单层二硫化钼纳米片的剥离制备和生物医学应用
陆佳莹1，吴琛1, 2，李菁菁*1, 2
(1.徐州医科大学 医学影像学院，江苏 徐州 221004；
2.徐州医科大学附属医院 医学影像科，江苏 徐州 221006）
摘要：作为一种具有类石墨烯结构的二维层状纳米材料，单层二硫化钼凭借其独特的带隙结构、光热传感以及良好的生物相容性在肿瘤光热治疗、生物传感等生物医学领域具有广阔的研究前景。结合近五年的研究综述了几种常见的二硫化钼剥离方法，同时介绍了单层二硫化钼纳米片在生物医学领域中的研究现状。
关键词：单层二硫化钼；剥离；生物医学
中图分类号 R445.2 文献标识码 A 文章编号：0258-3283（2018）
Exfoliation and Biomedical Applications of Monolayer Molybdenum Disulfide Nanosheets LU Jia-ying1，WU Chen1,2，LI Jing-jing*1,2 (1.School of Medical Imaging，Xuzhou Medical University，Xuzhou 221004, China; 2.Department of Radiology，Affiliated Hospital of Xuzhou Medical University ，Xuzhou 221006， China), Huaxue Shiji,2018,40(9)
Abstract: As a kind of two-dimensional layered nanomaterials with graphene-like structures, monolayer molybdenum disulfide nanosheets have broad research prospects in the field of tumor photothermal therapy, biosensor and other biomedical fields because of their unique band gap structure, photothermal sensing and good biocompatibility. In this work, several commonly used exfoliation methods for the preparation of molybdenum disulfide nanosheets are reviewed based on the research in the past five years. At the same time, the current research status of monolayer molybdenum disulfide nanosheets in the biomedicine field is also introduced.
Key words: monolayer molybdenum disulfide; exfoliation; biomedical application
TMB对SiO2双模型介孔结构的影响及其在Aldol反应中的应用
何煦，白诗扬，孙继红*
(北京工业大学 化学化工系 绿色催化与分离北京市重点实验室，北京 100124)
摘要：以正硅酸乙酯（TEOS）为硅源、十六烷基三甲基溴化铵（CTAB）为模板剂、均三甲苯（TMB）为扩孔剂制备双模型介孔分子筛（BMMs），通过溶胶凝胶过程详细考察了TMB添加量及晶化时间对BMMs结构性能的影响。采用后嫁接法通过负载Zn和联吡啶脯氨酸（Z）得到负载型催化剂Z@ZnT-BMMs，采用XRD、SEM、FT-IR、TG和低温N2吸附-脱附等表征手段探讨了对Aldol催化反应的影响。结果表明，TMB添加量与晶化时间对BMMS介孔结构和堆积孔均有显著影响，其中一级孔越大、Z负载量越大，催化效果越好。
关键词：双模型介孔分子筛；均三甲苯；结构；催化；醛酮缩合
中图分类号：O647.3 文献标识码：A 文章编号：
Effects of TMB Additiveon Structure Parameter of Bimodal Mesoporous Silicas and Its Catalytic Application in Asymmetric Aldol Reaction HE Xu, BAI Shi-yang, SUN Ji-hong*(Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2018, 40(9)
Abstract: Bimodal mesoporous silicas (BMMs) were prepared under room temperature via hydrothermal route with different addition of mesitylene (TMB) using cetyltrimethylammonium bromide (CTAB) as template, TEOS as silicon source, and TMB as expanding pore agent. The heterogeneous catalysts (Z@ZnT-BMMs) were obtained by grafting Zn and bipyridine-proline (Z) onto mesoporous channels using resultant BMMs as support, which was used to evaluate the effect of the bimodal mesoporous structures on the Aldol reaction via dr value and ee value. Meanwhile, by means of XRD, FT-IR, SEM, TG and N2 adsorption-desorption techniques, the results showed the significant effects of additive amount of TMB and crystallization time on the structure properties and textural parameters, in which the expansion of primary mespores and thereafter increased Z-loaded amount are beneficial to enhance the stereo-selectivity and yields for Aldol reaction.
Key words: bimodal mesopores silicas; TMB; structure; catalysis; aldol reaction
a-磺酰胺芳基酰胺化合物的合成
李飞龙1，胡雅雯2，王玉麟1，赵敏*1，陈建中*2
(1.华东理工大学 化学与分子工程学院，上海 200237；2.上海交通大学 化学化工学院，上海 200240)
摘要：以最常见的芳基乙酮为原料，经二氧化硒氧化得到相应芳基酮酸，在氯化亚砜氯化后直接与不同的胺反应得到一系列芳基酮酰胺，接着与磺酰胺加成得到a-磺酰亚胺芳基酰胺，最后还原得到目标产物a-磺酰胺芳基酰胺，具有原料易得、操作方便、收率较高等优点。其结构经1HNMR，13CNMR，高分辨质谱，红外和熔点等表征。该产物可以应用于生物活性物质的合成中。
关键词：a-氨基酰胺；a-磺酰胺芳基酰胺；合成；生物活性物质
中图分类号：O625; O622.6 文献标识码：A 文章编号：0258-3283（2018）
Facile Synthesis of α-Sulfonamides Aryl Amides LI Fei-long1, HU Ya-wen2, WANG Yu-lin1, ZHAO Min*1, CHEN Jian-zhong *2 (1,East China University of Science and Technology, Shanghai 200237) (2, Shanghai Jiao Tong University, Shanghai 200240)
Abstract： The aryl ketonic acid were prepared readily via oxidation reaction of substitutional acetophenones and subsequent chlorination and amination to afford the corresponding aryl keto-amides. The key intermediates a-sulfimide aryl amides were coupled in the presence of TiCl4 and Et3N with sulfamide. A series of a-sulfamide aryl amides were obtained with good yields after reduction. The structures were characterized by 1HNMR, 13CNMR, HRMS, IR and melting point measurement. The aminoamide products could subsequently be used in the synthesis of bioactive compounds.
Keywords：a-aminoamide；a-sulfamide aryl amides；synthesis；bioactive compounds
氧化镍/还原氧化石墨烯复合物的制备及其在超级电容器中的应用
徐欢*，陈新胜，王利芳
(宁夏理工学院 文理学院，宁夏 石嘴山 753000)
摘要：通过正负纳米片之间的静电吸引并热处理，有效合成了NiO/还原氧化石墨烯(rGO)复合物。并对样品进行了形貌、结构表征以及相应的电化学性能测试。研究结果表明，NiO/rGO的最佳质量为w（NiO）︰w（rGO）＝85︰15；复合物与纯NiO相比片状变薄，团聚现象有了明显改善。对样品进行循环伏安以及放电测试：最佳质量比的复合物在1 A/g时，比电容达到670 F/g，与纯材料相比比电容有了很大的提高。并且该复合材料在15 A/g时产物的比电容为486 F/g，其比电容是电流密度为1 A/g时的72.5%，具有良好的电化学性能。
关键词：NiO；还原氧化石墨烯；复合物；超级电容器
中图分类号：O646 文献标识码：A 文章编号：0258-3283（2018）
Fabricating Nickel Oxide/Reduced Graphene Oxide Composite for Supercapacitor Application XU Huan*, CHEN Xin-sheng, WANG Li-fang (College of Arts and Sciences, Ningxia Institute of Science and Technology, Shizuishan 753000, China), Huaxue Shiji, 2018, 40(9)
Abstract: NiO/reduced graphene oxide (rGO) composites were successfully synthesized by electrostatic attraction between positive and negative nanosheets.The morphology, structure of the obtained samples were characterized. In addition, the electrochemical properties of obtained samples were tested. The experimental results indicated that the composite of the optimum mass ratios(w（NiO）︰w（rGO）＝85︰15) were obtained. Compared with pure NiO, the composite sheet was thinner and the agglomeration was obviously improved. Cyclic voltammetry and discharge tests were carried out to example: the composite of the optimum mass ratios acquired the specific capacitance of 670 F/g at 1 A/g, compared with the pure material, the capacitance had been greatly improved. In addition, the specific capacitance of 486 F/g at 15 A/g was acquired by the composite, which was 72.5 % of 1 A/g. In conclusion, the composite had good electrochemical properties.
Key words: NiO; reduced graphene oxide; composite; supercapacitor
槲皮素酯的合成及其抗肿瘤活性研究
刘秋伟，翟广玉*，姜亚玲
(郑州工业应用技术学院 药学与化学工程学院，河南 郑州 450001)
摘要：槲皮素是一种具有多种生物活性的黄酮类化合物，可以预防和治疗肿瘤及心血管疾病。以槲皮素为先导物，合成了7个标题化合物，其中6个未见文献报道，目标产物结构经IR、1HNMR、ESI-MS确证。采用MTT法，初步评价了7个目标化合物对人食管癌细胞EC109、人食管鳞癌细胞EC9706、人胃癌细胞SGC7901及小鼠黑色素瘤细胞B16-F10 4株肿瘤细胞的体外增殖抑制作用。结果显示，槲皮素五乙酸酯对EC109和EC9706 细胞抑制作用明显优于母药槲皮素和5-FU，是一个很有潜力的新型抗肿瘤候选化合物。
关键词：槲皮素；酯；衍生物；合成；抗肿瘤活性
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2018）
Synthesis and Antitumor Activity of Quercetin Ester LIU Qiu-wei, ZHAI Guang-yu*, JIANG Ya-ling（College of Pharmacy and Chemical Engineering, Zhengzhou University of Industrial Technology, Zhengzhou 451100, China）, Huaxue Shiji, 2018, 40(9)
Abstract: Quercetin is a kind of flavonoids with a variety of biological activity, which can prevent and cure tumor and cardiovascular diseases. Seven quercetin esters were synthesized with quercetin as the leader. Six of them were not reported in the literature. The structures were confirmed by IR, 1HNMR and ESI-MS. The MTT assay was used to evaluate the in vitro proliferation of seven tumor cells in vitro against human esophageal carcinoma cell line EC109, human esophageal squamous carcinoma cell line EC9706, human gastric cancer cell line SGC7901 and mouse melanoma cell line B16-F10. The results showed that quercetin pentaacetate is a novel and potential antitumor candidate compound with significantly superior inhibitory activity to quercetin and 5-FU on EC109, B16-F10 and EC9706 cells.
Key words: quercetin; ester; derivatives; synthesis; antitumor activity
离子液体在多肽化学中的研究进展
凌青*，张传主，刘玉强，郭彩宏，李召良
（阿拉丁试剂（上海）有限公司 技术研发中心，上海 201417）
摘要：离子液体是由特定的阴阳离子组成的盐。离子液体作为一种极性非质子溶剂，具有非挥发性、足够的稳定性、良好的溶解性以及性质可调节性等优良特性。由于其独特的物理与化学性质，离子液体吸引了来自不同领域化学家们的极大关注。近年来，离子液体在多肽化学领域的应用得到广泛研究。介绍了近年来离子液体在多肽化学领域所取得的最新研究进展。
关键词：离子液体；多肽化学；进展；综述
中图分类号：O629.7 文献标识码：A 文章编号：0258-3283（2018）
Progress of Ionic Liquids in Peptide Chemistry LING Qing*, ZHANG Chuan-zhu, LIU Yu-qiang, GUO Cai-hong, LI Zhao-liang(Technology R&D Center, Aladdin Reagent (Shanghai) Co. Ltd., Shanghai 201417, China), Huaxue Shiji, 2018,40(9)
Abstract: Ionic liquids (ILs) are mainly composed of specific cations and anions. Ionic liquids, which are very polar aprotic solvents, exhibit lots of excellent properties, such as non-volatility, good stability, favorable dissolubility and easily tuned characteristic. Due to their unique physical and chemical properties, ionic liquids nowadays are very fascinating for chemists in various fields. In recent years, ionic liquids have been widely investigated and successfully applied to many areas of peptide chemistry. The latest research and application of ionic liquids in peptide chemistry is reviewed in the work.
Key words: ionic liquids; peptide chemistry; progress; review
环丙烷环加成反应的研究进展
高宏伟，李兴，常宏宏，魏文珑*
(太原理工大学 化学化工学院，山西 太原 030024)
摘要：环加成反应是有机合成化学中非常重要的一类反应，是两个或多个分子通过结合生成多元环状化合物的有效方法；环丙烷由于其特殊的三元环状结构及反应活性，可与许多不饱和化合物发生环加成反应来制备多种多元环状化合物。综述了近十年内环丙烷与一些化合物发生的环加成反应，主要包括[3+2]和[3+3]环加成反应，并对其发展方向进行了展望。
关键词：环丙烷；环加成；不饱和化合物
中图分类号：0626 文献标识码：A 文章编号：0258-3283（2017）
Progress in Cycloaddition Reactions of Cyclopropane GAO Hong-wei, LI Xing, CHANG Hong-hong , WEI Wen-long * (College of Chemistry and Chemcial Engineering, Taiyuan University of Technology, Taiyuan 030024, China)
Abstract：Cycloaddition is a very important reaction in organic synthesis chemistry. It is an efficient route for the synthesis of multiple-membered ring compounds via the reaction of two or more molecules. Cyclopropane can react smoothly with many unsaturated compounds to prepare various multiple-membered ring compounds due to its high ring strain and reaction activity. In this work, some cycloaddition reactions of cyclopropane with diverse compounds, including [3 + 2] and [3 + 3] are summarized and the prospectsare also discussed.
Key words：cycloaddition; cyclopropane; unsaturated compounds
异灯盏花乙素的制备研究进展
原云鹤1，王昆2，段银2，张伟*2
（1. 昆明医科大学 药学院 云南省天然药物药理重点实验室，云南 昆明 650500；2. 昆明龙津药业股份有限公司，云南 昆明 650503）
摘要：异灯盏花乙素作为灯盏花乙素的主要体内代谢物，可能发挥了主要的治疗效果，但是关于它的获取和药理学研究还相对较少。从植物提取、生物合成、化学合成3方面对异灯盏花乙素的制备研究进行了综述，以便为异灯盏花乙素的制备研究提供参考。
关键词：异灯盏花乙素；制备；植物提取；生物合成；化学合成
中图分类号：O626 文献标识码：A 文章编号：0258-3283(2018)
Progress in Preparation of Isoscutellarin YUAN Yun-he1, WANG Kun2, DUAN Yin2, ZHANG Wei*2
(1. Yunnan Key Laboratory of Pharmacology for Natural Products, School of Pharmaceutical Science, Kunming Medical University, Kunming 650500, China; 2. Kunming Longjin Pharmaceutical Co., Ltd, Kunming 650503, China), Huaxue Shiji, 2018, 40(9)
Abstract：Isoscutellarin as the main metabolite of scutellarin, may take a major therapeutic effect, but its access and pharmacological research is still relatively small. This work reviews the progress of the latest preparation methods of isoscutellarin, which have the plant extraction, biosynthesis, chemical synthesis.
Key words: isoscutellarin; preparation; plant extracts; biosynthesis; chemical synthesis
基于荧光铜纳米簇用于钴离子的超灵敏免标记检测
王宁a，爱军*a,b
(内蒙古师范大学，a. 化学与环境科学学院, b. 内蒙古自治区功能材料物理与化学重点实验室 ,内蒙古 呼和浩特 010022)
摘要：为了检测浓度超标的重金属离子，探讨了一种新的荧光探针传感器检测法。利用柠檬酸钠作为还原剂合成铜纳米晶，然后加入半胱氨酸作为刻蚀剂和保护剂与铜纳米晶配体交换反应合成荧光铜纳米簇，由此以铜纳米簇作为荧光探针建立了一种检测水样中重金属钴离子的方法。该方法是基于当钴离子存在时，破坏铜纳米簇，导致荧光迅速降低。当在较宽的钴离子浓度范围（10 mmol/L～1 μmol/L），铜纳米簇荧光猝灭程度呈现线性关系（R=0.9700），其检出限较低（0.5671 μmol/L）。铜纳米簇传感器特异性选择钴离子，不受其它金属离子干扰，检测的选择性较好。基于此完成对钴离子的超灵敏免标记检测，且EDTA可作为钴离子的螯合剂，实现了铜纳米簇传感器的循环反复利用。
关键词：铜纳米簇；荧光检测；钴离子
中图分类号： 文献标识码 A 文章编号：0258-3283(2018)
Application of Fluorescent Copper Nanoclusters for Ultra Sensitive and Free Labeling Detection of Cobalt Ions WANG Ninga, AI Jun*a, b (a.College of chemistry and environmental science, b. Key Laboratory of physics and chemistry of functional materials in the Inner Mongolia Autonomous Region, Inner Mongolia Normal University, Hohhot 010022, China), Huaxue Shiji, 2018, 40(9)
Abstract：A new fluorescent probe sensor was developed for the detection of heavy metal ions. The fluorescence of copper nanoclusters synthesized by using sodium citrate as reducing agent synthesis of nanocrystalline copper, then adding cysteine as etching agent and protective agent and copper nanocrystals ligand exchange reaction. A method for the detection of heavy metal cobalt ions in water samples was developed by using copper nanoclusters as fluorescent probes. The method is based on the presence of cobalt ions, which destroy the copper nanoclusters, resulting in the rapid reduction of fluorescence. When the concentration range of cobalt ions (10 mmol/L ～ 1 μmol/L), the fluorescence quenching degree of Cu nanoclusters showed a linear relationship (R=0.9700), and the detection limit was low (0.5671 μmol/L). The copper nanocluster sensor selects cobalt ions, which are not interfered by other metal ions, indicating that the selectivity of detection is good. Based on this, we complete the ultrasensitive label free detection of cobalt ions. And EDTA can be used as the chelating agent of cobalt ion, which can make use of the copper nanocluster sensor.
Key words：copper nanoclusters; fluorescence detection; cobalt ions
一种基于荧光素的新型荧光探针用于快速检测次氯酸及在活细胞成像的应用
汪文杰1*，朱龙3，江玉亮2, 3，韦国2
（1．江阴市产品质量监督检验所，江苏 江阴 214431；2.南京师范大学 ，江苏 南京 210023； 3. 江阴江化微电子股份有限公司，江苏 江阴 214423）
摘要：作为生物系统中一种主要的活性氧（ROS），次氯酸/次氯酸盐（HClO/ClO-）在免疫系统中扮演重要的角色。过量的次氯酸会引发很多疾病。因此，次氯酸的高灵敏检测对疾病早期预测而言具有重要意义。基于此，设计并合成了一种基于荧光素的新型荧光探针并用于次氯酸检测。结果表明，探针能够快速、高灵敏的检测次氯酸，其检测限低至0.50 nmol。同时，通过对活细胞成像的研究结果表明，该探针有潜在的生物应用前景。
关键词：次氯酸；活性氧；荧光探针；检测限；细胞成像
中图分类号：O625.66 文献标识码：A 文章编号：0258-3283(2018)09
A Novel Fluorescent Probe Based on Fluorescein for Rapid Detection of Hypochlorite and Its Application for Bioimaging WANG Wen-jie1, ZHU Long3, JIANG Yu-liang2,3, WEI Guo*2 (1.Jiangyin Product Quality Supervision and Testing Institute, Jiangyin 214431,China；2. , Nanjing Normal University, Nanjing 210023, China; 3. Jiangyin Jianghua Microelectronic Limited by Share Ltd., Jiangyin 214431, China), Huaxue Shiji, 2018, 40(9)
Abstract: As a major reactive oxygen species (ROS) in living systems, hypochlorous acid (HClO) and its salts (ClO-) take important roles in immune system. However, excessive hypochloric acid can cause many diseases, therefore the development for highly sensitive hypochloric acid probe is great significance for early prediction of diseases. A new fluorescence probe derived from fluorescein was designed and synthesized. This new probe performed a fast and highly sensitive detection for trace ClO- with the detection limit as low as 0.50 nmol. In addition, the results of live cell imaging indicate the probe has potential biological application.
Key words: hypochlorous acid; ROS; fluorescent probe; detection limits; cells imaging
4-(2,3-二氢-1H-1,3,2-苯并二唑硼烷)-苯甲醛的合成及氨气检测
田娣，卢继雷，吴伟，张晓云*
（中国石油大学（华东）理学院，山东青岛266580）
摘要：以4-甲酰苯硼酸与邻苯二胺衍生物为原料合成了3个4-(2,3-二氢-1H-1,3,2-苯并二唑硼烷)-苯甲醛衍生物。其中，标题化合物与氨和脂肪族胺发生相互作用后，荧光发射强度增强，且最大发射峰红移至380 nm。还可以将标题化合物沉淀在滤纸上制备检测试纸，试纸在紫外灯照射下不发光，润湿后暴露在氨气环境中可以发出肉眼可见的紫红色荧光，可以用于快速检测氨气。经1HNMR、IR、UV检测证实了探针化合物与氨气和脂肪族胺间的相互作用为醛基与氨基间的弱相互作用。
关键词：4-(2,3-二氢-1H-1,3,2-苯并二唑硼烷)-苯甲醛；氨气检测；荧光探针；相互作用
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2018）
Synthesis and Application of 4-(2,3-Dihydro-1H-1,3,2-benzodiazole)-benzaldehyde in Ammonia Detection TIAN Di, LU Ji-lei, WU Wei, ZHANG Xiao-yun* (College of Science, China University of Petroleum (East China), Qingdao 266580, China)
Abstract：Three derivatives of 4-(2,3-dihydro-1H-1,3,2-benzodiazole)-benzaldehyde were obtained by reacting 4-formylphenylboronic acid with o-phenylenediamine and its derivatives. When 4-(2,3-dihydro-1H-1,3,2-benzodiazole)-benzaldehyde interacts with ammonia and aliphatic amines, the fluorescence intensity increased and the maximum emission of the fluorescence emission spectrum shows a red-shifted to 380 nm. What’s more, the solution of the 4-(2,3-dihydro-1H-1,3,2-benzodiazole)-benzaldehyde was dropped on filter paper to provide a test paper of ammonia detection, which displayed non-emissive and became strong violet-red fluorescence emission after exposure to ammonia vapor. Therefore, 4-(2,3-dihydro-1H-1,3,2-benzodiazole)-benzaldehyde can be used for rapid detection of ammonia. The 1HNMR, IR and UV spectra confirmed that the interaction between the probe and ammonia or aliphatic amines was weak interaction of the aldehyde group and the amino group.
Key words:4-(2,3-dihydro-1H-1,3,2-benzodiazole)-benzaldehyde; ammonia detection; fluorescent probe; interaction
一种席夫碱化合物的合成及其对Sb3+的识别研究
陈爱乾，孔卓，颜佩，胡云＊
（遵义医学院 珠海校区 生物工程系，广东 珠海 519041）
摘要：过量存在的Sb3+对生物具有致毒性和致癌性，迄今有关其检测探针的报道非常少。介绍了一种席夫碱化合物(E)-N-((E)-3-(4-二甲基氨基苯基)烯丙基)-1，2-苯二胺的合成及其作为Sb3+比色探针的应用研究。该化合物与Sb3+结合后产生生色传感效应，席夫碱溶液由淡黄色迅速变成玫红色，最大吸收波长从398 nm红移至507 nm。而其他常见金属离子的加入则基本不引起明显变化。在一定浓度范围内，S1溶液在507 nm的吸光度与加入的Sb3+浓度呈良好的线性相关。计算其最低检测限为2.5×10-7 mol/L。配位比分析显示，S1与Sb3+形成了1∶1型的配合物。该席夫碱化合物对Sb3+的识别结合具有较好的选择性和灵敏度，可实现定量检测和比色检测。
关键词：席夫碱；比色探针；锑离子；重金属
中图分类号：TQ421 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of a Novel Schiff Base Deviratives and Its Recognition of Sb3＋ CHEN Ai-qian, KONG Zhuo, YAN Pei, HU Yun* (Department of Bioengineering, Zhuhai Campus, Zunyi Medical College, Zhuhai 519041, China), Huaxue Shiji, 2018, 40(9)
Abstract: Overexposure to Sb3+ could cause toxicities and carcinogenesis. However, chemical sensors used for Sb3+ detection are rarely developed up to now. In this work, a novel Schiff-base compound (E)-N1-((E)-3- (4-(dimethylamino)phenyl)allylidene)benzene-1,2-diamine is synthesized and evaluated as a colorimetric Sb3+ probe. Probe exhibits a good selectivity and sensitivity towards Sb3＋ in aqueous solution. Addition of Sb3＋to a solution results in a rapid color change from light yellow to rose red, which corresponds to a large red shift of the maximum absorption peak from 398 nm to 507 nm. Meanwhile, addition of other common metal irons induce no or minimal spectral changes. The absorbance at 507 nm is linearly related to the Sb3+ concentrations and the detection limit for Sb3＋ is 2.5×10-7 mol/L. Job's plot and Benesi—Hildebrand's plot confirmed that the stoichiometry ratio of probe with Sb3＋ is 1:1．
Key words: Schiff base; colorimetric probe; Sb3＋; heavy metal
3,3＇-二-(4-乙氧基苯基)-2,2＇-二羟基-1,1＇联萘的合成及其在不对称反应中的应用
刘海龙1，刘清雷2，王永飞*2，赵扬1
（1.河南应用技术职业学院 ，河南 郑州 450000；2.辽宁科技大学 ，辽宁 鞍山 114051）
摘要：以β-萘酚为原料，通过羟基保护、Suzuki反应、脱保护，在3, 3位上成功引入芳香基团制备出目标产物，获得最佳合成条件，并用13CNMR、1HNMR、元素分析及红外光谱对相关产物进行了表征。目标产物在诱导二乙基锌和芳基醛的不对称加成反应中具备良好的催化性能，R构型的联萘酚衍生物催化所得醇的产率和e.e.值均高于S构型。
关键词：联萘酚；不对成合成；催化
中图分类号：O621. 3 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of 3,3 - Bis (4-ethoxyphenyl) -2,2 - dihydroxy - (1,1,)binaphthyl and Its Use in Asymmetric Reaction LIU Hai-long1, LIU Qing-lei2, WANG Yong-fei*2, ZHAO Yang1（1.，Henan Vocational College of Applied Technology, Zhengzhou 450000, China; 2. ，University of Science and Technology Liaoning, Anshan 114051, China）, Huaxue Shiji, 2018, 40(9)
Abstract: 3, 3-Substituted binaphthol derivatives were prepared from β- naphthol by multi steps, via hy-droxy-protected, Suzuki reaction and deprotection, and the aromatic group was successfully introduced to 3, 3-position of binaphthol. The suitable reaction conditions were obtained and structures of the products were confirmed by1HNMR, 13CNMR, elemental analysis and IR. The title compound has been synthesized to conduct the enantioselective addition of diethylzinc to aromatic aldehydes, the yield and e.e. values of alcohol that were catalyzed by the R configuration of binaphthol derivatives are higher than the S configuration of binaphthol derivatives.
Key words: binaphthol derivatives; asymmetric synthesis; catalyze
枪击现场弹着痕迹显色剂——玫瑰红酸钠溶液改进配方研究
邢卓1，王晓琳2，杨瑞琴*1
（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：研究枪击现场弹着痕迹显色剂玫瑰红酸钠溶液的改进配方。采用分光光度法考察混合溶液中焦亚硫酸钠、玫瑰红酸钠、聚乙烯吡咯烷酮以及氯化铵4种物质浓度对玫瑰红酸钠溶液稳定性的影响，初步探讨增强溶液稳定性的相关原理，并对改进配方的有效性进行验证。果表明，当玫瑰红酸钠浓度为4 g/L、焦亚硫酸钠为3 g/L、聚乙烯吡咯烷酮为10 wt%时，溶液稳定性最强，在避光条件下间隔7 d后仍可以灵敏地显现枪弹在织物上遗留的铅残留物。该改进配方大幅增强了玫瑰红酸钠溶液的稳定性，从而简化了弹着痕迹中铅残留物现场显现的操作步骤，同时避免了因显色剂失效而造成假阴性结果的发生。
关键词：铅残留物；弹着痕迹；玫瑰红酸钠溶液；改进配方；稳定性
中图分类号：O6 文献标识码：A 文章编号：0258-3283(2018)
A Modified Formulation of the Sodium Rhodizonate for the Detection of Lead Residues on Impact Marks XING Zhuo1, WANG Xiao-lin2, YANG Rui-qin*1 (1. School of Forensic Science, People’s Public Security University of China, Beijing 100038, China; 2. Institute of Forensic Science, Ministry of Public Security, Beijing 100038, China), Huaxue Shiji, 2018, 40(9)
Abstract: A modified formulation of sodium rhodizonate solution for the detection of lead residues was investigated. The effect of the concentration of four additives, including sodium pyrosulfite, sodium rhodizonate, polyvinylpyrrolidone (PVP) and ammonium chloride, on the stability of the mixed solution was investigated by spectrophotometry. Meanwhile, the relevant mechanism that improves the stability of the solution was elucidated preliminarily. Additionally, the effectiveness of the modified formulation was verified. The results show that the modified formulation with the best stability was sodium rhodizonate of 4 g/L, sodium pyrosulfite of 3 g/L and polyvinylpyrrolidone of 10%. Lead residues on the fabric background were sensitively visualized even after 7 days since the preparation, if the solution was stored in light-resistant container. This novel formulation enhances the stability of sodium rhodizonate solution to a large extent, which simplifies the procedure of detecting lead residues on impact marks on spot and avoid the false-negative phenomenon resulting from the deterioration of chromogenic reagents.
Key words: lead residue; impact mark; sodium rhodizonate solution; modified formulation; stability
吡啶类离子液体在沙棘叶总黄酮提取中的应用研究
赵三虎*，王鸣姗，乔永生，董智云，刘改梅
(忻州师范学院 化学系, 山西 忻州 034000)
摘要：合成了6种吡啶类离子液体，并将其水溶液用于沙棘叶总黄酮的提取。研究结果表明, 在50 oC、采用1mol/L溴化-1-十二烷基-吡啶离子液体水溶液作为提取剂，提取自然阴干的沙棘叶总黄酮，微波辅助提取5 min，提取率可达3.65%。按照药典提取方法，使用乙醇提取沙棘叶中总黄酮，提取时间3 h，提取率仅为2.72%。微波辅助吡啶类离子液体提取沙棘叶总黄酮是一种高效、便捷的方法。
关键词：沙棘叶；黄酮；提取；离子液体；分光光度法
中图分类号： O628.2 文献标识码：A 文章编号：006466（2018）
Application of Pyridinium Ionic Liquids in Extraction of Total Flavonoids from Seabuckthorn Leaves ZHAO San-hu*, WANG Ming-shan, QIAO Yong-sheng，DONG Zhi-yun，LIU Gai-mei (Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000, China)
Abstract：In this work, six kinds of pyridinium ionic liquids were prepared and their aqueous solution was applied in extraction total flavonoids from seabuckthorn leaves. The results showed that using 1 mol/L aqueous solution of N-dodecylpyridinium bromide as the extraction agent to extract the total flavonoids from the seabuckthorn leaves dried naturally, under the microwave irradiation at 50 oC, the extraction rate 3.65% was obtained after 5 min. Based on the method of pharmacopoeia, using ethanol as extraction agent, the extraction rate was only 2.72% after 3h. So the microwave-assisted extraction total flavonoid with pyridinium ionic liquids as extraction agents is an efficient and convenient method.
Key words：seabuckthorn leaves; flavonoid; extraction; ionic liquid; spectrophotometry
2-取代苯基-4-苯基-1,5-苯并硫氮杂卓-3-甲酸乙酯的合成
许同绣1，田克情2，王冉冉1，王岩1，张萍*1
(1. 河北师范大学 化学与材料科学学院 化学国家级实验教学示范中心，河北 石家庄 050024；
2. 河北化工医药职业技术学院 化学与环境工程系，河北 石家庄 050026；)
摘要：以苯甲酰乙酸乙酯和取代苯甲醛为原料，经Knoevenagel缩合、迈克尔加成、分子内加成-消除等3步反应合成了10个新的标题化合物化合物，其中5个化合物是烯胺型结构，5个化合物是亚胺型结构。研究了目标化合物的形成条件，其中烯胺型目标物的收率明显高于亚胺型目标物。 新化合物的结构经IR、MS、1HNMR、13HNMR及X-射线衍射法确定。在2-氨基-4-氯苯硫酚和2-苯甲酰基-3-对氟苯基丙烯酸乙酯的反应中，分离出2个反应副产物，对其结构进行了确证，提出了其形成的可能历程。
关键词：1,5-苯并硫氮杂卓；氨基酮；2-苯基-5-氯苯并噻唑；合成
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283(2018)
Synthesis of Ethyl 2-Substituted Phenyl-4-Phenyl-1,5-Benzothiazepine-3-Formate XU Tong-xiu1，TIAN Ke-qing2，WANG Ran-ran1，WANG Yan1, ZHANG Ping*1（1. College of Chemistry and Material Science, National Demonstration Center for Experimental Chemistry Education, Hebei Normal University, Shijiazhuang 050024, China; 2. Enviroment and Chemical Engineering, Hebei Chemical and Pharmaceutical College, Shijiazhuang 050026, China）, Huaxue Shiji, 2018, 40(9)
Abstract: 10 New compounds of ethyl 2-substituted phenyl-4-phenyl-1,5-benzothiazepine-3-formate were synthesized through three steps of Knoevenagel condensation, Michael addition and intramolecular addition -elimination with ethyl benzoacetate and substituted benzaldehyde as starting materials, among them some were enamine and some were imine type structures. The formation conditions of target compounds were studied and the yield of was significantly higher than that . The structures of the new compounds were characterized by IR, MS, 1HNMR, 13CNMR and X-Ray diffraction method. Two by-products were separated and confirmed, the possible mechanism of them were proposed in the reaction of 2-amino-4-chloro thiophenol.
Key words: 1, 5-benzothiazepine; amino ketone; 2-phenyl-5-chlorobenzothiazole; synthesis
非布司他的合成研究
窦月，聂芳，王刚，张帆*
（锦州医科大学 药学院，辽宁 锦州 121001）
摘要：非布司他是由日本Teijin公司研发的黄嘌呤氧化酶抑制剂，用于具有痛风症状的高尿酸血症的长期治疗。以4-羟基苯甲醛为起始原料，经过亲核加成-消除-脱水、硫解、Hantzsch环合、Duff甲酰化、醚化、亲核加成-消除、脱水和水解反应制得标题化合物，并对合成工艺进行优化，反应总收率为55.1%（以4-羟基苯甲醛计）。通过一锅法分别合成了中间体4-羟基硫代苯甲酰胺和2-(3-氰基-4-异丁氧基苯基)-4-甲基噻唑-5-甲酸乙酯。改进后的工艺路线，操作步骤更简单，总收率更高，更加适用于工业生产。
关键词：非布司他；抗痛风药；黄嘌呤氧化酶抑制剂；工艺优化
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2018）
Study on Synthesis of Febuxostat DOU Yue, NIE Fang, WANG Gang, ZHANG Fan* (School of Pharmacy, Jinzhou Medical University, Jinzhou 121001, China), Huaxue Shiji, 2018, 40(9)
Abstract: Febuxostat is used for long-term treatment of hyperuricemia with gout symptoms，which was developed by Teijin company as a xanthine oxidase inhibitor. In this paper, using 4-hydroxybenzaldehyde as starting material, febuxostat was synthesized via nucleophilic addition-elimination-dehydration, thiolysis, Hantzsch cyclization, Duff formylation, etherification, nucleophilic addition-elimination, dehydration and hydrolysis reaction. Meanwhile, the synthetic process of febuxostat was optimized. The overall yield of febxostat was 55.1% (calculated by 4-hydroxybenzaldehyde). The intermediates 4-hydroxybenzothioamide and ethyl 2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazole-5-carboxylate were prepared by one-pot method, respectively. After optimization, the synthetic process is simple, the total yield is higher. It is more suitable for industrial production.
Key words: febuxostat; anti-gout agent; xanthine oxidase inhibitor; process optimization
7-溴-1-茚满酮的合成研究
高延峰，滕大为*
（青岛科技大学 化工学院，山东 青岛 266042）
摘要：研究了标题化合物的新合成方法。以邻溴苯乙酮为原料，经α-亚甲基化反应、亲电加成以及分子内傅克烷基化反应合成了目标产物。研究发现，影响总收率的关键步骤是邻溴苯乙酮α-亚甲基化反应。探讨了反应溶剂、反应温度、反应时间及铵盐类型等条件对邻溴苯乙酮α-亚甲基化反应的影响。结果发现，在以四氢呋喃为溶剂和使用二乙胺三氟乙酸盐条件下，可近定量得到邻溴苯乙酮α-亚甲基化产物。所有产物经NMR和MS进行表征。
关键词：邻溴苯乙酮；1-茚满酮；α-亚甲基化反应；傅克烷基化反应
中图分类号：0625.45 文献标识码：A
Synthesis of 7-Bromo-1-indanone GAO Yan-feng，TENG Da-wei*（College of Chemistry Engineering, Qingdao University of Science and Technology, Qingdao 266042）
Abstract：A new method for the synthesis of 7-bromo-1-indanone was developed by α-methylation of 2-bromoacetophenone, electrophilic addition with hydrochloride and subsequent intramolecular Friedel-Crafts alkylation. The effects of solvents, temperature, reaction time and ammonium salts on the yield of α-methylation of 2-bromoacetophenone were investigated. It is found that the product of α-methylation could be obtained near quantatively in tetrahydrofuran using diethylammoniumtrifluoroacetate. All products were confirmed by NMR and MS.
Key words：2-bromoacetophenone；1-indanone；α-methylation；Friedel-Crafts alkylation
抗呕吐药昂丹司琼相关杂质的合成
高飞飞，李明，高军龙*
（浙江先锋科技股份有限公司，浙江 临海 317021）
摘要：首次合成了欧洲药典9.0中规定的昂丹司琼相关杂质A、D、G和H。分别以1,2,3,9-四氢-9-甲基-4H-咔唑-4-酮和1,2,3,9-四氢-4H-咔唑-4-酮为原料，先与多聚甲醛、二甲胺盐酸盐发生曼尼希反应，最后与咪唑或2-甲基咪唑发生反应得到相关杂质。方法易于操作，所得杂质收率高。
关键词：昂丹司琼；相关杂质；曼尼希反应；合成
中图分类号: O626.4 文献标识码: A 文章编号： 0258-3283（2018）
Related Impurities Synthesis of Ondansetron Hydrochloride GAO Fei-fei, LI Ming, GAO Jun-long*（Zhejiang Xianfeng Technology Co., Ltd, Linhai 317021, China）, Huaxue Shiji, 2018, 40(9)
Abstract: In this work, the related impurities A, D, G and H of ondansetron in EP9.0 were synthesized for the first time. 2, 3-Dihydro-1H-carbazol-4(9H)-one and 9-methyl-2,3-dihydro-1H-carbazol-4(9H)-one were used as starting material respectively. At first, the starting material reacted with paraformaldehyde and dimethylamine hydrochloride. Impurities A and D were obtained via this Mannich reaction. Then the products in the first step reacted with imidazole or 2-methylimidazole and gave impurities G and H. This synthetic method is easy to operate and afforded these impurities with high yields and purities.
Key words: ondansetron；related impurities；Mannich reaction；synthesis
二碳酸二叔丁酯的合成工艺研究
吴飞1, 2，魏进2，严生虎*1, 2，张跃2，沈介发1, 2，刘建武1, 2，陈代祥1, 2
（1.常州大学 制药与生命科学学院，江苏 常州 213164; 2.石油和化工行业连续流技术工程实验室，江苏 常州 213164）
摘要：以三光气、叔丁醇等为原料在添加碱、相转移催化剂的条件下合成二碳酸二叔丁酯。考察了原料物质的量比、反应温度、催化剂种类、催化剂用量、碱的类型、碱的用量等对收率的影响。结果表明，四丁基溴化铵（TBAB）为相转移催化剂，TBAB用量为NaOH量的2 wt %，反应时间2 h时，二碳酸二叔丁酯收率最高。以三光气代替光气经相转移催化法合成二碳酸二叔丁酯，安全高效、反应时间短、收率高。
关键词：三光气；相转移催化；四丁基溴化铵；二碳酸二叔丁酯
中图分类号：TQ460 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of Di-tert-butyl Dicarbonate WU Fei1,2, WEI Jin2, YAN Sheng-hu*1,2, ZHANG Yue2, SHEN Jie-fa1,2, LIU Jian-wu1,2, CHEN Dai-xiang1,2 (1.School of Pharmaceutical and Life Sciences, Changzhou University, Changzhou 213164, China; 2.Continuous Flow Technology Engineering Laboratory of Petroleum and Chemical Industry, Changzhou 213164,China), Huaxue Shiji, 2018, 40(9)
Abstract: With tert-butanol, triphosgeneand alkali as starting material, di-tert-butyl dicarbonate was prepared by phase transfer catalysis synthesis process. The effects of molar ratio of the reactants, reaction temperature, catalyst type, catalyst dosage, alkali type and alkali dosage on the reaction results were mainly investigated. When using TBAB as phase transfer catalyst, the dosage of TBAB at 2 wt % of the quality of NaOH, reaction time around 2 h, the highest yield of di-tert-butyl dicarbonate was obtained. Triphosgene instead of phosgene for phase transfer catalytic synthesis of di-tert-butyl dicarbonate was safer and more efficient, which with shorten reaction time and higher yield.
Key words：triphosgene; phase transfer; tetrabutylammonium bromide; di-tert-butyl dicarbonate
1-苄基-4-氧代-1,4-二氢噌啉-3-甲酰胺类衍生物的合成
杨圣俊，刘洪涛*，杨玉鹏，任炳楠，庞国勋
（河北省人民医院，河北 石家庄 050051）
摘要：噌啉酮类衍生物，作为一类重要的有机功能小分子，具有抗菌、杀虫、降血压、抗癌、抗组胺、抗焦虑、抗炎等多种生物活性，在创新药物研究中具有广泛的应用。设计了一类新型噌啉酮类衍生物，并以邻硝基苯乙酮为起始原料，经还原、重氮化偶联、缩合、环合、水解、缩合、酰化、烃化等多步反应合成了6个标题化合物；结构经核磁、质谱等确证正确，并为未见文献报道的新化合物。为新型噌啉酮类小分子药物的研究提供了化合物基础。
关键词：1-苄基-4-氧代-二氢噌啉-3-甲酰胺类；噌啉酮；合成
中图分类号：O626 文献标识码：A 文章编号：
Synthesis of 1-Benzyl-4-Oxo-1,4-Dihydrocinnoline-3-Carboxamides YANG Sheng-jun, LIU Hong-tao*, YANG Yu-peng, REN Bing-nan, PANG Guo-xun (Hebei General Hospital, Shijiazhuang 050051,China)
Abstract：As a kind of functional small organic molecules, cinnolines have a variety of biological activities such as antibacterial, antiparasite, antihypertensive, antineoplastic, antihistamine, antianxiety, antiinflammatory etc and were widely used in the research and development of new drugs. In this paper, six 1-benzyl-4-oxo-1,4-dihydrocinnoline-3-carboxamides were synthesized form o-nitroacetophenone via reduction, diazotization, alkylation, condensation, cyclization, hydrolyzation, acylation and alkylation. The structures were confirmed by1HNMR and MS. This work provides a foundation of compounds on the development of novel cinnolines drugs.
Key words：1-benzyl-4-oxo-1,4-dihydrocinnoline-3-carboxamides; cinnoline; synthesis
