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《化学试剂》2020年第10期中英文摘要

农产品中内吸性农药残留检测技术与研究进展

陈亨业1,邓高琼1,付海燕*1,佘远斌2

1.中南民族大学 药学院,湖北 武汉  4300742.浙江工业大学 化学工程学院,浙江 杭州  310014

 

摘要:内吸性农药(Systemic pesticides)是一类能在植物生长过程中被植物种子、根、茎和叶吸收,并在植物体内进行传导扩散的农药。其可进入植物组织和器官内部,起到很好的除虫害效果,具有用药简单、药效时间长、雨水影响小和能有效杀灭隐藏害虫等优点,但上述优点使其在食品安全检测中存在残留时间长、提取困难和检测结果偏低或漏检等诸多缺点。综述了近五年来内吸性农药的特点、检测方法及其存在的问题,并对其检测技术的发展进行展望。

关键词:内吸性农药;农药残留;食品安全;快速检测
中图分类号S482.3    文献标识码:A          文章编号:0258-32832020

 

Advances in Detection of Systemic Pesticide Residues in Agricultural Products CHEN Heng-ye1, DENG Gao-qiong1, FU Hai-yan*1, SHE Yuan-bin2(1.School of Pharmaceutical Sciences, South-Central University for Nationalities, Wuhan 430074, China; 2.School of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China), Huaxue Shiji, 2020, 42(10)

AbstractSystemic pesticides are a group of pesticides that can be absorbed by plant seeds, roots, stems, and leaves during plant growth, and conduct conduction and diffusion in plants. It can enter the inside of plant tissues and organs to play a good role in microorganism and insect control. It has the advantages of simple medication, long efficacy time, less affected by rain and effective killing of hidden pests, but at the same time, the above advantages make it have many disadvantages such as long residual time, difficult extraction, low detection result or missed detection, etc. This work summarizes the characteristics, detection methods and detection problems of systemic pesticidesin recent five years, and looks forward the development of the detection technology.

Key wordssystemic pesticides; pesticide residues; food safety; rapid detection

引用本文:陈亨业,邓高琼,付海燕,等. 农产品中内吸性农药残留检测技术与研究进展[J]. 化学试剂, 2020, 42(10):1139-1147

 

 

介孔生物炭的合成、改性及其对染料的吸附性能研究

何红艳*,邹思佳

阿坝师范学院 资源与环境学院,四川 阿坝  623002

 

摘要:以菠萝叶子为原材料,磷酸作活化剂,通过热处理合成介孔生物炭,再利用十六烷基三甲基溴化铵进行改性,采用扫描电镜、比表面积测试和傅立叶转换红外光谱表征改性前后材料的结构,研究其作为吸附剂处理染料废水的性能。室温下,藏红T的初始浓度150 mg/LpH 11,吸附时间50 min,未改性吸附剂投加量0.6 g/L,去除率和吸附量分别达到96.33%234.1 mg/g。胭脂红的吸附实验中,当初始浓度100 mg/LpH 2,吸附时间50 min,改性吸附剂投加量0.5 g/L,去除率95.17%,吸附量是194.8 mg/g。分析数据表明,改性前后材料吸附染料的过程符合拟二级动力学模型和Langmuir等温线模型。

关键词:菠萝叶子;H3PO4;介孔结构;藏红T;胭脂红

中图分类号:X703TQ127.1      文献标识码A      文章编码0258-32832020--

 

Preparation and Modification of Mesoporous Biochar and Adsorption Properties for Dyes

HE Hong-yan*, ZOU Si-jia (College of Resources and Environment, A Ba Teachers University, A Ba, 623002, China), Huaxue Shiji, 2020, 42( ),

AbstractWith Pineapple leaves as biomass source and H3PO4 as an active agent, mesoporous biochar was synthesized by heat treatment, and then modified by hexadecyltrimethyl ammonium bromide (CTAB). The structure of the material before and after modification was confirmed by SEM, BET and FTIR. Meanwhile, the adsorption properties of sample were investigated for dye wastewater treatment. The results showed that, at room temperature, when the initial mass concentration of safranine T was 150 mg/L, pH 11, the adsorption time was 50 min and the dosage of mesoporous biochar was 0.6 g/L, the safranine T removal rate and adsorption capacity were presented about 96.33% and 234.1 mg/g. In the adsorption experiment of carmine, when the initial concentration is 100 mg/L, pH 2, the adsorption time is 50 min, the dosage of modified adsorbent is 0.5 g/L, the adsorption removal rate and adsorption capacity reached 95.17% and 194.8 mg/g, respectively. Based on the analysis data, the adsorption processes of dye waste water were in accordance with the pseudo-second-order kinetic model and Langmuir isotherm model.

Key words: Pineapple leaves; H3PO4; mesoporous structure; Safranine T; carmine

引用本文:何红艳,邹思佳. 介孔生物炭的合成、改性及其对染料的吸附性能研究[J]. 化学试剂, 2020, 42(10 ):1148-1153.

 

 

焦糖化香料的制备及其在卷烟中的应用研究

朱远洋1,郭鹏2,郑美玲1,茹琦2,单凯2,张文洁1,杨泽恩1,张峻松*1

 (1. 郑州轻工业大学 食品与生物工程学院,河南 郑州  450002

2. 红塔辽宁烟草有限责任公司 技术中心,辽宁 沈阳  110000)

 

摘要:为开发焦甜香突出的焦糖化香料,利用微波消解技术,以其香味物质总含量为考察指标建立了焦糖化香料最优模型体系,并将焦糖化香料添加到卷烟中进行感官评吸,同时通过吸烟机研究加香前后卷烟主流烟气粒相物的差异性。结果表明:焦糖化香料最优模型体系为:反应液浓度400 g/L,反应助剂用量为糖原料质量分数的20 %,反应温度160 ℃,保持时间3 min。葡萄糖、果糖焦糖化香料中香味物质总含量分别为3.532.51 mg/g。通过感官评吸结果,确定了葡萄糖焦糖化香料的最佳加香浓度为0.65 mg/支。加香后的卷烟主流烟气粒相物中香味物质总含量增加19.52 %,其中酮类、酯类、呋喃类、烯类、吡啶类化合物分别增加26.16 %25.33 %20.63 %20.55 %19.20 %,与感官评吸结果相一致。

关键词:焦糖化反应;焦甜香;微波消解;卷烟加香;主流烟气

中图分类号:TS41              文献标识码:A           文章编号:0258-32832020

Preparation of Caramelized Flavors and Application in Cigarettes ZHU Yuan-yang1,GUO Peng2, ZHENG Mei-ling1, RU Qi2, DAN Kai2, ZHANG Wen-jie1, YANG Ze-en1, ZHANG Jun-song*1 (1. School of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China; 2.Technical Center of Hongta Liaoning Tobacco Co., Ltd., Shenyang 110000, China), Huaxue Shiji, 20204210

Abstract: In order to develop the caramelized flavor with outstanding caramel flavor, the optimal model system of caramelized flavor was established by using microwave digestion technology and the total content of scent substances as the index of investigation, and the caramelized flavor was added to cigarettes for sensory evaluation. The differences of particulate matter in mainstream cigarette smoke before and after flavoring were tested by smoking machine. The results show that: the optimal model system of caramelized flavor is: the concentration of the reaction solution is 400 g / L, the amount of the reaction assistant is 20% of the mass fraction of the sugar raw material, the reaction temperature is 160 ℃, and the holding time is 3 minutes. The total content of aroma substances in glucose and fructose caramelized spices are 3.53 mg / g and 2.51 mg / g respectively. Glucose coke was determined through sensory evaluation The best flavoring concentration of saccharified flavor is 0.65 mg / branch. The total content of flavor substances in the mainstream smoke particles of flavored cigarettes increased by 19.52%, including ketones, esters, furans, olefins, Pyridine compounds increased by 26.16%, 25.33%, 20.63%, 20.55%, and 19.20%, respectively, consistent with the results of sensory evaluation.

Key words: caramelization reaction; sweet burnt fragrance; microwave digestion; cigarette flavoring; mainstream smoke

引用本文:朱远洋 ,郭鹏,郑美玲,等. 焦糖化香料的制备及其在卷烟中的应用研究[J]. 化学试剂,2020, 42101154-1159.

 

 

用于正电子发射断层技术的68Ga双功能螯合剂的研究进展

李恒,吴志文,武文超,马宇衡*,张振涛*

(内蒙古医科大学药学院,内蒙古 呼和浩特  010010

摘要:癌症是一种严重威胁人类健康的疾病,对其早期诊断有利于提高治疗率。目前,核医学以及PET技术的发展,实现了肿瘤部位可视化,达到早期诊断癌症或治疗的目的。PET成像依赖于放射性同位素通过双功能螯合剂与靶向配体的结合,因此双功能螯合剂的发展是PET成像中的重要一环,68Ga作为常用于PET成像的同位素之一,其双功能螯合剂得到了快速的发展及运用。简要概括了近年来常用的PET中放射性金属68Ga的双功能螯合剂。

关键词:正电子发射型计算机断层显像;68Ga;双功能螯合剂;癌症;核医学

中图分类号0621      献标识码:A      文章编号:0258-32832020-

 

Progress of 68Ga Bifunctional Chelating Agent for Positron Emission Tomography

LI Heng, WU Zhi-wen, WU Wen-chao, MA Yu-heng*, ZHANG Zhen-tao*(School of Pharmaceutical SciencesInner Mongolia Medical UniversityHohhot 010110China), Huaxue Shiji, 2020, 4210

Abstract: Cancer is serious, and its early diagnosis and treatment is still a major problem. With the progress of science and the development of nuclear medicine and PET, visualization and localization of tumors are allowed to achieve the goal of early diagnosis and treatment of cancer. PET imaging depends on the combination of radioisotopes with target ligands via bifunctional chelating agents. Therefore, the development of bifunctional chelating agents is an important part of PET imaging. As one of the isotopes commonly used in PET imaging, 68Ga has been rapidly developed and applied. This work briefly summarizes the most commonly used bifunctional chelating agents for radioactive metal 68Ga in PET technology.

Key words: PET; 68Ga; bifunctional chelating agent; cancer; nuclear medicine

引用本文李恒, 吴志文, 武文超, . 用于正电子发射断层技术的68Ga双功能螯合剂的研究进展[J]. 化学试剂, 2020, 42(10):1160-1168.

 

 

亲水作用色谱用于西妥昔单抗的N端糖链分析

高宗林,曹旭妮*

(华东理工大学 食品系 生物反应器工程国家重点实验室,上海  200237

 

摘要:单克隆抗体的糖链对其功能活性具有重要的影响,因此开展糖链分析技术的研究具有十分重要的意义。采用亲水作用色谱荧光检测方法建立了N-糖链的定量分析技术。对于常见的3N-糖链G0FG1FG2F,其线性范围分别为7.5´10-111.5´10-84.5´10-119.0´10-9、以及7.5´10-114.5´10-9mol/L;检测下限分别为2.8´10-112.5´10-112.6´10-11 mol/L;保留时间和峰面积的RSD值均小于3%,方法的回收率均大于95%。采用酶切N端糖链和2-氨基苯甲酰胺标记法可以实现西妥昔单抗的这3N端糖链的含量分析,分别为86.085.116.6μg/g。除了上述3种糖链,还利用UPLC-ESI-MS进一步对西妥昔单抗其他6种相对丰度较高的N-糖链的种类进行解析。这些研究不仅对单抗药物的N-糖链进行质控分析,而且对其糖链种类进行解析并开展相关生物学研究具有重要的意义。

关键词:亲水作用色谱;2-氨基苯甲酰胺;糖链;西妥昔单抗;液质联用技术

中图分类号O657.7    文献标识码A      文章编号:0258-32832020

 

Hydrophilic Interaction Chromatography for the Analysis of N-sugar Chains in Cetuximab GAO Zhong-lin, CAO Xu-ni* (State Key Laboratory of Bioreactor Engineering, Department of Food Science & Technology, East China University of Science & Technology, Shanghai 200237, China), Huaxue Shiji, 2020, 42(10)

Abstract:The sugar chains of the monoclonal antibody have an important influence on its functional activity, so it is of great significance to carry out a research on sugar chains analysis. To this end, a quantitative analysis technique of N-sugar chains was established by hydrophilic interaction chromatography coupled with fluorescence detection. For the three common N-sugar chains G0F, G1F, G2F, their linear ranges were 7.5 ´ 10-11~1.5´ 10-8,4.5´ 10-11~9.0 ´ 10-9 and 7.5´ 10-11~4.5 ´ 10-9mol/L while the detection limits were 2.8´ 10-11,2.5´ 10-11, 2.6 ´ 10-11 mol/L, respectively. The RSD values of reserved time and peak area were all found less than 3%, and their recoveries were greater than 95%. It meant that the established method was sufficient for the content analysis of these three N-sugar chains in a real sample, which were released by digesting cetuximab and further labeled with 2-aminobenzamide. Further results indicated they were 86.0, 85.1, 16.6μg/g protein, respectively. Besides, we also provided an UPLC-ESI-MS method to determine other six relatively abundant N-sugar chains of cetuximab. These work can be not only applied for quality control analysis of the N-sugar chains of monoclonal antibodies, but also determination of the types of sugar chains for further biological research.

Key words: HILIC; 2-aminobenzamide; N-sugar chains; cetuximab; UPLC-MS

引用本文:高宗林,曹旭妮. 亲水作用色谱用于西妥昔单抗的N端糖链分析[J]. 化学试剂, 2020, 42(10):1169-1175

 

 

疏水性低共熔溶剂超声辅助分散液液微萃取高效液相色谱法测定环境水中的除草剂残留

赵桐桐,郭振幅,孙艳红,王素利*

(河北北方学院 河北省农产品食品质量安全分析重点实验室,河北 张家口  075000

 

摘要:建立了疏水性低共熔溶剂超声辅助分散液液微萃取(DES-UA-DLLME)高效液相色谱法测定环境水中除草剂的农药残留分析方法。通过对不同种类低共熔溶剂的萃取效率进行筛选,以正癸酸(氢键给体)与四丁基氯化铵(氢键受体)在3:1形成的疏水性低共熔溶剂萃取效率最高,并且对影响萃取的一些参数(DES的体积、超声萃取时间、离心时间以及水样pH值等)进行优化。在最优条件下,最小检出限和定量限分别为0.0260.057 µg/L0.090.19 µg/L,添加回收率和相对标准偏差(RSD)分别为80.597.6%2.87.8%,并且应用于实际环境样本的检测,同时进行添加回收率实验,回收率为85.0% 99.3% ,能够满足农残分析要求。

关键词:疏水性低共熔溶剂; DES-UA-DLLMEHPLC;除草剂;正葵酸;四丁基氯化铵

中图分类号O658.2      文献标识码A      文章编号0258-32832020--

 

Ultrasonic Assisted Dispersive Liquid-liquid Microextraction Based on Hydrophobic Deep Eutectic Solvent for the Determination of Herbicide Residues in Environmental Water Samples by HPLC ZHAO Tong-tong, GUO Zhen-fu, SUN Yan-hong, WANG Su-li*( Hebei Key Laboratory of Quality and Safety Analysis-Testing for Agro-Products and Food , Hebei North University, Zhangjiakou 075000, China), Huaxue Shiji, 2020, 42(10)

Abstract: An ultrasound assisted dispersive liquid- liquid micextraction method base on hydrophobic deep eutectic solvent (DES-UA-DLLME) was developed for the determination of herbicide residues in environmental water samples by high performance liquid chromatography (HPLC). The types of deep eutectic solvents were selected for high extraction efficiencies and DES composed of n-decanoic acid and tetrabutylammonium chlorid  at 1:3 molar ratio provided higher extraction efficiencies. Several important factors affecting extraction efficiency conditions, including the volume of DES, ultrasonic time, centrifuge time and sample pH were optimized. Under the optimized conditions, limits of detection and limits of quantification of seven herbicides were in the range of 0.026 0.057 μg/L and 0.09 0.19 μg/L, respectively. The recoveries were ranged from 80.5 to 97.6%, and the relative standard deviations (RSD) were between 2.8% and 7.8%. Finally the developed method was successfully applied for determination of seven herbicides from several real environmental water samples. Then the proposed method on the real water samples was demonstrated by spiking the samples at different concentrations. The average recoveries were 85.0% 99.3% which could meet the requirements of pesticide residue analysis.

Key words: hydrophobic deep eutectic solvent; dispersive liquid- liquid micextraction; HPLC; herbicides; n-decanoic acid; tetrabutylammonium chlorid

引用本文:赵桐桐,郭振幅,孙艳红,等. 疏水性低共熔溶剂超声辅助分散液液微萃取高效液相色谱法测定环境水中的除草剂残留[J]. 化学试剂,202042101176-1180 .

 

 

三种卡马西平血药浓度测定方法比较

贾永娟,张杰,文江曼,李亦然,刘春冉,倪君君*

(北京和合医学诊断技术股份有限公司,北京  100176

 

摘要:探讨三种卡马西平血药浓度测定方法的可行性与测定结果的一致性。分别使用普通高效液相色谱法(HPLC)、高效液相色谱在线固相萃取法(HPLC-on line SPE)、高效液相色谱串联质谱法(HPLC-MS/MS)三种分析方法对46例临床患者血清样本进行检测,并使用SPSS 16.0对检测结果进行统计学分析。三种测定方法,卡马西平在0.532.0 mg/L范围内线性关系均良好(R20.99),平均回收率均在85%115%以内,精密度均小于15%,显著性P= 0.446。三种方法均满足卡马西平血药浓度的测定,且三种测定方法的检测结果无显著性差异。

关键词:卡马西平;血清;浓度;普通高效液相色谱法;高效液相色谱在线SPE法;高效液相色谱串联质谱法

中图分类号R 917     文献标识码A            文章编号0258-32832020

 

Comparison of Three Methods for Determination of Carbamazepine in Serum IA Yong-juan, ZHANG Jie, WEN Jiang-man, LI Yi-ran, LIU Chun-ran, NI Jun-jun*(Beijing Harmony Health Medical Diagnostics Co.,Ltd, Beijing 100176, China), Huaxue Shiji, 2020, 42(10)

Abstract: To explore the feasibility and  consistency of three methods for determination of carbamazepine in serum. Forty-six serum samples were detected by normal high performance liquid chromatography(HPLC), high performance liquid chromatography with on-line SPE (HPLC - on line SPE) and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS), and the results were analyzed statistically with SPSS 16.0. The concentration of carbamazepine in serum had a good linear relationship in the range of 0.5 32.0 mg / L (R2 > 0.99), the average recovery was within 85% 115%, and the precision was less than 15%, P= 0.446. The three methods were all suitable for the determination of carbamazepine in serum, and there was no significant difference within the three methods.

Key words: carbamazepine; serum; concentration; HPLC; HPLC - on line SPE; HPLC-MS/MS

引用本文:贾永娟,张杰,文江曼,等. 三种卡马西平血药浓度测定方法比较[J]. 化学试剂, 2020, 42(10):1181-1185

 

SPE净化-GC-MS/MS法快速检测大棚植土壤中5种杀菌剂方法的建立

吴伟*1,杨彬1,张翠华2

1. 河北省沧州生态环境监测中心,河北 沧州  0610002. 沧州师范学院 化学与化工学院,河北 沧州  061001

 

摘要:建立全自动固相萃取(SPE)净化大棚种植土壤中的嘧菌酯、肟菌酯、霜霉威、甲霜灵和烯酰吗啉杀菌剂的GC-MS/MS快速检测方法。土壤样品自然晾干,碾碎。经乙腈萃取后,于全自动固相萃取仪上净化,收集净化液并经氮气吹至近干。残渣用正己烷定容至1 mL,于气相色谱三重四级杆串联质谱仪分析,外标法定量。在0.044.0 μg/mL实验浓度范围内,5种杀菌剂质量浓度与对应的峰面积呈良好的线性关系,相关系数均大于0.995;检出限均在0.0140.042 mg/kg范围内。3个不同浓度水平平均加标回收率在89.8%103.2%之间;精密度测试结果的相对标准偏差均小于5% (n = 6)。该方法实用性强,定性定量结果准确、可靠,适用于土壤样品中农药残留的监测。

关键词:全自动固相萃取;GC-MS/MS;土壤;嘧菌酯;杀菌剂

中图分类号X833           文献标识码A     文章编号0258-32832020

 

GC-MS/MS Rapid Detection Method for Purification of Five Fungicides in Greenhouse Soil by Full-automatic Solid-phase Extraction WU Wei*1, YANG Bin1, ZHANG Cui-hua2 (1. Cangzhou Ecological Environment Monitoring Center of Hebei Province, Cangzhou 061000, China2. School of Chemistry and Chemical Engineering, Cangzhou Normal University, Cangzhou 061001, China), Huaxue Shiji, 2020, 42(10)

AbstractTo establish a GC-MS/MS method for rapid determination of azoxystrobin, oximectin, flumetoclopramide, metalaxyl and enylmorpholine in greenhouse soil by solid-phase extraction. The soil samples were dried and crushed. After extraction by acetonitrile, it was purified on the full-automatic solid-phase extractor, and the purified liquid is collected and blown to near dry by nitrogen. The residue was fixed with 1mln-hexane, which analyzed by gas chromatography triple quadrupole tandem mass spectrometer and quantified by external standard method. The mass concentration of five fungicides had a good linear relationship in range of 0.04 4.0 μg/mL with the corresponding peak area. The correlation coefficient was greater than 0.995.The detection limit was in range of 0.020 0.042 mg/kg. The average recovery of three different concentration levels was between 89.8% and 103.2%. The relative standard deviation of the precision test results was less than 5% (n=6). The method was practical, accurate and reliable, and was suitable for the monitoring of pesticide residues in soil samples.

Key words: full automatic solid phase extraction; GC-MS/MS; soil; azoxystrobin; fungicide

引用本文:吴伟,杨彬,张翠华. 全自动固相萃取净化大棚种植土壤中5种杀菌剂的GC-MS/MS快速检测方法的建立[J]. 化学试剂, 2020, 42(10):1186-1189

 

 

复合维生素B中烟酰胺含量的中红外分析模型和近红外分析模型的比较

姚婉清,吴定丽,吴云妹,彭梦侠*

(嘉应学院 化学与环境学院,广东 梅州  514015

 

摘要:建立了一种快速检测复合维生素B中烟酰胺含量的方法。以高效液相色谱法测定复合维生素B片中烟酰胺的含量为参比方法,采用红外分析技术结合偏最小二乘法,分别建立了复合维生素B片中烟酰胺含量的中红外定量分析模型和近红外定量分析模型。对比这两种定量分析模型,复合维生素B片中烟酰胺含量的近红外定量分析模型的检测更准确,用该模型检测样品绝对误差在-0.61%0.84%范围之间,相对误差在-4.91%5.75%范围之间。

关键词:复合维生素B;烟酰胺;近红外光谱法;中红外光谱法;偏最小二乘法;定量分析模型

中图分类号O657.33    文献标识码A    文章编号0258-32832020

 

Comparison of Mid-infrared Analysis Model and Near-infrared Analysis Model of Nicotinamide in Multi-vitamin B YAO Wan-qing, WU Ding-li, WUYun-mei, PENG Meng-xia*(School of Chemistry and Environment, Jiaying University, Meizhou 514015, China), HuaxueShiji, 2020, 42(10)

Abstract:A method for rapid detection of nicotinamide in compound vitamin B was established. Using high-performance liquid chromatography to determine the content of nicotinamide in compound vitamin B tablets as a reference method, using infrared analysis technology combined with partial least squares method, respectively established the mid-infrared quantitative analysis model and near infrared quantitative analysis model. Comparing the two quantitative analysis models, the results show that the near-infrared quantitative analysis model for the determination of nicotinamide content in the compound vitamin B tablets is more accurate. The model is used to detect samples, the absolute error is in the range of -0.61%0.84%, relative error in the range of-4.91%5.75%.

Key words: multivitamin Bnicotinamidenear infrared spectroscopymid-infrared spectroscopypartial least squaresquantitative analysis model

引用本文:姚婉清,吴定丽,吴云妹,等. 复合维生素B中烟酰胺含量的中红外分析模型和近红外分析模型的比较[J]. 化学试剂,202042101190-1195

 

 

高纯硫酸铜中17种稀土杂质元素ICP-MS法检测

程龙军*1,陈昌铭1,温炎燊1,彭义华2,郑冠立2

1. 深圳市深投环保科技有限公司,广东 深圳  5180492.深圳市艾科尔特检测有限公司,广东 深圳  518049

 

摘要:ICP-MS具有灵敏度高且能多元素同时测定的优点,将其应用到高纯硫酸铜中杂质元素测定,对样品前处理和仪器分析条件进行了优化,成功建立了ICP-MS外标法测定高纯硫酸铜中17种稀土杂质元素的方法。采用高纯硫酸铜样品进行了方法验证,各元素的标准曲线在0 5 µg/L范围内的相关系数R0.9998 1.0000,样品测定结果的相对标准偏差(以加标样测定结果计算)在1.9% 8.9%范围内,各元素的方法检出限为1.1 7.1 µg/kg。该方法简单、快速,能同时测定多元素含量,具有良好的精密度和准确度,灵敏度高,适用于高纯硫酸铜样品中痕量杂质元素的测定。

关键词:硫酸铜;高纯;稀土杂质元素;ICP-MS;外标法;

中图分类号:O657.6         文献标识码:A           文章编号:0258-32832020

 

Determination of 17 Rare Earth Impurities in High Purity Copper Sulfate by ICP-MS CHENG Long-jun*1, CHEN Chang-ming1, WEN Yan-shen1, PENG Yi-hua2, ZHENG Guan-li2(1. Shenzhen Shentou Environmental Technology Co., Ltd., Shenzhen 518049, China; 2. Shenzhen Accurate Testing Co., Ltd., Shenzhen 518049, China), Huaxue Shiji, 2020, 42(10)

Abstract: A external standard method with optimization of sample preparation and instrumental analysis for the determination of 17 rare earth impurities in high purity copper sulfate by ICP-MS which with the advantages of high sensitivity and simultaneous determination of multi-elements was established. The method was verified with the high purity copper sulfate sample and the result showed that the correlation coefficient of the standard curve (0 5 µg/L) of each element was in the range of 0.9998 1.0000, the relative standard deviation (RSD) of the determination results were in the range of 1.9% 8.9% and the detection limit of each element was in the range of 1.1 7.1 µg/kg. The method was simple, rapid, accurate and suitable for the determination of trace impurity elements in high purity copper sulfate samples.

Keywords: copper sulfate; high purity; rare earth impurities; ICP-MS; external standard method

引用本文:程龙军,陈昌铭,温炎燊,等. 高纯硫酸铜中17种稀土杂质元素ICP-MS法检测[J]. 化学试剂,2020, 4210):1196-1200.

 

 

云南不同产区臭灵丹中4种无机阴离子的超声波辅助提取-离子色谱法含量测定研究

鲁广秋1,梁建平3,李松1,李亮星1,田先娇2,杨新周*2

1. 玉溪师范学院 化学生物与环境学院,云南 玉溪  6531002.德宏师范高等专科学校 理工学院,云南 德宏  6784003. 德宏州科技情报研究所,云南 芒市  678400

 

摘要为了探究臭灵丹中无机阴离子的含量和组成,建立一种快速、经济、有效的超声波辅助提取-离子色谱测定臭灵丹中4SO42-PO43-Cl-NO3-阴离子的方法。通过阴离子分析柱分离,在选定的离子色谱检测条件下,经实验比较提取的方式、溶剂类别和用量、温度和时间,从而得出最佳预处理条件。超声波提取法优于冷浸提取法,40 mL水作提取溶剂、提取时间30 min、提取温度25 为最佳条件。臭灵丹样品中4种阴离子的回收率在97.3 %108.6 % 之间,RSD0.17 % 2.83 %。所建立的分析方法准确、可靠,能满足阴离子分析的要求。不同产区臭灵丹中阴离子含量存在差异,4种阴离子平均含量高低次序为SO42-6.805 mg/g)、PO43-6.561 mg/g)、Cl-5.986 mg/g)、NO3-1.354 mg/g)。其中NO3-含量变异系数较大,说明不同产区臭灵丹之间NO3-含量波动较大,而Cl-含量变异系数较小,说明Cl-含量在不同产区臭灵丹间较稳定。

关键词: 臭灵丹;无机阴离子;离子色谱;超声辅助提取;含量测定

中图分类号:O657.7      文献标识码:A      文章编号:0258-32832020--

 

Determination of Four Anions in Laggerapterodonta from Different Areas of Yunnan by Ion Chromatography with Ultrasonic-assisted Extraction LU Guang-qiu1, LIANG Jian-ping3, LI Song 1, LI Liang-xing 1, TIAN Xian-jiao2, YANG Xin-zhou*2 (1. College of Chemical Biology and Environment, Yuxi Normal University, Yuxi 653100, China; 2. Dehong Teachers College, Science and Engineering Department, Dehong 678400, China; 3. Dehong Institute of  Scientific  and Technological Information, Mangshi 678400, China) Huaxue Shiji, 2020, 42(  ),

Abstract: A rapid, economic and efficient method was developed to determine anions in Laggerapterodonta from different areas of Yunnan. It was used for researching contents and compositions of anions in Laggerapterodonta. The best pretreatment method was choosing after comparing with extraction method, solvent type and dosage, temperature and time. The sulfate, phosphate, chloride ions, nitrate(SO42-PO43-Cl-NO3-)in samples were separated by anion column and detected by the selected detection conditions of ion chromatography after extracting by ultrasonic assisted, and quantified by external standard method. The way of ultrasonic assisted was chose to extract samples, because it was better than cold soak extraction. The best pretreatment conditions to extract samples were using 40 mL ultrapure water as extraction solvent, with ultrasonic for 30 minutes at 25 ℃. The recoveries were in the range of 97.3 % 107.3 %and relative standard deviations were in the range of 0.17 % 2.83 %. This method was accurate and reliable, which can meet the requirements of anion analysis. The average concentration of four anions from high to low was: SO42-(6.805 mg•g-1), PO43-(6.561 mg•g-1), Cl-(5.986 mg•g-1), NO3-(1.354 mg•g-1). Variation coefficient of the contents of anions is diverse. The variation coefficient of NO3- is higher than another, it shows that the contents of NO3- in Laggerapterodonta from different areas were varied. The variation coefficient of Cl- is less. So the content of Cl-in Laggerapterodonta from different areas were equable.

Key words: Laggerapterodonta; ion chromatography; anions; ultrasonic-assisted extraction; determination

引用本文 鲁广秋, 梁建平, 李松, . 云南不同产区臭灵丹中4种无机阴离子的超声波辅助提取-离子色谱法含量测定研究[J]. 化学试剂, 42(10):1201-1206.

 

 

一维链状锌配合物的合成、晶体结构及性质研究

黄秋萍,曾振芳,黄秋婵,韦友欢*

(广西民族师范学院 化学化工学院,广西 崇左  532200

 

摘要采用溶剂热法,以2, 2′-联吡啶(bipy)为主配体,4, 4′-二苯乙烯二羧酸(H2SDA)为辅助配体合成了一个链状配位聚合物[Zn(SDA)(bipy)]n·2H2O。通过红外吸收光谱(IR)、元素分析和X-射线单晶衍射等方法对配合物的结构进行表征。配合物属于单斜晶系,空间群P21/c,是由羧酸桥联形成的一维链状配位聚合物。对配合物的Hirshfeld表面及2D指纹图进行分析,在配合物的相互作用力中,H···H作用占有率为43.3%,占主导作用,而C···H/H···C的作用力占有率为21.5%O···H/H···O的作用力占有率为18.3%。配合物的荧光传感性能研究表明不同金属离子对配合物荧光强度有不同程度的影响,该配合物可作为荧光传感材料选择性的检测Cu2+

关键词:锌配合物;链状结构;Hirshfeld表面;二苯乙烯二羧酸;荧光传感

中图分类号:O 641               文献标识码:A                文章编号:0258-32832020

 

Synthesis, Crystal Structure, Property of One-dimensional Chain  Zinc Complex HUANG Qiu-ping, ZENG Zhen-fang, HUANG Qiu-han, WEI You-huan*(College of Chemistry and Engineering, Guangxi Normal University for Nationalities, Chongzuo 532200, China), Huaxue Shiji, 2020, 42(10)

Abstract: The one-dimensional chain zinc complex[Zn(SDA)(bipy)]n·2H2O was synthesized by solvothermal method using2,2′-bipyridine as the main ligand and 4, 4′-stilbenedicarboxylic acid as the auxiliary ligand. The zinc complex was characterized by IR, elemental analysis and X-ray single crystal diffraction. The complex belong to the monoclinic system, space group P21/c, and formed one-dimensional chain coordination polymer by carboxylic acid bridging. Hirshfeld surface analysis and 2D fingerprint plots revealed that complex was supported mainly by H···H, the market share was 43.3%. The C···H/H···C and O···H/H···O interactions have 25.6%, 18.3% contribution to the total Hirshfeld surface, respectively. The fluorescence sensing ability of the complex was investigated. The results show that the effects of different metal ions on the fluorescence of the complex was difference, it can be used as a fluorescence sensing material to detect Cu2+.

Key words: zinc complex; chain structure; Hirshfeld surface; stilbenedicarboxylic acid; fluorescence sensing

引用本文:黄秋萍,曾振芳,黄秋婵,等. 一维链状锌配合物的合成、晶体结构及性质研究[J].化学试剂,202042101207-1212 .

 

 

硝基苯胺-冠醚包合物超分子晶体材料的合成、结构

及介电性质

张子钰,刘洋*,王娜,徐慧婷,王鹏,刘尊奇*

(新疆农业大学 化学工程学院,新疆 乌鲁木齐  830052

 

摘要:4-硝基苯胺和18-冠醚-6以物质的量比为1:1在乙醇溶液内反应,通过室温蒸发合成硝基苯胺-冠醚包合物超分子晶体材料(4-NO2C6H4NH2)(18-冠醚-6)。并通过红外光谱(IR)、单晶X-射线衍射、X-射线粉末衍射(XRD)、热重(TG)、介电等测试方法对晶体的结构和性能进行表征和分析。结果显示目标化合物在室温和低温下属于单斜晶系,空间群为P21/n,晶体内4-硝基苯胺夹在两个平行的冠醚层间形成夹层结构,随着温度改变,冠醚层间距离发生伸缩,导致硝基与苯环平面及硝基苯胺分子与冠醚平面夹角发生改变,引起化合物介电常数随着温度的升高在250 K附近产生明显的增大。

关键词:氢键;冠醚;4-硝基苯胺;晶体结构;超分子;介电性质

中图分类号:  O641.3      文献标识码:  A     文章编号:0258-32832020

Synthesis, Structure and Dielectric Properties of Supramolecular Crystal Materials Containing Nitroaniline and Crown Ether ZHANG Zi-yu, LIU Yang*, WANG Na, XU Hui-ting, WANG Peng, LIU Zun-qi*(Chemical Engineering College, Xinjiang Agricultural University, Urumqi 830052, China), Huaxue Shiji, 2020, 42(10)

Abstract: 4-Nitroaniline reacted with 18-crown-6 which was used as raw materials in ethanol solution at molar ratio of 1:1. One nitroaniline-crown ether inclusion complex supra molecular crystalline material (4-NO2C6H4NH2) (18-crown-6) was successfully synthesized by evaporation method at room temperature. The structure and properties of the crystal were analyzed by IR, single crystal X-ray diffraction, X-ray powder diffraction (XRD), thermo gravimetry (TG) and dielectric measurements. The compound belongs to monoclinic system at room temperature (296 K) and low temperature (100 K) with the space group P21/n. 4-Nitroaniline was sandwiched between the two parallel crown ether layers to form a sandwich structure in the crystal. The interlayer distances of crown ethers increase with the change of temperature, leading to the angle between nitro-benzene ring plane and nitroaniline molecule and crown ether plane is changed and the number of N-H···O hydrogen bonds in the supra molecular structure decreases. This compound displayed obvious dielectric anomaly at ca. 260 K.

Key words: hydrogen bond; crown ether; 4-nitroaniline; crystal structure; supramolecular; dielectric properties

引用本文:张子钰,刘洋,王娜,等. 硝基苯胺-冠醚包合物超分子晶体材料的合成、结构及介电性质[J]. 化学试剂,2020, 4210:1213-1219.

 

 

3-甲基-4-甲醛肟基苯甲酸乙酯的合成及其荧光性能研究

胡建梅,李天贵,张滢,姜玉,顾思,陈颖梅,王勇*

 (荆楚理工学院 药物合成与优化湖北省重点实验室,湖北 荆门  448000)

 

摘要:以3-甲基-4-溴苯甲酸为起始原料,经酰化和酯化反应制得3-甲基-4-溴苯甲酸乙酯,之后将其与氰化亚铜发生取代反应得到3-甲基-4-氰基苯甲酸乙酯,最后将3-甲基-4-氰基苯甲酸乙酯与盐酸羟胺在碱性条件下反应得到白色固体目标产物。对部分重金属离子(Fe(III)Pb(II)Co(II)Cr(III)Cd(II)Fe(II)Mn(II)Ni(II)Zn(II))的荧光响应表明,目标化合物对于Cu(II)Fe(III)Pb(II)金属离子均有比较好的选择性识别作用。

关键词:肟基;荧光光谱;氰基;设计合成;Fe(III)

中图分类号:O621.3         文献标识码:A      文章编号:0258-32832020  

 

Synthesis and Fluorescence Properties of 4-(Hydroxyimino-methyl)-3-methyl Benzoic Acid Methyl Ester HU Jian-mei, LI Tian-gui, ZHANG Ying, JIANG Yu, GU Si, CHEN Ying-mei, WANG Yong* (Hubei Key Laboratory of Drug Synthesis and Optimization, Jingchu University of Technology, Jingmen 444800, China), Huaxue Shiji, 2020, 42(10)

AbstractIn this work, 3-methyl-4-bromobenzoic acid was used as the starting material, and it was refluxed with thionyl chloride in ethanol solution to obtain 4-bromo benzoic acid ethyl ester. Reaction of 4-bromo benzoic acid ethyl ester with cuprous cyanide afforded 4-cyano benzoic acid ethyl ester. 4-(hydroxyimino-methyl) benzoic acid ethyl ester, a white solid, was obtained by reaction of 4-cyano benzoic acid ethyl ester with hydroxylamine hydrochloride under basic condition. The fluorescence response of selected heavy metal ions (Fe (III), Pb (II), Co (II), Cr (III), Cd (II), Fe (II), Mn (II), Ni (II), Zn (II)) on 3-methyl-4-formaldehyde oxime ethyl benzoate indicates it has better selective recognition for Cu (II), Fe (III) and Pb (II) metal ions.

Key wordsoxime group; fluorescence spectroscopy; cyano; design synthesis; Fe(III)

引用本文:胡建梅,李天贵,张滢, . 3-甲基-4-甲醛肟基苯甲酸乙酯的合成及其荧光性能研究[J].化学试剂,202042(10):1220-1225 .                                                                                           

 

 

超声辅助季膦离子液体提取艾草总黄酮的研究

贾晓丽,肖江,赵鑫悦,艾佳宏,赵三虎*

(忻州师范学院 化学系, 山西 忻州  034000)

 

摘要:探究含磷离子液体、超声对艾草总黄酮提取的影响,发展一种提取艾草总黄酮的高效方法。在超声辅助作用下,将季膦离子液体与含水乙醇组成的混合溶剂用于野生艾草总黄酮的提取,考察超声功率、超声时间、超声温度、液料比及乙醇浓度对总黄酮提取率的影响,进一步通过响应面试验的方法优化总黄酮的提取工艺。结果表明:在最优工艺条件下,即离子液体十二烷基三丁基溴化膦浓度0.20 mol/L、乙醇浓度78%、料液比1:55(g/mL)、超声功率230 W、超声温度60 及超声时间35 min,艾草总黄酮提取率为18.45 %。离子液体含水乙醇混合溶剂的使用及超声辅助的协同作用,显著促进艾草总黄酮的溶出,为艾草总黄酮的提取提供了新的思路和方法。

关键词:超声;离子液体;提取;艾草;黄酮

中图分类号: O628.2               文献标识码:A             文章编号:0258-32832020

 

Ultrasonic-assisted Extraction of Flavonoids from Artemisia Argyi by PhosphoniumIonic Liquid JIA Xiao-li, XIAO Jiang, ZHAO Xin-yue, AI Jia-hong, ZHAO San-hu*Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000, China, Huaxue Shiji, 2020, 42(10)

Abstract: Exploring the effect of phosphonium ionic liquid and ultrasound to the extraction total flavonoids from Artemisia argyi, and to develop an efficient method for extraction of total flavonoids from Artemisia argyi. With the help of ultrasound, the complex solvent of phosphonium ionic liquid with aqueous ethanol was used to extract total flavonoids from wild Artemisia argyi. The effects of ultrasonic power, ultrasonic time, ultrasonic temperature, liquid-solid ratio and ethanol concentration on the extraction rate of total flavonoids were investigated, and the extraction process was further optimized by using response surface experiments. Under the optimal process conditions, namely the concentration of ionic liquid tributyldodecylphosphonium bromide is 0.20 mol/L, ethanol concentration is 78 %, liquid to material ratio is 1:55(g/mL), ultrasonic power is 230 W, ultrasonic temperature is 60 and ultrasonic time is 35 min, the yield of total flavonoids was 18.45 %. Ultrasound-assisted extraction and the using of complex solvent of ionic liquid with aqueous ethanol can significantly promote the dissolution of total flavonoids from Artemisia argyi, which may provide a new idea and method for the extraction of total flavonoids from Artemisia argyi.

Key words: ultrasonic; ionic liquid; extraction; Artemisia argyi; flavonoids

引用本文:贾晓丽,肖江,赵鑫悦,等. 超声辅助季膦离子液体提取艾草总黄酮的研究[J]. 化学试剂,20204210:1226-1232.

 

 

煤矿区源Penicillium sp. XR046真菌次生代谢产物化学成分研究

张青艳a,b,杨斐玉c, 陈广桂a, 雷丹丹a, 徐国波*a,b

(贵州医科大学 a.药学院,b.教育部民族药与中药开发应用工程研究中心,c. 生物与工程学院, 贵州 贵阳  550004

 

摘要:对贵州省兴仁煤矿区土壤源Penicillium sp. XR046真菌代谢物中化学成分进行研究,为筛选活性先导化合物提供化学分子来源。采用大米固体培养对真菌Penicillium sp. XR046进行发酵培养,经乙酸乙酯提取获得总代谢产物;通过联合运用硅胶柱层析、Sephadex LH-20、制备高效液相等现代分离技术对其代谢物中的化学成分进行分离,运用NMRMS现代波谱技术对单体化合物的结构进行鉴定。从Penicillium sp. XR046真菌代谢物中分离得到20个化合物。其中12个化合物为首次从青霉属真菌代谢物中分离。丰富了Penicillium sp.次生代谢物化合物库,为相关药理活性筛选奠定基础。

关键词:真菌;Penicillium sp.;次生代谢产物;分离纯化;结构鉴定

中图分类号:R914.4        文献标识码:A     文章编号:0258-32832020

 

Study on the Chemical Constituents ofMetabolites fromPenicillium sp. XR046 ZHANG Qing-Yana,b,YANGFei-Yuc,CHENGuang-Guia,LEI Dan-Dana,XUGuo-Bo*a,b(a. School of Pharmacyb.Engineering Research Center for the Development and Application of Ethnic Medicine and TCM Ministry of Educationc.School of Biology & Engineering, Guizhou Medical University,  Guiyang 550004, China),HuaxueShiji, 2020, 42(10)

Abstract:To investigate chemical constituents from the metabolites of the Penicillium sp. XR046 which was collected in Xinren coal area of Guizhou province to provide source for screening active compounds. The fungus Penicillium sp. XR046 was cultured bysolid-state fermentation and the total metabolites were obtained by extraction with ethyl acetate. All compounds were isolated by comprehensive chromatography such as silica gel CCSephadex LH-20 CC, and semi-preparative HPLC, and were identified by NMR and MS spectra. Twenty known compounds were isolated and identified from metabolites of Penicillium sp. XR046. Twelve compounds were firstly isolated from the metabolites of the Penicillium sp. genus. This study enriched the chemical constitutes data of Penicillium sp. and provided foundation for the screening of pharmacological activities.

Key words: fungus; Penicillium sp.; secondary metabolites; isolation and purification; structure identification

引用本文:张青艳, 杨斐玉, 陈广桂,等.煤矿区源Penicillium sp. XR046真菌次生代谢产物化学成分研究[J]. 化学试剂, 2020,4210:1233-1239.

 

 

超声辅助乙醇提取荔枝核总皂苷工艺优化及其抗炎作用研究

王洋1,庞康1,钟远坚1,杨玉婷1,赵立春*1,王刚*2

 

1.广西中医药大学 药学院,广西 南宁 5302002.广西壮瑶药工程技术研究中心,广西南宁 530200

摘要:优选超声辅助乙醇提取荔枝核总皂苷的工艺条件,并研究其抗炎活性。在单因素的基础上,以乙醇浓度、提取时间、料液比为影响因素,通过正交实验优化提取工艺。进而以LPS诱导RAW 264.7细胞为炎症模型,考察其抗炎活性。最优提取工艺为70%乙醇为溶剂,料液比1:20,超声辅助提取30分钟,总皂苷的含量为4.61mg/g;抗炎活性研究结果表明荔枝核总皂苷在1100 μg/mL未表现出细胞毒性,但对NO释放的抑制率达到85.35%,对IL-6的抑制率达到了86.68%。超声辅助乙醇提取荔枝核总皂苷工艺稳定可靠,而且具有较低的细胞毒性和较好的抗炎活性。

关键词:荔枝核总皂苷;提取工艺;正交实验;细胞毒;抗炎

中图分类号: R284.2R285.5      文献标识码:A      文章编号:0258-32832020--

 

Extraction Method and Anti-inflammatory Activity of Total Saponins from Litchi Seeds Wang Yang1, Kang Pang1, Zhong Yuan-jian1, Yang Yu-ting1, Zhao Li-chun*1, Wang Gang*2 (1.          , Guang Xi University of Chinese Medicine, Nanning 530200, China; 2. Guangxi Zhuang Yao Medicine Center of Engineering and Technology, Nanning 530200, China), Huaxue Shiji, 2020, 42(10)

Abstract :To optimize the conditions of total saponins extracted from Litchi seed by ultrasound-assisted ethanol extraction and then evaluated its anti-inflammatory activity. On the basis of single factor, the orthogonal experiment was used to optimize the extraction of total saponins from Litchi seed and the concentration of ethanol, extraction time and solid-liquid ratio were selected as influence factors. The anti-inflammatory activity of total saponins was evaluated via RAW 264.7 cells induced by LPS. The optimal condition was concluded as follows: ethanol concentration was 70%, ratio of liquid to solid was 20:1, and extraction time was 30 min. The mean concentration of total saponins extracted by optimal conditions was 4.61mg/g. The total saponins from Litchi seed were shown no cytotoxic activity while showed significant NO (85.35%) and IL-6 (86.68%) inhibition activity. Ultrasound-assisted ethanol extraction of total saponins from litchi seed was stable and reliable, and has low cytotoxicity and good anti-inflammatory activity.

Key words: totalsaponins from litchi seeds; extraction technology; orthogonal experiment; cytotoxicity; anti-inflammatory activity

引用本文:王洋, 庞康, 钟远坚, . 超声辅助乙醇提取荔枝核总皂苷工艺优化及其抗炎作用研究[J]. 化学试剂, 2020, 42(10): 1240-1245.

 

 

5-(4-碘代苯基)-10,15,20-三苯基卟啉及其锌配合物的合成

任冬梅

(首都经济贸易大学 管理工程学院,北京  100070

 

摘要:标题化合物(TPPI)是一种含碘活性基团的不对称卟啉化合物,可应用于制备复杂不对称卟啉化合物及卟啉寡聚物。通过两种方法合成了TPPI,一是以两种醛和吡咯为原料一步直接合成,产率约8%;另一种以5,10,15,20-四苯基卟啉(TPP)为起始物,经硝化、还原和重氮化三步反应合成,总产率达27.8%TPPI进一步与锌盐反应得到金属锌配合物(ZnTPPI)。利用1HNMRMSUV-Vis、元素分析对TPPIZnTPPI进行了结构表征,确定合成产物为目标产物。一步直接合成法反应条件温和、易于操作、适于规模化制备;间接合成法路线步骤较短,后处理方便,产率较高。

关键词:碘代卟啉;合成;表征;重氮化

中图分类号O625.6      文献标识码A          文章编号:0258-32832020

 

Synthesis of 5-(4-Iodophenyl)-10, 15, 20-triphenylporphyrin and Zinc Complex REN Dong-mei(School of Management and Engineering, Capital University of Economics and Business, Beijing 100070, China), Huaxue Shiji, 2020, 42(10)

Abstract: The title compound (TPPI) is an asymmetric porphyrin compound containing an iodine active group and can be used to prepare complicated asymmetric porphyrin compounds and porphyrin oligomers. TPPI was synthesized by two methods, the direct synthesis of TPPI in one step has been achieved with two aldehydes and pyrrole as raw materials, and the yield was about 8%; The title compound was also synthesized from 5,10,15,20-tetraphenylporphyrin(TPP) by nitrification, reduction and diazotization. The total yield of the 3-step reaction of this route reached 27.8%. Then its zinc compound (ZnTPPI) was synthesized from metal salt and TPPI. The structures of TPPI and ZnTPPI were confirmed by 1HNMR, MS, UV-Vis. The synthetic products were identified as the target products. The direct synthesis method has the advantages of mild reactions, easy operation and suitable for large-scale preparation, the indirect synthesis route has short steps, convenient post-processing and high yield.

Key words: iodoporphyrinsynthesischaracterizationdiazotization

引用本文:任冬梅. 5-(4-碘代苯基)-10,15,20-三苯基卟啉及其锌配合物的合成[J]. 化学试剂, 2020, 42(10):1246-1250

 

 

稳定同位素标记双酚F-D8的合成研究

涂亚辉1,赵超敏3,徐仲杰*1, 2

(1.上海化工研究院有限公司,上海  200062

2.东华大学 材料科学与工程学院 化学纤维与高分子材料改性国家重点实验室,上海  201620

3.上海出入境检验检疫局 动植物与食品检验检疫技术中心,上海  200135)

 

摘要:以苯酚-D6为稳定同位素标记原料,在氘代磷酸的酸性催化作用下与多聚甲醛发生缩合反应,制备稳定同位素标记的双酚F-D8。通过对反应条件的优化,得到稳定的较优合成工艺路线,以消耗的苯酚-D6计算,双酚F-D8的产率为26.2%。通过核磁共振波谱仪、高效液相色谱仪和液质联用色谱仪等仪器对目标化合物的结构进行分析表征,确定为双酚F-D8,化学纯度为98.1%,同位素丰度为98.3atom%D。目标产物稳定同位素标记的双酚F-D8可以作为内标试剂应用于食品接触材料安全检测和环境监测等领域。

关键词:稳定同位素标记;双酚F-D8;内标试剂;合成;检测

中图分类号:TQ243.12   文献标识码:A     文章编号:0258-32832020

 

Synthesis of Stable Isotope Labeled Bisphenol F-D8 TU Ya-hui1, ZHAO Chao-min3, XU Zhong-jie*1, 2(1.Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China;2.State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China; 3. Technology Center for Animal Plant and Food Inspection and Quarantine, Shanghai Entry-Exit Inspection and Quarantine Bureau, Shanghai 200135, China), Huaxue Shiji, 2020, 42(10)

AbstractIn this work, using phenol-D6 as a stable isotope starting labeling raw material, reacted with paraformaldehyde under the catalytic action of deuterated phosphoric acid as an acidic catalyst to prepare stable isotope-labeled bisphenol F-D8. By the optimization of the reaction conditions, a stable and better synthetic process route was obtained. Based on the consumption of phenol-D6, the yield of bisphenol F-D8 was 26.2%. The structure of the target compound was analyzed by nuclear magnetic resonance spectrometer, high performance liquid chromatography and liquid chromatography-mass spectrometry, which was determined to be bisphenol F-D8 with a purity of 98.1% and an isotope abundance of 98.3atom%D.Bisphenol F-D8 as the target product of this study, could be used as an internal standard reagent in the fields of food contact material safety testing and environmental monitoring.

Key wordsstable isotope labeling; bisphenol F-D8; internal standard reagent; synthesis; detection

引用本文:涂亚辉,赵超敏,徐仲杰. 稳定同位素标记双酚F-D8的合成研究[J]. 化学试剂,202042(10)1251-1254

 

 

(R)-3-氨基-4-(2,4,5-三氟苯基)丁酸的合成

应佳妮,盛振华*

(浙江中医药大学 中医药科学院,浙江 杭州  310014

 

摘要:以2,4,5-三氟苯乙酸为起始原料,与2,2-二甲基-1,3-二噁烷-4,6-二酮缩合得到2,2-二甲基-5-[2-(2,4,5-三氟苯基)乙酰基]-1,3-二噁烷-4,6-二酮,其后经苯甲醇醇解得到3-氧代-4-(2,4,5-三氟苯基)丁酸苄酯,与(R)-α-苯乙胺缩合后经不对称还原及脱除苄基保护基得到西他列汀关键手性中间体标题化合物,总产率59.6%,纯度98.5%,其结构经1HNMR13CNMRMS(ESI)HR-MS(ESI)确证。该工艺具有反应条件温和、操作简单、产率高等优点,适合工业化生产。

关键词2,4,5-三氟苯乙酸;(R)-3-氨基-4-(2,4,5-三氟苯基)丁酸;西他列汀;关键手性中间体;合成

中图分类号:O625.42      文献标识码:A        文章编号:0258-32832020

 

Synthesis of (R)-3-Amino-4-(2,4,5-trifluorophenyl)butanoic Acid YING Jia-ni, SHENG Zhen-hua* (Academy of Chinese Medical Sciences, Zhejiang Chinese Medical University, Hangzhou 310014, China), Huaxue Shiji, 2020, 42(10)

Abstract (R)-3-Amino-4-(2,4,5-trifluorophenyl)butanoic acid has been obtained via five steps from 2,4,5-trifluorophenylacetic acid, which is easily transformed into 3-oxo-4- (2,4,5-trifluorophenyl) butyric acid benzyl ester by condensation with 2,2-dimethyl-1,3-dioxane-4,6-dione. Treatment of methyl 3-oxo-4-(2,4,5-trifluorophenyl) butanoate with (R)-α-phenylethylamine, followed by asymmetric reduction with sodium borohydride(NaBH4) provided diastereoisomers. The chiral auxiliary group and benzyl protecting group were removed by hydrogenation to obtain the key intermediate 1 with the total yield of 78.1% and the purity of 98.5%.The structure was confirmed by 1HNMR, 13CNMR, MS(ESI) and HR-MS(ESI). The experimental results showed that the process exhibited mild reaction conditions, simple operation and high yield, which was suitable for industrial production.

Key words2,4,5-tirflurobenzeneacetic acid; (R)-3-amino-4-(2,4,5-trifluorophenyl)butanoic acid; Sitagliptin; key chiral intermediate; synthesis

引用本文:应佳妮, 盛振华. (R)-3-氨基-4-(2,4,5-三氟苯基)丁酸的合成[J]. 化学试剂, 2020, 42(10):1255-1259

 

 

柠檬酸诱导人参须根皂苷转化为人参皂苷Rg3

张仔豪,叶安琪,何治平,唐良峥,李杰,董明月,成乐琴*

吉林化工学院 化学与制药工程学院,吉林 吉林  132022

 

摘要:利用改良索氏提取器,研究了柠檬酸诱导人参须根皂苷转化为人参皂苷Rg3的方法,并以人参皂苷20(R/S)-Rg3总得率为考察指标,通过单因素实验进行了工艺优化,同时探索了原人参二醇组皂苷到人参皂苷Rg3的生成路径。优化柠檬酸诱导人参须根皂苷转化为人参皂苷Rg3的制备工艺并探索Rg3生成路径。实验结果表明,酸浓度0.16 mol/L,固液比1:15g/mL),蒸馏瓶加热温度110 ℃,提取桶内加热温度60 ℃60%甲醇溶液中提取3 h20(R)-Rg320(S)-Rg3总得率为2.51%。柠檬酸诱导下,原人参二醇组皂苷不经过人参皂苷Rd,而是直接水解C-20位双糖生成Rg3。方法在人参皂苷提取过程中通过一步法直接完成人参粉中人参皂苷的提取、人参皂苷的结构修饰、人参粉与人参提取液的分离,可以显著提高稀有人参皂苷Rg3的制备效率,方法简单,可以为大量生产人参皂苷Rg3提供理论和技术支持。

关键词:人参须根皂苷;改良索氏提取器;人参皂苷Rg3;制备;生成路径;柠檬酸

中图分类号R284      文献标识码A      文章编号0258-32832020--

 

Citric Acid Induced Conversion of Fibrous Root Ginsenosidein PanaxGinseng C. A. Meyer to Ginsenosides Rg3 ZHANG Zi-hao, YE An-qi, HE Zhi-ping, TANG Liang-zheng, LI Jie, DONG Ming-yue, CHENG Le-qin*(Department of Pharmacy and Applied Chemistry, Jilin Institute of Chemical Technology ,Jilin 132022, China), Huaxue Shiji, 2020, 42(10)

Abstract To optimize the preparation process of ginsenoside Rg3 from ginseng root saponins induced by citric acid and explore the pathway of Rg3 generation. The method of transformation of ginsenosides from ginsenosides to ginsenosides Rg3 induced by citric acid was investigated by using modified soxhlet extractor, and the total rate of ginsenosides 20(R/S) -Rg3 was used as the index, and also explored the pathway from ginsenoside to ginsenoside Rg3. The acid concentration was 0.16 mol/L, the solid-liquid ratio was 1:15 (g/mL), the heating temperature of the distillation bottle was 110 , the heating temperature in the extraction barrel was 60 ,extracted 3h by 60% methanol solution and the total rates of 20(R) - Rg3 and 20(S) - Rg3 were 2.51%.Under the induction of citric acid, the ginsenoside in the protopanaxadiolsaponins did not undergo ginsenoside Rd, but directly hydrolyzed C-20 disaccharides to produce Rg3. This method can directly extract ginsenosides from ginseng powder, modify the structure of ginsenosides,and separate ginsenosides from ginseng extract by one-step method, which can significantly improve the preparation efficiency of Rg3. The method is simple and can provide theoretical and technical support for the mass production of ginsenoside Rg3.

Key wordsGinseng root saponins; improved soxhlet extractor; ginsenoside Rg3; preparation; production pathway; citric acid

引用本文:张仔豪,叶安琪,何治平,等. 柠檬酸诱导人参须根皂苷转化为人参皂苷Rg3[J].化学试剂,20204210:1260-1267

 

 

琥珀酸去甲文拉法辛一水合物的合成工艺的改进

张天一1,余一波1,尹树铸1,陈玮琳1,梁承武1,邵太丽*2,昌盛*1

1. 吉林医药学院 药学院,吉林 吉林  1320132. 皖南医学院 药学院,安徽 芜湖  241002

 

摘要:1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇盐酸盐为起始原料,在甲酸的存在下与甲醛经Eschweiler-Clarke反应得到1-[2-(二甲胺)-1-(4-甲氧苯基)乙基]环己醇,在甲醇钠存在下经与十二烷基硫醇反应脱除甲基得到去甲基文拉法辛,最后与琥珀酸成盐以57.03 %的总产率得到标题化合物,纯度>99.5%。标题化合物结构经1HNMR13CNMRESI-MS 确证,结晶水类型及数目经热重分析和差热分析确证。合成工艺反应条件温和、中间体易于纯化、成本低廉,适用于工业化生产。

关键词:琥珀酸去甲文拉法辛一水合物;合成;改进;Eschweiler-Clarke反应;抑郁症

中图分类号:R914.5       文献标识码:A          文章编号:0258-32832020--

 

Improved synthesis of Desvenlafaxine Succinate Monohydrate ZHANG Tian-yi1, YU Yi-bo1, YIN Shu-zhu1, CHEN Wei-lin1, LIANG Cheng-wu1, SHAO Tai-li*2, CHANG Sheng*1 (1. College of Pharmacy, Jilin Medical University,  Jilin 132013, China; 2. School of Pharmacy, Wannan Medical College, Wuhu 241002, China), Huaxue Shiji, 2020, 42(  ),

Abstract: 1-(2-Amino-1-(4-methoxyphenyl)ethyl)cyclohexan-1-olhydrochloride was used as startmaterial to synthesize1-(2-(dimethylamino)-1-(4-methoxyphenyl)ethyl)cyclohexan-1-ol via Eschweiler–Clarke reaction. O-desmethylvenlafaxine was synthesized by demethylation reaction with sodium dodecyl sulfate and then reacted with succinic acid to formdesvenlafaxinesuccinate in total yield of 57.03 % as well as purity more than 99.5%. The title compound was confirmed by 1HNMR13CNMR and HR-MS, the type and number of crystal water were confirmed by thermogravimetric analysis and differential scanning calorimeter.The optimized synthetic conditions were mild, low cost, and the intermediate was easily purified was suitable for industrial production.

Key words: desvenlafaxine succinate monohydrate; synthesis; improvement; Eschweiler-Clarke reaction; depression

引用本文:张天一, 余一波, 尹树铸, . 琥珀酸O-去甲文拉法辛合成工艺的改进[J]. 化学试剂, 2020, 42(10):1268-1272.