国内外高纯无机盐指标对比及杂质检测方法
凌芳1，顾小焱1，陈浩云1，洪亚云2，赵红莉*2
(1. 国药集团化学试剂有限公司，上海 20002；2. 华东理工大学 化学与分子工程学院，上海 200237)
摘要：随着高新技术领域的快速发展，对高纯无机盐的需求日益增加。高纯无机盐中杂质元素的存在，会不同程度地影响其应用性能，因此需对杂质离子含量进行严格限制并准确检测。仪器分析在产品纯度测定、所含杂质物质的种类和含量测定等方面具有无可替代的作用。以高纯硝酸银为例，对比了国内外无机盐产品的技术指标和分析检测方法，进一步对高纯无机盐中痕量杂质的检测方法，主要包括原子吸收光谱法和电感耦合等离子体光谱法进行了综述。
关键词：高纯无机盐；技术指标；杂质；检测方法
中图分类号：O657. 7 文献标识码：A 文章编号：0258-3283（2018）
Comparison of Technique Index at Home and Abroad and Determination Methods of Impurities for High Purity Inorganic Salts LING Fang1, GU Xiao-yan1, CHEN Hao-yun1, HONG Ya-yun2, ZHAO Hong-li*2(1.Sinopharm Chemical Reagent Co.,Ltd, Shanghai 200002,China; 2.School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China), Huaxue Shiji, 2018, 40(7)
Abstract：In recent years, the demand for high purity inorganic salts by various high-technology industries has increased. Because impurities in inorganic salts could effects the properties, it is significant to control strictly impurities and to develop determination methods. In this work, the technique index for high purity inorganic salts at home and abroad was compared firstly. And then, the determination methods were reviewed, mainly including atomic absorption spectroscopy and inductively coupled plasma atomic emission spectrometry, for high purity inorganic salts.
Key words：High purity inorganic salts; technique index; impurities; determination methods
Synthesis, Characterization and Antiproliferative Evaluation of Some Heterosteroids Possessing Side Chain of Pyrazoles or 1,2,4-Oxadiazoles CUI Jian-guo, PANG Li-ping, LIU Chang, SHENG Hai-bin, GAN Chun-fang *, ZHAN Jun-yan, LIU Xiao-lan, PANG Chun-lin, HUANG Yan-min*( College of Chemistry and Materials Science, Guangxi Teachers Education University, Nanning 530001, China)
Abstract: Two series of novel heterosteroids possessing pyrazole or 1,2,4-oxadiazole ring as the side chain were prepared from pregnenolone via different pathway. All compounds synthetized are the compounds which are not reported in the literatures. The antiproliferative activity of the compounds was evaluated against HeLa (human cervical carcinoma), TPC-1 (Papillary thyroid cancer cells), A549 (human lung carcinoma) and CNE-2 (nasopharyngeal carcinoma) cancer cell lines. The result shows that the steroidal pyrazole derivatives exhibit a moderate cytotoxicity against these cancer cell lines, but are almost inactive to normal kidney epithelial cells. However, almost all of the 1,2,4-oxadiazole derivatives are ineffective (IC50 >80 μmol/L) to tested cancer cell lines. The result of our research demonstrates that 17-pyrazole ring in steroid is a better pharmacophore than 17-oxadiazole for the antiproliferative acitivity of the compounds. The information obtained from the studies is valuable for the design of novel steroidal chemotherapeutic drugs.
Key words: heterosteroids; pregnenolone; pyrazole; 1,2,4-oxadiazole; antiproliferative acitivity
CLC number: 0626.2 Document code: A Article ID: 0258-3283（2018）
某些具有吡唑和1,2,4-噁二唑支链的杂环甾体化合物的合成、表征及抗肿瘤活性评价
崔建国，庞丽萍，刘畅，盛海兵，甘春芳*，展军颜，刘晓兰，庞春玲，黄燕敏*
（广西师范学院 化学与材料科学学院，广西 南宁 530001）
摘要：从孕烯醇酮出发，经不同途径制备了两个系列具有17-吡唑及17-1,2,4-噁二唑支链的杂环甾体化合物，所有合成物文献中未见报道。评估了化合物对HeLa（人宫颈癌），TPC-1（乳头状甲状腺癌），A549（人肺癌）和CNE-2（鼻咽癌）癌细胞系的抗增殖活性。结果表明，具有吡唑支链的甾体衍生物对这些癌细胞系表现出中等强度的细胞毒性，但对正常肾脏上皮细胞几乎没有活性。然而，几乎所有的具有1,2,4-噁二唑支链的甾体衍生物对所测试的癌细胞系没有明显活性（IC50>80μM）。研究结果表明，对于此类化合物的抗增殖活性来说，甾体中的17-吡唑环比17-噁二唑环是更好的药效基团。所获得的信息对于设计新的甾体化疗药物具有很好的参考价值。
关键词：杂环甾醇；孕烯醇酮；吡唑；1,2,4-噁二唑；抗增殖活性
GO/介孔TiO2复合材料的制备及性能研究
温馨a，刘静a，赵斯琴*a, b，庄晓娟a，长山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：以硫酸钛为钛源、聚乙二醇为模板剂，采用水热法制备了一系列具有吸附及光催化双功能的GO（氧化石墨烯）/介孔TiO2复合材料，采用XRD、TEM、BET和紫外-可见漫反射等测试手段对所制备系列样品的微观结构、孔结构和谱学性能进行了初步表征，并以甲基橙溶液为目标污染物测试其吸附性能及光催化活性，进而探讨了GO/介孔TiO2复合材料的最佳制备条件。结果表明，GO/介孔TiO2复合材料中氧化钛均为锐钛矿相，晶粒尺寸均在7 nm左右，系列复合材料均属Langmuir IV型介孔结构，GO的复合适当拓宽体系光响应范围；水热温度为110 ℃、水热时间为24 h、GO的复合比为5wt%时，对甲基橙溶液的吸附及光催化活性最强，1 h内降解率可达到100%。
关键词：GO；介孔TiO2；复合；吸附性能；光催化活性
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2018）
Preparation and Properties of GO/TiO2 Mesoporous Composites WEN Xina, LIU Jinga, ZHAO Si-qin*a,b, ZHUANG Xiao-juana, S.ASUHA a,b ( a. College of Chemical and Environmental Science, b. Inner Mongolia Key Laboratory of Functional Materials of Physics and Chemistry, Inner Mongolia Normal University, Hohhot 010022, China), Huaxue Shiji, 2018, 40(7)
Abstract：A series of GO/TiO2 mesoporous composites that have bi-functions of absorption and photocatalytic properties were prepared by hydrothermal method using titanium sulfate as titanium source and polyethylene glycol as template agent. The microstructure, pore structure and spectroscopic properties of as-prepared GO/TiO2 samples were thoroughly characterized by X-ray power diffraction(XRD), transmission electron microscopy(TEM), N2 adsorption-desorption(BET), ultraviolet-visible spectrometer. And the methyl orange solution was used as the target pollutant to test the adsorption performance and photocatalytic activity of degradation of organic pollutants. The best preparation condition for GO/TiO2 composite was then investigated using the adsorption performance and photocatalytic activity as indicators. The results showed that the as-obtained GO/TiO2 composites were all in anatase phase, and their grain sizes were about 7nm, and had the Langmuir IV pore structures. Compositing titanium dioxide with graphene oxide can broaden its light response range. Results found that GO (5.0 wt%) -TiO2 prepared under the hydrothermal temperature of 110 ℃ and reaction time of 24 h had the best adsorption performance and photocatalytic activity of degrading methyl orange, and the degradation rate can reach up to 100% within 1 h.
Key words: graphene oxide; mesoporous TiO2; composite; adsorption performance; photocatalytic activity
双通道激发稀土上转换发光材料用于荧光成像
蒋威，石爱平，陈小勇，吴勇权，李勋*
（赣南师范大学 化学化工学院 江西省有机药物化学重点实验室，江西 赣州 341000）
摘要：稀土上转换发光材料作为生物发光标记材料，拥有化学稳定性高、发光稳定性好、窄带发射、发光寿命较长的优点。采用核-壳包裹的方法，设计与制备了双通道激发NaYF4:Yb3+、Nd3+、Tm3+、Er3+@NaYF4:Nd3+（CS-Nd）纳米材料，所合成的材料CS-Nd可在980 nm和808 nm激光激发下实现上转换发光。通过透射电子显微镜、上转换发光测试和小鼠活体荧光成像研究了纳米材料CS-Nd的形貌大小、上转换发光性质和生物成像性能。
关键词：稀土纳米粒子；上转换发光；双通道；荧光成像
中图分类号：O611.4 文献标识码：A 文章编号：0258-3283（2018）
Luminescence Imaging of Dual-Channel Excited Upconversion Nanoparticles JIANG Wei, SHI Ai-ping, CHEN Xiao-yong, WU Yong-quan, LI Xun* (Key Laboratory of Organo-pharmaceutical Chemistry, School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000, China), Huaxue Shiji, 2018, 40(7)
Abstract: Rear-earth upconverting luminescent nanophosphors as bioluminescent materials have advantages of high chemical stability and optical stability, sharp emission band，long emission lifetimes. In this work, dual-channel excited upconversion nanoparticles NaYF4:Yb3+,Nd3+,Tm3+,Er3+@NaYF4:Nd3+(CS-Nd) as core/shell nanostructures were designed and synthesized. The nanoparticles can emit upconverting luminescence under excitation at 980 nm and 808 nm. The structures were confirmed by transmission electron microscope. The luminescent properties of CS-Nd were investigated by fluorescence spectroscopy. Furthermore, these nanoparticles were used for luminescence imaging in vivo.
Key words: Rear-earth nanoparticles; upconverting luminescence; dual-channel; luminescence imaging
超声辅助浊点萃取荞麦壳总黄酮工艺及抗氧化活性研究
印鑫1，何伟平2，黄 菊*1
(1. 徐州工程学院 化学化工学院，江苏 徐州 221111；
2. 徐州工业职业技术学院 化工学院，江苏 徐州 221140)
摘要：以DPPH自由基清除率作为考察指标，采用单因素和正交试验相结合的方法进行了工艺优化，研究超声辅助浊点萃取荞麦壳中黄酮最佳工艺及抗氧化活性。通过极差分析得出的最佳条件：平衡时间为50 min，液料比为35 : 1，离子强度为0.6 mol/L，表面活性剂（TritionX-114）质量浓度为30 g/L。该条件下荞麦壳总黄酮提取率为1.78%。当荞麦壳中黄酮的提取液浓度为40 g/L时，对羟基自由基的清除率为84.77%，对DPPH自由基的清除率为86.36%，对DPPH自由基清除率的IC50值为18.63 g/L，荞麦壳总黄酮提取液具有较强的抗氧化活性。
关键词：荞麦壳；超声波辅助；浊点萃取；正交法；黄酮类化合物；抗氧化活性
中图分类号：Q586 文献标识码：A 文章编号：
Optimization of Ultrasonic Assisted Cloud Point Extraction of Total Flavonoids from Buck-wheat Shell and Antioxidant Activity YIN Xin1，HE Wei-ping2，HUANG Ju*1 (1.School of Chemistry & Chemical Engineering, Xuzhou Institute of Technology, Xuzhou 221111, China; 2 School of Chemical Engineering, Xuzhou College of Industrial Technology, Xuzhou 221140, China), Huaxue Shiji, 2018, 40(7)
Abstract：The optimization of ultrasonic assisted cloud point extraction of flavonoids from buck-wheat shell and its antioxidant activity were investigated. The extraction technology was optimized by single factor experiments and orthogonal method with scavenging ratio of free radical of 1, 1-diphenyl-2-trinitro-phenyl hydrazine (DPPH) as indicator for antioxidant activity. The optimum extraction conditions were obtained as follows: equilibration time 50 min, liquid material ratio 35︰1, ion strength 0.6 mol/L, and surfactant (TritionX-114) mass concentration 30 g/L The yield of flavonoids achieved 1.78%. When the concentration of total flavonoids was 40 g/L, the scavenging rate of hydroxyl radical was 84.77%, the scavenging rate of DPPH radical was 86.87%, and the 50% inhibiting concentration (IC50) of DPPH radical was 18.63 g/L. All represent a strong anti-oxidant activity.
Key words：buck-wheat shell; ultrasonic-assisted; cloud point extraction; orthogonal method; flavonoids;anti-oxidant activity
水杨醛亚胺锆配合物的合成及其催化乙烯聚合研究
杨超1，郭建双1，康必显*1，王新威1，李建龙1, 2，赵春保2
(1. 上海化工研究院有限公司 聚烯烃催化技术与高性能材料国家重点实验室，上海 200062；
2. 河南沃森超高化工科技有限公司，河南 濮阳 457000)
摘要：以2, 4-二取代苯酚与多聚甲醛为原料，在氯化镁和三乙胺催化下反应，合成出了一系列3, 5-二取代水杨醛衍生物，然后与2-甲基环己胺进行醛胺缩合得到水杨醛亚胺配体，再与四氯化锆四氢呋喃配合物配位，得到4种水杨醛亚胺锆配合物催化剂。利用1HNMR对合成的配体和金属配合物的结构进行了表征。最后考察了配体结构对乙烯聚合反应的影响，结果表明，以MAO为助催化剂，在n（Al）︰n（Zr）=50000︰1、聚合温度为50 ℃的条件下，增大酚氧邻位的位阻可提高催化活性，活性达到308 × 106 g PE/molZr。
关键词：水杨醛亚胺；超高聚乙烯；锆配合物；FI催化剂
Synthesis of (Salicylaldinato) Zr Complexes and Catalysis for Ethylene Polymerization YANG Chao1, GUO Jian-Shuang1, KANG Bi-Xian*1，WANG Xin-Wei1, LI Jian-Long1, 2, ZHAO Chun-Bao2(1. State Key Laboratory of Polyolefins and Catalysis, Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China; 2. Henan Wosen Ultra-high Chemical Industry Science and Technology Co., Ltd., Puyang 457000, China), Huaxue Shiji, 2018, 40(7)
Abstract: Taking magnesium chloride and triethylamine as catalysts, a series of 3, 5-substituted salicylaldehydes were synthesized with 2, 4-substituted phenol and paraformaldehyde, and Zr complexes were synthesized. The salicylaldiminato ligands and corresponding Zr complexes were confirmed by 1H-NMR. Ethylene polymerization was investigated under certain polymerization conditions with the 4 catalysts. Using methylaluminumoxane as co-catalyst, the catalytic activity increases as the steric bulk of the ortho position of phenoxyl group increases, and is up to 308×106 g PE/mol Zr under the conditions of n(Al)︰n (Ni)=50000:1 and T=50 ℃。
Key words： salicylaldiminato ligand; UHMWPE; Zr complex; FI catalyst
化妆品中合成着色剂分析方法研究进展
陈丹丹，茹歌，郑荣，王柯*
（上海市食品药品检验所，上海 201203）
摘要:着色剂是化妆品添加剂中的一类重要成分，在各类化妆品中有着广泛的应用。由于化妆品种类繁多，基质差异较大，同时各着色剂的结构性质也有很大区别，为分析检测工作带来挑战。从样品前处理和检测方法两个方面，对近十年化妆品中着色剂的分析检测技术进行综述，为化妆品中着色剂检测方法的开发与研究提供参考。前处理方法包括常用的溶液萃取法、固相萃取法、基质固相分散法等，检测方法主要介绍了较为常用的高效液相色谱法及高效液相色谱-质谱法。
关键词:化妆品；着色剂；分析方法
中图分类号： 文献标识码：A 文章编号：0258-3283（2018）
Research Progress of Synthetic Colorant Analysis in Cosmetics CHEN Dan-dan, RU Ge, ZHENG Rong , WANG Ke* (Shanghai Institute for Food and Drug Control，Shanghai 201203, China), Huaxue Shiji, 2018, 40(7)
Abstract: Colorant is a kind of important component of cosmetic additives, and it is widely used in various cosmetics. The diversity of cosmetic matrixes and properties of colorants bring challenges to the analysis work. In this work, the cosmetic colorants analysis in recent ten years were reviewed from two aspects of sample preparation and detection method. It could provide the reference for the detection of cosmetic colorants. The preprocessing methods include solvent extraction, solid-phase extraction, matrix solid-phase dispersion and so on. The detection methods mainly include HPLC and HPLC-MS.
Key words: cosmetics；colorants；analysis method
啶酰菌胺合成方法研究进展
朱思佳1，刘明成1，杨建华2，宋华月1，王洋洋1，刘雷芳*1
（1. 德州学院 山东高校配位化学与功能材料重点实验室，山东 德州 253023；2. 山东省德州市第一中学 化学教研组，山东 德州 253023）
摘要：作为一种广谱、低毒、高效的新型杀菌剂，啶酰菌胺引起了国内外的广泛关注，研究、开发和改进现有啶酰菌胺的工业生产路线是势在必行，这不但能提升我国农药生产企业的核心竞争力，而且还将给农业增收、农药市场带来巨大的发展机遇。到目前为止，文献中报道了较多啶酰菌胺的合成方法。为了让大家更好的把握啶酰菌胺的合成现状，根据原料的不同，从氯代芳烃、碘代芳烃、溴代芳烃和其他原料四个角度对啶酰菌胺的合成路线进行了综述，以期对同行工作者有所启发和帮助。
关键词：啶酰菌胺；合成；研究进展
中图分类号：O625.13 文献标识码：A 文章编号：0258-3283（2018）
Progress on Synthesis of Boscalid ZHU Si-jia1, LIU Ming-cheng1, YANG Jian-hua2, SONG Hua-yue1, WANG Yang-yang1, LIU Lei-fang*1(1. Key Laboratory of Coordination Chemistry and Functional Materials in Universitiesof Shandong, Dezhou University, Dezhou 253023, China; 2. Chemical Teaching and Research Group, Dezhou No.1 Middle School, Dezhou 253023, China), Huaxue Shiji, 2018, 40(7)
Abstract: Boscalid, a new and important fungicide, has attracted wide attention both at home and abroad due to its broad spectrum, low toxicity and high efficiency. It is very necessary to study, explore, and improve the existing synthetic route of Boscalid, which are very important not only for the competitive power of pesticide production enterprises but also for agriculture incomes and the development of pesticide market. There have been many synthetic methods in literature. This work, which should be helpful for the researchers of Boscalid, reviewed the synthetic methods for Boscalid in literature. Based on the raw materials used, this work is organized in the sequence of aryl chlorides, aryl iodides, aryl bromides and other materials.
Keywords: Boscalid; synthesis; research progress
电还原硝基苯合成对氨基苯酚的高效液相色谱分析法
（太原理工大学 化学化工学院, 山西 太原 030024）
摘要：建立了一种对电还原硝基苯反应产物进行检测的高效液相色谱法。选用Shim-pack VP-ODS色谱柱（250 mm × 4.6 mm，4.6 μm），流动相为60%甲醇溶液，检测波长为235 nm，流速为1.0 mL/min，柱温为25 ℃，采用标准曲线法对硝基苯、苯胺和对氨基苯酚进行定量分析。得到了硝基苯、苯胺和对氨基苯酚的标准曲线，三者在 5.0 ～ 55.0 μg/mL浓度范围内，其相关系数分别为r = 0.9994(n =11）、r =0.9995(n=11)和r =0.9995(n =11)，且此方法的精密度良好，其相对标准偏差分别≤1.52%、≤1.45%和≤1.35%。利用此方法检测电还原硝基苯反应的产物，其加标回收率分别为90.8%～107.3%、93.8% ～ 108.2%和92.0% ～ 103.4%之间，表明此方法可用于硝基苯、苯胺和对氨基苯酚3组分的同时测定。
关键词：高效液相色谱法；同时测定；硝基苯；苯胺；对氨基苯酚
中图分类号:O657.7 文献标识码:A
High Performance Liquid Chromatography of Electro - reduction of Nitrobenzene to p-Aminophenol YIN Yue, JIN Peng-jiao, LI Yan-wei* (Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China), Huaxue Shiji, 2018, 40(7)
Abstract: A high performance liquid chromatography (HPLC) method was developed for the detection of the electro-reduced nitrobenzene reaction product. The experiment was performed on a Shim-pack VP-ODS column (250 mm × 4.6 mm, 4.6 μm) with a mobile phase of 60% methanol at a detection wavelength of 235 nm and a flow rate of 1.0 mL / min with a column temperature of 25 ℃. Nitrobenzene, aniline and p-aminophenol were quantitatively analyzed by standard curve method. The calibration curves of nitrobenzene, aniline and p-aminophenol were obtained from the experiment. In the range of 5.0 ～ 55.0 μg/mL, the correlation coefficients were r = 0.9994 (n = 11), r = 0.9995 (n = 11) and r = 0.9995 (n = 11), and the precision of this method was good with the relative standard deviations of ≤1.52%, ≤1.45% and ≤1.35%, respectively. Using this method to detect the product of electro-reduction of nitrobenzene, the spiked recoveries were 90.8% ～ 107.3%, 93.8% ～ 108.2% and 92.0% ～ 103.4%, respectively, indicating that this method can be used for simultaneous determination of nitrobenzene, aniline and p-aminophenol 3 components.
Key words: high performance liquid chromatography; simultaneous determination; nitrobenzene; aniline; p-aminophenol
气相色谱—质谱法测量有机溶剂的水分含量
裴从莹1，苏衡2，王海峰*1，叶青3，刘百军3，宋小平3，李占元3
（1.北京工业大学 环境与能源工程学院，北京 100022；
2.中国石油大学 化学工程学院，北京 102249；3.中国计量科学研究院纳米所，北京 100029）
摘要：水分是有机溶剂的主要杂质之一，需要快速准确的测定，以保证产品质量合格。采用气相色谱-质谱仪（GC-MS）测量11种有机溶剂中的水分含量。采用重量法配制水的辛醇标准溶液来校准GC-MS，使得水分含量溯源到纯水质量的SI单位；采用标准加入法测定空白辛醇的水分含量，使GC-MS成为一种完全独立的水分测量方法。11种有机溶剂的水分含量在200 ～ 3300 mg/kg范围内，测量结果的相对标准偏差在0.6%～22%范围内，测量方法的检出限为85 mg/kg。水分含量在200～1500mg/kg范围内的8种有机溶剂，相对误差在-8.5% ～ 27%范围内，准确度较好。该方法适用于中低水分含量的有机溶剂的测量，可以广泛应用在水分快速筛查和生产工艺控制等领域。
关键词：有机溶剂；水分；GC-MS；卡尔•费休库仑法
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2018）
Determination of Water Content of Organic Solvents by GC-MS PEI Cong-ying1, LIU Wei2, WANG Hai-feng*3, YE qing3, MA Kang3, SONG Xiao-ping3, LI Zhan-yuan3 (1. , Beijing University of Technology, Beijing 100022, China; 2. Shanghai Research Institute of Chemical Industry, Shanghai 200062, China; 3. National Institute of Metrology of China, Beijing 100013, China), Huaxue Shiji, 2018, 40(7)
Abstract: Water content, one of main impurities in organic solvents, should be determined accurately and fastly for the assurance of the quality. In this work, gas chromatography – mass spectrometry (GC-MS) was employed to measure 11 organic solvents. Home-made water standard of water in octanol prepared by the gravimetry were used to calibrate GC-MS, which makes the water content result traceable to SI unit. The water content of the blank octanol was calculated based on the standard addition method, which makes GC-MS independent from other methods. The measured water contents ranged from 200 to 3300 mg/kg and the standard deviation ranged from 0.6% to 22%. Limit of detection (LOD) of GC-MS is 85 mg/kg. 8 organic solvents with water contents ranging from 200 to 1500 mg/kg have the relative errors ranging from -8.5% to 27%. This new method is suitable for the measurement of organic solvents and can be applied in the screening of product and the control of production.
Key words: organic solvents; water content; GC-MS; Karl Fischer coulometry
商品纳氏试剂在地表水氨氮分析中的应用
王炜*，陈晶，廖爱仙，章佳
（浙江环境监测工程有限公司，浙江 杭州 310012）
摘要：考察3种商品纳氏试剂在地表水氨氮分析中的适用性。研究了纳氏试剂在不同显色时间和加入量下的使用效果，得出3种商品纳氏试剂的最佳使用条件。通过检出限试验、实际地表水样测定以及加标回收试验对商品纳氏试剂进一步筛选，确定了适合地表水氨氮分析的纳氏试剂，并为商品纳氏试剂的可靠性提供了可行的检验方法。
关键词：商品纳氏试剂；地表水；氨氮；适用性
中图分类号：X830.2 文献标识码：A 文章编号：0258-3283（2018）
Application of Commercial Nessler Reagent in Ammonia Nitrogen Determination for Surface Water WANG Wei*, CHEN Jing, LIAO Ai-xian, ZHANG Jia (Zhejiang Environmental Monitoring Engineering Co., Ltd., Hangzhou 310012, China ), Huaxue Shiji, 2018, 40(7)
Abstract: The applicability of ammonia nitrogen determination in surface water by 3 commercial Nessler reagents was evaluated. The using effect of Nessler reagent under different chromogenic times and dosages was investigated, and the optimum working conditions of 3 commercial Nessler reagents were obtained. The detection limit test, determination of actual surface water and recovery test were applied for the further selection of commercial Nessler reagents. The most suitable Nessler reagent for ammonia nitrogen determination in surface water was ascertained, and the feasible test method for the reliability of commercial Nessler reagent was also provided.
Key words: commercial Nessler reagents; surface water; ammonia nitrogen; applicability
ICP-AES法测定太原市售8种粗粮中的多种金属元素
刘芳
（山西工程职业技术学院 冶金系，山西 太原 030009）
摘要：采用HNO3-H2O2微波消解法对太原市售的小米等8种粗粮样品进行处理，以ICP-AES法同时测定了样品中钙、钾、镁、锌、铁、铜、锰等7种金属元素的含量，并与大米样品进行了对比。实验结果表明，这8种粗粮中均富含人体所需的金属元素，尤以小米品质更为突出。所建方法的回收率为90% ～ 101%，相对标准偏差 ≤1.37%，检出限介于0.001 ～ 0.366 μg/mL之间。该方法简便、快速,适用于粗粮中多种金属元素含量的同时测定。
关键词：微波消解；电感耦合等离子体发射光谱法；粗粮；金属元素
中图分类号：O657.31 文献标识码：A 文章编号：0258-3283(2018)
Determination of Several Metal Elements in Eight Coarse Grains from Taiyuan By ICP-AES LIU Fang( , Shanxi engineering vocational technical college, Taiyuan 030009, China), Huaxue Shiji, 2018, 40(7)
Abstract: Eight kinds of coarse grains sold in Taiyuan supermarket were treated using HNO3-H2O2-microwave digestion method, and a number of metal elements including calcium，potassium，magnesium，zinc，iron，copper，manganese were determined by ICP-AES. Compared with the experimental result of rice, these coarse grains contain more metal elements which are necessary to body, especially in millet. The recovery of the method was 90% ～ 101%, the relative standard deviation was less than 1.37%, the detection limit was between 0.001 ～ 0.366 μg/mL. The method of using ICP-AES to measure the content of various metal elements in coarse grain simultaneously is simple and fast.
Key words: microwave digestion; inductively coupled plasma emission spectrometry; the coarse grains; metal elements
环境监测用乙酸乙酯气体标准样品制备方法研究
杜健，杨静，钱萌，李宁*
（环境保护部标准样品研究所 国家环境保护污染物计量和标准样品研究重点实验室，北京 100029）
摘要：依照GB/T 5274-2008《气体分析 校准用混合气体的制备 称量法》的相关要求开展了浓度水平为1 μmol/mol氮气中乙酸乙酯气体标准样品的研制工作。根据乙酸乙酯的物理化学性质确定了采用两步稀释的方法进行样品的制备。建立了样品的分析方法，对分析方法精密度、制备重现性及制备的线性进行了考察。针对国产普通气瓶和国产涂层气瓶开展气瓶内壁的吸附作用研究，确定采用国产涂层气瓶制备乙酸乙酯气体标准样品。结果表明，研制浓度水平为1 μmol/mol氮气中乙酸乙酯气体标准样品是可行的，将继续开展时间稳定性、瓶内均匀性等内容的研究，将为相关环境监测工作提供技术支持。
关键词：乙酸乙酯；气体标准样品；环境监测；制备
中图分类号：X830.5 文献标识码：A
Preparation Method of Ethyl Acetate Gas Standard for Environment Monitoring DU Jian，YANG Jing，QIAN Meng，LI Ning *( State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials, Institute for Environmental Reference Materials，Beijing 100029，China), Huaxue Shiji, 2018, 40(7)
Abstract: Accordance with the relevant technical requirements of GB/T5274-2008“gas analysis-preparation of calibration gas mixtures-gravimetric method”, ethyl acetate gas standard with concentration level of 1μmol/mol was prepared. Based on the physical and chemical properties of ethyl acetate, the preparation method was determined with two steps dilution. The precision of analysis method, linearity and reproducibility of preparation were investigated. The adsorption of cylinder inner wall based on domestic coated and ordinary cylinders was investigated. Based on the result of adsorb ability, the domestic coated cylinder was used to prepare ethyl acetate gas standard. The result of this work suggest that development ethyl acetate gas standard with 1μmol/mol was feasible. Future research will focused on the homogeneity and long term stability, that will provide technical support for environmental monitoring.
Key words: ethyl acetate; gas standard; environmental monitoring; preparation
新型双核Zn化合物和双核Ni化合物的合成、晶体结构及荧光性质研究
张骁勇1，张玉恒2，高俊芳1，王美荣1，马学林* 1
(1.包头师范学院 化学学院，内蒙古 包头 014030；
2. 包头市第二十八中学，内蒙古 包头 014030）
摘要：采用水合1,10-菲啰啉（Phen·H2O）和3,3’,4,4’-偶氮苯四羧酸（ABCT）为配体，分别以Zn（Ⅱ）和Ni（Ⅱ）为金属配位中心，通过溶剂挥发法合成了新型双核Zn化合物[Zn2(ABCT)2(Phen)2(H2O)8]•4H2O和新型双核Ni化合物 [Ni2(ABCT)2(Phen)2(H2O)8] •3H2O，利用X-射线单晶衍射仪和元素分析对二者的分子结构进行了表征。两种化合物晶系均为三斜晶系，空间群均为P-1(2)。晶体结构表明，在两种化合物中，金属Zn和Ni均是与4个水中的氧原子、1,10-菲啰啉的两个氮原子配位，形成六配位八面体几何构型，两个3,3’,4,4’-偶氮苯四羧酸在晶体结构中均是游离状态。两个化合物均通过分子间游离的3,3’,4,4’-偶氮苯四羧酸分子作为形成氢键的桥梁，堆积成三维网格结构。在 250 nm 激发波长激发下，两种化合物分别在405 nm和407 nm处有荧光发射峰。
关键词；Zn（Ⅱ）和Ni（Ⅱ）；3,3’,4,4’-偶氮苯四羧酸；1,10-菲啰啉；晶体结构；荧光性质
中图分类号：O641.4 文献标识码：A 文章编号：
Synthesis, Crystal Structure and Fluorescence Property of New Dinuclear Zn Complexe and Dinuclear Ni Complexe ZHANG Xiao-yong1, ZHANG Yu-heng2, Gao Jun-fang1, WANG Mei-rong1, MA Xue-lin*1 (1. Department of Chemistry, Baotou Teacher’s College, Baotou 014030, China; 2. ), Huaxue Shiji,2018, 40(7)
Abstract Two novel dinuclear complexes [Zn2(ABCT)2(Phen)2(H2O)8]•4H2O and [Ni2(ABCT)2(Phen)2 (H2O)8]•3H2O were synthesized based on the ligand Phen, ABTC, Zn (Ⅱ) and Ni(Ⅱ) by solvent evaporation method. The structures were confirmed by X-ray single crystal diffraction technique and elemental analysis. The two complexes belong to triclinic, and the space groups are P-1(2). The crystal structures of complexes shows that Zn and Ni are six-coordinated with octahedral coordination geometry by three O atoms from three coordinated water molecules and two N atoms from Phen. The 3-D network structures are built via the hydrogen bonds from the free ABTC as the bridges of hydrogen bonds. Complexes exhibit fluorescence emission peak at 405 nm and 405 nm under excitation of 250 nm, respectively．
Key words：Zn(Ⅱ) and Ni(Ⅱ); 3,3’,4,4’-azobenzene tetracarboxylic acid; 1,10-phenanthroline monohydrate; crystal structure; fluorescence property
稠氮杂芳环修饰的Salen配体合成及离子识别性能研究
(河北工业大学 化工学院，天津 300130)
摘要：由于低浓度的金属离子也能够对环境、生物体产生毒害，因此痕量离子识别具有现实意义。基于Salen配体的荧光性有望专一性识别金属离子，以乙酰丙酮、乙二胺、2-甲基苯并噻唑为原料合成[ONNO]型Salen配体，通过1HNMR、13CNMR、红外等手段进行表征。紫外光谱研究发现，Salen配体与多种金属离子具有配位作用；荧光光谱研究表明，Salen配体与Co2+结合荧光显著减弱，检测限为3.16×10-5 mol/L，并且具有较好的抗干扰能力；荧光滴定分析说明，Salen配体与Co2+为1:1配位。结果表明，Salen配体是一种能够选择性识别Co2+的荧光猝灭型探针，在环境监测等领域具有潜在的应用价值。
关键词 Salen配体；Co2+；离子识别；荧光光谱
中图分类号：0657 文献标识码：A 文章编号：0258-3283（2018）
Heteroaromatic Heterocyclic Modified Salen Ligand Synthesis and Ions Recognition Performance KANG Yu, LI Miao, HUANG Jie, DUAN Zhong-yu* (School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China), Huaxue Shiji, 2018, 40(7)
Abstract：Even low concentrations of metal ions can also be toxic to the environment and biometric, it is practical significance to learn identification of trace ions. Based on the fluorescence of Salen ligands, the metal ions can be specifically identified. In this work, [ONNO] Salen ligand L was synthesized from acetylacetone, ethylenediamine and 2-methylbenzothiazole which was confirmed with 1HNMR、13CNMR and IR. UV spectroscopy showed Salen ligand L has coordination with many metal ions. Fluorescence spectroscopy showed that the fluorescence of Salen ligand L and Co2+ significantly decreased, and the detection limit was down to 3.16×10-5 mol/L which has an excellent anti-interference ability. Fluorescence titration showed that the Salen ligand L and Co2+ 1:1 coordination. The results show that Salen ligand L is a fluorescence quenching probe which can selectively recognize Co2+ and has potential applications in environmental monitoring and other fields.
Key words：Salen ligand; Co2+; ion recognition; fluorescence spectrum
负载型联三吡啶钯催化剂的制备及在Suzuki-Miyaura偶联反应中的应用
黄一波*，陈绘如，张文雯
（常州工程职业技术学院 制药与环境工程学院 江苏省应用酶工程技术开发中心，江苏 常州 213164）
摘要：以4-（对羟基苯基）-2, 2’;6’, 2’-联三吡啶为配体，盐酸活化的硅胶为载体，制备了二氧化硅负载的钯催化剂SiO2-tpy-Pd。120 ℃下，DMF为溶剂、K2CO3作为碱，四丁基溴化铵（TBAB）为相转移催化剂，负载型SiO2-tpy-Pd催化剂用量为0.5 mol %，可有效促进芳基卤与芳硼酸的Suzuki-Miyaura偶联反应。该负载钯催化剂循环使用6次，催化活性无显著降低。
关键词：联三吡啶；钯催化剂；偶联反应
中图分类号：O 62；O 69 文献标识码：A 文章编号
Preparation of Supported Terpyridine-palladium Based Catalyst and Application on the Suzuki-Miyaura Coupling Reaction HUANG Yi-bo, CHEN Hui-ru, ZHANG Wen-wen(School of Pharmaceutical and Environmental Engineering, Jiangsu Provincial Applied Enzyme Engineering Technology and Development Center, Changzhou Vocational Institute of Engineering, Changzhou 213164, China) , Huaxue Shiji, 2018, 40(7)
Abstract: The SiO2 supported terpyridine-palladium (SiO2-tpy-Pd) catalyst was prepared by 4-([2, 2': 6', 2''-terpyridin]-4'-yl) phenol as ligand and silica gel as carrier. The Suzuki-Miyaura reaction of aryl halide with aryl boric acid can be effectively promoted under the reaction temperature of 120 oC, DMF as solvent, K2CO3 as base, TBAB as phase transfer catalyst, supported catalyst loading 0.5 mol%. The catalyst can be reused at least six times without distinct activity decrease.
Key words: terpyridine; palladium catalyst; coupling reaction
无毒、可降解离子液体氢氧化胆碱催化合成吡喃并[3,2-c]色烯衍生物
王英磊*a, b，杜朝军a, b，刘学国a, b，张群安a, b
(南阳理工学院 a.生物与化学工程学院，b. 河南省工业微生物资源与发酵技术重点实验室，河南 南阳 473004)
摘要：氯化胆碱是动物体内维持生理活动所必需的一种水溶性维生素，以其作为原料或主要骨架结构，制备而得的胆碱类离子液体具有良好的生物相容性和环境友好性。在安全无毒、可生物降解的离子液体氢氧化胆碱的催化作用下，芳香醛、丙二腈和4-羟基香豆素于水相中三组分“一锅煮”反应，以86% ～ 96%的产率合成了一系列吡喃并[3,2-c]色烯衍生物。该方法反应条件温和，适用范围广泛，催化剂易回收套用，具有潜在工业应用价值。
关键词：氢氧化胆碱；吡喃并[3,2-c]色烯；一锅煮；循环使用
中图分类号：TQ463.2 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of Pyrano[3,2-c]chromene Derivatives Catalyzed by Non-toxic and Biodegradable Ionic Liquid Choline Hydroxide WANG Ying-lei*a,b, DU Chao-juna, b, LIU Xue-guoa,b, ZHANG Qun-ana,b (a. School of Biological and Chemical Engineering, Nanyang Institute of Technology, b. Henan Key Laboratory of Industrial Microbial Resources and Fermentation Technology, Nanyang 473004, China), Huaxue Shiji, 2018, 40(7)
Abstract：Choline chloride is a kind of necessary and water-soluble vitamin for maintaining physiological activities in animals. The choline-based ionic liquids have good biocompatibility and environmental friendliness, which were prepared with choline chloride as a raw material or a main skeleton structure. A series of pyrano[3,2-c]chromene derivatives were synthesized via one-pot three-component reaction of aromatic aldehyde, malononitrile and 4-hydroxycoumarin in aqueous medium, with non-toxic and biodegradable ionic liquid choline hydroxide as the catalyst, in yield of 86% ～ 96%. The mild reaction condition, wide substrate flexibility and easily recyclable catalyst, made this protocol more potential value in industrial application.
Key words： choline hydroxide; pyrano[3,2-c]chromene; one-pot; recycle
3-(3-异丙基苯基)丁醛的合成
张寒冰，阎峰*，关瑾，卓桢成
（沈阳化工大学 应用化学学院，辽宁 沈阳 110142）
摘要：通过逆合成分析法设计一条合成3-(3-异丙基苯基)丁醛的路线，以4-异丙基苯胺为原料，经溴化反应和重氮化—去氨基还原反应生成3-溴异丙苯，再经格氏反应和Michael加成反应，最终得到目标化合物，通过IR、1HNMR和MS对主要产物和中间体结构进行表征。对溴化反应和重氮化—去氨基还原反应的工艺进行了改进，并对Michael加成反应的条件进行了探究。结果表明：当n(MnCl2)=30 mol%，n(MnCl2)︰n(LiCl) = 1︰2，n(CuCl)=5 mol%，t=-20 ℃时，Michael加成反应的产率为85%，总收率为73.5%。
关键词：3-(3-异丙基苯基)丁醛；Michael加成；3-溴异丙苯；逆合成分析
中图分类号：O625.41 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of 3-(3-Isopropylphenyl)butanal ZHANG Han-bing, YAN Feng*, GUAN Jin, ZHUO Zhen-cheng (Applied Chemistry College, Shenyang University of Chemical Technology, Shenyang 110142, China), Huaxue Shiji, 2018, 40(7)
Abstract: Designed a synthetic route by retro synthetic analysis of 3-(isopropylphenyl)butanal, 3-bromocemene was prepared from 4-isopropylaniline as raw material by the bromination and diazo-deaminate reduction, then Grignard reaction and Michael addition to obtain the target compound 3-(3-isopropylphenyl)butanal. The structure of main product and intermediate was confirmed by IR, 1H-NMR and MS. Improved the technology of bromination and diazo-deaminate reduction, and explored the conditions of Michael addition. The result indicated that: n%(MnCl2)=30 mol%, n(MnCl2)︰n(LiCl)=1:2, n%(CuCl)=5 mol%, t= -20 ℃, the yield in this condition of Michael addition is 85%, the total yield is 73.5%.
Key words: 3-(3-isopropylphenyl)butanal; Michael addition; 3-bromocumene; retro synthetic analysis
1, 2, 3-三唑修饰黄酮的合成
牛雁宁*1，袁媛1，董翔2，吴禄勇3
(1. 南京林业大学 教学科研部，江苏 淮安 223003；2. 兰州大学淮安高新技术研究院，江苏 淮安 223003；3. 海南师范大学 化学与化工学院，海南 海口 571127)
摘要：主要以苯胺为原料，通过重氮化反应后与乙酰乙酸乙酯发生环加成反应得到中间体5-甲基-1-苯基 -1H-1,2,3-三唑-4-甲酸，进一步酰氯化后与邻羟基苯乙酮反应成酯，并在碱作用下发生Baker-Venkatarama重排反应，再经过酸催化发生闭环反应合成目标化合物。产物的结构经1HNMR、13CNMR、IR、元素分析进行确认。结果显示Baker-Venkatarama重排反应最适宜的条件为以叔丁醇钾作碱，DMF作溶剂；在闭环反应中4-甲基苯磺酸为最适宜的催化剂。该合成路线原料易得，成本较低，操作简单。
关键词：1, 2, 3-三氮唑；合成；黄酮
中图分类号：TQ245.3 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of 1, 2, 3-Triazoles Substituted Flavone NIU Yan-ning* 1, YUAN Yuan1, DONG Xiang2, WU Lu-yong3(1. Department of Teaching and Research, NanJing Forestry University, Huaian 223003,China; 2.Huaian High Tech Research Institute of Lanzhou University, Huaian 223003, China; 3.Department of Chemistry, Hainan normal university, Haikou 571128, China), Huaxue Shiji, 2018, 40(7)
Abstract：In this work, aniline was used as raw materials, after the diazotization reaction, it was reacted with ethyl acetoacetate by cyclic addition reaction to form the intermediate 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid. After the intermediate was treated with SOCl2, and further reacted with ortho–hydroxyacetophenone, the classical Baker-Venkatarama rearrangement was occured under the strong base. Finally, the target compound was synthesized by ring-closing reaction under the acid catalysis. The structure of the product was confirmed by 1HNMR, 13CNMR, IR, and elemental analysis. The results showed that the most suitable synthesis conditions for Baker-Venkatarama rearrangement reaction were using potassium tert-butanol as base and DMF as solvent, the most suitable catalyst for ring-closing reaction was using 4-methylbenzene sulfonic acid. The synthetic method has advantages on readily available materials, low cost, simple operation.
Key words：1, 2, 3-triazole; synthesis; flavone
高纯度N-甲基邻氟苯胺的合成新工艺
李爱军*a,b，史帅帅a
(河北科技大学 a. 化学与制药工程学院，b.河北省药用分子化学重点实验室-省部共建国家重点实验室培育基地，河北 石家庄 050018)
摘要：对N-甲基邻氟苯胺的合成新工艺法进行研究。以邻氟苯胺为起始原料，经甲酸甲酰化、甲磺酸甲酯甲基化、盐酸-甲醇水解得到N-甲基邻氟苯胺。在优化的反应条件下，总收率为83.0%，纯度99.5%。该方法操作简单，原料易得，避免了精馏分离，适合工业化生产。[2]
关键词：N-甲基邻氟苯胺；邻氟苯胺；甲酰化；合成
中图分类号：TQ457.2 文献标识码：A 文章编号：
New Synthesis Process of High Purity of N-methyl-2-fluoroaniline LI Ai-jun*a,b, SHI Shuai-shuaia（a.College of Chemical and Pharmaceutical Engineering, b. State Key Laboratory Breeding Base –Kye Laboratory of Molecular Chemistry for Drug of Hebei Province, Hebei University of Science and Technology , Shijiazhuang 050018,China), Huaxue Shiji, 2018, 40(7)
Abstract: A new method for the synthesis of N-methyl-2-fluoroaniline was investigated. N-Methy-2-fluoroaniline was obtained from 2-fluoroaniline as starting material via the process of formylation, methylsulfonate methylation and hydrochloric acid-methanol hydrolysis reaction. Under the optimal conditions, the total yield was 83.0% and the purity was 99.5%.The synthetic process has simple operations and is suitable for industrial production.
Key words: N-methyl-2-fluoroaniline; 2-fluoroaniline;formylation; synthesis
高光学纯度的氯吡格雷合成工艺研究
潘岩1，谢其亮2，陈重1，陈琼1，杨俊杰*1
（1.信阳农林学院 生物与制药工程学院，河南 信阳 464000；
2.河南羚锐制药股份有限公司，河南 信阳 464000）
摘要:以(R)-(-)-邻氯扁桃酸为原料合成中间体(R)-2-(4-硝基苯磺酰氧基)-2-(2-氯苯基)乙酸甲酯，以2-噻吩乙胺为原料合成中间体4,5,6,7-四氢噻吩并[3,2-c]吡啶盐酸盐，以上两种中间体缩合得氯吡格雷，产物光学纯度（e.e.%）＞99%。通过正交试验设计方法考察反应温度、反应溶剂和投料比对氯吡格雷e.e.%的影响。结果表明，温度对反应的影响最大，优化后工艺：反应温度为25 ℃，丙酮为溶剂，投料比为1.3 : 1；在该条件下，缩合步骤产率为91.9%，氯吡格雷的e.e.%＞99%。有效解决了氯吡格雷光学纯度问题，且工艺简单易行、重现性好、适合工业化生产。
关键词：氯吡格雷; 光学纯度; 合成
中图分类号:R914.2 文献标识码：A 文章编号：
Synthesis of High Optical Purity Clopidogrel PAN Yan1, XIE Qi-liang2, CHEN Zhong1, CHEN Qiong1, YANG Jun-jie*1 (1. College of Biological and Pharmaceutical Engineering, Xinyang Agriculture and Forestry University, XinYang 464000, China; 2.Henan Lingrui Pharmaceutical Co., Ltd., Xinyang 464000, China), Huaxue Shiji, 2018, 40(7)
Abstract: To synthesize clopidogrel, and ensure its optical purity (＞99%). Intermediate 3 and 5 was synthesized using thiophene-2-ethylamine and (R)-(-)-2-Chloromandelic acid as the raw materials, respectively. Clopidogrel was obtained via condensation of the two intermediate. Orthogonal test was used to investigate the effect of reaction time, reaction temperature and the ratio of intermediate 3 and intermediate 5 on the e.e.% of clopidogrel. The result showed that the reaction temperature had the most significant effect and the optimum reaction condition as follows: reaction temperature for 25 ℃，solvent for acetone and the ratio of intermediate 3 and intermediate 5 for 1.3:1. The yield of condensation process was 91.5%, and the e.e.% of clopidogrel＞99%. The optimal purity problem of clopidogrel was effectively resolved, and the preparation process of clopidogrel was easy and reliable, it can be applied on industrial production.
Key words: Clopidogrel; optical purity; synthesis
