新型多功能抗癌烷化剂研究进展
葛瑶，任婷，赵丽娇*，钟儒刚
(北京工业大学 生命科学与生物工程学院 环境与病毒肿瘤学北京市重点实验室，北京 100124)
摘要：癌症是危害全球人类健康的重大疾病，烷化剂类药物广泛应用于癌症的治疗过程中。但是，在长期临床实践中发现，单功能烷化剂普遍存在治疗效率较低、毒副作用强等缺陷，很难达到理想的化疗效果。随后发展起来的多功能烷化剂引入了新的生物活性基团，具有选择性高、药物活性高等特点，其临床效果明显优于单功能烷化剂，近年来已成为抗癌药物的研究热点。综述了近年来作为抗癌药物的多功能烷化剂，并阐述了其抗癌作用机理的研究进展，为新型多功能烷化剂类抗癌药物的进一步研发提供依据。
关键词：癌症；多功能烷化剂；抗肿瘤活性；生物活性分子
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Progress of the Research on the Novel Multifunction Anticancer Alkylating Agents GE Yao, REN Ting, ZHAO Li-jiao*,ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, College of Life Science & Bioengineering, Beijing University of Technology, Beijing 100124, China)
Abstract: Cancer is a serious disease that endangers human health. Alkylating agents are widely used in the treatment of cancer. However, in long-term clinical practice, it was found that monofunctional alkylating agents hardly provided satisfactory chemotherapeutic effects because of their undesirable therapeutic efficiency and serious toxicity side effects. Later developed multifunctional alkylating agents introduced the new bioactive groups, which have the characteristics of high selectivity and high drug activity. Because of their good chemotherapeutic effect, multifunctional alkylating agents have been the focus of cancer treatment study in recent years. In this paper, advances on multifunctional alkylating agents are reviewed, and their anticancer activity as well as the mechanism of action are also stated which can provide reference and basis for the research of novel multifunctional alkylating agents.
Key word: cancer; multifunctional alkylating agents; anticancer activity; bioactive molecules
Fabricating Bowl-like Carbon via Interfacial Dehalogenation
DU Ke-wen, QIU Chao-chao, GUO Mei, DOU Gang, ZHANG Guo-xin(College of Electrical Engineering and Automation, Shandong University of Science and Technology, Tsingtao, 266590, China)
Abstract: Desirable structure and morphology of carbon materials can significantly improve their mechanical and electrochemical properties. In this study, we report the facile fabrication of bowl-like carbon via interfacial dehalogenation of polyvinyl dichloride (PVDC) amphipathic shells by mild alkaline of sodium sulphide (Na2S), the spherical PVDC amphipathic shells were primarily formed by the alignment of solvent-philic and -phobic parts during the dissolution of PVDC into dimethylformamide (DMF). We confirmed several important factors that have significant impacts on the morphology of resulted carbon bowls through setting up control experiments including the concentration of PVDC in DMF, the amount of Fe2+ species, and the addition of protonic solvent (such as ethanol). Due to the merits of good mechanical properties under high packing mode, we may safely envision that the carbon bowls can potentially deliver reasonably good electrochemical performance at high areal and volume packing densities.
Keywords: carbon materials; bowl-like carbon; dehalogenation; interface
表界面脱卤反应制备碗状碳材料
杜克文1，邱超超2，郭梅2，窦刚3，张国新*1
（山东科技大学电气与自动化工程学院，山东 青岛 266590）
摘要：碳材料的形貌和结构可显著提升其机械性能和电化学性能。在这项研究中，我们报导通过硫化钠（Na2S）促进的球状聚氯乙烯（PVDC）颗粒表界面的脱卤反应来制备具有碗状的碳材料。将球状PVDC悬浮在二甲基甲酰胺（DMF）中时，PVDC微球表界面会形成对DMF亲和与不亲和的部分并完成一定程度的规整排列。通过考察包括PVDC在DMF中的浓度、Fe2+的浓度以及质子性溶剂（如乙醇）的添加等因素，证实了影响碗状碳形成的三个重要的因素。由于在高填充模式下所具有了良好的机械性能的优点，可以预见到碳状碗可能在高面积和体积填充密度下可以提供良好的电化学性能。
关键词：碳材料；碗状碳；脱卤反应；表界面
亲和素引发金纳米粒子聚集的影响因素研究
杨爽，吴学，金艳花，朴晶玉*
(延边大学 师范学院，吉林 延吉 133002)
摘要：首次以亲和素作为凝聚剂与金纳米粒子（表面未经修饰）作用，通过中和金纳米粒子表面负电使粒子间斥力减弱、距离减小而聚集。通过探讨亲和素浓度和体积、缓冲溶液浓度以及金纳米粒子尺寸等因素对金纳米粒子聚集程度的影响发现，当与金纳米粒子溶液反应的亲和素体积≤5 mL时，PBS缓冲溶液中的离子对金纳米粒子影响可忽略；当与金纳米粒子溶液反应的亲和素的浓度介于50～100 mg/mL时，金纳米粒子呈现最大程度的聚集；相比于较小尺寸的金纳米粒子，大尺寸的金纳米粒子更易聚集；3种尺寸的金纳米粒子的聚集程度都随亲和素浓度变化而改变。本实验将为以金纳米粒子聚集为基础的生物检测研究以及金纳米粒子自组装方面的深入研究提供可靠的文献资料。
关键词：金纳米粒子；聚集；亲和素；凝聚剂；静电斥力
中图分类号：O648 文献标识码：A 文章编号：0258-3283（2018）
Effecting on Avidin-Induced Gold Nanopartical Aggregation YANG Shuang, WU Xue, JIN Yan-hua, PIAO Jing-yu* ( , Yanbian University, Yanji 133002, China), Huaxue Shiji, 2018, 40(7)
Abstract：In this work, the positively charged avidin was firstly employed as a “coagulant” of gold nanoparticles to cause nanoparticle aggregation, through strong electrostatic interaction between positively charged avidin and negatively charged gold colloids. Several factors effecting on gold nanoparticle aggregation have been investigated including the concentration and volume of avidin solution, the concentration of PBS buffer and the size of gold colloids. When the volume of avidin used was 5 mL or lower, the degree of gold nanoparticle aggregation was not dependent on the concentration of PBS buffer. The largest degree of gold nanoparticle aggregation was obtained with avidin concentration within the range of 50 ～ 100 mg/mL. The larger the size of gold nanoparticles, the easier the aggregation of gold colloids. For the three gold colloids with the same concentration, the aggregation degree of gold colloids was more closely related with avidin concentration than the size of gold colloids. The practical applicability was proved in field of colorimetric detection of biomolecules and nanoparticle self-assemble related work.
Key words：gold nanoparticles；aggregation；avidin；coagulant；electrostatic repulsion
甘蔗渣炭基固体酸的制备及催化合成乙酸甲酯研究
左卫元1，仝海娟1，欧阳辉祥1，廖安平*2，李媚2
(1.百色学院 化学与环境工程学院 广西高校桂西生态环境分析和污染控制重点实验室，广西 百色 533000；2.广西民族大学 化学化工学院 广西高校化学与生物转化过程新技术重点实验室，广西 南宁 530006）
摘要：以甘蔗渣为原料通过炭化-磺化的方法制备了甘蔗渣炭基固体酸，探讨了制备工艺条件对固体酸催化剂性能的影响。以正交实验对酯化反应温度、固体酸加入量、酸醇物质的量比、反应时间等影响合成乙酸甲酯的因素进行了优化，并考察了催化剂的稳定性。实验结果表明，较合理的制备固体酸催化剂的条件为：炭化温度300 ℃，炭化时间2.0 h，磺化温度90 ℃，磺化时间8.0 h。正交实验结果表明，在催化剂用量为乙酸质量的3%，酯化反应时间2.5h，n（乙酸）：n（甲醇）＝1∶3，酯化反应温度65 ℃的条件下，乙酸转化率为86.5%,且催化剂的稳定性良好，可循环使用7次。该研究结果为乙酸甲酯的合成提供了一种新型催化剂。
关键词：固体酸催化剂；乙酸甲酯；催化；合成
中图分类号：TQ413.23 文献标识码：A 文章编号：0258-3283（2018）
Preparation Of Solid Acid Catalyst From Bagasse And Its Catalytic Performance In Esterification Of Methyl Acetate(ZUO Wei-yuan1,TONG Hai-juan1, OU YANG Hui-xiang1,LIAO An-ping2*,LI Mei2)(1.Guangxi colleges and universities key laboratory of regional ecological environment analysis and pollution control of West Guangxi, College of Chemistry＆Environment Engineering, Baise University, Guangxi Baise 533000, China；2. School of Chemistry and Chemical Engineering of Guangxi University for Nationalities, Guangxi Colleges and Universities Key Laboratory of Chemical and Biological Transformation Process Technology,Guang xi Nanning 530006, China)
Abstract: A solid acid catalyst prepared through cooperated carbonization with sulfonation bagasse,and the prepared condition affected solid acid performance were investigated.The conditions affected the synthesis of methyl acetate including reaction time, reaction temperature, acid and methanol mole ratio and catalyst adding amount were researched by orthogonal test,and catalyst stability was also studied. It showed that the optimum conditions of prepared solid acid catalyst were carbonization temperature 300℃, carbonization time 2.0h, sulfonation temperature 90℃, sulfonation time 8.0h,respectively.In addition,the suitable conditons for synthesis of methyl acetate by orthogonal test with the acetic acid conversion 86.5% were molar ratio of acid to methanol 1:3, reaction time 2.5h, reaction temperature 65℃, catalyst adding amount to 3% of the acid mass,respectively.The catalytic performance maintain stability after being used 7 times. The results provide a new type of catalyst for the synthesis of methyl acetate.
Key words: solid acid catalyst;methyl acetate;catalytic;synthesis
以Peterson烯基化反应合成α, β–不饱和手性亚胺酯
刘剑剑1，曾永明*1，卢崇道*1, 2
(1．昌吉学院 化学与应用化学系，新疆 昌吉 831100；2．中国科学院 新疆理化技术研究所，新疆 乌鲁木齐 830011)
摘要：发展了一种以Peterson烯基化反应合成一系列α，β–不饱和N–叔丁基亚磺酰基手性亚胺酯的方法。以α-三甲基硅基-N-叔丁基亚磺酰亚胺酯为底物，KHMDS为碱，再对醛进行亲核加成，诱发硅基C→O的1, 3迁移，经过顺式消除，以71% ～ 96% 的分离产率得到一系列立体专一的E式α, β-不饱和N-叔丁基亚磺酰亚胺酯化合物。该方法无论对芳香醛、杂环芳香醛、α，β-不饱和醛还是易烯醇化的脂肪醛都有很好的反应性，对芳环上的给电子基和吸电子基都具有很好的兼容性。大部分反应都可以放大到克级水平，且通过将双键氢化，可得到一系列烷基化的带手性助剂的亚胺酯类化合物。
关键词：α-三甲基硅基-N-叔丁基亚磺酰亚胺酯；亲核加成；顺式消除；立体专一性合成；烷基化
中图分类号：O621.3 文献标识码：A 文章编号：0258–3283（2018）
Studies on the synthesis of α,β–unsaturated N–tert–butylsulfinyl imidates via Peterson olefination reaction LIU Jian–jian 1, YONG Ming-zeng* 1, LU Chong dao *1,2 ( 1. Department of Chemistry and Applied Chemistry, Changji University, Changji 831100, China; 2. Xinjiang Technical of Physics ＆ Chemistry, Chinese Academy of Science, Urumqi 830011, China).
Abstract: Synthesis of α，β–unsaturated N–tert–butylsulfinyl imidates via Peterson olefination reaction was developed. In this report, nucleophilic addition of α–trimethylsilyl–N–tert–butylsulfinyl imidates to aldehydes using KHMDS as base initiated 1,3–silyl migration from carbon to oxygen, subsequent syn–elimination led to stereospecific preparation of a range of α,β–unsaturated N–tert–butylsulfinyl imidates in 71% ～ 96% isolated yields. Regardless of the method of aromatic aldehyde, heterocyclic aromatic aldehyde, α，β–unsaturated aldehyde or easy enolized aliphatic aldehyde has good reactivity, and regardless of electron donate or electron withdraw groups on the aromatic ring has excellent compatibility. Most of the reactions can be scaled up to gram levels and a series of alkylated imine ester compounds which possess chiral auxiliary can be obtained by hydrogenating the double bonds.
Key words: α–trimethylsilyl–N–tert–butylsulfinyl imidates; nucleophilic addition; syn–elimination; stereospecific synthesis; alkylation
新型六芳基苯类衍生物的合成及其光物理性能
李思，袁龙飞，张月成，尹国辉，赵继全*
(河北工业大学 化工学院，天津 300131)
摘要：以菲醌、二苯丙酮、对甲氧基苯乙酸和丙二腈等为原料，通过Knoevenagel和Diels-Alder反应，设计合成了两个新型六芳基苯衍生物。利用核磁和高分辨质谱对化合物结构进行了表征，并研究了化合物的光物理性质。结果表明，化合物具有大斯托克斯位移（高达219 nm）、明显的溶剂致变色性能和聚集诱导发光增强（AIEE）。
关键词：六芳基苯；聚集诱导发光增强；溶剂致变色；斯托克斯位移
中图分类号：O621.2 文献标识码： 文章编号：
Synthesis and Photophysical Properties of Novel Hexarylbenzene Derivatives LI Si, YUAN Long-fei, ZHANG Yue-cheng, YIN Guo-hui, ZHAO Ji-quan* (Hebei University of Technology, School of Chemical Engineering, Tianjin 300131)
Abstract：Two novel hexaarylbenzene derivatives were synthesized viaKnoevenagel condensation and Diels-Alder reactions using phenanthraquinone, diphenylacetone, p-methoxyphenylacetic acid and malonitrile, etc. Their structures were confirmed by NMR and HR-MS. Subsequently, the photophysical properties of the two compounds were investigated, which revealed that the two compounds exhibited large Stokes shifts (up to 219 nm), obvious solvatochromism and aggregation-induced emission enhancement (AIEE).
Key words：hexaaryl benzene; aggregation-induced emission enhancement; solvatochromism; Stokes shift
对甲苯磺酸酯修饰的18F标记策略
赵慧敏1,2，杨敏2，马宇衡*1，张振涛*1
(1.内蒙古医科大学 药学院，内蒙古 呼和浩特 010110；2.江苏省原子医学研究所，江苏 无锡 214063)
摘要：核素示踪是新药研发的重要手段之一，具有灵敏度高、特异性好、直观、真实等优点，结合microPET等影像设备能提供化合物在活体内的吸收、分布、排泄、转移或转化规律等全面、系统的信息，已成为新药研发中不可或缺的新手段。核素标记是核素示踪的基石。18F具有和H相似的化学性质，可通过取代反应对化合物进行标记，且半衰期良好、显像性能优良，是理想的示踪核素。主要介绍取代作为修饰基团的对甲苯磺酸酯达到18F标记目的的标记方法，包括直接标记法和间接标记法两种。
关键词：18F；标记；对甲苯磺酸酯
中图分类号：R9 文献标识码：A 文章编号：0258-3283（2018）
18F Labeling Strategy: p-Toluenes Modification ZHAO Hui-Min 1, YANG Min 2, MA Yu-Heng *, ZHANG Zhen-Tao* (1. School of Pharmaceutical Sciences, Inner Mongolia Medical University, Hohhot 010110, China; 2. Molecular Imaging Centre, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, China)
Abstract: Radionuclide tracing, which is superior in sensitivity and specificity, is an intuitive measurement in new drug research and investigation. Nuclide labeling is the cornerstone of nuclide tracing. 18F, an ideal tracer nuclide, which owns the same chemical properies of H, can labele compounds by substitution reaction, as well as suitable half-life and imaging performance. The review of 18F labeling is mainly about replacing p-toluenesulfonate, which contains the direct and indirect methods.
Key words: 18F; labeling; p-toluenesulfonate
过渡金属催化芳香偶氮化合物的合成研究进展
马姣丽，李成凤，周立超，程辉成*
(广东石油化工学院 化学工程学院，广东 茂名 525000)
摘要：芳香偶氮化合物具有独特的结构和性质，在光电材料、有机染料及有机合成等领域有着广泛的应用。开发高效合成芳香偶氮化合物的方法成为有机合成化学的研究热点之一，受到化学家们的广泛关注。近些年来，化学家们通过过渡金属催化合成芳香偶氮化合物研究取得了重要进展。从芳香肼、芳香胺及芳基硝化物这3类底物出发，根据不同的过渡金属催化剂进行分类，综述芳香偶氮化合物的合成研究进展及其反应机理，就该研究领域的局限性和未来的发展前景进行了总结和展望。
关键词：芳香偶氮化合物；合成；过渡金属催化；研究进展
中图分类号：0625 文献标识码：A 文章编号：0258-3283(2018)
Progress in the Synthesis of aromatic azo compounds via transition metal catalysis MA Jiao-li, LI Cheng-feng , ZHOU Li-chao, CHENG Hui-cheng * (College of Chemcal Engineering, Guangdong University of Petrochemical Technology, Maoming 525000,China)
Abstract：Aromatic azo compounds are widely used in the fields of light electric materials, organic dyes and organic synthesis etc due to its unique structures and properties. The efficient synthesis of aromatic azo compounds has become one of the highlights in organic synthesis and aroused extensive attention of chemists. In recent years, chemists have made significant progress in the study of the catalytic synthesis of aromatic azo compounds by transition metals. In this paper, starting from aryl hydrazides, anilines and nitroaromatics, we reviewed the progress in the synthesis of aromatic azo compounds and the reaction mechanisms according to different types of transition metal catalysts. The limitations of the research are summarized and the future development is prospected.
Key words：aromatic azo compounds; synthesis; transition metal catalysis; research progress
核磁共振定量法测定恩曲他滨绝对含量
李宏伟1，张红芹3，郝海军*2
（1.黄河科技学院，河南 郑州 450063；2.上海医药工业研究院，上海 201203；3. 辅必成（上海）医药科技有限公司，上海 201203）
摘要：分别采用氢核磁共振定量法和氟核磁共振定量法测定恩曲他滨绝对含量。氢核磁共振定量法以恩曲他滨δ 8.32 ～ 8.40处质子峰和对苯二甲酸二甲酯δ 8.12处为定量峰，在恒温27 ℃，采样时间4.01 s，弛豫延迟时间10 s，扫描次数为64条件下采集氢谱。氟核磁共振定量法以4-溴-2-氟-乙酰苯胺为内标，在恒温27℃，谱宽为29296.87 Hz，中心频率为-54667.50 Hz下采集氟谱。结果显示，氢核磁共振定量法和氟核磁共振定量法测定结果基本与质量平衡法结果一致。因此，核磁共振法测定恩曲他滨绝对含量具有专属性高、准确、快速等优势。
关键词：恩曲他滨；核磁共振法；氢核磁共振定量法；氟核磁共振定量法
中图分类号：O652.1 文献标识码：A 文章编号：0258-3283（2018）
Determination of Emtricitabine by Quantitative Nuclear Magnetic Resonance LI Hong-wei1, ZHANG Hong-qin3, HAO Hai-jun*2 (1. Huanghe Science & Technology College, Zhengzhou 450005, China; 2. Shanghai Institute of Pharmaceutical Industry, Shanghai 201203, China; 3. FuBiCheng (shanghai) Pharmaceutical Technology Co. Ltd., Shanghai 201203, China), Huaxue Shiji, 2018, 40(7)
Abstract: Proton nuclear magnetic resonance (HqNMR) and fluorine nuclear magnetic resonance (FqNMR) were employed to determine the content of emtricitabine. The 1H-NMR spectra were collected at 300 K with 4.01 s acquisition time, 10 s relaxation delay and 64 scanning times. Proton signal peaks at δ 8.32 ～ 8.40 of emtricitabine and δ 8.08 of dimethyl terephthalate were served as quantitative peaks. The 19FNMR spectra were obtained at 27 ℃ with spectral width was 29296.87 Hz and transmitter frequency offset (O1) was -54667.50 Hz. 4’-Bromo-2’-fluoroacetanilide was employed as internal standard of FqNMR. The results of HqNMR and FqNMR were generally consistent with that of the mass balance method. Quantitative nuclear magnetic resonance could be used for the quantitative determination of emtricitabine.
Key words: emtricitabine; nuclear magnetic resonance; proton nuclear magnetic resonance; fluorine nuclear magnetic resonance
气相色谱-质谱法测定甘蔗中13种除草剂
黄敏兴,高裕锋*,甄振鹏,庞扬海，王小鹏,余构彬,郭剑雄
（广东省生物工程研究所（广州甘蔗糖业研究所） 广东省甘蔗改良与生物炼制重点实验室
国家糖业质量监督检验中心，广东 广州 510316）
摘要：建立了甘蔗中13种除草剂的气相色谱质谱（GC-MS）多残留检测方法。甘蔗样品用乙腈提取，经QuEChERS方法净化后，采用GC-MS进行分析检测，在选择离子模式（SIM）下，外标法定量，线性良好（r2＞0.998），检出限为0.71～3.17μg/kg。分别在样品中添加13种除草剂标准溶液10、20、100 μg/kg，进行标准添加回收率实验，方法回收率为 85.4%～105.5%，相对标准偏差为1.9%～9.1%（n=6）。该方法前处理简单快捷、节省溶剂，灵敏度、准确度、精密度均符合农药残留检测要求，适用于甘蔗中除草剂多残留检测。
关键词：甘蔗；除草剂；QuEChERS；气相色谱-质谱法
中图分类号:0657.63 文献标识码 :A 文章编号
Determination of 13 Herbicide Pesticide Residues in Sugarcane by GC-MS HUANG1,2 minxing, GAO yufeng1,2*, ZHEN zhenpeng1,2, PANG yanghai1,2, WANG xiaopeng1,2, YU goubing1,2, GUO jianxiong1,2 (1. Guandong Bioengineering Institute (Guangzhou Sugarcane Industry Research Institute) Guangdong Key Lab of Sugarcane Improvement and Biorefinery; 2 .China Sugar Inspection Center, Guangzhou 510316)
Abstract: A method was developed for the determination of 13 herbicide pesticide residues in Sugarcane by gas chromatograph-mass spectrometry (GC-MS). The residues in the Sugarcane were extracted by acetonitrile，cleaned up by developed QuEChERS method and then analyzed by using GC-MS in selecting ion mode (SIM). External standard method was used to determine the residue contents with a good linear relationship (r2 > 0.998). The limits of detection (LOD) were 0.71~3.17 μg/kg. The recoveries of 13 herbicide pesticide residues at three levels of 10, 20 and 100 μg/kg were from 85.4% to 105.5% with the relative standard deviations (RSDs) of 1.9%～9.1%(n=6) in sugarcane. The method is simple, reproducible, solvent saving and characterized with acceptable sensitivity and accuracy to meet the requirements of the pesticide residues analysis, and this developed procedure is suitable for the determination of herbicide pesticide residues in sugarcane.
Keywords: Sugarcane; herbicide; GC-MS; QuEChERS
红外光谱法建模快速筛查抗风湿类中成药中的乙酰水杨酸
彭梦侠*，姚婉清，陈梓云
（嘉应学院 化学与环境学院，广东 梅州 514015）
摘要：对抗风湿类中成药中添加乙酰水杨酸的快速筛查方法进行了研究。以13种市售抗风湿类中成药为研究对象，采集研究样品的红外光谱图（FTIR），采用判别分析法（Discriminant Analysis）建立了抗风湿类中成药中乙酰水杨酸的快速筛查模型。用此模型检测了另外17种市售抗风湿类中成药，结果表明：阴性样品和阳性样品的识别正确率为100%，误判数为0。
关键词：抗风湿类中成药；乙酰水杨酸；红外光谱；快速筛查
中图分类号：O657.33 文献标识码：A 文章编号：0258-3283（2018）
Rapid Screening of Acetylsalicylic Acid in Anti-rheumatic Chinese Medicines PENG Meng-xia*, YAO Wan-qing, CHEN Zi-yun (School of Chemistry and Environment，Jiaying University，Meizhou 514015，China), Huaxue Shiji, 2018, 40(7)
Abstract: The method of rapid screening of acetylsalicylic acid in anti-rheumatic Chinese medicines was investigated. Taking 13 kinds of anti-rheumatic Chinese medicines as the objects, the recognition model of acetylsalicylic acid was established using FTIR combined with discriminant analysis. The model was used to detect other 17 samples, and the results showed that the correct recognition rate of model was 100%, and the miscarriage of justice was 0.
Key words: anti-rheumatic Chinese medicine; acetylsalicylic acid; FTIR; rapid screening
固相萃取-等离子体质谱联用测定宠物食品中铅、镉、铜、锌
马兴*，肖亚兵，张静，倪松
（天津出入境检验检疫局，天津 300461）
摘要：建立了固相萃取（Solid-phase Extraction，SPE）-电感耦合等离子体质谱（Inductively Coupled Plasma – Mass Spectrometry，ICP-MS）联用的方法用以测定宠物食品中铅、镉、铜、锌。结果表明，试验所采用的检测方法在测定宠物食品中铅、镉、锌、铜等元素方面具有一定的简便性与可靠性，试验的准确度和精密度较高。本方法测定猫粮和狗粮中铅、镉、铜、锌含量，所得结果与原子吸收光谱法（Atomic Absorption Spectrometer，AAS）一致。
关键词：固相萃取；ICP-MS；宠物食品；元素
Determination of Pb, Cd, Cu, Zn in pet food by ICP-MS with solid-phase extraction Ma Xing*, Xiao Ya-Bin, Zhang Jing, Ni Song (Tianjin Entry-Exit Inspection and Quarantine Bureau, Tianjin 300461, China)
Abstract：A method for the determination of Pb, Cd, Cu, Zn in pet foods by inductively coupled plasma-mass spectrometry (ICP-MS) with solid-phase extraction was developed. The results show that this method is simple, reliable, has higher accuracy and precision in the determination of Pb, Cd, Cu, Zn in pet foods. Using this method to quantitative analyze Pb, Cd, Cu, Zn in cat foods and dog foods, the results are consistent with the atomic absorption spectrometer method.
Key words：solid-phase extraction; ICP-MS; pet food; element
硫色烯并嘧啶类化合物的合成、晶体结构及反应机理
齐慧1，李生彬1，张超超2，冯佳佳1，孙晓阳1，宋亚丽*1
（1. 河北大学 药学院 河北省药物质量分析控制重点实验室，河北 保定 071002；
2. 隆尧县医院，河北 邢台 055350)
摘要：以甲酸、氨基硫脲和6-氯-4-氧代硫色满-3-甲醛为原料，采用“一锅法”合成8-氯-5-硫氰基-2H-硫色烯并[4,3-d]嘧啶。该化合物的结构经1HNMR、13CNMR、FT-IR、ESI-HRMS、X-射线进行确证，分析了其单晶结构，并探究了该反应的机理。该化合物收率为86%，属于单斜精系，P21/c空间群，晶胞参数为a = 20.871(8) nm，b = 7.032(3) nm，c = 18.125(7) nm，β = 114.665(6) °，V = 2417.3(16) Å3，Z = 8。晶体结构的稳定主要靠π-π键的堆积作用。在以盐酸为溶剂的体系中有利于该反应的进行。
关键词：8-氯-5-硫氰基-2H-硫色烯并[4,3-d]嘧啶；X-射线；硫氰基；反应机理
中图分类号：O626.41 文献标识码：A 文章编号：0258-3283（2018）
Synthesis, Crystal Structure and Reaction Mechanism of Thiochromeno [4,3-d] Pyrimidine QI Hui1, LI Sheng-bin1, ZHANG Chao-chao2, FENG Jia-jia1, SUN Xiao-yang1, SONG Ya-li*1 (1.Key Laboratory of Pharmaceutical Quality Control of Hebei Province, College of Pharmaceutical Sciences, Hebei University, Baoding 071002, China; 2. Longyao County Hospital of Hebei Province, Xingtai 055350, China), Huaxue Shiji, 2018, 40(7)
Abstract: 8-Chloro-5-thiocyanato-2H-thiochromeno [4,3-d] pyrimidine was synthesized with methanoic acid, thiosemicarbazide and 6-chloro-4-oxothiochroman-3-formaldehyde by the method of one-pot reaction. The structure was confirmed by 1HNMR, 13CNMR, FT-IR, ESI-HRMS andX-ray diffraction. Besides, the structure of monocrystal was analyzed, and the reaction mechanism was proposed. Yeild of the compound was 86%. The crystal of the compound belongs to monoclinic, space group P21/c with cell parameters a = 20.871(8) nm, b = 7.032(3) nm, c = 18.125(7) nm, β = 114.665(6) °, V = 2417.3(16) Å3, Z = 8. The stabilization of the crystal structure mainly depends on the accumulation of π-π bonds. Hydrochloric acid was benefited for the reaction in the system of the solvents with hydrochloric acid.
Key words: 8-chloro-5-thiocyanato-2H-thiochromeno [4,3-d] pyrimidine; X- ray diffraction; thiocyanato; reaction mechanism
有机催化苯并三氮唑与查耳酮的不对称aza-Michael加成反应
王黎明，熊蕊，穆宏文，金瑛*
（吉林医药学院 药物化学教研室，吉林 吉林 132013）
摘要:将脯氨醇衍生物用于有机催化苯并三氮唑与查耳酮的不对称aza-Michael加成反应，制备手性氮杂环化合物。通过1HNMR、13CNMR和HRMS光谱技术对其结构进行表征，通过HPLC手性色谱柱测定产品的对映体过量值（ee）。考察溶剂、温度及催化剂用量对反应立体选择性影响，优化催化剂体系。结果表明：最佳催化条件为10 mmol%催化剂, 甲苯为溶剂, 0 oC反应。将此条件用于7种不同取代查耳酮的反应，得到了58％ ～ 70％的收率和最高达72%ee的对映选择性，拓宽了该反应的催化剂类型和底物范围。
关键词: 脯氨醇衍生物；不对称催化; aza-Michael加成反应；苯并三氮唑；查耳酮
中图分类号: O621. 3 文献标识码: A 文章编号：0258-3283（2018）
Organocatalytic Asymmetric Aza-Michael Reaction of Benzotriazole with Chalcones WANG Li-Ming, XIONG Rui, MU Hong-Wen, JIN Ying* (Department of Pharmaceutical Chemistry, Jilin Medical University, Jilin 132013, China)
Abstract: Prolinol derivatives as organocatalysts were applied in asymmetric aza-Michael addition reaction of 1,2,3-benzotriazole with different chalcones to prepare chiral N-heterocycles. The structure of compounds were confirmed by 1HNMR , 13CNMR and HRMS and the enantioselectivities of adducts were determined by HPLC chiral column. The effect of solvent, temperature and catalyst loading ammount were investigated. The optimized conditions were confirmed to include toluene as the solvent with a 10 mol% loading of catalyst at 0 oC. The 7 desired products were obtained in 58-70% yield with up to 72% ee under the screened catalysis condition. The catalyst type and the substrate scope were broadened in this methodology.
Key words: Prolinol derivative; asymmetric catalysis, aza-Michael addition, chalcones, benzotriazole
基于萘酰肼的铜离子选择性荧光探针在溶液和薄膜中的应用
喻淼*，张宁
（黄淮学院 化学与制药工程学院，河南 驻马店 463000）
摘要：对萘酰肼衍生物的铜离子识别特性进行了研究。基于紫外可见光谱和荧光光谱研究，发现该化合物能够选择性识别铜离子，检出限达到8.9 × 10-9 mol/L。在溶液中加入铜离子后溶液颜色由无色变为黄色，在紫外灯照射下溶液荧光发生了明显淬灭。因此借助该化合物可以实现对铜离子的肉眼辨识，并且将该化合物制备得到荧光薄膜材料后，该荧光薄膜材料也能实现对铜离子的选择性识别，这为进一步制备铜离子识别器件奠定了基础。
关键词：铜离子；萘酰肼；探针；检出限
中图分类号：O657.32 文献标识码：A 文章编号：0258-3283（2018）
Convenient and Highly Effective Detection of Cu2+ in Solution and Thin Film YU Miao*, ZHANG Ning（College of Chemical and Pharmaceutical Engineering, Huanghuai University, Zhumadian 463000, China）.
Abstract：The sensing ability of a Schiff base derivative based sensor (HHMN) for copper ions has been investigated. The UV-vis and fluorescence experiments showed that it can be used as a selective sensing probe for copper ion (Cu2+) with the detection limit of 8.9 nmol/L. Further experiments showed that HHMN can readily distinguish Cu2+ in either aqueous solution or the PVA-based thin film. These finding would enable this compound to be used as an efficiently colorimetric and fluorescent probe for Cu2+.
Key words：copper ion; naphthoic hydrazide; sensor; detection limit
不同提取方法对南果梨挥发性香气成分的影响研究
张博1，李小兰2，黄世杰1，陈志燕1，黄善松1，李志华2，胡志忠2，张峻松*1
(1. 郑州轻工业学院 食品与生物工程学院，河南 郑州 450002；
2. 广西中烟有限责任公司技术中心，广西 南宁 530001)
摘要：为比较不同提取方法对南果梨香气成分的影响，采用静态顶空法（SHS）、同时蒸馏萃取法（SDE）、固相微萃取法（SPME）提取南果梨的挥发性香气成分，并结合气相色谱-质谱法(GC-MS)分析检测。3种方法共检测出78种香气成分，其中SHS法检测出香气成分22种；SDE法检测出香气成分53种；SPME法检测出香气成分33种。SHS法提取更多相对含量的酯类、醛酮类、酚类；SDE法提取出更多相对含量的醇类；SPME法提取出更多相对含量的烃类、酸类。进一步分析已确定的成分发现，无论从提取香气成分数量还是典型香气成分的充分程度，SDE法均效果最佳。
关键词：南果梨；静态顶空法；同时蒸馏萃取法；固相微萃取法；香气成分
中图分类号：S661.2 文献标识码：A 文章编号：
Effect of Different Extraction Methods on the Aroma Components of Nan Guo Pear ZHANG Bo1, LI Xiao-lan2, HUANG Shi-jie1, CHEN Zhi-yan1, HUANG Shan-song1, LI Zhi-hua1, HU Zhi-zhong1, ZHANG Jun-song* 1 (1.School of Food and Bioengineering,Zhengzhou University of Light Industry, Zhengzhou 45002; 2. Technology Center of Guangxi Tobacoo Industry Co.,Ltd., Nanning 530001)
Abstract: In order to compare the impact of different extraction methods on the aroma components of Nanguo pear, static headspace (SHS), simultaneous distillation extraction (SDE), solid phase microextraction extraction (SPME) of Nanguo pear aroma components and combined with gas chromatography-mass spectrometry (GC-MS) analysis. The results showed that 78 kinds of aroma components were detected by three extraction methods, 22 kinds of aroma components were detected by SHS method; 53 kinds of aroma components were detected by SDE method; 33 kinds of aroma components were detected by SPME method. More relative content of esters, aldehydes and ketones, phenols were detected by SHS method；More relative content of alcohol were detected by SDE method. More relative content of hydrocarbons, acids were detected by SPME method. Further analysis of the composition found, SDE method was the best one in terms of the amount of aroma components extracted and the adequacy of typical aroma components.
Key words: Nan guo pear; static headspace; simultaneous distillation-extraction; solid phase microextraction; aroma components
天然产物查尔酮Sanjuanolide的首次合成
李方辉，杨金会*，牛明杰，马涛，冯月基，严志明
(宁夏大学 化学化工学院 省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏 银川 750021)
摘要：2′,4′-二羟基-3′-（2″-羟基-3″-甲基-3″-丁烯基）查尔酮Sanjuanolide是从Dalea frutescens（当地人称为达列亚草原草）中提取出来的，该天然产物对前列腺癌细胞具有明显的的抗增殖活性。以廉价的2,4-二羟基苯乙酮、苯甲醛等为原料，以总收率4.8%完成了Sanjuanolide的首次全合成，并经过路线优化将总收率提高至15.3%，有效提高了合成效率，可用于较大量合成。合成的关键步骤是利用光氧化法将取代的异戊烯基侧链变成（2″-羟基-3″-甲基-3″-丁烯基）侧链。所有新化合物的结构都经过NMR、HR-MS、IR确认。
关键词：光氧化；查尔酮；全合成；抗癌
中图分类号： TQ28 文献标识码：A 文章编号：0258-3283（2018)
Total Synthesis of Natural Chalcone Sanjuanolide LI Fang-hui,YANG Jin-hui*, NIU Ming-jie , MA Tao , FENG Yue-ji, YAN Zhi-ming( State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering，College of chemistry and chemical engineering, Ningxia University, Ningxia 750021, China)
Abstract：2′,4′-Dihydroxy-3′-(2-methyl-3-hydroxy-1-butanyl) chalcone sanjuanolide was isolated from daleafrutescens. The compound has obvious antiproliferative activity to prostate cancer cells.Chalcone sanjuanolide was first total synthesized from cheap starting material 2,4-didroxyacetophenone and benzaldehyde and the total yield was 4.8%.Then the total yield was increased to 15.3% by route optimization. Greatly improved the efficiency of synthesis.The structures of all new compounds were confirmed by NMR, IR and HR-MS .
Key words：photooxidation; chalcone; total synthetic;antibacteria
吡氟草胺的合成工艺研究
王涛
（漯河职业技术学院 轻工系，河南 漯河 462000）
摘要：以2-氯-3-三氯甲基吡啶为原料，经3步反应制得标题化合物。原料在路易斯酸的催化作用下生成2-氯烟酰氯，再与2,4-二氟苯胺生成酰胺中间体2-氯-N-(2,4-二氟苯基)烟酰胺；进一步与间三氟甲基苯酚缩合得到吡氟草胺。对各步单元反应进行了条件优化，确认了最佳合成工艺，反应总收率达72%。该工艺原料易得、操作简单、无大量废酸产生，适合工业化生产。
关键词：2-氯-3-三氯甲基吡啶；吡氟草胺；工艺
中图分类号：TQ45 文献标识码：A
Synthesis Process of diflufenican Wangtao(Luohe Vocational Technology College HeNan LuoHe 462000)
Abstract: Taking 2-chloro-3-(trichloromethyl)pyridine as raw material, diflufenican can be synthesized via 3 steps reaction. Acylation reaction with Lewis acid as catalyst to prepare the acyl chloride, amide intermediate can be cured by amidation reaction, the target compound was synthesized via condensation reaction. The study aims to optimize each step of synthetic process, the total yield is 72% under the optimal condition.. The raw material is available easily, and the operations are simple, the whole process is suitable for industrial production without waste acid.
Key words: 2-chloro-3-(trichloromethyl)pyridine; diflufenican; process
微通道反应器内合成二氯乙二肟的工艺研究
张建功，何琦文，毛明珍，宁斌科*
(西安近代化学研究所 氟氮化工资源高效开发与利用国家重点实验室，陕西 西安 710065)
摘要：研究了微通道反应器中乙二肟经氯化反应制备二氯乙二肟的工艺过程，考察了反应温度、原料物质的量配比、停留时间对反应的影响。通过实验得到了较好的工艺条件：反应温度为-10 ℃，n（氯气）：n（乙二肟）＝2.2，停留时间90 s，二氯乙二肟的收率为85%。传统釜式反应器中最佳工艺条件：反应温度-30 ℃，n（氯气）：n（乙二肟）＝2.5，反应时间6 h，收率最高为78%。相较于传统工艺方法，利用微通道技术降低了反应条件的要求，减少了氯气的使用量，大大提高了生产效率，过程安全可控。
关键词：微通道反应器；乙二肟；氯化；二氯乙二肟
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2018）
Research on synthesis of Dichloroglyoxime in Micro-Channel ReactorZhang Jian-gong1,2， Mao Ming-zhen1,2 , He Qi-wen1,2，Ning Bin-ke1,2* ( 1. Xi’an Modern Chemistry Research Institute, Xi’an 71065, China; 2. State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an, Shanxi 710065, China)
Abstract：The synthesis process of dichloroglyoxime via the chlorination of glyoxime in micro-channel reactor was researched, and the influence of reaction including reaction temperature, raw material mol rate, retention time were observed. The optimum technical condition from the test results was: temperature at -10 degree, the mol rate of chlorine and glyoxime at 2.2, retention time at 90s, the yield of dichloroglyoxime at 85%. The optimum technical condition from the traditional batch reactor was: temperature at -30 degree, the mol rate of chlorine and glyoxime at 2.5, retention time at 6h, the yield of dichloroglyoxime at 78%. Compared to the traditional method, the technique of using microchannel reactor not only improve the effect of reaction, reduce the requirements for the reaction conditions, and reduce the use of chlorine gas, but also improve production efficiency, make the process more safe and easy control.
Key words： micro-channel reactor; glyoxime; chlorination; dichloroglyoxime
3-氟-4-碘二苯醚的合成
王婷a, b，李飞a, b，周志旭a, b，陈方鑫a, b，赵春深*a, b, c
（贵州大学 a. 化学与化工学院, b. 贵州药物合成工程实验室, c. 贵州发酵工程与生物制药重点实验室，贵州 贵阳 55002）
摘要：标题化合物是合成觉醒促进剂、Lp-LPA2抑制剂、酪氨酸激酶抑制剂等药物的重要中间体，因此，在医药领域有着重要的地位。虽然3-氟-4-碘二苯醚在医药领域应用较为广泛，但化合物的合成工艺未见文献报道。通过大量的实验研究与工艺优化，最终形成了以4-溴-2-氟苯胺为原料，经保护、成醚、脱保护和Sandmeyer反应得到目标化合物的最佳工艺。该合成路线具有原料简单易得，合成条件安全易操作，产率较高的优点，总产率为87 %，适合工业化生产，为其工业化合成降低成本，也为该化合物的研究与发展提供了推动作用。
关键词：3-氟-4-碘二苯醚；4-溴-2-氟苯胺；合成
中图分类号：O626.1 文献标识码：A 文章编号：0258-3283（2018）
The synthesis of 1-iodine -2- fluorine -4- phenoxy benzene WANG Tinga, b, LI Feia, b, ZHOU Zhi-xua,b, CHEN Fang-xina, b, ZHAO Chun-shen*a, b, c(a. School of Pharmaceutical Sciences, b. Guizhou Engineering Laboratory for Synthetic Drugs, c. Key Laboratory of Guizhou for Fermentation Engineering and Biomedicine, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 2018, 40(7)
Abstract: 1-Iodine -2- fluorine -4- phenoxy benzene is an important intermediate of synthetic arousal promoter, lp-lpa2 inhibitor, tyrosine kinase inhibitor and other drugs, so it has an important position in the field of medicine. Although it is widely used in the field of medicine, the synthesis process of the compound has not been reported. In this paper, 4- bromine -2- fluoroaniline as original material, and it through the protectreaction, ether reaction, amino protection, Sandmeyer reaction to produce target product of 1-, iodine -2- fluorine -4- phenoxy benzene. Synthetic route of the process has many advantages , such as the raw materials are easily obtained, the synthesis conditions are safely operation, high yield of the target compound, and the total yield was 87%.So this synthetic route is suitable for industrial production. The synthesis of 1-iodine -2- fluorine -4- phenoxy benzene reduce the cost and it also contributed to the research and development of the compound.
Key words: 1-iodo-2-fluoro-4-phenoxybenzene; 4-bromo-2-fluoroaniline; synthesis
五种苯乙醇胺类β受体激动剂的合成研究
王易，刘慧艳，陈武炼*
(上海安谱实验科技股份有限公司，上海 201600)
摘要：研究了以廉价的4-氨基苯乙酮为原料，苯环被溴化或氯化后，再经腈化、α-氢溴化、有机胺胺化后，最后通过硼氢化钾将羰基还原后，可以得到溴布特罗，克伦特罗，西布特罗，西马特罗，溴氯布特罗，五种苯乙醇胺类β受体激动剂。通过合成路线的合理设计，原料卤代反应后的中间体都可以作为后续反应的物料，原子利用率高，实现绿色合成化学的目的。我们对产物结构经行了1H NMR确认，其HPLC纯度在99%以上，可作为测定β受体激动剂的对照品试剂，满足食品安全的检测需求。
关键词：合成；苯乙醇胺类β受体激动剂；4-氨基苯乙酮；对照品
中图分类号：O622.3 文献标识码：A 文章编号: 0258-3283（2018）
Synthesis of Five kinds of Phenyl ethanolamine β Agonists Wang Yi1, Liu Hui-Yan1, Chen Wu-Lian*1 (Anpel Laboratory Technologies (Shanghai) Inc., Shanghai, 201600, China)
Abstract：Five kinds of phenyl ethanolamine β agonists, including brombuterol, clenbuterol, cimbuterol, cimaterol, and bromoclenbuterol, were synthesized by using 4-aminoacetophenon as raw materials, which were obtained via benzene ring chlorination or bromination, cyanation, α-hydrogen bromination, amination with organic amines and reduction of carbonyl group by potassium borohydride. Through the rational design of the synthetic route, the intermediate of the halogenated reaction can be used as the material for the subsequent reaction, and the utilization of the atom is high, so as to achieve the purpose of green synthetic chemistry. The chemical structure of the products were confirmed by 1H NMR, and their chemical purity was above 99%. The obtained products could be used as reference reagents for determination of β agonists in food safety detection fields.
Key words：synthesis; phenyl ethanolamine β agonist; 4-aminoacetophenone; reference substance
