc., was performed by GC-MS on selected ion mode. In the range of 0.5～50 mg/L, the linearity was acceptable (correlation coefficients R > 0.99). The spiked recoveries of real sample were 85%～104% with the RSD in the range of 1.1%～5.1%; With the established test method, different contents of organic acids in different type tobacco leaf were found. With the simplification, good reproducibility, proper accuracy, the developed method can be used for the determination of 24 organic acids in tobacco samples.
Key words: tobacco leaf; organic acids; gas chromatography- mass spectrometer (GC-MS); novel sampling bottle
共振光散射光谱法应用于甲氨蝶呤的定量测定
刘小莲1, 2，张传林*1
（1.江西医学高等专科学校第一附属医院 药剂科，江西 上饶 334000；2.江西医学高等专科学校 药剂科，江西 上饶 334000）
摘要：建立测定甲氨蝶呤含量的方法。在pH 12的Britton-Robinson缓冲液中，形成n（甲氨蝶呤）: n（Hg(Ⅱ)）: n（氯化十六烷基吡啶） = 1 : 1 : 4的离子缔合物，引起吸收光谱和共振光散射光谱的明显变化，最大散射峰位于464 nm处。研究表明，体系散射强度的增加与甲氨蝶呤的浓度在一定范围内有良好的线性关系，其检出限为11 ng/mL。甲氨蝶呤片和尿液中甲氨蝶呤的平均回收率分别为97.9%和88.6%，相对标准偏差分别为3.3%和3.6%（n = 6）。该方法灵敏、快速，可用于甲氨蝶呤的定量测定。
关键词：甲氨蝶呤；Hg(Ⅱ)；氯化十六烷基吡啶；共振光散射
中图分类号：O657.39 文献标识码：A 文章编号：0258-3283(2019)--
Determination of Methotrexate by Resonance Light Scattering Spectra LIU Xiao-lian1,2, ZHANG Chuan-lin*1(1. Department of Pharmacy, the First Affiliated Hospital of Jiangxi Medical College, Shangrao 334000, China; 2. Department of Pharmacy, Jiangxi Medical College, Shangrao 334000, China), Huaxue Shiji, 2019, 41(4)
Abstract: To establish a method for determination of methotrexate(MTX), in a Britton-Robinson buffer medium (pH 12.00), methotrexate reacted with Hg(Ⅱ) and cetylpyridinium chloride(CPC) to form a 1:1:4 ion-associated complex, which resulted in the change of absorption spectra and resonance light scattering(RLS) spectra. The maximum scattering peak was located at 464 nm. The increment of the enhancement of RLS was linear to the concentration of methotrexate in a certain range. The limit of detection was 11 ng/mL. The average recoveries of methotrexate in tablets and the urine were 97.9% (RSD = 3.3%, n = 6), 88.6% (RSD = 3.6%, n = 6). The method was quick and sensitive, and could be applied in the determination of methotrexate.
Key words: methotrexate; Hg(Ⅱ); cetylpyridinium chloride; resonance light scattering
重量法测定二乙基次膦酸铝磷含量的研究
杨丽a，毛祖莉*b
（湖南工学院 a.安全与环境工程学院，b.汽车零部件技术研究院，湖南 衡阳 421002）
摘要：为了建立二乙基次膦酸铝（AlPi）中磷含量的分析方法，采用磷钼酸喹啉沉淀法（重量分析法），分别探讨氧化剂过硫酸铵的添加量、喹钼柠酮试剂添加量、过滤时采用砂芯漏斗规格等检测条件对磷测定值的影响。结果表明，试样为0.1 ～ 0.2 g，过硫酸铵添加量为2.5 g，喹钼柠酮体积为30 mL，选择G4规格的砂芯漏斗过滤时，其结果与理论值更接近，通过精密度试验，精确度高，准确度好，加标回收率为98.84% ～ 99.34%，较仪器分析更接近理论值，适用于AlPi产品磷含量的检测。
关键词：二乙基次膦酸铝；磷含量；磷钼酸喹啉；过硫酸铵；
中图分类号：O622.4 文献标识码：A 文章编号：0258-3283(2019)--
Determination of Phosphorus in Aluminum Diethylphosphinate by Gravimetric Method YANG Lia, MAO Zu-li*b (a. School of Safety and Environmental Engineering, b. Research Institute of Automobile Parts Technology, Hunan Institute of Technology, Hengyang 421002, China)，Huaxue Shiji, 2019, 41(4)
Abstact: To establish an analytical method for phosphorus content in aluminum diethylphosphinate (AlPi), the quinolinephosphomolybdate precipitation method (gravimetric analysis) was adopted to investigate and discuss the influence on the measured value of phosphorus by the addition amount of oxidant ammonium persulfate, quinoxalyl ketone reagent, and the specifications of sand core funnel during the filtration. The results suggested: when the sample weighed between 0.1～ 0.2g, the additional amount of ammonium persulfate added was 2.5 g, and the volume of quimociac was 30 mL, and the result was closer to the theoretical value when the sand core funnel of G4 size was selected for filtration. The precision test suggested that this method had high precision and good accuracy, with the recoveries of the standard addition between 98.84%～99.34%, which was closer to the theoretical value than the instrumental analysis, making it suitable for the detection of phosphorus content in AlPi products.
Key words: aluminum diethylphosphinate; phosphorus content; quinolinemolybdophosphoric acid; ammonium persulfate
硫醇还原α, α, α-三溴甲基酮类化合物的研究
王慧，杨莹，阿布都热西提·阿布力克木*
(新疆师范大学 化学系，新疆 乌鲁木齐 830000)
摘要：报道了一种合成α, α-二溴甲基酮类化合物的新方法，该反应以硫醇作为还原剂，高效还原α, α, α-三溴甲基酮类化合物为目标化合物，合成了12种α, α-二溴甲基酮类化合物，该方法适用于脂肪族、芳香族和杂环类α, α, α-三溴甲基酮类化合物。最佳的反应条件是n（α, α, α-三溴甲基酮）：n（还原剂）：n（碳酸钾）=1：2：1.2，二氯甲烷中0 ℃反应1 h，α, α-二溴甲基酮类化合物收率达81% ～ 96%。其结构通过1HNMR、13CNMR、HR-MS 进行了表征和确认。该反应条件温和、操作简单、效率高，为α,α-二溴甲基酮类化合物的合成提供了新途径。
关键词 ：2-苯硫代乙醇；α, α-二溴甲基酮；还原反应；α, α, α-三溴甲基酮
中图分类号：O622.4 文献标识码：A 文章编号：0258-3283（2019）--
Reduction of α,α,α-Tribromomethylketones by Mercaptan Wang Hui, YANG Ying, ABULIKEMU Abudu Rexit (Department of Chemistry, Xinjiang Normal University, Urumqi, 830054,China), Huaxue Shiji, 41(5), ～
Abstract： A new method for synthesizing α, α-dibromomethylketones is reported. This reaction uses thiol as a reducing agent to efficiently reduce α, α, α-tribromomethylketones as target compounds. 12 Kinds of α, α-dibromomethyl ketone compounds were suitable for aliphatic, aromatic and heterocyclic α, α, α-tribromomethyl ketones. The optimum reaction conditions are n(α, α, α-tribromomethylketone): n (reducing agent): n (potassium carbonate) ＝ 1:2: 1.2, and reacted in dichloromethane at 0 ° C for 1 h, The yield of α, α-dibromomethyl ketone compound is 81% ～ 96%. The structure was confirmed by 1H NMR, 13C NMR, HR-MS. The protocol features mild conditions, simple operation and high efficiency, providing a new approach for synthesizing α,α-dibromomethylketones.
Key words: 2-phenylthioethanol; α,α-dibromomethylketones; reduction; α,α,α-tribromomethylketones
三氟甲磺酸铋催化的Beckmann重排反应在酰胺类化合物
合成中的应用研究
陈琦，吕春欣*，吕亚维，朱冰冰，余蕙敏，裘超颖，刘阳
(嘉兴学院 生物与化学工程学院，浙江 嘉兴 314001)
摘要：发展了一种利用三氟甲磺酸铋（Bi(OTf)3）催化Beckmann重排反应。以三氟甲磺酸铋为催化剂，通过Beckmann重排反应制备酰胺类化合物。考察了催化剂、溶剂、温度、催化剂用量、反应时间等对Beckmann重排反应的影响。结果表明，结构对称的酮肟底物相对于不对称底物更容易发生Beckmann重排反应。结构中含有—OCH3、—CH3等供电子基团的底物，则底物活性更高。对酰胺类化合物进行核磁、红外表征。
关键词：酮；肟；酰胺；催化；Beckmann重排反应
中图分类号：O614.53+2 文献标识码：A 文章编号：0258-3283（2019）--
Application of Beckmann Rearrangement Reaction Using Bi(OTf)3 as the Catalyst in the Synthesis of Amide Compounds CHEN Qi, LV Chun-xin*, LV Ya-wei, ZHU Bing-bing, YU Hui-min, QIU Chao-ying, LIU Yang (College of Biological and Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China), Huaxue Shiji, 2019, 41(5), ～
Abstract: A Beckmann rearrangement reaction using Bi(OTf)3 as the catalyst was developed. A series of amide compounds were synthesized by Beckmann rearrangement reaction using Bi(OTf)3 as the catalyst. The effects of catalyst, solvent, temperature, catalyst amount and reaction time on the rearrangement of Beckmann were investigated. The results show that the structural symmetric ketoxime substrates are more likely to undergo Beckmann rearrangement reaction than asymmetric substrates. Substrates containing -OCH3, -CH3, etc. groups in the structures have higher activity. The amide compounds were comprehensively confirmed by NMR and IR.
Key words: ketone; oxime; amide; catalysis; Beckmann rearrangement reaction
三氯化铝-氯化锂体系中5-取代-1-茚酮化合物的合成研究
潘继刚*，张光辉，姚兵，陶勇凯
（山西大学 化学化工学院，山西 太原 030031）
摘要：茚酮类化合物不仅广泛存在于天然产物中，而且在药物研发、杀虫剂等方面有广阔的应用前景。本研究工作以3-氯丙酰氯及取代苯（Cl-、Br-、CH3-及CH3O-）为原料，通过路易斯酸催化，先后经过付克酰基化、付克烷基化来合成相应的5-取代-1-茚酮化合物（Cl-、Br-、CH3-及HO-）。优化了这类化合物的合成条件，选择新型的AlCl3-LiCl熔盐体系作为付克烷基化的路易斯酸催化剂和反应溶剂，大大提高了茚酮类化合物的合成产率，总收率可达到77% ～ 82%。目标化合物的结构通过核磁共振分析确定。
关键词：5-取代-1-茚酮；付克反应；AlCl3-LiCl熔盐；路易斯酸催化剂
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2019）
Synthesis of 5-Substituted-1-indanone in AlCl3-LiCl Systems PAN Ji-gang*, ZHANG Guanghui, YAO Bing, TAO Yong-kai (School of Chemistry and Chemical Engineering，Shanxi University，Taiyuan 030031，China), Huaxue Shiji, 2019, 41(5),
Abstract: Indanone compounds not only exist widely in natural products, but also have broad application prospects in drug development, insecticides and so on. With 3-chloroacetic chloride and substituted benzene（Cl—, Br—, CH3— and CH3O—）as raw materials, 5-substituted-1-indanone（Cl—, Br—, CH3— and HO—）were synthesized via Friedel-Crafts acylation reaction and alkylation reaction in the presence of Lewis acid catalyst. The reaction conditions were optimized using the new type AlCl3-LiCl molten salt as Lewis acid catalyst and reaction solvent for Friedel-Crafts alkylation reaction, the yield of 5-substituted-1-indanone is up to 77-82%. The compounds were characterized by 1HNMR and 13CNMR.
Key words: 5-substituted-1-indanone; Friedel-Crafts reaction; AlCl3-LiCl molten salt; Lewis acid catalyst
阿西美辛杂质F和阿西美辛一水合物晶体的制备及表征
姚明*1，张静静1, 2，董志强1，杨森1，熊航行1，李立威1
(1.荆楚理工学院 化工与药学院，湖北 荆门 448000；2.武汉工程大学 化工与制药学院，湖北 武汉 430205)
摘要：为控制阿西美辛的质量，建立阿西美辛杂质F和阿西美辛一水合物晶体的制备和表征方法。以阿西美辛为原料实现了阿西美辛杂质F的制备，并通过1HNMR、13CNMR和高分辨质谱确证结构。以阿西美辛为原料，通过丙酮和水重结晶制备阿西美辛一水合物，利用红外光谱、粉末X-射线衍射法和X-射线单晶衍射对该晶体晶型进行表征，获得了阿西美辛一水合物晶型的表征方法。
关键词：阿西美辛一水合物；阿西美辛杂质F；单晶结构；制备；
中图分类号：TQ46 文献标识码：A 文章编号：0258-3283（2019）
Preparation and Characterization of Impurity F of Acemetacin and Acematacin Monohydate YAO Ming*1, ZHANG Jing-jing2, DONG Zhi-qiang1, YANG Sen1, XIONG Han-xing1, LI Li-wei1 (1.College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen 448000, China; 2.School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China), Huaxue Shiji, 2019,
Abstract：In order to control the quality of acemetacin, the preparation and characterization of impurity F of acemetacin and acemetacin monohydrate were established. The impurity F of acemetacin was synthesized by the reaction of acemetacin, and its structure was confirmed by 1HNMR, 13CNMR and high resolution mass spectrum. Acemetacin monohydrate was obtained by re-crystallization using water and acetone as the solvent and was confirmed by infrared spectroscopy, powder X-ray diffractometry and X-ray diffraction. The characterization method for the crystal form of acemetacin monohydrate was achieved.
Key words：acemetacin monohydrate; impurity F of acemetacin; crystal structures; preparation
无溶剂研磨法合成二氢三嗪类化合物
甘信燃2，夏强强*1，史作冬1，边启龙1，袁江培1，徐元清*1
(1. 河南大学 化学化工学院，河南 开封 475000；2. 郑州大学 材料科学与工程学院，河南 郑州 450000)
摘要：采用无溶剂研磨法，以醛和苯甲脒为底物，首先，醛与苯甲脒发生亲核加成反应形成席夫碱中间体；然后，中间体与另一分子苯甲脒发生共轭加成，最后经氧化得到相应的二氢三嗪类杂环衍生物，收率高达90%。其结构经1HNMR、13CNMR和熔点进行确证，同时探究了研磨介质、物质的量比和放置时间对反应收率的影响。该方法操作简单、条件温和、无污染，为二氢三嗪提供了一条绿色的合成方法，并且为以后药物的开发提供了关键的中间体。
关键词：二氢三嗪；脒盐；无溶剂；研磨法；绿色合成方法
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2019）
Synthesis of Dihydrotriazine Derivatives via Solvent-free Grinding Method GAN Xin-ran 2, XIA Qiang-qiang *1, SHI Zuo-dong 1, BIAN Qi-long 1, YUAN Jiang-pei 1, XU Yuan-qing *1, (1. College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China; 2. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450000, China), Huaxue Shiji, 2019, 41(5),
Abstract：Dihydrotriazine heterocyclic derivatives were synthesized in up-to 90% yields via solvent-free grinding method, using aldehydes and benzamidine as substrates. Initially, aldehyde reacts with benzamidine and forms an intermediate (Schiff base). Then, the intermediate undergoes conjugate addition reaction with another molecule of benzamidine to give which on oxidation offers product. The structures were confirmed by 1HNMR, 13CNMR and melting point. The effects of grinding medium, molar ratio and storage time on the yield of the reaction were also investigated. This method has advantages such as simplicity of operates, mild reaction conditions, and pollution-free, which provides a new green strategy for the synthesis of dihydrotriazine compounds and a key intermediate for future drug development.
Key words：dihydrotriazine; amidine salt; no solvent; grinding method; green synthetic method
