羧基化荧光碳量子点的合成及其在汞离子检测中的应用
牛静*1，王利瑶1，杨恩暖2，张宁1，胡鹏1
（1. 黄淮学院 化学与制药工程学院，河南 驻马店 463000；2. 河南黄淮检测科技有限公司，河南 驻马店 463000）
摘要：试验通过一步法高压热处理柠檬酸粉末制备了羧基功能化的荧光碳量子点，荧光光谱表征显示所合成荧光碳量子点的最大激发波长为316 nm，最大发射波长为394 nm。Hg2+对其具有较好的淬灭效果，在5～300 µmol/L的浓度范围内，Hg2+的浓度和体系荧光强度呈较好的线性关系，线性回归方程为F0＝152.1695-0.1535c，相关系数R2＝0.998。这种碳量子点的制备技术将为合成功能化荧光纳米材料提供有益的借鉴作用，并为开发新型传感检测技术提供支持。
关键词：柠檬酸；热处理；荧光；碳量子点；羧基功能化；汞离子检测
中图分类号：X832 文献标识码：A 文章编码：0258-3283（2020）
Synthesis of Carboxylated Fluorescent Carbon Quantum Dots and Its Application in Mercury Ion Detection NIU Jing*1, WANG Li-yao1, YANG En-nuan2, ZHANG Ning1, HU peng1 (1. College of Chemistry and Pharmaceutical Engineering, Huanghuai University, Zhumadian 463000, China; 2. Henan Huanghuai Testing Technology Co., Ltd., Zhumadian 463000, China), Huaxue Shiji, 2020, 42(3)
Abstract: In this study, carboxyl functionalized fluorescent carbon quantum dots(CQDs) was prepared by one-step high-pressure heat treatment of citric acid powder. The CQDs maximum excitation and emission wavelength was 316 nm and 394 nm, respectively. Hg2+ had a good quenching effect on its fluorescence. The CQDs fluorescence intensity decreased with the increase of Hg2+ concentrations and showed a good linear relationship ranging from 5～300 µmol/L. The linear equation for Hg2+ was F0=152.1695-0.1535c and correlation coefficient R2 was 0.998. The preparation methodology for CQDs would provide a useful reference for functionalized fluorescent nanomaterials synthesis and lay a foundation for new sensing technology development.
Key word: citric acid; heat treatment; fluorescence; carbon quantum dots; carboxyl functionalized; mercury ion detection
引用本文：牛静, 王利瑶, 杨恩暖, 等. 羧基化荧光碳量子点的合成及其在汞离子检测中的应用[J]. 化学试剂, 2020, 42(3): 221-225.
壳聚糖超细纤维的制备及其铬离子吸附性能研究
钟少锋*，吉婉丽，刘晓云
（浙江工业职业技术学院 鉴湖学院，浙江 绍兴 312000）
摘要：利用静电纺丝和热交联技术，制备了良好形貌的交联壳聚糖/聚甲基丙烯酸（CS/PMAA）纤维膜，然后采用正丙醛化学改性得到改性CS/PMAA纤维膜。Cr(VI)离子吸附实验发现，铬元素浓度6.50 mg/L时，CS/PMAA纤维膜的吸附量可以达到4.98 mg/g；而当铬元素浓度为3.75 mg/L时，铬的去除率可以达到81.0%；而且提高壳聚糖的含量有利于提高CS/PMAA纤维膜的吸附性能。改性CS/PMAA纤维膜吸附结果显示，正丙醛改性CS/PMAA纤维膜降低吸附性能，而进一步还原后的纤维膜的吸附性能优于未改性CS/PMAA纤维膜。实验结果表明，CS/PMAA纤维膜对铬离子具有良好地吸附性能；CS/PMAA纤维膜的吸附性能主要通过纤维氨基与Cr2O72-的相互作用进行的，提高氨基的碱性和数量有利于提高纤维膜的吸附性能。
关键词：壳聚糖, 静电纺丝, 纳米纤维膜, 铬离子, 吸附
中图分类号：O636.1 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Chitosan/Poly(Methacylic Acid) Superfine Fiber Mat and Its Application in Chromium Ion Removal ZHONG Shao-feng*, JI Wan-li, LIU Xiao-yun (Department of Jianhu, Zhejiang Industry Polytechnic College, Shaoxing 312000, China ), Huaxue Shiji, 2020, 42(3), ～
Abstract: Well defined chitosan (CS) hybrid fiber mats were prepared by electrospinning with poly(methyacrylic acid) (PMAA) as the co-spinning agent, and then they were cross-linked at 160 oC. The cross-linked CS/PMAA fiber was modified by propionaldehyde. The adsorption of Cr(VI) ion in aqueous solution showed that the adsorption capacity of this novel crosslinked CS/PMAA fiber mat could be up to 7.89 mg/g when the Cr(VI) concentration was 6.50 mg/L; the removal efficiency could be up to 81.0 % when the Cr(VI) concentration was 3.75 mg/L. Moreover, the adsorption efficiency could be improved by increasing the basicity of amino-group in the fiber and the content of CS in the CS/PMAA fiber. The results demonstrate that Cr2O72- anion is adsorbed onto the amine group of the CS chain, and the adsorption ability of CS/PMAA fiber mat can be enhanced by increasing the basicity and amount of amine group.
Key words: chitosan, electrospinning, nanofiber, chromium ion, adsorption
引用本文：钟少锋, 吉婉丽, 刘晓云, 等. 壳聚糖超细纤维的制备及其铬离子吸附性能研究[J]. 化学试剂, 2020, 42(3): 226-231.
磁性多壁碳纳米管的制备及对恩诺沙星的吸附性能
王栋，张雅明，刘富永，贺丽华，冯建华，赵海香*
（河北北方学院 理学院化学系，河北 张家口 075000）
摘要：利用混酸H2SO4-HNO3对多壁碳纳米管（MWCNTs）进行羧化处理，再经化学共沉淀法制备磁性MWCNTs。采用FTIR和SEM对制备的样品进行表征。FTIR表明羧化后有效引入羧基、羟基等含氧官能团，磁化后引入了磁性Fe-O基团。SEM表明磁化后MWCNTs表面粗糙，包覆铁的氧化物。以HPLC/UV为检测手段，研究了制备的磁性MWCNTs对恩诺沙星的吸附性能。结果表明50 mg 磁性MWCNTs对5 mg/L恩诺沙星在30 ℃、30 min时吸附率达到了97.27 %。对磁性MWCNTs吸附恩诺沙星进行等温吸附线性拟合，Langmuir方程的拟合系数r＝0.8612。吸附恩诺沙星达平衡的磁性MWCNTs被10 mL 10%氨水-甲醇洗脱，解析率达到89.23%。50 mg磁性MWCNTs SPE柱对5 mg/L恩诺沙星的穿漏体积为20 mL，磁性MWCNTs对恩诺沙星吸附容量为2 mg/g。
关键词：多壁碳纳米管（MWCNTs）；磁性多璧碳纳米管（MAGCNTs）；制备；表征；恩诺沙星；吸附
中文分类号：O657.7 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Magnetic Multiwall Carbon Nanotubes and Its Adsorption Properties for Enrofloxacin WANG Dong, ZHANG Ya-ming, LIU Fu-yong, HE Li-hua, FENG Jian-hua, ZHAO Hai-xiang* (Department of Chemistry, College of Science, Hebei North University, Zhangjiakou 075000, China), Huaxue Shiji, 2020, 42(3)
Abstract: The multi wall carbon nanotubes (MWCNTs) were carboxylated by mixed acid H2SO4-HNO3, and then magnetic MWCNTs (MAGCNTs) were prepared by chemical coprecipitation. The MAGCNTs were characterized by FTIR and SEM. FTIR showed that carboxylation could effectively introduce oxygen-containing functional groups such as carboxyl and hydroxyl groups, and magnetic Fe-O groups were introduced after magnetization. SEM showed that the surface of MAGCNTs was rough and covered with iron oxides. The adsorption properties of MAGCNTs for enrofloxacin were studied by HPLC/UV. The results showed that the adsorption rate of 5 mg/L enrofloxacin on 50 mg MAGCNTs reached 97.27% at 30 ℃ and 30 min. The isotherm adsorption linear fitting of enolfloxacin on MAGCNTs was performed, and the fitting coefficient (r) of Langmuir equation was 0.8612. The elution rate of enrofloxacin on adsorbed equilibrium MAGCNTs was 89.23% with 10 mL 10% ammonia-methanol. The leakage volume of 50 mg/3 mL MAGCNTs SPE column to 5 mg/L enrofloxacin was 20 mL, and the adsorption capacity of MAGCNTs for enrofloxacin was 2 mg/g.
Key words: multi wall carbon nanotubes (MWCNTs); magnetic multi wall carbon nanotubes (MAGCNTs); prepare; characterize; enrofloxacin; adsorption
引用本文：王栋, 张雅明, 刘富永, 等. 磁性多壁碳纳米管的制备及对恩诺沙星的吸附性能[J]. 化学试剂, 2020, 42(3): 232-237.
磁性纳米Fe-S复合材料的制备及其对Cr(VI)的处理性能研究
高卫民*1, 2，程寒飞1, 2，詹茂华1, 2，张志杨1
（1. 中冶华天南京工程技术有限公司，江苏 南京 210019；
2. 中冶华天工程技术有限公司，安徽 马鞍山 243005）
摘要：通过“一步法”制备了磁性纳米Fe-S复合材料，测试其粒径分布，并用Ｘ-射线衍射（XRD）和傅里叶红外光谱（FT-IR）等对其结构进行表征，初步探讨磁性纳米Fe-S复合材料组成，研究了pH值、添加量和盐对磁性纳米Fe-S复合材料处理Cr(VI)性能的影响。结果表明磁性纳米Fe-S复合材料是由四氧化三铁（Fe3O4）和硫化亚铁（FeS）复合而成的材料，平均粒径为284.8 nm，磁分离性好；磁性纳米Fe-S复合材料对Cr(VI)有较好的吸附还原处理效果，添加量为20 mg/L处理浓度为2 mg/L的Cr(VI)废液30 min即可达到去除率98%以上；且磁性纳米Fe-S复合材料在酸性体系中处理性能好于碱性体系；盐对磁性纳米Fe-S复合材料处理Cr（VI）的性能几乎没有影响。
关键词：磁性；纳米Fe-S复合材料；Cr(VI)废液；吸附；还原
中图分类号：X506 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Magnetic Nano-Fe-S Composite and Its Treatment Performance of Cr(VI) GAO Wei-min*1, 2, CHENG Han-fei1, 2, ZHAN Mao-hua1, 2, ZHANG Zhi-yang1 (1. MCC Nanjing Huatian Engineering & Technology Corporation, Nanjing 210019, China; 2. MCC Huatian Engineering & Technology Corporation, Maanshan 243005, China), Huaxue Shiji, 2020, 42(3)
Abstract: Magnetic nano-Fe-S composites were prepared by one-step method, and their particle size distribution was tested. Their structures were characterized by X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). The composition of magnetic nano-Fe-S composites was preliminarily discussed. The effects of pH value, addition amount and salt on the treatment of Cr (VI) properties of magnetic nano-Fe-S composites were studied. The results showed that the magnetic nano-Fe-S composite was composed of iron tetroxide (Fe3O4) and ferrous sulfide (FeS), with an average particle size of 284.8 nm and good magnetic separation. The magnetic nano-Fe-S composite had a good adsorption and reduction effect on Cr (VI), and the removal rate of the magnetic nano-Fe-S composite could reach more than 98% after 30 minutes with the addition of 20 mg/L to treat the waste liquid containing 2 mg/L of Cr (VI). The treatment performance of the material in acidic system was better than that in alkaline system. Salt had little effect on the treatment performance of Cr (VI) by magnetic nano-Fe-S composite.
Key words: magnetic; nano-Fe-S composite; Cr (VI) waste; adsorption; reduction
引用本文：高卫民，程寒飞，詹茂华，等. 磁性纳米Fe-S复合材料制备及其对Cr(VI)的处理性能研究[J]. 化学试剂, 2020, 42(3): 238-243。
含三氟甲基或3,4,5-三甲氧基二苯乙烯腈衍生物的制备
及其活性研究
刘漫钰，金慧玲，刘新，陈志豪，田玉顺*
(延边大学 药学院，吉林 延吉 133002)
摘要：以4-三氟甲基苯甲酸和3,4,5-三甲氧基苯甲酸为原料合成出2-(4-(三氟甲基)苯基)乙腈和2-(3,4,5-三甲氧基苯基)乙腈，将其作为中间体和几种醛类合成一系列含4-三氟甲基及3,4,5-三甲氧基二苯乙烯腈衍生物。所合成的化合物通过氢谱、碳谱与高分辨质谱进行表征后用MTT法在12种细胞上测得其细胞增殖抑制率，其中(Z)-3-(4-丙氧基苯基)-2-(3,4,5-三甲氧基苯基)丙烯腈显示最好的抗癌活性及选择性抑制活性，经进一步研究发现通过抑制细胞迁移与抑制集落形成达到抗癌活性，具有进一步开发研究的价值。
关键词：二苯乙烯腈衍生物；MTT法；迁移实验；集落形成实验；选择性抗癌活性
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Pharmacological Evaluation of Diphenylacrylonitrile-bearing Trifluoromethyl or 3,4,5-Trimethoxy Group(s) LIU Man-yu, JIN Hui-ling, LIU Xin, CHEN Zhi-hao, TIAN Yu-shun* (College of Pharmacy, Yanbian University, Yanji 133002, China), Huaxue Shiji, 2020, 42(3)
Abstract: Intermediates 2-(4-(trifluoromethyl)phenyl)acetonitrile and 2-(3,4,5-trimethoxyphenyl)acetonitrile were synthesized using 4-(trifluoromethyl)benzoic acid and 3,4,5-trimethoxybenzoic acid as the starting materials respectively. Then reacted with kinds of aldehyde to synthesized a series of diphenylacrylonitrile-bearing trifluoromethyl or 3,4,5-trimethoxy group(s), and then characterized with 1H NMR, 13C NMR and HRMS and the anti-proliferatory activities were evaluated by MTT assay against 12 cell lines. The results indicated that (Z)-3-(4-propoxyphenyl)-2-(3,4,5-trimethoxyphenyl)acrylonitrile expressed the best anti-tumor activity and the best selectivity. Further studies have shown that it achieved anti-tumor activity by inhibiting cell migration and colony-formation with treatment, and has further development value.
Key words: diphenylacrylonitrile derivatives; MTT assay; migration assay; colony-forming assay; selective anti-tumor activity
引用本文：刘漫钰, 金慧玲, 刘新, 等. 含三氟甲基或3,4,5-三甲氧基二苯乙烯腈衍生物的制备及其活性研究[J]. 化学试剂, 2020, 42(3): 244-249.
2-甲基-3-甲氧基苯甲酰肼衍生物酰腙的合成与活性研究
王晓雅*，黄婷，孙安霞
（安康学院化学化工学院，陕西安康725000）
摘要：酰腙类化合物具有强且广泛的生物活性，在医药及农药领域都有较为深入的研究报道。以合成农药甲氧基虫酰肼杀虫剂的中间体2-甲基-3-甲氧基苯甲酸为原料，经过酯化反应，再和水合肼反应得到酰肼，进一步与芳香醛反应合成出了4种未见文献报道的酰腙化合物。所得化合物抑制小麦赤霉菌、玉米弯胞病菌、马铃薯干腐病菌的活性研究表明：苄亚甲基的苯环上含活化基CH3的酰腙抑菌活性明显低于含吸电子基溴原子的酰腙抑菌活性，并且邻溴苯亚甲基的酰腙抑菌活性明显要强于溴原子处于间位的。
关键词：甲氧基苯甲酰肼；酰腙；合成；抑菌活性；小麦赤霉菌；玉米弯胞病菌；马铃薯干腐病菌
中图分类号：O622.65 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Activity of 2-Methyl-3-methoxy BenzohydrazideDerivativesWANG Xiao-ya*, HUANG Ting, SUN An-xia (School of Chemistry and Chemical Engineering, Ankang University, Ankang 725000, China), HuaxueShiji, 2020, 42(3)
Abstract:Acylhydrazone compounds have strong and extensive biological activities and have been reported in the field of medicine and pesticides.The intermediate of the synthetic pesticide methoxyhydrazine 2-methyl-3-methoxybenzoic acid was used as raw material，and reacted with hydrazine hydrate to form 2-methyl-3-methoxybenzoyl hydrazide, then reacted with methylbenzaldehyde and bromobenzaldehyde to formfour new hydrazone compounds.Bacteriostatic activity was studied that: benzyl methylene containing activation on the benzene ring of bacteriostatic activity was lower than that of the acyl-hydrazone CH3 containing electronic base of bromine atom absorption acylhydrazone, antibacterial activity, and its adjacent bromine benzylidene acyl hydrazone bacteriostatic activity was obviously superior to the bromine atoms in a bit.
Key words: Methoxy benzoyl hydrazide ; Acyl hydrazone ; Synthesis ; Antibacterial activity ; Wheat gibberellus ; Campylobacter of maize ; Potato dry rot bacteria
引用本文：王晓雅, 黄婷, 孙安霞. 2-甲基-3-甲氧基苯甲酰肼衍生物酰腙的合成与活性研究[J]. 化学试剂, 2020, 42(3):250-253.
高效液相色谱手性冠醚固定相的制备研究
徐文，何义娟，张鹏，艾萍，袁黎明*
（云南师范大学 化学化工学院，云南 昆明 650500）
摘要：冠醚是具有空腔且有非常好的识别能力的大环聚醚化合物。本文系统地研究了将R-(3,3'-二溴基-1,1'-二萘基)-20-冠-6涂覆在粗制硅胶、精制硅胶、大孔硅胶、苯环修饰粗制硅胶、苯环修饰精制硅胶、苯环修饰大孔硅胶、十八烷基修饰粗制硅胶、十八烷基修饰精制硅胶、十八烷基修饰大孔硅胶、氨丙基修饰粗制硅胶表面制备10种不同支撑体的手性固定相用于苯甘氨酸和对羟基苯甘氨酸的拆分研究。研究表明大孔硅胶以及氨丙基修饰硅胶直接涂覆冠醚的柱皆不能拆分这2种氨基酸，另外硅胶表面是否修饰、以及修饰的基团对手性柱的分离能力具有影响，不同来源的硅胶也强烈地影响着手性柱的拆分效率。
关键词：冠醚；硅胶；手性固定相；高效液相色谱；手性识别
中图分类号：0657.7 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Chiral Crown Ether Stationary Phase in HPLC XU Wen, HE Yi-juan, ZHANG Peng, AI Ping, YUAN Li-ming* (School of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China), Huaxue Shiji, 2020, 42(3)
Abstract: Crown ether is a macrocyclic polyether compound with a cavity and very good recognition ability. This paper systematically studied the coating of R-(3,3'-dibromo-1,1'-dinaphthyl)-20-crown-6 on ten kinds of silica gels for the resolution of phenylglycine and p-hydroxyphenylglycine. The experimental results have shown that amino group of aminopropyl silica gel affects the chiral recognition of crown ethers. In addition, the enantioselective resolution of crown ether columns can be strongly effected by the silica gels modified with different functional group and prepared with different methods. .
Key words: crown ether; silica gel; chiral stationary phase; high performance liquid chromatography; chiral recognition
引用本文：徐文, 何义娟, 张鹏, 等. 高效液相色谱手性冠醚固定相的制备研究[J]. 化学试剂, 2020, 42(3):254-258.
改性香菇多糖铁(Ⅲ)配合物的制备及其应用研究
张霞忠，陈美君，李大林，宋佳宝，王丹，周文俊，翟好英*
（内江师范学院 化学化工学院，四川 内江 641112）
摘要：采用95%乙醇对香菇粉进行脱脂预处理后，再用超声波法提取香菇多糖（LNT）。为提高其水溶性，采用过氧化氢氧化法对提取的香菇多糖进行化学改性。探究了过氧化氢浓度、pH值、改性时间等因素对改性香菇多糖（MLNT）水溶性的影响。利用傅里叶变换红外光谱和X射线粉末衍射技术对改性香菇多糖进行了结构表征。结果表明，改性后香菇多糖的分子结构发生改变，其水溶性以及与Fe (Ⅲ)的配位能力增强。采用共振散射技术研究了改性香菇多糖与三价铁离子的配位作用，并考察了反应介质、pH值、改性多糖用量等因素的影响。在最优实验条件下，在0.40 ～ 6.0 μg/mL范围内，体系的共振散射强度变化值DI与Fe (Ⅲ)浓度之间有一定的线性关系，其检出限为0.81 ng/mL。据此，分别分析测定了矿渣和布袋灰中的铁含量，相对标准偏差为3.8%和3.4%，回收率为102%和112%。
关键词：超声法；香菇多糖；改性；铁(Ⅲ)；共振散射法
中图分类号：TQ914.1；O657. 3 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Modified Lentinan-Fe (Ⅲ) Complexes and Its Application ZHANG Xia-zhong, CHEN Mei-jun, LI Da-lin, ZOU Zi-li, GUO Han-long, SONG Jia-bao, WANG Dan, ZHOU Wen-jun, ZHAI Hao-ying* (College of Chemistry and Chemical Engineering, Neijiang Normal University, Neijiang 641112, China), Huaxue Shiji, 2020, 42(3)
Abstract: Lentinan (LNT) was extracted from Lentinus edodes by ultrasonic method after pretreatment with 95% ethanol. To improve its water solubility, LNT was chemically modified with hydrogen peroxide. The effects of hydrogen peroxide concentration, pH value and modification time on the water solubility of modified lentinan (MLNT) were investigated. The structure of MLNT was characterized by FTIR and XRD. The results showed that the molecular structure of MLNT was changed, and its water solubility and coordination ability with Fe (Ⅲ) were enhanced. The coordination between MLNT and ferric ions was studied by resonance scattering technique, and the effects of reaction medium, pH value and MLNT dosage were investigated, respectively. Under the optimal experimental conditions, there was a linear relationship between the resonance scattering intensity (ΔI) and Fe (Ⅲ) concentration in the range of 0.40～6.0 μg/mL, and the detection limit was 0.81 ng/mL. Therefore, iron content in slag and bag ash was analyzed, respectively. The relative standard deviations were 3.8% and 3.4%, and the recoveries were 102% and 112%, respectively.
Key words: ultrasonic method; lentinan; modification; iron (Ⅲ); resonance scattering method
引用本文：张霞忠，陈美君，李大林, 等. 改性香菇多糖铁(Ⅲ)配合物的制备及其应用研究[J]. 化学试剂, 2020, 42(3): 259-263.
卤代甘脲衍生物的合成及杀菌活性
王治国
（湖北理工学院 化学与化工学院 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：为寻求高效且环保的新型杀菌剂，分别以2,4-(1,3-亚丙基)甘脲和2,4-(1,3-邻苄二基)甘脲为原料，通过氯代、溴代和碘代反应获得2类6种二卤代甘脲衍生物。采用菌落计数法和菌丝生成速率法测试目标衍生物对大肠杆菌、枯草杆菌、金黄色葡萄球菌、酵母菌、链球菌和放线菌等6种常见菌种的杀菌率和EC50值，结果表明卤代甘脲衍生物都具有良好的杀菌活性，且遵照碘取代甘脲>溴取代甘脲>氯取代甘脲的规律。
关键词：甘脲；卤代反应；衍生物；合成；杀菌剂；杀菌活性
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Fungicidal Activity of Halogenated Glycoluril Derivatives WANG Zhi-Guo (Hubei Key Laboratory of Mine Environmental Pollution Control & Remediation, School of Chemistry and Chemical Engineering, Hubei Polytechnic University, Huangshi 435003, China), Huaxue Shiji, 2020, 42(3)
Abstract: To search for new fungicides with high-effective and environmental advantages, two kinds of six dihalogenated glycoluril derivatives were synthesized according to chlorination reaction, bromination reaction and iodination reaction using 2,4-(1,3-propylidene) glycoluril and 2,4-(o-benzyl) glycoluril as starting materials, respectively. Based on dihalogenated glycoluril derivatives on six common species escherichia coli, bacillus subtilis, staphylococcus aureus, saccharomyces cerevisiae, streptococcus and actinomycete, colony counting method was used for determining sterilizing rate, and mycelium formation rate method was used for obtaining the EC50 values. The result showed that the target halogenated glycoluril derivatives have good fungicidal activity, followed the regularities of iodinated glycoluril, brominated glycoluril and chlorinated glycoluril.
Key words: glycoluril; halogenate; derivatives; synthesis; fungicide; fungicidal activity
引用本文：王治国. 卤代甘脲衍生物的合成及杀菌活性[J].化学试剂，2020, 42（3）：264-268.
药用植物内生真菌多糖研究进展
乔新荣 叶润
（信阳农林学院 生物与制药工程学院，河南 信阳 464000）
摘要：真菌多糖具有多种生理活性，广泛应用于医药、农业、食品等行业。基于植物内生真菌生长过程中会产生与宿主相同或相似的生理活性成分，药用植物生理活性的多样性赋予了其内生真菌活性的多样性，药用植物内生真菌是开发新型天然活性多糖的资源宝库。综述了近些年来关于药用植物内生真菌多作为诱导子调节植物生长、代谢及其体外抗氧化、抗肿瘤、抑菌、降血糖等多种生理作用的研究进展。并对今后的研究方向进行展望，以期为药用植物内生真菌多糖的开发利用提供参考。
关键词: 内生真菌；多糖；诱导子；抗氧化活性；抗肿瘤活性
中图分类号：Q936 文献标识码：A 文章编号：0258-3283（2020）
Recent Advances of Polysaccharides from Medicinal Plant Endophytic Fungi QIAO Xin-rong YE Run（College of Biological &Pharmaceutical Engineering, Xinyang College of Agriculture and Forestry, Xinyang 464000, China）, Huaxue Shiji, 2020, 42(3)
Abstract: Fungal polysaccharides have a variety of physiological activities and are widely used in medicine, agriculture, food and other industries. Based on the fact that plant endophytic fungi produce the same or similar physiological active components as the host during their life cycle, plant endophytic fungi are endowed with the diversity of physiological activities because of the physiological characteristic of their host. endophytic fungi of medicinal plants are a treasure house of resources for the development of new natural active polysaccharides. This paper reviewed the research progress of various physiological effects of medicinal plant endophytic fungal polysaccharides including as elicitor of growth and bioactive metabolite biosynthesis, antioxidant, anti-tumor，antimicrobial and hypoglycemic activity in vitro, and finally the future research direction was prospected. It will provide the reference for exploitation and utilization of endophytic fungal polysaccharides.
Key words: endophytic fungi; polysaccharides; Elicitor; antioxidant activity; anti-tumor activity
引用本文：乔新荣，叶润. 药用植物内生真菌多糖研究进展[J]. 化学试剂, 2020, 42(3):269-274.
不同产地、不同种属黄精的红外光谱鉴别研究
高韵1，司雨柔1，王元媛1，解玫莹1，庄新港2，程旺兴*1
(1.安徽中医药大学 药学院 现代中药安徽省工程技术研究中心，安徽 合肥 230012；
2.中国电子科技集团公司第四十一研究所，安徽 蚌埠 233010)
摘要：采用傅里叶红外光谱技术结合二阶导数光谱对不同产地的黄精进行鉴别。研究结果表明，不同产地多花黄精的红外光谱图在整体上比较相似，其主要吸收峰均在3270、2933、1623、1411、1372、1319、1269、1103、1019、926、865、815 cm-1附近，但吸收峰的位置、峰强度等方面存在明显差异，在1018 cm-1附近是糖类的特征吸收峰，由红外光谱图可推测安徽省池州市、岳西县、江西省宜春市多花黄精中糖类成分含量较高，湖北省黄冈市、安徽省黄山区、石台县次之，安徽省休宁县、金寨县相对较少。6种黄精属植物的红外光谱图在吸收峰的位置、形状、强度等方面均有差异，故可推测黄精属不同植物在化学成分及含量上均存在明显差异。二阶导数图呈现出许多原始图谱中被掩盖谱峰的变化特征，将谱图间的差异更为明显得表现出来，进一步提高了谱图的分辨率，与普通红外光谱图相比，二阶导数红外光谱图进一步直观地验证了上述结果。
关键词：黄精；不同产地；不同种属；鉴别；傅里叶红外光谱法；二阶导数光谱
中图分类号：O 657.33 文献标识码：A 文章编号：0258-3283（2020）
Identification of Flavin from Different Habitats and Species by Infrared Spectroscopy GAO Yun1, SI Yu-rou1, WANG Yuan-yuan1, XIE Mei-ying1, ZHUANG Xing-gang2, CHENG Wang-xing*1 (1.Anhui Engineering Technology Research Center of Modern Chinese, School of Pharmacy and Medicine, Anhui University of Chinese Medicine, Hefei 230012, China; 2. The 41st Research Institute of CETC, Bengbu 233010, China), Huaxue Shiji, 2020, 42(3)
Abstract: Fourier transform infrared spectroscopy(FT-TR) and second derivative infrared spectroscopy are used to study Polygonatum cyrtonema Hua. The results showed that the main absorption peaks are in the vicinity of 3270, 2933, 1623, 1411, 1372, 1319, 1269, 1103, 1019, 926, 865 and 815 cm-1. The FT-IR spectra of Polygonatum cyrtonema Hua from different origins are similar, but the intensity and position of the absorption peaks are different. The absorption peak near 1018 cm-1 is the characteristic absorption peak of glucose. From the infrared spectrum, it can be inferred that the content of glucose components in Chizhou, Yuexi, and Yichun is high. Huanggang, Huangshan, Shitai are less. Xiuning and jinzhai are relatively the least. The infrared spectra of six species of Polygonatum Mill. are different in the position, shape and intensity of absorption peaks, so it can be inferred that there are obvious differences in chemical composition and content among different plants of Polygonatum Mill. The second derivative spectrum can spectrally strip the overlapping peaks in the original spectrum, further improving the resolution of the spectrum. Compared with the ordinary infrared spectra spectrum, the second derivative infrared spectrum further intuitively verify the above results.
Key words: Polygonatum cyrtonema Hua; different producing areas; different species; identify; fourier transform infrared spectroscopy; second derivative infrared spectroscopy
引用本文：高韵，司雨柔，王元媛，等. 不同产地、不同种属黄精的红外光谱鉴别研究[J]. 化学试剂, 2020, 42(3): 275-279.
超高效液相色谱-串联质谱法筛查血液中29种常见毒品
白利文1，王瑞花*2，于忠山2，常靖2，王爱华2
（1.中国人民公安大学 刑事科学技术学院，北京 100038；2.公安部物证鉴定中心，北京 100038）
摘要：以超高效液相色谱-三重四级杆质谱法建立了血液中苯丙胺、甲基苯丙胺、MDA、MDMA、MDEA、麻黄碱、氯胺酮、卡西酮、甲卡西酮、4-甲基甲卡西酮、吗啡、O6-单乙酰吗啡、可待因、乙酰可待因、海洛因、可卡因、苯甲酰爱康宁、四氢大麻酚、乙酰芬太尼、丁酰芬太尼、MCPP、TFMPP、地芬诺酯、美沙酮、舒芬太尼、曲马多、丁丙诺啡、哌替啶、芬太尼共29种常见毒品的筛查方法，血液样品经4%磷酸水溶液稀释后，震荡、离心，取上清液过Oasis PRiME HLB固相萃取柱，淋洗，洗脱后接收洗脱液，氮吹至干、定容，过膜后，装瓶、进样分析。采用ACQUITY UPLC HSS C18 色谱柱(150 mm×2.1 mm，1.8 μm)，流动相为乙腈-5 mmol甲酸铵-甲酸水溶液（pH 3），电喷雾电离，正离子模式，质谱多反应监测(MRM)。检出限在0.1～50 ng/mL，定量限在0.5～80 ng/mL，回收率介于71.3%～96.8%之间，精密度在2.8%～11.4%范围内，提供的筛查方法灵敏度高、重现性好，样品前处理简便、快捷，适用于实际血液样品中常见毒品成分的筛查分析。
关键词：超高效液相色谱-串联质谱；毒品；筛查；血液；固相萃取
中图分类号：O652.1 文献标识码：A 文章编号：0258-3283（2020）
Ultra-high Performance Liquid Chromatography-Tandem Mass Spectrometry Screening of 29 Common Drugs in the Blood BAI Li-wen1, WANG Rui-hua*2, YU Zhong-shan2, CHANG Jing2, WANG Ai-hua2 (1. College of Forensic Science, People’s Public Security University of China, Beijing 100038, China；2. Public Security Department Material Identification Center, Beijing 100038, China), Huaxue Shiji, 2020, 42(3)
Abstract: In this work, screening methods for 29 common drugs such as amphetamine, methamphetamine, MDA, MDMA, MDEA, ephedrine, ketamine, cathinone, methcathinone, 4-methylmethcathinone, morphine, O6-acetylmorphine, codeine, acetylcodeine, heroin, cocaine, benzoylecgonine, tetrahydrocannabinol, acetylfentanyl, butyryl fentanyl, MCPP, TFMPP, diphenoxylate, methadone, sufentanil, tramadol, buprenorphine, meperidine and fentanyl were established by ultra performance liquid chromatography-triple quadrupole mass spectrometry. Blood samples were diluted with 4% phosphoric acid solution, then shaken and centrifuged. The supernatant was taken through an Oasis PRiME HLB solid phase extraction column, and the eluent was received after rinsing and elution. The supernatant was blown to dry with nitrogen and fixed to volume. After passing through the membrane, put the solution into a special vial for liquid chromatography mass spectrometry and analysed. The method used ACQUITY UPLC HSS C18 column (150 mm × 2.1 mm, 1.8 μm). Mobile phase was acetonitrile-water / formic acid / ammonium formate (5 mmol, pH 3). The method used electrospray ionization, positive ion scanning mode and multiple reaction options ion monitoring mode (MRM) detection. The detection limit of the method was 0.1～50 ng/mL. The limit of quantification was 0.5～80 ng/mL. The recovery rate was between 71.3%～96.8%, and the precision was in the range of 2.8%～11.4%. The screening method provided in this work had high sensitivity and good reproducibility. The sample preparation was simple and fast, and it was suitable for screening and analysis of common drug components in actual blood samples.
Key words: UPLC-MS/MS; screening; drug; blood; SPE
引用本文：白利文, 王瑞花, 于忠山, 等. 超高效液相色谱-串联质谱法筛查血液中29种常见毒品[J]. 化学试剂, 2020, 42(3): 280-284.
差示扫描量热熔点分析法的应用性分析
吴锐1，林兰*2，严菁2，刘万卉1，刘毅*2
(1.烟台大学 药学院，山东 烟台 264005；2.中国食品药品检定研究院，北京 102629)
摘要：选择不同温度段熔融的5个代表性品种、国内外不同来源的13个法定熔点标准物质作为研究对象，进行差示扫描量热法和毛细管法两种熔点分析方法的关联性研究，并进一步开展差示扫描量热熔点分析法关键参数的应用性分析。研究表明，毛细管法的熔点分析结果一般延后1～2 ℃；差示扫描量热熔点分析法的准确性和精密度更好，并且推荐采用10 ℃/min的升温速率参数，而升温起点、气体流量等方法参数影响较小。质量分析还证实，我国药典熔点标准物质已经具备国际竞争力。
关键词：熔点；差示扫描量热法；毛细管法；升温速率；化学标准物质
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2020）
Applicability Studies of Differential Scanning Thermal Melting Point Analysis WU Rui1, LIN Lan*2, YAN Jing2, LIU Wan-hui1, LIU Yi*2 (1.School of Pharmacy, Yantai University, Yantai 264005, China; 2.National Institutes for Food and Drug Control, Beijing 102629, China), Huaxue Shiji, 2020, 42(3)
Abstract：The purpose of the study was to evaluate the correlation of differential scanning calorimetry (DSC) and capillary method as melting point measurements. Study objects included thirteen official chemical reference substances (CRS) for melting point from different domestic and foreign sources, representing five CRS categories of different melting temperature ranges. Applicability analysis was further carried out on the key parameters of DSC melting point measurement. The results demonstrated that melting points analyzed by capillary method were generally delayed by 1～2℃, and that the accuracy and precision of DSC method were better. We recommended the DSC melting point analysis as the preferred method with heating rate of 10 ℃/min as basic parameter value of DSC method. Impacts of Other parameters such as initial temperature and gas flow rate were not significant. Quality assessment also indicated that the Chinese official CRS for melting point were comparable to current international CRS.
Key words：melting point; differential scanning calorimetry; capillary method; heating rate; chemical reference substance
引用本文：吴锐, 林兰, 严菁, 等. 差示扫描量热熔点分析法的应用性分析[J]. 化学试剂, 2020, 42(3):285-290.
微波消解-电感耦合等离子体发射光谱法准确测定原油中S、Ni和V
任丹华1, 2，张艾蕊1，王海*1，王海峰1，王梅玲1，韩艳祥1, 2，张鑫2
（1.中国计量科学研究院，北京 100029；2.中国石油大学（北京） 化学工程与环境学院，北京 102249）
摘要：开展了微波消解结合电感耦合等离子体发射光谱（ICP-OES）分析测量原油中有害元素（S、Ni和V）的方法研究。通过优化样品微波消解前处理条件（样品量、酸体系、消解程序等），实现了4种不同来源、有害元素含量不同的原油样品的完全消解。ICP-OES测量结果表明：原油中Ni和V元素的检测限介于0.34～0.45 μg/kg、定量限介于1.14～1.51 μg/kg，原油中S元素的检测限和定量限分别为2.72、9.07 μg/kg，原油中3种元素测量重复性均小于2.8%。燃料油和原油有证标准物质分析测量结果表明，3种元素的回收率均介于98%～104%，说明了所建立微波消解结合ICP-OES方法的准确可靠性。所建立的原油中S、Ni和V元素的准确测量方法，能够用于原油样品中有害元素的质量控制以及相应标准物质的定值。
关键词：电感耦合等离子体发射光谱；原油；有害元素；微波消解；前处理
中图分类号：TE622.1 文献标识码：A 文章编号：0258-3283（2020）
Determination of Sulfur, Nickel and Vanadium in Crude Oil by Microwave Digestion-Inductively Coupled Plasma Optical Emission Spectrometry REN Dan-hua1,2, ZHANG Ai-rui1, WANG Hai*1, WANG Hai-feng1, WANG Mei-ling1, HAN Yan-xiang1, 2, ZHANG Xin2 (1.National Institute of Metrology, Beijing 100029, China; 2.College of Chemical Engineering and Environment, China University of Petroleum (Beijing), Beijing 102249, China), Huaxue Shiji, 2020, 42 (3)
Abstract：A analytical method of microwave acid digestion combined with inductively coupled plasma optical emission spectrometry (ICP-OES) had been used to determine the content of harmful elements including S, Ni and V in crude oils. Four different crude oils with different contents of interested elements were completely digested by optimizing of sample amount, acid system and microwave digestion procedures. The ICP-OES analytical results of crude oils indicated the limit of detection of Ni and V elements ranging from 0.34 to 0.45 μg/kg, the limit of quantitation of Ni and V elements ranging from 1.14 to 1.51 μg/kg, the limit of detection of S element being 2.72 μg/kg and the limit of quantitation of S element being 9.07 μg/kg. The measurement repeatability of three elements was less than 2.8% for their ICP-OES analyses. The ICP-OES results of two certified reference materials for fuel oil and crude oil showed that the recovery rates of three elements were between 98 % and 104 %, which verified the accuracy and reliability of the developed analytical method of microwave acid digestion combined with ICP-OES. This work had established a good technical foundation for the quality control of crude oil and the development of certified reference materials for three elements in crude oil in the future.
Key words：ICP-OES；crude oil；harmful elements；microwave digestion；pretreatment
引用本文：任丹华, 张艾蕊, 王海, 等. 微波消解-电感耦合等离子体发射光谱法准确测定原油中S、Ni和V [J]. 化学试剂, 2020, 42(3): 291-294.
藤茶中抗氧化成分--二氢杨梅素在碱性溶液中的自氧化作用机理
姚元勇*，王云洋，何来斌，袁立军，陈仕学*
(铜仁学院，材料与化学工程学院，应用化学研究所，贵州 铜仁 554300)
摘要 目的：为了进一步研究具有优异抗氧化能力的天然药物--二氢杨梅素，在碱性溶液中结构不稳定性原因及自氧化作用机制。方法：实验分别采用了HPLC色谱法、1H-NMR、13C-NMR、ESI-Ms及电子顺磁共振（EPR）技术，对二氢杨梅素在不同碱性环境中的行为变化进行研究。结论：实验结果表明：首先，二氢杨梅素分别在相同条件下，不同碱性的缓冲溶液（buffer：PBS，pH =7.4；Tris-HCl，pH=8.5；Borax-NaOH，pH= 9.4）中，室温搅拌，均发现有杨梅素成分生成，并经1H-NMR、13C-NMR和ESI-Ms技术进行结构表征确认。其次，分别向等量的二氢杨梅素不同缓冲溶液（buffer：PBS，pH =7.4；Tris-HCl，pH=8.5；Borax-NaOH，pH= 9.4）中，加入DMPO自由基捕获剂，经电子顺磁共振（EPR）技术，均能检测到DMPO-O2.-加合物的特征峰存在，且强度不同。相反，在氮气的条件下，其DMPO-O2.-加合物的特征峰强度大幅度降低。该实验结果充分地证明了二氢杨梅素在有氧且碱性溶液中，会导致自身分子结构不稳定，而产生超氧阴离子自由基的作用机制。
关键词：二氢杨梅素；碱性缓冲溶液；超氧阴离子自由基；作用机制
中图分类号：R914.5 文献标志码： A 文章编号：
Exploring self-oxidative mechanism of Dihydromyricetin as an antioxidant isolated from Vine tea in alkaline solutions YAO Yuan-yong *, WANG Yun-yang, HE Lai-bing, YUAN Li-jun, CHEN Shi-xue* (Institute of applied chemistry; School of material and chemical engineering, Tongren university, Tongren 554300, (P.R) China.)
Abstract： Objective: to further understand cause of instability and self-oxidative mechanism of Dihydromyricetin(DMY) as an excellent natural antioxidant in alkaline surroundings. Methods: Experiments were carried out to study behavioral effect of Dihydromyricetin(DMY) in varied alkaline solution, and observed by Liquid Chromatography (HPLC), Nuclear Magnetic Resonance (1H-NMR and 13C-NMR), ESI-Ms and Electron Paramagnetic Resonance (EPR) technology. Results and Conclusions: The results demonstrated that, firstly, when Dihydromyricetin(DMY) was transferred to varied alkaline buffer solutions(buffer：PBS，pH =7.4；Tris-HCl，pH=8.5；Borax-NaOH，pH= 9.4), respectively, with stirring at room temperature, it was found that there is a component, by means of isolation and purification by column chromatography, subsequently, was confirmed to be Myricetin by 1H-NMR, 13C-NMR and ESI-Ms. Secondly, in mechanism of behavioral effect of Dihydromyricetin in alkaline buffer solution, the superoxide anion free radical generated from DMY in air-saturated alkaline buffer solution(buffer：PBS，pH =7.4；Tris-HCl，pH=8.5；Borax-NaOH，pH= 9.4), was determined by typical signals of DMPO-O2.- adduct, using Electron Paramagnetic Resonance (EPR) technology. Adversely, when DMY was dissolved in nitrogen-saturated alkaline buffer solution, the intensity of typical signals of DMPO-O2.- was reduced dramatically. Therefore, relying on above data, it indicated well that DMY in alkaline solution enable to generate reactive oxygen species of superoxide anion free radical. Resultly, it is adequately witnessed that behavioral effect of dihydromyricetin in alkaline solution conforms to self-oxidation process, with generating superoxide anion.
Key words：Dihydromyricetin; alkaline buffer solution; superoxide anion free radical; mechanism
引用本文：姚元勇，王云洋，何来斌, 等. 藤茶中抗氧化成分--二氢杨梅素在碱性溶液中的自氧化作用机理[J]. 化学试剂, 2020, 42(3): 295-300.
复配表面活性剂体系对漆酶降解菲和吲哚的影响研究
叶俊a, b，任大军*a, b，刘海a, b ，张晓晴a, b，张淑琴a, b，吴健a, b，李胜a, b
（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）
摘要：为了研究复配表面活性剂体系对漆酶降解有机污染物的影响机理，选用聚氧乙烯月桂醚（Brij-35）和聚山梨酯（Tween-80）复配体系，将漆酶作用于降解多环芳烃菲和氮杂环化合物吲哚，考察了菲和吲哚在不同pH、温度、表面活性剂浓度、漆酶活力浓度4种条件下的降解率，并进行降解动力学分析。结果表明，降解反应最优为pH 3.5，最佳反应温度为40 ℃，酶活力浓度最佳选择为4 U/mL。表面活性剂浓度分别为1.2、1.0 mmol/L时，菲和吲哚的降解率最高。表面活性剂的加入促进了漆酶对菲和吲哚的降解，菲和吲哚的降解符合一级动力学方程，且降解速率常数K（吲哚）＞K（菲）＞K（吲哚，空白）＞K（菲，空白）。研究结果为漆酶在废水中去除持久性有机污染物的应用提供了参考。
关键词：漆酶；表面活性剂；复配体系；菲；吲哚；降解；动力学
中图分类号：X506 文献标识码：A 文章编号：0258-3283（2020）
Study on the effect of compound surfactant system on laccase degradation of phenanthrene and Indole YE Juna, b, REN Da-jun*a, b, LIU Haia, b, ZHANG Xiao-qinga, b, ZHANG Shu-qina, b, WU Jiana, b, LI Shenga, b (a. School of Resource and Environment Engineering, b. Key Laboratory of High-efficiency Utilization and Agglomeration of Metallurgical Mineral Resources in Hubei Province, Wuhan University of Science and Technology , Wuhan 430081, China), Huaxue Shiji, 2020, 42(3)
Abstract: In order to study the mechanism of complex surfactant system on the degradation of organic pollutants by laccase, we choosed the polyethylene glycol monooleyl ether (Brij-35) and polysorbate 80(Tween-80) complex system, used laccase to degrade phenanthrene and indole, investigated the degradation rate under four conditions of different pH, temperature, surfactant concentration and laccase activity concentration and carried out the degradation kinetic analysis. The results showed that the optimum pH of degradation reaction was 3.5, the optimal reaction temperature was 40 °C, and the optimal concentration of enzyme activity was 4 U/mL. When the surfactant concentration was 1.2 mmol/L and 1.0 mmol/L respectively, the degradation rates of phenanthrene and indole were the highest. The addition of surfactant promoted the degradation of phenanthrene and indole by laccase, the degradation of phenanthrene and indole conforms to the first-order kinetic equation, and the degradation rate constant K(indole) > K(phenanthrene) > K(indole, control) > K(phenanthrene, control). The results provided reference for the application of laccase to remove persistent organic pollutants in wastewater.
Key words: laccase; surfactant ; complex system; phenanthrenne; indole; degradation; dynamics
引用本文：叶俊, 任大军, 刘海, 等. 复配表面活性剂体系对漆酶降解菲和吲哚的影响研究[J]. 化学试剂, 2020, 42(3): 301-306.
4-丁胺-N-氨基吡啶-1,8-萘酰亚胺的合成及金属离子识别作用研究
赵丽娅1, 2, 蒋彩娜1，彭兰兰1，刘汉甫1，辛懋*1
（1. 桂林医学院 药学院, 广西 桂林 541004；2. 河南省医药卫生学校, 河南 平顶山 467000）
摘要: 以4-溴-1, 8-萘酐为起始原料，通过与N-氨基吡啶发生酰化反应制得4-溴-N-氨基吡啶-1, 8-萘酰亚胺后，再与正丁胺缩合得到目标化合物，并以荧光光谱法研究了目标化合物对Cd2+、Cr3+、Cu2+、Fe3+、Sm3+、K+、La3+、Mg2+、Ba2+、Zn2+、Ni2+、Ir3+、Al3+ 13种金属离子的识别作用。结果表明，随着各种金属离子的加入，目标化合物的荧光光谱发生了不同程度猝灭现象；在pH 7.4时，目标化合物对Fe3+的识别作用最优，检出限为2.55×10-3 mol/L，络合常数为6.02×105 L/mol，表现出良好的选择性。
关键词：金属离子荧光探针；1, 8-萘酰亚胺；合成；识别作用；荧光猝灭效应；结合常数
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Metal Ion Recognition Abilities of 4-Butylimide-N-pyridine Amino-1,8 -naphthalimide ZHAO Li-ya1, 2, JIANG Cai-na1, PENG Lan-lan1, LIU Han-pu1, XIN Mao*1 (1. School of Pharmacy, Guilin Medical University, Guilin 541004, China; 2. Henan Medical and Health School, Pingdingshan 541001, China), Huaxue Shiji, 2020, 42(3)
Abstract: 4-Bromo-N-pyridine amino-1,8-naphthalimide (2) was obtained by the condensation of 1,8-anhydride naphthalene and aminopyridin, and then reacted with butyl amine to afford 4-butylimide-N-pyridine amino-1,8-naphthalimide (3) . Its recognition properties on some metal were measured by fluorescence quenching spectroscopy. The results showed that the metal ions led to different quenching of fluorescence spectroscopy. Compound 3 showed good selective recognition ability on Fe3+ at pH 7.40, with the detection limit of 2.55×10-3 mol/L and the dissociation constant of 6.02×105 L/mol, respectively.
Key words: metal ion fluorescence probe; 1,8-naphthalimide; synthesis; recognition; fluorescence; quenching effect; binding constant
引用本文：赵丽娅, 蒋彩娜, 彭兰兰, 等. 4-丁胺-N-氨基吡啶-1,8-萘酰亚胺的合成及金属离子识别作用研究[J]. 化学试剂, 2020, 42(3):307-310.
一种新型罗丹明pH光学探针的合成及性能研究
李冬梅，杨金清，刘玉芳，保志娟*
（云南农业大学 烟草学院，云南 昆明 650201）
摘要：以罗丹明6G、水合肼及对苯二甲醛为原料设计合成了一种新型pH光学探针（RGP），探针化合物的结构通过核磁共振波谱及电喷雾质谱（ESI-MS）进行确认。研究了该探针在不同pH溶液中紫外-可见吸收光谱的变化。结果显示，该探针本身为无色，加入H+时，探针的溶液颜色变为粉红色，在532 nm波长处有最大吸收，pKa值为4.52。在最佳测量条件下，H+在浓度为5.15×10-5～3.09×10-4 mol/L范围内线性关系良好 (r = 0.9902)。该探针有望发展成为识别H+的高选择性探针。
关键词：pH探针；罗丹明；染料；识别；合成
中图分类号: O657.3 文献标识码: A 文章编号：0258-3283（2020）
Synthesis and Spectral Characterization of A Novel Rhodamine-based pH Probe LI Dong-mei, YANG Jin-qing, LIU Yu-fang, BAO Zhi-juan* (College of Tobacco Science, Yunnan Agricultural University, Kunming 650201, China), Huaxue Shiji, 2020, 42(3)
Abstract: A novel pH spectral probe (RGP) was synthesized by using rhodamine 6G, hydrazine hydrate and 1,4-phthalaldehyde as raw materials. The structure of the target compound was confirmed by NMR and ESI-MS. The UV-Vis spectra properties were studied in solution at different pH value. The results showed that in V（methanol）：V（water）=3:7～1:1 solution, the presence of H+ can induced a strong absorbance of RGP at 532 nm accompanied by a naked-eye color change from colorless to deep pink. The pKa value of probe was 4.52. Under the optimum measurement conditions, there was good linear relationship between the absorbance of RGP and the concentration of H+ in the range of 5.2×10-5～3.1×10-4 mol/L (r = 0.9902). RGP was expected to develop into a highly selective probe for H+.
Key words: pH probe; rhodamine; dye; recognition; synthesis
引用本文：李冬梅, 杨金清, 刘玉芳, 等. 一种新型罗丹明pH光学探针的合成及性能研究[J]. 化学试剂, 2020, 42(3): 311-314.
三种表面活性剂对Fe3O4纳米颗粒的形貌影响
魏茂琼，林昕*，刘宏程，兰珊珊
（云南省农业科学院质量标准与检测技术研究所农业部农产品质量安全风险评估实验室(昆明)，云南昆明 650223）
摘要：选用十六烷基三甲基溴化铵（CTAB）、聚乙烯吡咯烷酮（PVP）、十二烷基磺酸钠（SDS）3种表面活性剂，研究了这3类不同表面活性剂和不同添加量对Fe3O4纳米颗粒的形貌调控作用，利用透射电镜（TEM）对样品进行表征分析，并给出了机理解释。结果证实：1）3种不同的表面活性剂的加入都获得球形或近球形的纳米颗粒。根据TEM及沉积时间的综合分析，3种活性剂的平均粒径比较：SDS<CTAB<PVP，证明加入SDS表面活性剂获得较小的Fe3O4纳米颗粒；2）以CTAB作为表面活性剂，当其用量增加到一定程度，纳米粒径呈现减小的趋势。以SDS和PVP作为表面活性剂，随着SDS和PVP表面活性剂的用量增加，纳米粒径呈现逐渐减小的趋势。对Fe3O4纳米颗粒的制备及应用具有一定的参考价值。
关键词：Fe3O4纳米颗粒；CTAB表面活性剂；PVP表面活性剂；SDS表面活性剂；形貌控制
中图分类号：TQ586.5文献标识码：A文章编号：0258-3283（2020）
Research of Morphology Control of Fe3O4Nanoparticles by Addition of Three SurfactantsWEI Mao-qiong,LINXin*,LIU Hong-cheng, LAN Shan-shan (Laboratory of Quality & Safety Risk Assessment for Agro-Product, Ministry of Agriculture (Kunming), Agri-Food Quality Standard & Testing Technology Institute, Yunnan Academy of Agricultural Sciences, Kunming 650223, China), HuaxueShiji, 2020, 42(3)
Abstract：Surfactants were utilized in the fabrication of Fe3O4 nanoparticles because they couldregulate the surface properties of the nanoparticles.Morphology regulation of theFe3O4 nanoparticles were investigated systematically by adding three kinds of surfactants whichcontaincetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP) and sodium dodecyl sulfonate (SDS) and different amount of surfactants.The samples were characterized by transmission electron microscopy (TEM), and the mechanism was explained.The results showed that: 1) Spherical or near-spherical nanoparticles were obtained with the addition of three different surfactants. According to the comprehensive analysis of TEM and deposition time, the average particle size of the three surfactants was compared: SDS < CTAB < PVP. It was proved that the smaller Fe3O4 nanoparticles could be obtained by adding SDS surfactant; 2) When CTAB was used as surfactant, the nanoparticle size tendedto decrease with the increase of CTAB dosage. The nanoparticle size decreased gradually when the amount of SDS and PVP surfactantswereincreased. Based on the research results, whichhad certainreference value toward the fabrication and applications ofFe3O4nanoparticles.
Keywords:Fe3O4nanoparticles;CTABsurfactant; PVPsurfactant; SDSsurfactant; morphology control
引用本文：魏茂琼, 林昕, 刘宏程, 等. 三种表面活性剂对Fe3O4纳米颗粒的形貌影响 [J]. 化学试剂, 2020, 42(3): 315-320.
超声波促进新型席夫碱类化合物的水相合成
邓仰平，高旭，谢晓蓉，蒋小强，王世范*
(海南大学 生命科学与药学院 热带生物资源教育部重点实验室，海南 海口 570228)
摘要：在超声波促进下以聚乙二醇（PEG6000）为相转移催化剂，在水相中合成了8个席夫碱类化合物。采用1H NMR、13C NMR、IR、ESI MS和X-射线衍射对其结构进行了表征，结果与目标化合物一致。采用相转移催化剂水相超声波合成，与传统的加热反应或有机溶剂相超声波合成相比较，水相超声波合成不但可以避免酸碱催化剂和乙醇等挥发性溶剂，而且使得反应时间从数小时缩短至0.5 h左右，产率高达76% ～ 92%。经查证，其中6个席夫碱类化合物是未见文献报道的新化合物。
关键词：PEG6000；超声辅助；相转移催化剂；席夫碱；水相合成
中图分类号：R914.2 文献标识码：A 文章编号：0258-3283(2020)
Ultrasound-Assisted Synthesis of Novel Schiff Bases in Aqueous Condition DENG Yang-ping, GAO Xu, XIE Xiao-rong, JIANG Xiao-qiang, WANG Shi-fan* ( Key Laboratory of Tropical Biological Resources of the Ministry of Education, Department of Pharmacy, School of Life and Pharmaceutical Sciences, Hainan University, Haikou 570228, China), Huaxue Shiji, 2020, 42(3)
Abstract：Eight Schiff bases were synthesized by aqueous phase with polyethylene glycol (PEG6000) as phase transfer catalyst under ultrasonic radiation. The structures were characterized by 1H NMR、13C NMR、IR、ESI MS and X-Ray and were consistent with the target compounds. Compared with the traditional heating reaction or the organic solvent phase ultrasonic synthesis, the aqueous phase ultrasonic synthesis with phase transfer catalyst could not only avoid the volatile solvents such as acid-base catalyst and ethanol, but also shorten the reaction time from several hours to about 0.5 h, and the yield is as high as 76% to 92%. It was verified that six Schiff bases were new compounds which were not reported in the literature.
Key words：PEG6000; ultrasonic radiation; phase transfer catalyst; Schiff bases; aqueous-phase synthesis
引用本文：邓仰平，高旭，谢晓蓉, 等. 超声波促进新型席夫碱类化合物的水相合成[J]. 化学试剂, 2020, 42(3): 321-325.
钯催化无氧化剂烷烃脱氢制备烯烃研究
杨娜，张晨阳，杨德骏，刘仁华*
(华东理工大学 药学院，上海 200237)
摘要：二苯乙烯类化合物是一类具有多种生物活性以及优良荧光性能的有机化合物，它们广泛存在于天然药物和食物中。目前文献所报道的合成二苯乙烯类化合物方法存在反应路线较长、反应条件苛刻、副产物多、反应收率低、底物范围窄等缺点。发展了一种 Pd/C 催化烷烃脱氢制备烯烃并释放氢气的方法。该反应体系不需要加入任何的氧化剂和氢接受体，即可高转化率、高选择性地将烷烃转化为烯烃并释放出氢气，反应过后 Pd/C 催化剂可以回收并循环使用。该反应体系条件温和、环境友好，符合以原子经济性为核心的绿色化学的发展要求。
关键词：Pd/C；二苯乙烯类化合物；脱氢；原子经济性；无氢接收体
中图分类号：O625.12 文献标识码：A 文章编号：0258-3283（2020）
Oxidant-free Dehydrogenation of Alkanes to Alkenes Catalyzed by Palladium YANG Na1, ZHANG Chen-yang2, YANG De-jun2, LIU Ren-hua * (School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China), Huaxue Shiji, 2020, 42(3)
Abstract：Stilbene compounds are an important class of organic compounds with various biological activities and excellent fluorescence properties, which are widely found in natural medicines and foods. The synthesis methods of stilbene compounds reported in the literature suffered from many disadvantages such as long reaction route, harsh reaction conditions, low selectivity, low reaction yields, and a narrow substrate range. In this paper, a method for dehydrogenation of alkanes to produce olefins and to release hydrogen has been developed. The reaction was catalyzed by Pd/C without adding any oxidizing agents and hydrogen acceptors with high conversion and high selectivity, and hydrogen was only the by-product. After the reaction, the Pd/C catalyst can be recovered and recycled. The reaction system was mild and environmentally friendly, and meets the development requirements of green chemistry with atomic economy as the core.
Key words：Pd/C; stilbene compounds ; dehydrogenation; atomic economy; without hydrogen acceptors
引用本文：杨娜，张晨阳，杨德骏，等. 钯催化无氧化剂烷烃脱氢制备烯烃研究[J].化学试剂, 2020, 42(3)：326-331.
稳定同位素标记[2H4]-β-紫罗兰酮的合成及表征
白冰1，钟闻英1，黄备备1，张改红1，贾春晓2，毛多斌*1
（郑州轻工业大学 a. 食品与生物工程学院，b. 材料与化学工程学院，河南 郑州 450000）
摘要：以柠檬醛为原料，以D6-丙酮为稳定同位素标记前体物，经碱催化羟醛缩合及酸催化关环反应合成了[2H4]-β-紫罗兰酮，考察了碱和酸的种类、用量及温度对反应的影响，确定了最优路线：先在20% NaOH重水溶液中于55 ℃反应2 h合成假性紫罗兰酮，再经浓硫酸于-10 ℃反应10 min合成目标产物，2步总收率为60%。目标化合物结构通过质谱、核磁共振氢谱、核磁共振碳谱、红外光谱进行表征，经高效液相色谱确认化学纯度为99%，经计算同位素丰度为98.1%。该方法所得目标产物可作为稳定同位素稀释分析法中的的对照物质。
关键词：同位素标记；合成；[2H4]-β-紫罗兰酮；柠檬醛；对照品
中图分类号：O628.1 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Characterization of Stabilized Isotope [2H4]-β-Ionone BAI Bing1, ZHONG Wen-ying1, HAUNG Bei-bei1, ZHANG Gai-hong1, JIA Chun-xiao2, MAO Duo-bin*1 (a. School of Food & Biological Engineering, b. College of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450000, China), Huaxue Shiji, 2020, 42(3)
Abstract：Stabilized isotope-labeled [2H4]-β-ionone was synthesized by using citral as starting material and d6-acetone as a stable isotope-labeled precursor with two steps. The optimal reaction conditions were investigated. The first step was aldol condensation of citral with d6-acetone in the presence of 20% NaOH at 55 ℃ for 2 h. The second step was cyclization of the acquired pseudoionone in the presence of concentrated H2SO4 at -10 ℃ for 10 min. The total yield was 60%. The target compound was confirmed by MS, 1H NMR, 13C NMR and IR. The chemical purity was 99% detected by HPLC, and the isotope abundance was 98.1% by calculation. The compound could be used as standard in the method of stable isotope dilution.
Key words：isotope labeling; synthesis; [2H4]-β-ionone; citral; reference substance
引用本文：白冰, 黄备备, 钟闻英, 等. 稳定同位素标记[2H4]-β-紫罗兰酮的合成及表征[J]. 化学试剂, 2020, 42(3): 332-336.
5-(4-(二氟甲氧基)苯基)-1H-吡咯-2-甲酸的合成研究
易琴a, c，朱雄b, c，周志旭b, c，赵春深*b, c, d
(贵州大学 a.化学与化工学院，b.药学院，c.贵州省合成药物工程实验室，
d.贵州省发酵工程与生物制药重点实验室，贵州 贵阳 550025)
摘要：目标化合物是一种重要的医药及农药等精细化工产品的中间体，该化合物暂无文献报道其合成工艺，具有非常好的研究价值。根据文献报道，具有类似结构的化合物对IDO具有良好的抑制作用，能够有效地治疗、减轻或预防由免疫抑制引起的各种疾病，包括由肿瘤或病毒感染引起的自身免疫性疾病。设计并优化了该化合物的合成工艺，以N-Boc-2-吡咯硼酸为原料，经Suzuki反应、脱保护、羧酸化等步骤合成目标化合物，其结构经1H NMR、13C NMR和MS确证，总收率为40.8%。
关键词：N-Boc-2-吡咯硼酸；5-(4-(二氟甲氧基)苯基)-1H-吡咯-2-甲酸；合成；中间体；核磁氢谱
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283（2020）
Synthesis of 5-(4-(Difluoromethoxy)phenyl)-1H-pyrrole-2-carboxylic Acid YI Qina, c, ZHU Xiongb, c, ZHOU Zhi-xub, c, ZHAO Chun-shen*b, c, d (a.School of Chemistry and Chemical Engineering, b.School of Pharmaceutical Sciences, c.Guizhou Engineering Laboratory for Synthetic Drugs, d.Key Laboratory of Guizhou for Fermentation Engineering and Biopharmacy, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 2020, 42(3)
Abstract: The target compound is an important intermediate for pharmaceuticals, pesticides and other fine chemical products. The synthesis of the target product has not been reported in the literature at present. According to the literature report, compounds with similar structure has an excellent inhibitory effect against IDO, and can effectively treat, mitigate and prevent various diseases caused by immunosuppression, including an autoimmune disease caused by a tumor or viral infection. Its synthetic route would be designed and optimized in this work. N-Boc-2-pyrroleboronic acid was used as raw material to synthesize the target compound by Suzuki reaction, Boc cleavage and carboxylation. The structure was confirmed by 1H NMR, 13C NMR and MS. The total yield was 40.8%.
Key words: N-Boc-2-pyrroleboronic acid; 5-(4-(difluoromethoxy)phenyl)-1H-pyrrole-2-carboxylic acid; synthesis; intermediate; H NMR
引用本文：易琴, 朱雄, 周志旭, 等. 5-(4-(二氟甲氧基)苯基)-1H-吡咯-2-甲酸的合成研究[J]. 化学试剂, 2020, 42(3):337-339.
