茶多酚的提取及抑菌活性研究
蔡静，叶润，贾凯，孙伟*，赵丽平
（信阳农林学院 生物与制药工程学院，河南 信阳 464000）
摘要：茶多酚是信阳绿茶中的一种生物活性成分，起着主要的抑菌作用，为了更好的开发茶多酚抗菌性的食用、药用等价值，有必要对茶多酚的提取及抑菌活性研究进行综述。根据国内外对茶多酚抑菌性的研究现状，对绿茶多酚的有效成分、提取方法、抑菌活性、抑菌机理及抑菌性应用作了系统介绍，可为绿茶多酚在食品、医药、化妆品及潜在应用领域提供一定的理论参考。
关键词：信阳绿茶；茶多酚；提取方法；抑菌活性；抑菌性应用
中图分类号：TQ917 文献标识码：A 文章编号：0258-3283（2020）--
Research on extraction and antibacterial activity of tea polyphenols CAI Jing, YE Run, JIA Kai, SUN Wei*, ZHAO Li-Ping (College of Biological and Pharmaceutical Engineering, Xinyang Agriculture and Forestry University, Xinyang 464000, China), Huaxue Shiji, 2020, 42(2), ～
Abstract: Tea polyphenols, as a kind of bioactive ingredient in xinyang green tea, play a major role in bacteriostasis. In order to develop the edible, mdicinal and other values of tea polyphenols in antibacterial activity, it is necessary to summarize the extraction and antibacterial activity of tea polyphenols. In this paper, according to the research of bacteriostasis of tea polyphenols both at home and abroad, we systematically introduced the effective components, extraction methods, bacteriostasis activities, bacteriostasis mechanisms and bacteriostasis applications of tea polyphenols, which can provide some theoretical references for the application of tea polyphenols in food, medicines, cosmetics and other potential fields.
Key words: xinyang green tea; tea polyphenols; extraction methods; antibacterial property; bacteriostatic applications
引用本文: 蔡静，叶润，贾凯，等. 茶多酚的提取及抑菌活性研究. 化学试剂, 2020, 42(2): 105-114.
含喹啉基片段的水杨醛席夫碱类化合物的合成及其淬灭1,1-二苯基-2-三硝基苯肼自由基性能
孙凤梅*，毛广秀
(淮阴师范学院 化学化工学院，江苏 淮安 223300)
摘要：通过2-甲基-5-氨基喹啉和取代水杨醛缩合反应，合成了10个含喹啉基片段的水杨醛席夫碱类化合物。通过1HNMR、13CNMR、IR、LC-MS和元素分析技术确证了产物的结构，并测定了目标化合物在不同浓度时淬灭1,1-二苯基-2-三硝基苯肼（DPPH）自由基活性。结果表明，所有化合物在测试浓度0.02 ～ 0.10 g/L时都表现出一定的淬灭DPPH自由基活性，清除率主要集中在19% ～ 35%之间，但是4-溴-2-甲氧基-6-{[(2-甲基-5-喹啉基)亚氨基]甲基}苯酚在浓度0.06 g/L时表现出特别优异的活性，清除率高达43.1%。目标化合物质量浓度的变化对活性的影响不明显或者没有明显的变化规律。
关键词：喹啉；席夫碱；合成；1,1-二苯基-2-三硝基苯肼；自由基
中图分类号： O625 文献表示码：A 文章编号：0258-3283（2020）
Synthesis and Quenching Activity of Schiff Bases Containing Quinoline Fragments for 1,1-Diphenyl-2-picryhydrazyl Radical SUN Feng-mei*, MAO Guang-xiu ( School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai’an 223300, China), Huaxue Shiji, 2020, 42(2), ～
Abstract：10 Kinds of salicylaldehyde Schiff bases containing quinoline fragments were synthesized by the condensation reaction of 2-methyl-5-aminoquinoline and substituted salicylate. The structures were confirmed by 1HNMR, 13CNMR, IR, LC-MS and elemental analysis. 1,1-Diphenyl-2-picryhydrazyl (DPPH) radical quenching activity of Schiff bases were also investigated. All compounds showed certain quenching activity of DPPH radical at concentrations of 0.02 ～ 0.10 g/L, the scavenging rates were between 19%～35%, but 4-bromo-2-methoxy-6-{[(2-methylquinolin-5-yl)imino]methyl}phenol showed excellent activity at 0.06 g/L, with the scavenging rate of 43.1%. For all the compounds, the effect of the change of mass concentration on the activity was not obvious.
Key words: quinoline; Schiff base; synthesis; 1,1-diphenyl-2-picryhydrazyl; radical
引用本文: 孙凤梅，毛广秀. 含喹啉基片段的水杨醛席夫碱类化合物的合成及其淬灭1,1-二苯基-2-三硝基苯肼自由基性能. 化学试剂, 2020, 42(2): 115-120.
Mn掺杂ZnCo2O4纳米片阵列的制备及电化学性能研究
吕洋*，韩丹丹，刘岩，沈启慧，刘志刚，任红
（吉林化工学院 化学与制药工程学院，吉林 吉林 132022）
摘要：通过先水热合成再煅烧的方法在泡沫镍表面生长出了Mn掺杂的ZnCo2O4纳米片阵列。利用XRD、SEM、EDS-面扫描、XPS对样品的结构/形貌和掺入的Mn元素的分布情况进行了表征。然后，再进一步对样品进行了循环伏安曲线，恒电流充放电和循环稳定性的测试。结果标明，样品在电流密度为3 mA/cm2时，比电容达到了2134.1 F/g；在电流密度为10 mA/cm2时，循环1000圈，电容保持率为98.59%。所以，合成的样品比电容较高且循环稳定，是一种较为理想的超级电容器的电极材料。
关键词：ZnCo2O4；Mn掺杂；水热法；泡沫镍；超级电容器；电极材料
中图分类号：O611.4 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis and Electrochemical Performances of Mn Doped ZnCo2O4 Nanosheet Arrays LV Yang*, HAN Dan-dan, LIU Yan, SHEN Qi-hui, LIU Zhi-gang, REN Hong (School of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology，Jilin 132022), Huaxue Shiji, 2020, 42(2), ～
Abstract: Mn doped ZnCo2O4 nanosheet arrays were synthesized on Ni foam via a hydrothermal method followed by a calcination process. The structural, morphological and distribution of Mn in ZnCo2O4 nanosheet arrays have been confirmed via XRD, SEM, EDS mapping and XPS, respectively. The cyclic voltammetry, galvanostatic charge/discharge and cycling performance experiments were carried out, subsequently. Results show that the fabricated sample exhibited a specific capacitance as high as 2134.1 F/g at a current density of 3 mA/cm2 and retained 98.59% of initial capacitance after 1000 cycles at current density of 10 mA/cm2. Due to its high specific capacitance and stable cycling performance, the Mn doped ZnCo2O4 nanosheet arrays on Ni foam was an ideal electrode material for super capacitor.
Keywords: ZnCo2O4; Mn doped; hydrothermal method; Ni foam; Super capacitor; electrode material
引用本文: 吕洋，韩丹丹，刘岩，等. Mn掺杂ZnCo2O4纳米片阵列的制备及电化学性能研究. 化学试剂, 2020, 42(2): 121-125.
基于氮掺杂碳纳米颗粒荧光猝灭-恢复方法检测还原型谷胱甘肽
刘辉1，赵永福1，韩怀远1，刘亚雯1，冶保献*2
(1. 郑州师范学院 化学化工学院，河南 郑州 450044；2. 郑州大学 化学与分子工程学院，河南 郑州 450001)
摘要：分别以海藻酸钠和色氨酸为碳源和氮源，采用固相法一步合成出了量子产率为47.9%氮掺杂荧光碳纳米颗粒（N-CNPs）。根据铜离子存在的条件下，N-CNPs荧光强度的恢复情况与还原型谷胱甘肽浓度成正比的关系，建立基于N-CNPs检测还原型谷胱甘肽的新方法。优化了溶液pH及反应时间等条件。在pH 6.0、铜离子浓度30 µmol/L条件下，谷胱甘肽在0.2～45 µmol/L浓度范围内与N-CNPs荧光恢复强度呈良好的线性关系，检出限为50 nmol/L。方法具有灵敏度高、选择性好、操作简单等优点，可用于实际样品中谷胱甘肽的检测。
关键词：荧光碳纳米颗粒；氮掺杂；谷胱甘肽；海藻酸钠；色氨酸
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2020）--
Nitrogen-doped Carbon Nanoparticle Modulated Turn-on Fluorescent Probes for Glutathione Detection LIU Hui1, ZHAO Yong-fu1, HAN Huai-yuan1, LIU Ya-wen1, YE Bao-xian *2 ( 1. College of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China; 2. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China), Huaxue Shiji, 42(2), ～
Abstract：Highly photo luminescent nitrogen-doped carbon nanoparticles (N-CNPs, fluorescent quantum yield of ~47.9%) were prepared by a solid-phase synthesis strategy employing sodium alginate as a carbon source and tryptophan as nitrogen. Based on the relationship between the fluorescence intensity of N-CNPs/Cu2+ and the concentration of reduced glutathione, a novel assay for reduced glutathione was established. Under the optimized conditions, a linear relationship between the fluorescence recovery intensity of N-CNPs and the concentration of reduced glutathione was established in the range of 0.2-45 μmol/L. The detection limit was 50 nmol/L. The method has the advantages of high sensitivity, good selectivity and simple operation, and can be used for detecting glutathione in real samples.
Key words：fluorescent carbon nanoparticle; nitrogen-doped; glutathione; sodium alginate; tryptophan
引用本文: 刘辉，赵永福，韩怀远，等. 基于氮掺杂碳纳米颗粒荧光猝灭-恢复方法检测还原型谷胱甘肽. 化学试剂, 2020, 42(2): 126-130.
板栗壳对罗丹明B的吸附性能研究
马艳梅*，刘仁植，李晓严
（信阳学院 理工学院，河南 信阳 464000）
摘要：利用信阳本地板栗的板栗壳粉作为吸附剂，用于吸附罗丹明B。探究了用量、时间、pH以及温度对其吸附效果的影响。结果表明，板栗壳粉对罗丹明B的最佳吸附条件为：用量3 g/L、吸附时间5 h、pH 3、温度为40 °C，在此条件下板栗壳对罗丹明B的吸附率达到92.92%。相较于Langmuir模型，Freundlich模型更适合模拟板栗壳对罗丹明B的吸附。板栗壳对罗丹明B染料的吸附过程符合准二级动力学。
关键词：板栗壳；罗丹明B；吸附；动力学拟合；准二级动力学
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2020）--
Adsorption Performance of Chestnut Shells for Rhodamine B MA Yan-mei*, LIU Ren-zhi, LI Xiao-yan (School of Science and Technology, Xinyang College, Xinyang 464000, China), Huaxue Shiji, 2020, 42(2), ～
Abstract: The chestnut shells power of xinyang local chestnut were used as adsorbent to adsorb Rhodamine B.The effects of dosage, time, pH and temperature on the adsorption were investigated. The best adsorption conditions for Rhodamine B by the chestnut shells powder were dosage 3 g/L, adsorption time 5 h, temperature 40 °C. The adsorption rate for Rhodamine B by the chestnut shells was 92.92% on the best adsorption condition. Compared with Langmuir model, Freundlich model is more suitable to simulate the adsorption of chestnut shells on Rhodamine B. The adsorption process of chestnut shells on Rhodamine B well fitted by the pseudo-second-order equation.
Key words: chestnut shell; Rhodamine B; adsorption; dynamic fitting; pseudo-second-order equation
引用本文: 马艳梅，刘仁植，李晓严. 板栗壳对罗丹明B的吸附性能研究. 化学试剂, 2020, 42(2): 131-136.
In2O3基纳米材料气敏性能研究综述
严超，杨方源，杨占金，匡代洪*
(新疆农业大学 数理学院，新疆 乌鲁木齐 830052)
摘要：In2O3半导体纳米材料由于具有较高的响应灵敏度、较快的响应-恢复时间，是气敏领域的明星材料，得到了广大研究者的青睐。然而，In2O3气敏材料由于化学组份单一往往催化能力有限，气敏性能不太理想（灵敏度较低、相应的恢复时间较长、功耗较高），严重限制了其在日常生产生活中的应用。实验证明：对单一的气敏材料修饰改性可以有效提升材料的气敏性能。国内外广大研究者相继对In2O3进行了大量的研究工作并取得了显著的成果。综述了In2O3气体传感器最新的研究进展，对近些年In2O3半导体纳米材料发展存在的问题及改性方法进行概括，并对以后的发展进行了展望。
关键词：In2O3；制备；材料改性；异质结；气敏传感器；综述
中图分类号：O469 文献标识码：A 文章编号：0258-3283（2020）
Progress of In2O3-based Sensing Materials YAN Chao, YANG Fang-yuan, YANG Zhan-jin, KUANG Dai-hong* (School of Math and physics, Xinjiang Agricultural University, Wulumuqi 830052, China), Huaxue Shiji, 2020, 42 (2), ～
Abstract: In2O3 is one of the most promising sensing materials, which has appealed many researchers’ interest due to high response and fast response-recovery time. However, In2O3 usually can’t get an ideal performance due to the single component and limited catalytic capacity, thus lead to the materials with low sensitivity, long response-recovery time and high working temperature, which severely restricted the application. Many researchers have modified the surface of the materials and the results confirmed that this is an effective way to improve the sensing performance. Thus, we have summarized the latest research progress of In2O3, included the problems and effective measures of the In2O3 nanomaterial in gas sensor. Finally we have proposed the future development of the In2O3 nanomaterial.
Key word: In2O3; preparation; modify material; heterojunction; gas sensor; review
引用本文: 严超，杨方源，杨占金，等. In2O3基纳米材料气敏性能研究综述. 化学试剂, 2020, 42(2): 137-141.
基于化学计量学结合现代分析技术的古代食物残留物分析研究
宋晶晶1，樊军1，王洋洋1，于永杰*2
（1. 宁夏回族自治区文物考古研究所，宁夏回族自治区 银川 750004；2. 宁夏医科大学，宁夏回族自治区 银川 750004）
摘要：针对考古出土的有机残留物特别是食物残留物研究分析以推测食物的可能来源是当前化学分析研究中极具挑战性的工作。以稳定同位素技术结合气相色谱联用质谱现代分析技术相结合，提出了将化学计量学与多种分析技术结合的策略研究了宁夏回族自治区固原地区西汉墓葬群出土的食物残留样本。该策略首先通过分析样本中的稳定同位素分布，研究食物残留物在食物链中的等级，并推断其可能的来源，随后利用气相色谱联用质谱技术检测样本中的挥发、半挥发成分，利用化学计量智能化解析算法提取其中的化学成分，并与可能来源的食物样本进行比对，最终讨论了食物残留物的可能来源。
关键词：稳定同位素；气质联用；古代食物残留物；化学计量学
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2020）--
A Strategy based on Chemometrics Coupled with Advanced Analytical Technique for Analysis of Ancient Food Residues SONG Jing-Jing1, FAN Jun1, WANG Yang-Yang1, YU Yong-Jie*2 (1. Ningxia Institute of Cultural Relics and Archeology, Yinchuan 750004, China; 2. Ningxia Medical University, Yinchuan 750004, China), Huaxue Shiji, 42(2), ～
Abstract：The analysis of ancient organic residues, especially for ancient food residual analysis, to infer their origins is one of the most challenging tasks in current scientific fields. To address this problem, the present work proposes a comprehensive strategy that integrates techniques of stable isotope and gas chromatography-mass spectrometry (GC-MS), and chemometrics for analyzing ancient food residues collected from Western Han tombs in Guyuan, China. This strategy firstly analyzes the composition and content of stable isotopes to find their possible positions in the food chain and concludes several origins that these food residues may come from. Then, the GC-MS is introduced to analyzing semi-volatile and volatile compounds in the sample, whose data is transformed into our laboratory developed software for analyzing the underlying components. Finally, a comparison between the ancient food residuals and modern food resources is performed to infer the possible origin.
Key words：stable isotopes; GC-MS; ancient organic residues; chemometrics
引用本文: 宋晶晶，樊军，王洋洋，等. 基于化学计量学结合现代分析技术的古代食物残留物分析研究. 化学试剂, 2020, 42(2): 142-146.
微量QuEChERS/气相色谱质谱法快速测定土壤中15种农药残留
谭华东1, 2, 3，赵淑巧1, 2, 3，吴东明1, 2, 3，张汇杰1, 2, 4，武春媛*1, 2, 3
(1.中国热带农业科学院 环境与植物保护研究所，海南 海口 571101；2.农业农村部儋州农业环境科学观测实验站，海南 儋州 571737；3.海南省热带生态循环农农业重点实验室，海南 海口 571101；4.华中农业大学 资源与环境学院，湖北 武汉 430070)
摘要：为实现瓜菜种植土壤中常见农药的快速、灵敏测定，以改进的微量QuEChERS（μ-QuEChERS）辅助超声提取法，结合气相色谱质谱（GC-MS）分析，建立了土壤中15种农药残留的同时快速检测方法。土壤中15种农药残留采用含有V（1%乙酸的乙腈）：V（二氯甲烷）＝ 2 : 1的混合溶液提取，上清液经过w（N-丙基乙二胺（PSA））: w（C18） = 4 : 1混合吸附剂与无水Na2SO4净化。目标物在TG-5MS弱极性石英毛细管柱进行GC分离，以电子轰击电离源（EI）、选择离子监测（SIM）模式的外标法定量。结果表明，超过13种有机污染物在1.0 ～ 1000 μg/L范围内呈良好线性关系，且相关系数（r）均超过0.990。所建方法的检测限（LOD，S/N = 3）为0.1 ～ 1.2 μg/kg，定量限（LOQ，S/N = 10）为0.5 ～ 4.3 μg/kg。3个不同添加浓度（5.0、50、200 μg/kg）的回收率在85.6% ～ 109.8%范围内，相对标准偏差（RSD，n = 3）在1.1% ～ 11.4%范围内。将所建方法应用到海南南渡江流域瓜菜产区土壤中农药残留检测中，观察到土壤中均含有滴滴涕、六六六，且均存在农药多残留情况（≥7种），其中联苯菊酯检测浓度最高。该方法简单、快速且灵敏，有机试剂种类和用量少，适合土壤中15种常见农药多残留的同时快速批量检测。
关键词：QuEChERS；快速提取；气相色谱质谱；土壤；农药
中图分类号：O656.31 文献标识码：A 文章编号：0258-3283（2020）
Simultaneous Determination of 15 Pesticides Residue in Soil by Micro-QuEChERS Coupled with Gas Chromatography-Mass Spectrometry TAN Hua-dong1, 2, 3, ZHAO Shu-qiao1, 2, 3, WU Dong-ming1, 2, 3, ZHANG Hui-jie1, 4, WU Chun-yuan*1, 2, 3 (1.Environment and Plant Protection Institute, Chinese Academy of Tropical Agricultural Sciences, Haikou 571101, China; 2.Danzhou Scientific Observing and Experimental Station of Agro-environment, Ministry of Agriculture and Rural Affairs, Danzhou 571737, China; 3.Hainan Key Laboratory of Tropical Eco-circular Agriculture, Academy of Tropical Agricultural Sciences, Haikou 571101, China; 4.School of Resources and Environment, Central China Agricultural University, Wuhan 430070, China), Huaxue Shiji, 2020, 42(2), ～
Abstract：In order to achieve rapid and batch determination of common pesticides in vegetable planting soils, a rapid and sensitive method for simultaneous determination of 15 pesticide residues in soils was established by using gas chromatography-mass spectrometry (GC-MS) coupled with modified micro-QuEChERS (μ-QuEChERS) and assisted ultrasonic extraction. A 1.0 g soil sample was extracted by 2.0 mL acetonitrile and dichloromethane (volume ratio 1 : 1) with 1.0% acetic acid after in the presence of 2 mL deionized water. After centrifugation at 4000 r/min for 5 min, the supernatant was purified by the mixed adsorbent of primary secondary amine (PSA) and C18 (w/w = 4 : 1). After centrifugation and conversion solvents, the targets were separated on a TG-5MS chromatographic column and quantified by selective ion monitoring (SIM) mode with external standard method. The results showed that the linear was good in the concentration range of 1.0-1000 μg/L for 13 pesticides with the correlation coefficients of more than 0.990. The limit of detection (LOD, S/N=3) and the limit of quantitation (LOQ, S/N=10) were 0.1-1.2 μg/kg and 0.5-4.3 μg/kg. At the three spiked concentration (5.0, 50, 200 μg/kg), the recoveries of targets compounds were 85.6%-109.8% with relative standard deviation (RSD, n=3) of 1.1%-11.4%. The method was used to the determination of pesticide residues in 4 soils from Nandu River Basin (Hainan Province). The DDTs and BHCs were occurred in the all soils, and also multi-pesticide residues (≥7 kinds) were observed with the highest concentration of bifenthrin. The method is simple, rapid and sensitive, which is suitable for rapid batch detection of 15 common pesticides in soil.
Key words：QuEChERS; rapid extraction; Gas chromatography-mass spectrometry; soil; pesticides
引用本文: 谭华东，赵淑巧，吴东明，等. 微量QuEChERS/气相色谱质谱法快速测定土壤中15种农药残留. 化学试剂, 2020, 42(2): 147-153.
NH2-MIL-125(Ti)/TiO2纳米复合材料分子印迹光电化学传感器的构建及测定蔬菜中毒死蜱
金党琴*，徐洁，王珍，吴耀月，龚爱琴，王元有，周慧
（扬州工业职业技术学院 化学工程学院， 江苏 扬州 225127）
摘要：以NH2-MIL-125(Ti)/TiO2纳米复合材料为载体，毒死蜱为模板分子，戊二醛为交联剂，采用电聚合的方法合成了毒死蜱分子印迹聚合物膜，并以此印迹膜构建光电化学传感器，采用电流-时间法（I-t）对蔬菜中毒死蜱进行检测，结果表明在1.0×10-8～2.0×10-6 mol/L浓度范围内与峰电流线性良好，相关系数R2=0.9923，检测限为2.0×10-9 mol/L，并且具有较高的选择性识别能力、良好的再生性和稳定性。方法实现了蔬菜样品中痕量毒死蜱的检测。
关键词：NH2-MIL-125(Ti)/TiO2；毒死蜱；分子印迹；蔬菜；光电化学；传感器
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2020）--
Construction of amino-MIL-125(Ti)/TiO2 Nanocomposite Molecularly Imprinted Photoelectrochemical Sensor and Determination of Chlorpyrifos in Vegetables JIN Dang-qin*, XU Jie, WANG Zhen, WU Yao-yue, GONG Ai-qin, WANG Yuan-you, ZHOU Hui (Chemical Engineering Institute, Yangzhou Polytechnic Institute, Yangzhou 225127, China), Huaxue Shiji, 2019, 42(2), ～
Abstract: Using NH2-MIL-125(Ti)/TiO2 nanocomposite as carrier, chlorpyrifos as template molecule and glutaraldehyde as crosslinker, chlorpyrifos molecularly imprinted polymer membrane was synthesized by electropolymerization, and photoelectrochemical sensor was constructed by using this membrane. The sensor was tested by current-time method (I-t). The peak current was linear in the concentration range of 1.0×10-8～2.0×10-6 mol/L, and the correlation coefficient was R2＝0.9923. The detection limit is 2.0×10-9 mol/L, and has high selectivity recognition, good reproducibility and stability. The method achieves the detection of trace chlorpyrifos in vegetable samples.
Key words: NH2-MIL-125(Ti)/TiO2; chlorpyrifos; molecular imprinting;vegetable; photoelectrochemistry; sensor
引用本文: 金党琴，徐洁，王珍，等. NH2-MIL-125(Ti)/TiO2纳米复合材料分子印迹光电化学传感器的构建及测定蔬菜中毒死蜱. 化学试剂, 2020, 42(2): 154-158.
小鼠体内金果榄提取物古伦宾的药动学研究
杨慧杰，糜志远，张紫薇，邵君前，陈子良，郑婉榕，余庆节，张佳*
（湖北工业大学 生物工程与食品学院，湖北 武汉 430064）
摘要：建立高效液相色谱（HPLC）法测定小鼠血浆古伦宾浓度并研究小鼠体内金果榄提取物古伦宾的药动学。采用灌胃的方式对小鼠给与金果榄提取物古伦宾，血浆样品用甲醇沉淀蛋白处理后经HPLC检测，色谱柱为C18柱，流动相V(乙腈) : V(水) = 40 : 60，检测波长为210 nm，流速为1.0 mL/min，柱温35 ℃，进样量为20 μL。古伦宾的主峰保留时间在8.66 min，峰形正态分布，分离良好，古伦宾在0.7815 ～ 400 μg/mL范围内线性关系良好，标准曲线方程为y = 0.0768x + 0.293，R² = 0.9993，最低检测限和定量限分别为15.625 ng和62.5 ng，日内与日间精密度均小于15%，血浆、肝脏、肾脏中的平均回收率分别为92.65%、93.88%、92.27%，各浓度水平回收率的RSD在2.53% ～ 6.36%之间，均符合药代动力学研究要求。研究所采用的HPLC方法专属性良好，适用于古伦宾在小鼠体内的药代动力学研究。
关键词：小鼠；金果榄；古伦宾；药动学；高效液相色谱
中图分类号：R969.1 文献标识码：A 文章编号：0258-3283（2020）
Pharmacokinetics of Columbin from Tinospora Capillipes in Mice YANG Hui-jie, MI Zhi-yuan, ZHANG Zi-wei, SHAO Jun-qian, CHEN Zi-liang, ZHENG Wan-rong, YU Qing-jie, ZHANG Jia* (School of Bioengineering and Food, Hubei University of Technology, Wuhan 430064, China), Huaxue Shiji, 2020, 42(2), ～
Abstract objective: To establish HPLC method for the determination of columbin in mice plasma and to investigate the pharmacokinetics of columbine from tinospora capillipes in mice. The columbin from tinospora capillipes were given to the mice by the method of intragastric. After precipitation by methanol, the plasma samples were detected by HPLC C18 column. Mobile phase: V (acetonitrile) : V (water) ＝ 40:60. Detection wavelength: 210nm. Flow rate: 1.0 mL/min. Tempreture: 35℃. Sample size: 20μL. Retention time of columbin was about 8.66 min, the peak shape is normally distributed and well separated, the liner range of columbin was from 0.7815μg/mL to 400μg/mL, the standard curve equation is y＝0.0768x＋0.293, R²＝0.9993. The minimum detection limit and quantitative limit were 15.625ng and 62.5ng, respectively. The intra-day and inter-day precision were less than 15%, and the average recoveries in plasma, liver and kidney were 92.65%, 93.88% and 92.27%, respectively. The RSD of the recoveries of each concentration was between 2.53% and 6.36%, which met the requirements of pharmacokinetic study. The HPLC method has a good specificity and is suitable for the pharmacokinetic study of columbin in mice.
Key words: mice; Tinospora capillipes; columbin; Pharmacokinetics; HPLC
引用本文: 杨慧杰，糜志远，张紫薇，等. 小鼠体内金果榄提取物古伦宾的药动学研究. 化学试剂, 2020, 42(2): 159-164.
美拉德反应产物对卷烟主流烟气挥发性成分的影响
赵琪1，李瑞丽1, 2，苏加坤2，徐达2，张峻松1，黄贵元1，黄晓玉1，蔡继宝*2
（1.郑州轻工业大学 食品与生物工程学院，河南 郑州 450001；
2.江西中烟工业有限责任公司，江西 南昌 330096）
摘要：为研究美拉德反应产物对主流烟气挥发性成分的影响，以果糖和3种氨基酸的MRPs为研究对象，通过剑桥滤片捕集卷烟主流烟气粒相物，利用超声辅助溶剂萃取法提取其中香味成分，GC-MS对比分析空白卷烟和加香烟气中挥发性成分差异，并进行感官评价。结果表明：添加MRPs后，主流烟气中的酮类、呋喃类、苯酚类、酯类及烯类化合物均有明显提升，其中4-羟基-2,5-二甲基-3 (2H)呋喃酮增加了72%，2, 3-二氢-3, 5二羟基-6-甲基-4 (H)-吡喃-4-酮由添加前的32.416 µg/支增加到36.060 µg/支，糠醛增加了26%，5-羟甲基糠醛增加了70%，3,4-二甲基吡啶、柠檬烯、3-甲基吲哚、3-羟基-β-大马酮及巨豆三烯酮等香味物质均有所增加，对卷烟抽吸时的感官质量均有积极影响；感官评吸结果表明，MRPs加入卷烟中可以明显提高卷烟抽吸品质，主要表现在香气质量提升、杂气及刺激性均减小、回甜感增加。
关键词：美拉德；主流烟气；挥发性成分；感官评价
中图分类号：TS 41 文献标志码：A 文章编号：0258-3283（2020）
Effect of Maillard Reaction Products on Volatile Components of Cigarette Mainstream Smoke ZHAO Qi1, LI Rui-li1,2, SU Jia-kun2, XU Da2, ZHANG Jun-song1, HUANG Gui-yuan1, HUANG Xiao-yu1, CAI Ji-bao*2 (1.Colloge of Food and Bioengineering, Zhengzhou University of light Industry, Zhengzhou 450001, China; 2.China Tobacco Jiangxi Industrial Co., Ltd., Nanchang 330096, China), Huaxue Shiji, 2020, 42(2)
Abstract: In order to study the effect of Maillard reaction products on the volatile components of mainstream smoke, the MRPs of fructose and three amino acids were used as research objects. The total particulate matters of cigarette mainstream smoke were collected with Cambridge filter and aromatic components were extracted by ultrasonic assisted solvent extraction. GC-MS were used to compare and analyze the difference in volatile components between blank cigarettes and cigarette gas, and perform sensory evaluation. After adding MRPs, the ketones, furans, phenols, esters and alkenes in mainstream smoke were significantly improved. Among them, 4-hydroxy-2,5-dimethyl-3(2H)furanone increased by 72%, 2,3-dihydro-3,5-dihydroxy-6-methyl-4(4H)-pyranone increased from 32.41g/branch to 36.06g/branch. Furfural increased by 26%, 5-hydroxymethyl furfural increased by 70%. 3,4-dimethylpyridine, limonene, 3-methylindole, 3-hydroxy-beta-damadone and megastrodonone all increased, which had a positive impact on the sensory quality of cigarettes during smoking. Sensory evaluation results showed that MRPs could significantly improve the smoking quality of cigarettes, mainly in the improvement of aroma quality, the decrease of impurity and irritation, and the increase of sweetness.
Key words: Maillard; mainstream smoke; volatile components; sensory evaluation
引用本文: 赵琪，李瑞丽，苏加坤，等. 美拉德反应产物对卷烟主流烟气挥发性成分的影响. 化学试剂, 2020, 42(2): 165-170.
沿海地区紫菜中总砷含量及砷形态分析
薛雯蔚，何凤云，陈圆圆，季正芯，陈昌云*
（南京晓庄学院 环境科学学院，江苏 南京 211171）
摘要：建立高效液相色谱-氢化物发生-原子荧光光谱联用法分析紫菜中4种砷的形态。在优化仪器参数的基础上，采用正交试验法分析样品前处理中的酸浓度、萃取温度和超声时间对砷提取量的影响。当硝酸浓度0.15 mol/L、萃取温度80 ℃、超声时间1 h时，萃取效果最佳。对低、中、高3个水平进行方法验证，砷形态的回收率为84.0% ～ 113.6%，精密度为1.3% ～ 4.6%，结果显示，沿海地区的紫菜产品中总砷含量高，但有毒砷占比小。该方法快速高效，可用于测定紫菜中砷形态的含量。
关键词：紫菜；HPLC-HG-AFS；形态分析；正交试验设计；砷含量
中图分类号：R284 文献标识码：A 文章编号：0258-3283（2020）
Analysis of Total Arsenic Content and Arsenic Species in Laver in Coastal Area XUE Wen-wei, HE Feng-yun, CHEN Yuan-yuan, JI Zheng-xin, CHEN Chang-yun* (School of Environmental Sciences, Nanjing Xiaozhuang University, Nanjing 211171, China), Huaxue Shiji, 2020, 42(2)
Abstract: To establish a high performance liquid chromatography coupled with hydride generation-atomic fluorescence spectrometry to analyze the morphology of four arsenic species in laver. On the basis of optimizing instrument parameters, the orthogonal test design method was used to analyze the effect of sample pretreatment acid concentration, extraction temperature and ultrasonic time on arsenic extraction. When the concentration of nitric acid was 0.15 mol/L, the extraction temperature was set to 80 °C, and the ultrasonic time was 1 h, the extraction effect was the best. The method was validated at three levels: low, medium and high. The recovery of arsenic was 84.0 %～113.6 %, and the precision was 1.30 %～4.36 %. The total arsenic content in seaweed products in coastal areas is high, but the proportion of toxic arsenic is small. This method is fast and efficient, and can be used to determine the content of arsenic in laver.
Key words：laver; HPLC-HG-AFS; morphological analysis; orthogonal experimental design; arsenic content
引用本文: 薛雯蔚，何凤云，陈圆圆，等. 沿海地区紫菜中总砷含量及砷形态分析. 化学试剂, 2020, 42(2): 171-174.
生活饮用水中10种卤代乙酰胺的全自动固相萃取-气相色谱测定方法研究
周闰，徐志飞，丁新良*
（无锡市疾病预防控制中心，江苏 无锡 214023）
摘要：建立了全自动固相萃取-气相色谱测定生活饮用水中10种卤代乙酰胺（HAcAms）的方法。10 mL水样在全自动固相萃取仪上用PPL柱萃取净化，经真空冷冻离心浓缩，气相色谱-电子捕获检测器检测。优化并考察了影响萃取效率的各项参数如固相萃取柱的选择，萃取剂的种类与用量。在最佳实验条件下，在0.5～150 μg/L，线性范围内10种HAcAms线性关系良好，其相关系数均大于0.997。该方法的检出限2 ～ 3 ng/L，定量限5 ～ 10 ng/L，加标回收率介于72.4% ～ 108.5%，RSD为3.3% ～ 9.1%。方法所需的样品量及试剂少、重复性好，可用于生活饮用水中10种卤代乙酰胺的测定。
关键词：消毒副产物；卤代乙酰胺；全自动固相萃取；气相色谱；饮用水
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2020）
Determination of 10 Haloacetamides in Drinking Water by Gas Chromatography Based on Automated Solid Phase Extraction ZHOU Run, XU Zhi-fei, DING Xin-liang* (Wuxi Center for Disease Control and Prevention, Wuxi 214023, China), Huaxue Shiji, 2020, 42(2), ～
Abstract: To establish a gas chromatography method for determination of 10 haloacetamides in drinking water based on automated solid phase extraction. 10 mL of water sample was extracted by automatic solid phase extraction instrument with a PPL sorbent, then concentrated by vacuum freezing centrifugation, and detected by gas chromatography-electron capture detector. The parameters affecting extraction efficiency, such as the selection of solid phase extraction column, the types and dosages of extractants and impurity removers were optimized and investigated. Under the optimum experimental conditions, the regression equation of the 10 haloacetamides in the range of 0.5～150 μg/L was good and their correlation coefficient were all greater than 0.997. The limits of detection for the method were2～3 ng/L, the quantification limits of the method were 5～10 ng/L, the average recovery rates were 72.4%～108.5% and the relative standard deviations were 3.3%～9.1% respectively. The method which requires fewer samples and reagents with good reproducibility, can be used for the determination of 10 haloacetamides in drinking water.
Key words: disinfection by-products; haloacetamide; fully automated solid phase extraction; gas chromatography; drinking water
引用本文: 周闰，徐志飞，丁新良. 生活饮用水中10种卤代乙酰胺的全自动固相萃取-气相色谱测定方法研究. 化学试剂, 2020, 42(2): 175-179.
高效液相色谱法测定地表水中四环素类抗生素
周晚晴1，黄金飞2，金小玲1，李键1，卢浈乐1，叶明立1，陈梅兰*1
（1. 浙江树人大学 生物与环境工程学院，浙江 杭州 310015；
2. 浙江省家具与五金研究所，浙江 杭州 310013）
摘要：利用1-己基-3-甲基咪唑六氟磷酸盐离子液体萃取-高效液相色谱法检测养殖场周边地表水中四环素类抗生素的含量。样品前处理比较了锰、铜、锌和钴金属离子与抗生素络合后的离子液体萃取效果。在流动相中比较草酸，柠檬酸，磷酸二氢钾，三氟乙酸作为流动相添加剂对四环素类抗生素峰型的改善效果。结果表明，锰离子作为金属络合剂，萃取效率更高，以磷酸二氢钾作为流动相添加剂，基线噪声较小，检测限最低，3种抗生素峰型较好。方法的线性范围为0.05～8.00 mg/L，具有良好的线性关系（0.9994～1.0000），较低的检出限（3.5×10-3～8.4×10-3mg/L）及较好的精密度RSD（0.31%～0.68%）。实际样品重复检测3次的方法的回收率为 86.4%～103%。相对标准偏差<2.10％。
关键词：四环素类抗生素；养殖场；1-己基-3-甲基咪唑六氟磷酸盐；离子液体；锰离子
中图分类号：X820.2 文献标志码：A 文章编号：0258-3283（2020）--
Determination of Tetracycline Antibiotics in Surface Water by High Performance Liquid Chromatography ZHOU Wan-qing1, HUANG Jin-fei2, JIN Xiao-ling1, LI Jian1, LU Zhen-le1, YE Ming-li1, Chen Mei-lan*1(1. College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, China; 2. Zhejiang Furniture and Hard- ware Research Institute，Hangzhou 310013，China), Huaxue Shiji, 2020, 42(2), ～
Abstract: A method was developed for the determination of tetracycline antibiotics in surface water neighboring livestock farm by high performance liquid chromatography with ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) as extraction. In order to obtain better extraction efficiency, four kinds metal ions (Mn2+, Cu2+, Zn2+ and Co2+) as tetracycline antibiotics complexant were added to the samples during sample pretreatment respectively. The extraction efficiency with Mn2+ as the complexing agent is higher than the others. Furthermore, the effects of oxalic acid, citric acid, potassium dihydrogen phosphate and trifluoroacetic acid as mobile phase additives on the peak shape improvement of tetracycline antibiotics were investigated. It is better for baseline, noise and detection limit when the mobile phase was added potassium dihydrogen phosphate. The correlation coefficient of proposed method was more than 0.9994 in the range of 0.05～8.00 mg/L. The limits of detection were ranged from 3.5～8.4×10-3 mg/L and RSDs for peak area were from 0.31%～ 0.68%. The recovery rate of real sample is 86.4% to 103% and the RSDs were less than 2.10％ for peak area(n＝3).
Key words: tetracycline antibiotic; farm; 1-hexyl-3-methylimidazolium hexafluorophosphate; ionic liquid; manganese ion
引用本文: 周晚晴，黄金飞，金小玲，等. 高效液相色谱法测定地表水中四环素类抗生素. 化学试剂, 2020, 42(2): 180-185.
不同有机物对硝酸盐氮测试的影响
赖俊瑶，陈滢*
（四川大学 建筑与环境学院，四川 成都 610065）
摘要:研究了红糖、葡萄糖、乙酸钠、甲醇、乙醇、乙酸、丙酸、丁酸、正戊酸、混合有机溶剂等10种不同有机物对麝香草酚光谱法和离子色谱法测试硝酸盐氮的影响，结果表明，溶液中含有红糖或葡萄糖时，均会对麝香草酚法测试硝酸盐氮造成影响，使得测试结果偏大；在无硝酸根离子存在时，红糖和葡萄糖的质量浓度与硝酸盐氮的测试浓度非线性相关；而乙酸钠、甲醇、乙醇、乙酸、丙酸、丁酸、正戊酸和混合有机溶剂则对麝香草酚法测试硝酸盐氮没有影响。实验发现，红糖和葡萄糖在浓硫酸的作用下与麝香草酚发生Molisch反应，形成有色复合物和红棕色不溶性沉淀。实验采用离子色谱法测试硝酸盐氮时，红糖和葡萄糖等糖类有机物对测试结果均无影响。
关键词: 有机物；硝酸盐氮测试；麝香草酚法；Molisch反应；离子色谱法
中图分类号：X502 文献标识码：A 文章编号：0258-3283（2020）--
Effect of Different Organic Compounds on Nitrate Nitrogen Test LAI Jun-yao, CHEN ying*(College of Architecture and Environment, Sichuan University, Chengdu 610065, China), Huaxue Shiji, 2020, 42(2), ～
Abstract: The effects of ten different organic compounds, brown sugar, glucose, sodium acetate, methanol, ethanol, acetate, propionate, butyrate, valerate, fermentation products on the determination of nitrate nitrogen by thymol spectrophotometry method and ion chromatography method were investigated. When the solution contains brown sugar or glucose, it would affect nitrate nitrogen test by thymol spectrophotometry method, which made the test results higher than the actual values. In the absence of nitrate ions, the concentration of brown sugar and glucose were nonlinearly related to the test concentration of nitrate nitrogen; while sodium acetate, methanol, ethanol, acetate, propionate, butyrate, valerate and fermentation products did not affect nitrate nitrogen test. It was found that brown sugar and glucose reacted with thymol in the presence of concentrated sulfuric acid to form colored complexes and reddish brown insoluble precipitate. When the nitrate nitrogen was tested by ion chromatography, brown sugar and glucose had no effect on the test results.
Key words: organic compound; nitrate nitrogen test; thymol spectrophotometry method; Molisch reaction; ion chromatography method
引用本文: 赖俊瑶，陈滢. 不同有机物对硝酸盐氮测试的影响. 化学试剂, 2020, 42(2): 186-192.
氰桥化合物 [cis-Fe(bpy)2(CN)2Mn(L)]2[PF6]4的合成
及其对金属离子选择识别作用
于孟1,2，万方2，胡建梅2，王勇* 2，李立2，刘生鹏1
(1. 武汉工程大学 化工与制药学院，湖北 武汉 430205；2.荆楚理工学院 药物合成与优化湖北省重点实验室，湖北 荆门 448000)
摘要：将Mn(II)离子、有机配体L（L ＝ 1，6-二苯基-2，5-双（2-甲基吡啶基）-2，5二重氮己烷）和氰基化合物cis-FeII(bpy)2(CN)2·3H2O（bpy = 2, 2’-联吡啶）在NH4PF6存在下得一个四元环异核氰桥化合物即标题化合物，并对其结构进行表征。重金属离子对标题化合物的荧光响应研究表明，标题化合物对Cu(Ⅱ)和 Fe(Ⅲ)有很好的选择性。随着金属离子Cu(Ⅱ)和Fe(ⅡI)的加入，标题化合物的荧光强度逐渐降低至基本消失。随着金属离子Pb(Ⅱ)和Fe(II)的加入，标题化合物的荧光强度逐渐降低，当金属离子加到一定浓度，标题化合物的荧光强度不随金属离子的变化而变化。对于Co(II)、Cr(ⅡI)、Mn(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)等离子，随着金属离子的加入标题化合物的荧光强度改变甚微或不改变。
关键词：荧光光谱；氰桥；Cu(Ⅱ)离子；晶体结构；识别
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of Cyanide-bridge Complex [cis-Fe(bpy)2(CN)2Mn(L)]2[PF6]4 and Interactions with Selected Metal Ions YU Meng1,2, WAN Fang 2, HU Jian-mei2, WANG Yong*2, LI Li2, LIU Sheng-peng1 (1. School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China; 2. Hubei Key Laboratory of Drug Synthesis and Optimization, Jingchu University of Technology, Jingmen 444800, China), Huaxue Shiji, 2020, 42(2), ～
Abstract：A cyanide-bridged square title complex was synthesized by the reaction of Mn(II) ions, organic ligand L and compound cis-FeII(bpy)2(CN)2×3H2O in the presence of NH4PF6. The title compound was confirmed by electronic absorption spectroscopy, elemental analysis, IR and X-ray single crystal diffraction analysis. The fluorescence response of heavy metal ions shows that the title compound has a good selectivity for Cu(II), Fe(III) and Pb(II) ions. With the addition of metal ions Cu(II) and Fe(III), the fluorescence intensity of the title compound gradually decreased or even disappeared completely. With the addition of metal ions Pb(II) and Fe(II), the fluorescence intensity of the title compound gradually decreases. When metal ions are added to a certain concentration, the fluorescence intensity of the title compound does no change with the addition of metal ions Pb(II) and Fe(II). For Co(II), Cr(III), Mn(II), Cd(II), Ni(II), Zn(II) ions, the fluorescence intensity of the title compound changes a little or no change with the addition of metal ions.
Key words：fluorescent spectroscopy; cyanide-bridge; Cu(II) ion; crystal structure
引用本文: 于孟，万方，胡建梅，等. 氰桥化合物 [cis-Fe(bpy)2(CN)2Mn(L)]2[PF6]4的合成及其对金属离子选择识别作用. 化学试剂, 2020, 42(2): 193-198.
新型香豆素类Hg2+荧光探针的合成及性能研究
陈清勉，罗俏，陈建华，彭明生*
(海南师范大学 化学与化工学院 热带药用植物化学教育部重点实验室，海南 海口 571158)
摘要：以4-二乙胺基水杨醛、三氟乙酰乙酸乙酯以及噻吩甲酰肼为原料合成了新型含氟香豆素类硫代酰腙型荧光探针化合物，经1HNMR、13CNMR、19FNMR、HR-MS对化合物结构进行了确认。通过荧光光谱法研究了化合物在乙腈溶液中对金属离子的识别性能。在pH4.5～9.5的范围内，Hg2+的加入使得化合物在464 nm处的荧光发射峰发生猝灭，其它金属离子的存在未对该现象造成明显干扰。Hg2+浓度越高，猝灭效果越明显。因此，化合物对Hg2+具有良好的荧光选择性和抗干扰性。Job`s 曲线表明，化合物与Hg2+的络合比为1:1。
关键词：香豆素；荧光探针；Hg2+；硫代酰腙；三氟甲基；席夫碱
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis and Performance of Novel Coumarin Fluorescent Probe for Hg2+ CHEN Qing-mian, LUO Qiao, CHEN Jian-hua, PENG Ming-sheng * (Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, China), Huaxue Shiji, 2020, 42(2), ～
Abstract：A novel fluorine-containing coumarin thiohydrazide-type fluorescent probe was synthesized from 4-diethylaminosalicylaldehyde, ethyl 4,4,4-trifluoroacetoacetate and thiophene-2-carbohydrazide. The structure of the probe was confirmed by 1HNMR, 13CNMR, 19FNMR and HR-MS. The probe has a high fluorescence selectivity for Hg2+ in acetonitrile with pH 4.5～9.5. Upon the addition of Hg2+, the probe displayed remarkable fluorescence quenching, which could not be disturbed with other metal ions. The job`s plot indicated that the complex ratio of the probe and Hg2+ is 1:1.
Key words：coumarin; fluorescent probe; Hg2+; thiohydrazone; trifluoromethyl; Shiff base
引用本文: 陈清勉，罗俏，陈建华，等. 新型香豆素类Hg2+荧光探针的合成及性能研究. 化学试剂, 2020, 42(2): 199-202.
重结晶法提纯制备尿素方法研究
孟娇然，段嫚雷，夏娃，齐钰，丁敏*
(上海市计量测试技术研究院，上海 201203)
摘要：通过对尿素重结晶温度及提纯次数的优化，建立了一种尿素的重结晶提纯方法。经提纯后的尿素样品采用红外光谱法和核磁共振法对其结构进行定性表征，并与美国国家标准与技术研究院（NIST）的尿素标准物质进行对照验证。样品纯度采用质量平衡法和差示扫描量热法进行测试，结果表明经重结晶后的样品纯度可达到99.9%。该方法可有效提纯尿素并应用于尿素纯度标准物质的研制。
关键词：尿素；重结晶；提纯；质量平衡法；差示扫描量热法
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2020）--
Recrystallization Purification Method for Urea MENG Jiao-ran, DUAN Man-lei, XIA Wa, QI Yu, DING Min* (Shanghai Institute of Measurement and Testing Technology, Shanghai, 201203, China), Huaxue Shiji, 2020, 42(2), ～
Abstract: A recrystallization method of urea is established through optimization of recrystallization conditions, including recrystallization temperature and purification times. The structure of the purified sample was confirmed by FT-IR and NMR and compared with the urea reference materials of the National Institute of Standards and Technology (NIST). The purity of the urea sample was quantitatively detected by mass balance method and differential scanning calorimetry (DSC), which demonstrated that the purity of the recrystallized sample can reach to 99.9%. This proposed method can purify urea effectively and could be applied to the preparation of urea standard materials.
Key words: urea; recrystallization; purification; mass balance method; differential scanning calorimetry
引用本文: 孟娇然，段嫚雷，夏娃，等. 重结晶法提纯制备尿素方法研究. 化学试剂, 2020, 42(2): 203-206.
5-（1-苯乙基）-8-氨基喹啉的合成工艺
张奥文，牛恬静，徐金娣，刘景辉*，胡国勤
（郑州大学 化工与能源学院，河南 郑州 450000）
摘要：以N-（喹啉-8-基）新戊酰胺和DL-1-苯乙醇为原料，酸酐为添加剂，无水三氯化铁为催化剂，1，2-二氯乙烷为溶剂制备标题化合物，产品结构经1HNMR和13CNMR表征。通过单因素实验，考察添加剂的种类、反应时间、反应温度、催化剂用量、添加剂用量对反应收率的影响，最终确定合成标题化合物的最佳条件为：n（N-（喹啉-8-基）新戊酰胺)：n（DL-1-苯乙醇）：n（添加剂）＝1：3：3，催化剂为20 mol% 无水三氯化铁，溶剂为1，2-二氯乙烷，反应温度为140 ℃、反应时间为24 h，产品收率可达83%。方法原料易得、操作简单、步骤节省，为产品的工业化奠定了基础。
关键词：喹啉；DL-1-苯乙醇；酸酐；苄基化；铁催化
中图分类号：TQ46 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of 5-(1-Phenylethyl)quinolin-8-amine ZHANG Ao-wen, NIU Tian-jing, Xu Jin-di, Liu Jing-hui*, Hu Guo-qin （College of Chemical Engineering and Energy，Zhengzhou University，Zhengzhou 450000，China）, Huaxue Shiji, 2020, 42( ), ～
Abstract: 5-(1-Phenylethyl)quinolin-8-amine was prepared by N-(quinolin-8-yl)pivalamide and DL-1-phenylethanol, anhydride, iron(III) chloride (anhydrous)and 1,2-dichloroethane are used as additive, catalyst and solvent, respectively. The structure of the product was confirmed by 1HNMR and 13CNMR. Based on single factor experiments, the effects of anhydride, reaction time, reaction temperature, amount of reaction catalyst and the amount of additive on the yields were investigated. The optimal conditions for the synthesis of 5-(1-phenylethyl)quinolin-8-amine were as follows: n (N-(quinolin-8-yl)pivalamide): n (1-phenylethanol): n (succinic anhydride) = 1:3:3, 20 mol% of iron(III) chloride and 1,2-dichloroethane as solvent, reaction temperature is 140 ℃, the reaction time is 24 h, the product yield can reach 83%. The method has the advantages of easy availability of raw materials, simple operation, and step saving, and lays a foundation for industrialization of products.
Key words: quinoline; DL-1-phenylethanol; anhydride; benzylation; iron catalyzed
引用本文: 张奥文，牛恬静，徐金娣，等. 5-（1-苯乙基）-8-氨基喹啉的合成工艺. 化学试剂, 2020, 42(2): 207-210.
一种新型二胺类空穴传输材料和NPB的合成及表征
房树清1，钱家盛*1，杭德余1，班全志2，段陆萌2
（1.安徽大学 化学化工学院，安徽 合肥 230601；2.北京燕化集联光电技术有限公司 北京 102422）
摘要：以N-苯基-1-萘胺和对溴碘苯为起始原料，经Buchwald-Hartwing偶联反应合成有机发光二极管空穴传输材料N,N'-二[4-(1-萘基苯基氨基)苯基]-N,N'-二苯基-[1,1'-联苯]-4,4'-二胺（2）。以1-溴化萘（1-溴萘）为初始原料与N,N'-二苯基联苯二胺经Buchwald-Hartwing偶联合成了N,N'-[二(1-萘基)-N,N'-二苯基]-1,1'-联苯基)-4,4'-二胺（NPB）。利用1HNMR、LC-MS等对产品结构进行表征。通过差示扫描量热仪（DSC）测得化合物2和NPB失重5%的温度分别为510 ℃和491 ℃，化合物2的玻璃化转变温度Tg为126 ℃，化合物2和NPB的升华温度分别为395 ℃和290 ℃，并通过UV-Vis紫外吸收光谱、荧光光谱研究了两种传输材料的光学性质。
关键词：空穴传输材料；OLED；N,N'-二苯基联苯二胺；NPB；升华温度
中图分类号：O753.2 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Characterization of Novel Diamine Hole Transport Material and NPB FANG Shu-qing1, QIAN Jia-sheng*1, HANG De-yu1, BAN Quan-zhi2, DUAN Lu-meng2 (1.College of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China; 2.Beijing Yanhua Jilian Optoelectronic Technology Co., Ltd., Beijing 102422, China), Huaxue Shiji, 2020, 42(2) ～
Abstract: The organic light-emitting diode (OLED) hole transporting material N,N'-bis[4-(1-nap- hthalenylphenylamino)phenyl]-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (2) was synthesized by a Buchwald- Hartwing coupling reaction using 1-naphthylaminobenzene and pbromoiodobenzene as starting materials. NPB was synthesized by coupling Buchwald-Hartwing with 1-bromonaphthalene as starting material and N, N'-diphenylbiphenyldiamine. Structure of compound 2 was confirmed by 1HNMR and LC-MS. The temperature at which 5% weight loss of compound 2 and NPB was measured by differential scanning calorimetry was 510 °C and 491 °C, respectively. The glass transition temperature Tg of compound 2 was 126 °C and the sublimation temperature of compound 2and NPB are 395 ℃ and 290 ℃, respectively. The optical properties of the two hole transporting materials were investigated by UV-Vis ultraviolet absorption spectroscopy and fluorescence spectroscopy.
Key words: hole transport material; OLED; N,N'-diphenylbiphenyldiamine; NPB; sublimation temperature
引用本文: 房树清，钱家盛，杭德余，等. 一种新型二胺类空穴传输材料和NPB的合成及表征. 化学试剂, 2020, 42(2): 211-215.
丙酮噻唑腙类衍生物的合成研究
石云飞，叶圣丰，陈淑兰，司红燕，陈尚钘，王宗德，廖圣良*
（江西农业大学 林学院 a.国家林业和草原局木本香料（华东）工程技术研究中心, b.国家林业和草原局/江西省樟树工程技术研究中心, c.江西特色林木资源培育与利用协同创新中心，江西 南昌 330045）
摘要：噻唑类化合物具有良好的杀菌、抗病毒、抗肿瘤等活性，而以噻唑及其衍生物作为母体与其他具有良好活性的基团构建成具有更高活性的新化合物逐渐成为研究的热点。腙类化合物在抑菌、消炎、抗肿瘤等方面也表现出较强的生物活性。因此，将噻唑基团和腙基团构建在同一化学结构中有望得到具有更高生物活性的化合物。以α-溴代苯乙酮、氨基硫脲和丙酮为原料，回流反应1 h，通过“一锅法”合成了7个同时 对所得的7个目标化合物结构进行表征，结果表明，数据与分子结构相匹配。与以往的噻唑腙类化合物的合成相比，该方法具有反应时间短、选择性高、副产物少及后处理简单等优点。
关键词：氨基硫脲；合成；噻唑腙；一锅法；席夫碱
中图分类号：TQ252.5 文献标识码：A 文章编号：0258-3283（2020）
Synthesis of Acetone Thiazole Hydrazone Derivatives SHI Yun-fei, YE Sheng-feng, CHEN Shu-lan, SI Hong-yan, CHEN Shang-xing, WANG Zong-de, LIAO Sheng-liang* (a.East China Woody Fragrance and Flavor Engineering Research Center of National Forestry and Grassland Administration, b.Camphor Engineering Research Center of National Forestry and Grassland Administration/Jiangxi Province, c.Collaborative Innovation Center of Jiangxi Typical Trees Cultivation and Utilization, College of Forestry, Jiangxi Agricultural University, Nanchang 330045, China), Huaxue Shiji, 2020, 42(2)
Abstract：Thiazole compounds have good bactericidal, antiviral, anti-tumor and other activities. Combination of thiazole or its derivatives with other groups, whichobtained good activity, to build novel compounds with higher activity has gradually become a research hotspot. Hydrazone compounds also show strong biological activity in bacteriostasis, anti-inflammatory, anti-tumor and other aspects. Therefore, it is expected to obtain compounds with higher biological activity by constructing thiazole group and hydrazone group in the same chemical structure. Seven acetone thiazole hydrazone compounds with thiazole ring and hydrazine as active groups are synthesized by one-pot method by using α-bromophenylacetone, thiosemicarbazide and acetone as raw materials under reflux condition for 1 h. The structure of these seven target compounds are confirmed by 1H NMR, 13C NMR 、ESI-MS and FT-IR. The characterization data of these compounds match with their molecular structures. Compared with the previous methods, this method has the advantages of short reaction time, high selectivity, few by-products and simple post-treatment.
Key words: thiosemicarbazide; synthesis; thiazole hydrazon; one-pot method; Schiff base
引用本文: 石云飞，叶圣丰，陈淑兰，等. 丙酮噻唑腙类衍生物的合成研究. 化学试剂, 2020, 42(2): 216-220.
编辑：MCM
