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您的位置:中国色谱网 >> 资讯 >> 技术应用 >> 图书期刊 >> 《色谱》2012年第11期内容摘要
《色谱》2012年第11期内容摘要
2012年11月27日 来源:中国色谱网 责编:李华静

1093-1093

DOI: 10.3724/SP.J.1123.2012.11001

完善地沟油检测方法 健全食品安全检测体系——“色谱技术在地沟油检测中的应用”专栏引言

陈吉平*

(中国科学院大连化学物理研究所, 辽宁 大连 116023)

近年来,食品卫生与安全成为备受关注的热门话题,继“苏丹红”、“三鹿奶粉”和“瘦肉精”等事件之后,“地沟油”掺杂使假问题又一次牵动了广大民众的心,使人们谈“地沟油”而色变。“地沟油”或非正常食用植物油,一般指从下水道中的油腻漂浮物或泔水提炼出的油、劣质动物器官组织加工提炼的油和煎炸老油,以及含有这些油的勾兑油。由于这类非正常食用油的主体化学成分与正常食用植物油具有很大的相似性,很难找到特征性的化学物质,因而其指示物筛选及检测非常困难,现有的食用油检验标准不能满足检测需要。

因此,完善食用植物油安全检测方法,健全食用植物油安全保障体系已成为当务之急,防止“地沟油”滥用的安全监督检验工作也日益受到人们的重视,各种分析检测技术应运而生。其中,色谱技术尤其是色谱质谱联用技术,在甄别“地沟油”或者掺杂“地沟油”的植物油分析检测方面发挥了举足轻重的作用,大大提高了“地沟油”分析检测的分离度和灵敏度。

为了展示我国科研和质检人员在攻克“地沟油”检测难关方面的最新成果,受《色谱》编辑部委托,特组织撰写并由编辑部安排在本期出版“色谱技术在地沟油检测中的应用”专栏,集中报道了在国家有关部门征集“地沟油”检测方法中涌现的色谱方法。其中既有利用不同色谱质谱技术开展多种目标物的分析检测工作;也有着眼于研究“地沟油”内、外源性物质及其提取、鉴定技术,探索“地沟油”中典型的特征指示物的报道。相信所报道的方法和技术在我国“地沟油”检测方法体系建设中会得到快速的发展和应用,为完善我国食用植物油安全保障体系发挥作用。

 

 

1094-1099

DOI: 10.3724/SP.J.1123.2012.08051

*通讯联系人: 陈吉平,研究员,主要从事分析化学与环境化学及其相关的基础与应用研究. Tel: (0411)84379686, E-mail: chenjp@dicp.ac.cn.

基金项目: 国家自然科学基金项目(20977091).

收稿日期: 2012-08-29

 

非正常食用油鉴别新方法(一): 三种辣椒碱残留量的液相色谱-质谱分析

王龙星, 金静, 王淑秋, 王幸福, 田玉增, 陈吉平*

(中国科学院大连化学物理研究所, 辽宁 大连 116023)

摘要: 非正常食用油(俗称地沟油)是我国食品安全领域亟须解决的问题。准确可行的地沟油检测方法被分析工作者广泛关注。由于国人的饮食习惯,辣味调料在餐饮业应用广泛,而辣椒碱是引起辣味的主要化学物质,因此可作为鉴别地沟油的潜在指标。本文采用固相萃取-液相色谱-串联质谱技术,建立了食用油中3种微量辣椒碱(辣椒素、二氢辣椒素及壬酸香草酰胺)的检测方法。首先用20 g/L氢氧化钠水溶液提取油样中的辣椒碱,再将提取液用C18小柱富集净化后进行液相色谱-质谱检测。用该法对国家食品安全风险评估中心提供的67个盲样进行了分析,结果表明辣椒碱是一个良好的地沟油特征指示物。凭借这3种辣椒碱指标,阳性样品正确识别率达到75%,阴性样品正确识别率达到100%。目前本方法已经成为国家卫生部最新公布的4种地沟油仪器检测方法之一。

关键词: 液相色谱-质谱|辣椒碱|地沟油|食品安全

文章编号: 1000-8713(2012)11-1094-06

 

A novel method for the identification of illegal cooking oil (1): detection of three capsaicinoids with liquid chromatography-mass spectrometry

WANG Longxing, JIN Jing, WANG Shuqiu, WANG Xingfu, TIAN Yuzeng, CHEN Jiping*

(Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China)

Abstract: Illegal cooking oil (ICO, also named swill-cooked dirty oil) has recently become a serious food safety problem in China. Now, the identification method of ICO is also a hot research area. Owning to the special eating habits of Chinese people, cayenne is widely used in catering business. Capsaicinoids are main spicy compounds in cayenne. So, they are potential evaluation indices for the identification of ICO. In this study, a solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) method has been developed to detect the trace residues of three capsaicinoids (capsaicin, dihydrocapsaicin and nonylic acid vanillylamide) in cooking oil. The oil sample was first extracted with 20 g/L sodium hydroxide, the C18 SPE cartridge was then used to clean-up the sample and enrich the analytes before the liquid chromatography-mass spectrometry (LC-MS) detection. With this method, sixty seven blind samples provided by China National Center for Food Safety Risk Assessment were analyzed. The results showed that the capsaicinoids are good evaluation indices for the identification of ICO. In all the 48 ICO samples, 36 samples were successfully recognized. All the 19 normal oil samples were accurately identified. This method has been chosen and authorized as one of the four standard instrumental identification methods for ICO by the National Ministry of Health of China.

Key words: liquid chromatography-mass spectrometry (LC-MS)| capsaicinoids| illegal cooking oil| food safety

 

1100-1107

DOI: 10.3724/SP.J.1123.2012.08052

*通讯联系人: 陈吉平,博士,研究员,主要从事分析化学与环境化学及其相关的基础与应用研究. Tel: (0411)84379562, E-mail: chenjp@dicp.ac.cn.

基金项目: 国家自然科学基金项目(20977091).

收稿日期: 2012-08-29

 

非正常食用油鉴别新方法(二): 特征奇数碳脂肪酸的多维气相色谱-质谱检测

金静, 王龙星, 陈吉平*, 田玉增, 邹黎黎, 张保琴, 王淑秋, 王幸福

(中国科学院大连化学物理研究所, 辽宁 大连 116023)

摘要: 通过对脂肪酸的非靶标/靶标筛查,确立了非正常食用油(俗称地沟油)的内源性特征指示物: 两种奇数碳脂肪酸,包括源自动物油的13-甲基十四烷酸和源自加热植物油的十一烷酸。并借助多维气相色谱-质谱技术,依据不同极性气相色谱柱的保留作用,不仅实现了不同碳数烷酸以及同碳数烷酸异构体之间的有效分离,达到了对13-甲基十四烷酸和十一烷酸准确定量的目的;而且实现了对目标化合物的在线净化、富集。凭借该项检测方法,参加了国家食品安全风险评估中心组织的第四、五批地沟油盲样考核。经过不断完善,该方法阴性样品的正确率提高到100%,阳性样品的正确率分别达到71%和75%。再结合辣椒碱指标,从内、外源指示物两方面全面、准确地对食用油样品进行判定,使得阳性样品的正确率分别提高至89%和100%。目前,该方法已经入选国家卫生部公布的四大地沟油鉴定仪器分析方法,正等待权威部门的协同性验证。

关键词: 多维气相色谱-质谱法|13-甲基十四烷酸|十一烷酸|奇数碳脂肪酸|地沟油|食品安全

文章编号: 1000-8713(2012)11-1100-08

 

A novel method for the identification of illegal cooking oil (2): determination of special odd-chain fatty acids by multidimensional gas chromatography-mass spectrometry

JIN Jing, WANG Longxing, CHEN Jiping*, TIAN Yuzeng, ZOU Lili, ZHANG Baoqin, WANG Shuqiu, WANG Xingfu

(Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China)

Abstract: Endogenesis referents from illegal cooking oil (ICO), namely, 13-methyl-tetradecanoic acid and undecanoic acid have been confirmed via non-target and target screening of fatty acids. The former is mainly originated from animal oil, and the later from heated vegetable oil. Based on the retention interactions between gas chromatographic columns with different polarities and alkyl acids, the alkyl acids with various carbon chain or their isomers with the same carbon chains can be separated effectively using multidimensional gas chromatography-mass spectrometry. And the accurate quantification of 13-methyl-tetradecanoic acid and undecanoic acid was obtained. The target compounds can be cleaned up online and enriched with the developed method. Subsequently, the fourth and fifth assessments organized by China National Center for Food Safety Risk Assessment were performed in our laboratory. After continuous improvement, the precision of the method was increased. In detail, 100% vegetable oils, 71% ICO (the 4th batch) and 75% ICO (the 5th batch) have been identified. In combination with the capsaicinoid contents, edible oils can be identified in a comprehensive way, and the precision for ICO samples was increased to 89% and 100% for the 4th batch and the 5th batch samples, respectively. Owing to the aforementioned advantages, the developed method has been chosen as one of the four instrumental methods for the identification of ICO by China Ministry of Public Health, waiting for the validation from authoritative departments.

Key words: multidimensional gas chromatography-mass spectrometry (MDGC-MS)| 13-methyl-tetradecanoic acid| undecanoic acid| odd-chain fatty acids| illegal cooking oil (ICO)| food safety

 

1108-1112

DOI: 10.3724/SP.J.1123.2012.08054

*通讯联系人: 张忠,主任法医师,主要从事理化检验工作. Tel: (023)63751660, E-mail: zhangzhong5123@126.com.

收稿日期: 2012-08-28

 

液-液萃取-液相色谱-串联质谱法测定“地沟油”中辣椒碱类化合物及丁香酚

张忠*, 任飞, 张盼

(重庆市公安局物证鉴定中心, 重庆 400021)

摘要: 建立了“地沟油”中辣椒碱类化合物(包括辣椒素、二氢辣椒素、合成辣椒素)及丁香酚的液-液萃取及液相色谱-串联质谱(LC-MS/MS)检测方法。“地沟油”中辣椒碱类化合物及丁香酚用甲醇萃取,采用SUPEL COSIL ABZ+Plus dC18色谱柱(150 mm×4.6 mm, 5 μm)分离,电喷雾离子源在正、负离子模式下电离,多反应监测(MRM)模式扫描。对辣椒素、二氢辣椒素、合成辣椒素及丁香酚的检出限分别为0.02、0.03、0.03和0.6 μg/L,且在一定的质量浓度范围内线性良好。同一操作人员与不同操作人员间测定的精密度低于5%。该方法专属性强、灵敏、准确,可以作为“地沟油”的判定标准之一。

关键词: 液相色谱-串联质谱|辣椒碱|丁香酚|地沟油

文章编号: 1000-8713(2012)11-1108-05

 

Determination of capsaicinoids and eugenol in waste-edible-oil by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry

ZHANG Zhong*, REN Fei, ZHANG Pan

(Material Evidence Identification Center of Chongqing Public Security Bureau, Chongqing 400021, China)

Abstract: A method was developed for the determination of capsaicinoids (capsaicin, dihydrocapsaicin and synthetic capsaicin) and eugenol in waste-edible-oil extracted by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The capsaicinoids and eugenol in waste-edible-oil were extracted by methanol, and then separated by a SUPEL COSIL ABZ+Plus dC18 column (150 mm×4.6 mm, 5 μm). The analysis was performed by MS/MS with electrospray ionization in positive and negative ion modes with multiple reaction monitoring (MRM). The limits of detection for capsaicin, dihydrocapsaicin, synthetic capsaicin and eugenol were 0.02, 0.03, 0.03 and 0.6 μg/L, respectively. The good linear relationships were obtained in certain concentration ranges of capsaicinoids and eugenol. The relative standard deviations (RSDs, n=5) of same-worker and different-worker were less than 5%. The method is exclusive, sensitive and accurate, and can be used in waste-edible-oil determination.

Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS)| capsaicinoids| eugenol| waste-edible-oils

 

1113-1116

DOI: 10.3724/SP.J.1123.2012.08053

*通讯联系人: 张忠,主任法医师,主要从事理化检验工作. Tel: (023)63751660, E-mail: zhangzhong5123@126.com.

收稿日期: 2012-08-25

 

离子色谱法测定“地沟油”中钠离子和氯离子的含量及其比例关系

张忠1*, 王力春1, 鲁蕴甜2

(1. 重庆市公安局物证鉴定中心, 重庆 400021; 2. 重庆市九龙坡区环境监测站, 重庆 400050)

摘要: 采用离子色谱法测定“地沟油”样品中钠离子和氯离子的含量,通过计算两者的比例关系确定样品中是否含有“地沟油”。使用去离子水提取“地沟油”样品中钠离子和氯离子。氯离子以20 nmol/L KOH溶液为淋洗液,AS19分离柱(250 mm×4 mm)分离,抑制器电流112 mA;钠离子以20 nmol/L甲基磺酸(MSA)为淋洗液,CS12分离柱(250 mm×4 mm)分离,抑制器电流59 mA;两者分离采用的其他相同色谱条件为: 柱温、检测器温度30 ℃,电导检测器检测,进样量25 μL,流量1 mL/min,峰面积定量。氯离子的检出限为0.005 mg/L,在0-5 mg/L范围内有良好的线性关系(r2=0.999988);钠离子的检出限为0.001 mg/L,在0-5 mg/L范围内有良好的线性关系(r2=0.999926)。氯离子平均加标回收率为94.2%,相对标准偏差(RSD)为2.4%;钠离子平均加标回收率为92.5%, RSD为2.7%。经测定、计算,正常食用油中钠离子和氯离子的物质的量比约为1,而“地沟油”中钠离子与氯离子的物质的量比高于4。“地沟油”中钠离子和氯离子的含量及其比例关系可作为判断“地沟油”的重要依据。

关键词: 离子色谱|氯离子|钠离子|比例关系|地沟油

文章编号: 1000-8713(2012)11-1113-04

 

Determination of sodium and chloride in hogwash oil and their molar ratio by ion chromatography

ZHANG Zhong1*, WANG Lichun1, LU Yuntian2

(1. Material Evidence Identification Center of Chongqing Public Security Bureau, Chongqing 400021, China; 2. Environmental Monitoring Station, Jiulongpo District, Chongqing 400050, China)

Abstract: By reference to edible oil using process as well as hogwash oil refining technology, a method is presented to determine the contents of the sodium and chloride in hogwash oil based on ion chromatography. The molar ratio of the sodium and chloride was analyzed in order to determine whether the sample contained hogwash oil. A hogwash oil sample was extracted by deionized water before analysis. The ion chromatographic separation of the chloride was carried out on an AS19 column (250 mm×4 mm) at 30 ℃, using 20 nmol/L KOH solution as mobile phase at a flow rate of 1 mL/min and suppressor current of 112 mA. The ion chromatographic separation of the sodium was carried out on a CS12 column (250 mm×4 mm) at 30 ℃, using 20 nmol/L methanesulfonic acid (MSA) as mobile phase at a flow rate of 1 mL/min and suppressor current of 59 mA. The injection volume was 25 μL and the detector was an electron capture detector (ECD). The external standard method was used to quantify chloride and sodium. The detection limits of this method were 0.005 mg/L for chloride and 0.001 mg/L for sodium. The linear range was from 0 to 5 mg/L with r2=0.999988 for chloride and r2=0.999926 for sodium. The average recoveries and relative standard deviations were 94.2% and 2.4% for chloride and 92.5% and 2.7% for sodium, respectively. The molar ratio of sodium and chloride in edible oil was approximately 1, while that in hogwash oil was more than 4. The determination of the contents and molar ratio of the chloride and sodium in hogwash oil can be used as an important basis for the judgment of hogwash oil.

Key words: ion chromatography (IC)| chloride| sodium| molar ratio| hogwash oil

 

1117-1126

DOI: 10.3724/SP.J.1123.2012.07009

*通讯联系人: 陈兴国,教授,博士生导师,主要从事毛细管电泳、纳米材料、药物与蛋白相互作用等相关研究工作. Tel: (0931)8912763, E-mail: chenxg@lzu.edu.cn.

基金项目: 国家自然科学基金项目(No. 21075056)和中央高校基本科研业务费项目(lzujbky-2012-214).

收稿日期: 2012-07-05

 

高效毛细管电泳在食品安全检测中的应用进展

董亚蕾, 陈晓姣, 胡敬, 陈兴国*

(兰州大学化学化工学院, 甘肃省有色金属化学与资源利用重点实验室, 甘肃 兰州 730000)

摘要: 近年来,食品安全问题频发,对人们的健康和社会发展造成了严重的危害,食品安全已成为人们关注的焦点问题之一。食品成分的复杂性、多样性对食品分析技术和方法提出了很高的要求。毛细管电泳(CE)由于分离模式多、分离效率高、分析速度快、试剂和样品用量少、对环境污染小等优点,在食品安全分析方面的应用日趋广泛。本综述对2009年以来CE在食品中非食用添加剂、农药残留、兽药残留、重金属离子污染、食品毒素以及食品包装材料中双酚A和塑化剂的检测方面的应用进行了总结,并对毛细管电泳在食品安全检测领域的主要发展方向进行了展望。共收录文献63篇。

关键词: 毛细管电泳|食品安全|综述

文章编号: 1000-8713(2012)11-1117-10

 

Recent advances in the application of high performance capillary electrophoresis for food safety

DONG Yalei, CHEN Xiaojiao, HU Jing, CHEN Xingguo*

(College of Chemistry and Chemical Engineering of Lanzhou University, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, China)

Abstract: In recent years, food safety incidents become a serious social problem. Foods are usually complex mixtures consisting of a large diversity of molecules. Analysis of foods is a topic that demands the development of rapid, robust, efficient, sensitive and cost-effective analytical methodologies. Therefore, new techniques for food safety purpose are required by analytical chemists. Capillary electrophoresis (CE) is a popular separation technique that possesses fast and efficient performances in an automated way with minimum consumption of sample and reagents. Nowadays, CE represents a desired strategy for the determination of many compounds or molecules in various kinds of food. In this paper, the review intends to provide the recent innovative developments reported in food safety analysis using CE methods for a full overview. As a fundamental review, it focuses on the introduction and detection of several common hazardous materials existing in food such as non-food additives, pesticide residues, veterinary drug residues, heavy metal ion contaminants, toxins, biphenol A and phthalates in packaging materials and so on. Furthermore, this review prospects the main development direction of CE in this field for the future. A total of 63 papers published during the period of Jan 2009~Jun 2012 are included in the present review.

Key words: capillary electrophoresis (CE)| food safety| review

 

1127-1132

DOI: 10.3724/SP.J.1123.2012.07019

*通讯联系人: 邓玉林,教授,博士生导师,主要从事蛋白质组学新技术和新方法的研究等. Tel: (010)68915996, E-mail: deng@bit.edu.cn.

基金项目: 科技部科技支撑计划(2009BAK59B01)和北京市科技专项(Z111102055311077).

收稿日期: 2012-07-11

 

基于核酸适配体的微流控芯片酶反应器用于蛋白质的分析

肖鹏, 李大雷, 满燕, 耿利娜, 吕雪飞, 邓玉林*

(北京理工大学生命学院, 北京 100081)

摘要: 将核酸适配体作为胰蛋白酶固定化介质,制备了一种新型的微流控芯片酶反应器,并与高效液相色谱-串联质谱联用,搭建了在线分析平台;分别使用标准蛋白及混合蛋白样品对芯片的酶解效率及联用平台的分析能力进行了初步评价。结果表明,5 ng肌红蛋白经该平台分析后肽段覆盖率可达到37%;对500 ng混合蛋白进行3次平行分析,肽段覆盖率及相对标准偏差分别为44.3%、6.5%(牛血清白蛋白), 65.0%、2.7%(肌红蛋白)和62.0%、5.6%(细胞色素c);初步实验表明,该在线分析平台具有检测灵敏度高、重现性好、酶解效率高的特点,有望在蛋白质组学分析中发挥重要作用。

关键词: 高效液相色谱-串联质谱|胰蛋白酶|蛋白质|核酸适配体|芯片酶反应器

文章编号: 1000-8713(2012)11-1127-06

 

An enzyme reactor based on aptamer modified microfluidic chip for protein analysis

XIAO Peng, LI Dalei, MAN Yan, GENG Lina, L Xuefei, DENG Yulin*

(School of Life Science, Beijing Institute of Technology, Beijing 100081, China)

Abstract: As a kind of recognition molecule, aptamer has been studied and applied widely in numerous science fields in recent years. Immobilized enzymatic reactor has drawn much attention because of its striking advantages, such as high digestion efficiency and ease in coupling with the separation and detection systems. In this study, a novel microfluidic enzymatic chip, which immobilized trypsin based on aptamer, was prepared and proposed. An online analysis platform, which consisted of an aptamer-based chip and high performance liquid chromatography tandem mass spectrometry, was established by using a 6-port valve and applied to protein analysis. The enzymatic capacity and stability performance of chip reactor were characterized by using mixed protein sample, which consisted of bovine serum albumin (BSA), myoglobin (Mb) and cytochrome c (Cyt.c). The sample digestion time of the chip reactor was about 5.76 s while 1 μL/min of flow rate was adopted; and moreover, 5 ng of Mb was identified successfully with the sequence coverage of 37%. Furthermore, the sequence coverages and the relative standard deviations were 44.3% and 6.5% for BSA, 65.0% and 2.7% for Mb, 62.0% and 5.6% for Cyt.c respectively when 500 ng digest of mixed proteins were analyzed in three runs. According to experimental results, the online analysis platform possesses the ability of high sensitivity and good stability, which can provide a promising tool for rapid and high-throughput proteomics study in the near future.

Key words: high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS)| trypsin| protein| aptamer| chip immobilized enzymatic reactor (chip IMER)

 

1133-1142

DOI: 10.3724/SP.J.1123.2012.08034

*Corresponding author: HUANG Xiaojia, Professor. Tel: +86-592-2189278, E-mail: hxj@xmu.edu.cn.Foundation item: The project was supported by National Natural Science Foundation of China (21077085); Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry; Program for New Century Excellent Talents in Fujian Province University.Received date: 2012-08-20

 

分子印迹固相萃取搅拌棒的制备及对复杂样品中双烯雌酚和己烷雌酚的萃取性能

农舒予, 林福华, 黄晓佳*, 袁东星

(近海海洋环境科学国家重点实验室 厦门大学环境与生态学院, 福建 厦门 361005)

摘要: 以己烯雌酚为替代模板,利用整体材料的“原位”合成技术制备了分子印迹聚合物,并将其作为固相萃取搅拌棒的涂层(MIP-SBSE)制备了新的搅拌棒。详细考察了分子印迹聚合物制备条件中模板分子及功能单体用量对MIP-SBSE选择性萃取性能的影响,同时利用元素分析、扫描电镜和红外光谱对聚合物进行表征。以双烯雌酚(DS)和己烷雌酚(HS)为目标化合物,将MIP-SBSE与高效液相色谱-二极管阵列检测器联用,建立起复杂样品中DS和HS的分离分析方法。考察了吸附和解吸时间、解吸溶剂、离子强度和样品pH值等萃取条件对MIP-SBSE选择性萃取性能的影响。结果表明,在最佳萃取条件下,MIP-SBSE对DS和HS具有较高的选择性萃取性能,线性范围分别为1.0-400.0 μg/L和5.0-400.0 μg/L,利用氮吹再定容的方法,对DS和HS的检出限(S/N=3)分别可低至0.04和0.14 μg/L。在对实际污水、蜂蜜和牛尿样品的分析中取得了良好的加标回收率,其值为61.3%-120%。所建方法具有简便、高选择性和灵敏等特点,可用于复杂样品中双烯雌酚和己烷雌酚的分析监测。

关键词: 搅拌棒固相萃取|己烯雌酚|分子印迹聚合物|萃取|双烯雌酚|己烷雌酚

文章编号: 1000-8713(2012)11-1133-10

 

Preparation of a stir bar sorptive extraction coating based on molecularly imprinted polymer and its application in the extraction of dienestrol and hexestrol in complicated samples

NONG Shuyu, LIN Fuhua, HUANG Xiaojia*, YUAN Dongxing

(State Key Laboratory of Marine Environmental Science, College of the Environment and Ecology, Xiamen University, Xiamen 361005, China)

Abstract: A new stir bar sorptive extraction (SBSE) coating based on molecularly imprinted polymer (MIP) with diethylstilbestrol as replaced template molecule was prepared. The influences of the contents of template molecule and monomer in the polymerization mixture on the extraction performance of MIP-SBSE were investigated thoroughly. The MIP was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to evaluate the usability of the new coating, the MIP-SBSE was combined with high performance liquid chromatography (HPLC) and diode array detector (DAD) with dienestrol (DS) and hexestrol (HS) as detected solutes. To achieve optimally selective extraction performance for DS and HS, several parameters, including extraction and desorption times, desorption solvent, ionic strength and pH value in sample matrix were investigated. The results showed that under the optimized experimental conditions, the present method has high selectivity and sensitivity. When drying-redissolving procedure was taken during sample preparation, the limits of detection for DS and HS were as low as 0.04 μg/L and 0.14 μg/L, respectively. Good linearities were obtained for analytes with the correlation coefficients (R2) above 0.99. Finally, the proposed method was successfully applied to the determination of DS and HS in wastewater, honey and cow urine samples. The recoveries of spiked target compounds in real samples ranged from 61.3% to 120%. The developed method is simple, selective, sensitive and applicable for the analysis of trace DS and HS in complicated samples.

Key words: stir bar sorptive extraction (SBSE)| diethylstilbestrol| molecularly imprinted polymer| extraction| dienestrol| hexestrol

 

1143-1147

DOI: 10.3724/SP.J.1123.2012.06024

*通讯联系人: 王利兵,博士,研究员,研究方向为食品安全与检验检疫安全. Tel: (0731)85627689, E-mail: wanglb1@163.com.

基金项目: 国家“十二五”科技支撑计划项目(2011BAK10B05, 2012BAD29B05).

收稿日期: 2012-06-20

 

高效液相色谱-串联质谱法检测乳制品中10种氨基糖苷类抗生素残留

龚强, 丁利, 朱绍华, 焦艳娜, 成婧, 付善良, 王利兵*

(湖南出入境检验检疫局技术中心, 食品安全科学技术湖南省重点实验室, 湖南 长沙 410004)

摘要: 建立了乳制品中链霉素、双氢链霉素、新霉素、卡那霉素、妥布霉素、庆大霉素、安普霉素、潮霉素B、巴龙霉素、阿米卡星等10种氨基糖苷类抗生素(aminoglycosides, AGs)残留的高效液相色谱-串联质谱(HPLC-MS/MS)检测方法。乳制品提取液经亲水-亲脂平衡(hydrophilic- lipophilic balance, HLB)柱净化后,采用反相离子对高效液相色谱分离,电喷雾串联四极杆质谱检测。对样品前处理条件、液相色谱流动相以及质谱条件进行了优化。结果表明: 10种AGs在20-1000 μg/L范围内定量离子的峰面积和样品的质量浓度之间有很好的线性关系;在乳制品中的加标回收率为71.2%-101.7%,相对标准偏差为3.4%-13.8%。该方法简便、灵敏、准确,可用于乳制品中多种AGs残留的同时检测。

关键词: 高效液相色谱-串联质谱|亲水-亲脂平衡柱|氨基糖苷类抗生素|乳制品

文章编号: 1000-8713(2012)11-1143-05

 

Determination of ten aminoglycoside residues in milk and dairy products using high performance liquid chromatography-tandem mass spectrometry

GONG Qiang, DING Li, ZHU Shaohua, JIAO Yanna, CHENG Jing, FU Shanliang, WANG Libing*

(Technology Center of Hunan Entry-Exit Inspection and Quarantine Bureau, Hunan Key Laboratory of Food Safety Science & Technology, Changsha 410004, China)

Abstract: A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analytical method was developed for the simultaneous determination of ten aminoglycoside residues (streptomycin, dihydrostrepmycin, neomycin, kanamycin, tobramycin, gentamycin, apramycin, hygromycin B, paromomycin, and amkacin) in milk and dairy products. The sample was extracted with 5% trichloroacetic acid aqueous solution, then the extract was purified by a hydrophilic-lipophilic balance (HLB) cartridge. The ten aminoglycoside residues were separated by ion-pair reversed phase high performance liquid chromatography. Heptafluorobutyric acid was used as ion pair agent due to its volatility. Then the analytes were detected by electrospray ionization tandem mass spectrometry. The pretreatment condition of the sample, the HPLC condition and the MS operation parameters were optimized. The results showed that the linearities of the ten aminoglycoside residues in 20~1000 μg/L had the correlation coefficient between 0.9946~0.9997. The recoveries ranged from 71.2% and 101.7% with the relative standard deviations of 3.4%~13.8%. The proposed method was successfully applied to the determination of the mass concentrations of the analytes in related samples, which provides a simple, and convenient method for the quality control of milk and dairy products. Furthermore, this method is effective for the safety monitoring of aminoglycoside residues in milk and dairy products.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)| hydrophilic-lipophilic balance (HLB) cartridge| aminoglycosides| milk and dairy products

 

1148-1152

DOI: 10.3724/SP.J.1123.2012.07015

*通讯联系人: 刘耀,中国工程院院士,主要研究方向为法医毒物分析. E-mail: liuyao1123@yahoo.cn.

基金项目: 中央高校基本科研业务费专项资金(YX11013).

收稿日期: 2012-07-09

 

超高效液相色谱-串联质谱法检测唾液中3种毒品及其代谢物

陈跃1, 朱军2, 于忠山2, 张云峰2, 刘耀2*

(1. 中国人民公安大学刑事科学技术系, 北京 100038; 2. 公安部物证鉴定中心, 北京 100038)

摘要: 建立了超高效液相色谱-串联质谱测定唾液中甲基苯丙胺、吗啡、O6-单乙酰吗啡等3种毒品及其代谢物的方法。以乙腈为提取液沉淀蛋白质法提取,采用基质提取溶液配制标准溶液制作定量曲线。采用BEH HILIC超高效液相色谱柱对待测毒品进行分离;采用电喷雾离子源正离子(ESI+)模式和多反应监测(MRM)模式进行质谱分析,以被测毒品的同位素内标进行定量。结果表明,在10、20、50、100 μg/L 4个添加水平下的回收率范围为(68.7±6.5)%-(110.8±4.6)%,日内精密度小于16.5%,日间精密度小于16.3%; 3种毒品的检出限(LOD,以信噪比(S/N)>3计)和定量限(LOQ,以S/N>10计)分别为0.02-0.05 μg/L和0.1-0.2 μg/L。方法快速、简便、定量准确、灵敏度高;在1 h之内即可对采集的唾液样品进行毒品定性和定量分析,可用于涉嫌吸毒者的快速认定。

关键词: 超高效液相色谱-串联质谱|基质效应|同位素内标|毒品|唾液

文章编号: 1000-8713(2012)11-1148-05

 

Determination of three drugs and their metabolites in saliva by ultra performance liquid chromatography-tandem mass spectrometry

CHEN Yue1, ZHU Jun2, YU Zhongshan2, ZHANG Yunfeng2, LIU Yao2*

(1. Department of Forensic Science, Chinese People’s Public Security University, Beijing 100038, China; 2. Institute of Forensic Science, Ministry of Public Security, Beijing 100038, China)

Abstract: An ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method has been developed for the methamphetamine, morphine and O6-acetylmorphine in saliva. The sample was extracted and the protein was precipitated with acetonitrile. The matrix-matched standard solutions were used to prepare the curve of quantitative analysis. The drugs were separated on a BEH HILIC UPLC column. The mass spectrometric acquisition was carried out by means of electrospray ionization in positive mode (ESI+) with multiple reaction monitoring (MRM) method. The isotope internal standards were used to check the drugs. The average recoveries at four levels of 10, 20, 50 and 100 μg/L ranged from (68.7±6.5)% to (110.8±4.6)%. The intraday precisions were lower than 16.5% and interday precisions were lower than 16.3%. The detection limits (LOD, S/N>3) and the quantification limits (LOQ, S/N>10) of the three drugs were 0.02~0.05 μg/L and 0.1~0.2 μg/L, respectively. The saliva matrix effect was investigated. The method is rapid, simple, accurate and highly sensitive. The qualitative analysis and quantitative analysis of the collected saliva samples for the drugs can be finished within one hour, which is conducive to the rapid identification of the suspected drug addicts.

Key words: ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)| matrix effect| isotope internal standard| drugs| saliva

 

1153-1158

DOI: 10.3724/SP.J.1123.2012.06040

*通讯联系人: 徐远金,博士,教授,研究方向为色谱、质谱分析. Tel: (0771)3237743, E-mail: yjxu@gxu.edu.cn.

基金项目: 广西自然科学基金项目(桂科自0832034).

收稿日期: 2012-06-28

 

超高效液相色谱-串联质谱同时测定加味左金丸中的9种有效成分

覃莎1,2, 王锦2, 徐远金1,2*

(1. 亚热带农业生物资源保护与利用国家重点实验室, 广西大学, 广西 南宁 530004; 2. 广西大学化学化工学院, 广西 南宁 530004)

摘要: 建立了同时测定加味左金丸中9种药效成分含量的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法。采用Zorbax RRHD Eclipse Plus C18色谱柱,以含0.2%甲酸的水-甲醇为流动相进行梯度洗脱,流速0.4 mL/min,在电喷雾电离(ESI)正离子模式下,采用多重反应监测模式进行检测。结果表明,芍药苷、延胡索乙素、药根碱、小檗碱、巴马汀、吴茱萸碱、柴胡皂苷C、柴胡皂苷A、柴胡皂苷D的线性范围分别为0.025-5.0 mg/L、0.0010-2.0 mg/L、0.0023-7.2 mg/L、0.0027-28.9 mg/L、0.0023-9.1 mg/L、0.0050-1.0 mg/L、0.050-10 mg/L、0.005-1.0 mg/L、0.0075-1.5 mg/L;检出限分别为5.0、0.20、0.45、0.54、0.45、1.0、10、1.0、1.5 μg/L。9种成分的加样回收率为99.3%-105%,相对标准偏差均不大于2.6%。该法快捷、准确、重复性好,已成功用于实际样品的分析。

关键词: 超高效液相色谱-串联质谱(UPLC-MS/MS)|有效成分|加味左金丸|中成药

文章编号: 1000-8713(2012)11-1153-06

 

Simultaneous determination of nine effective components in Jiaweizuojin Pills by ultra performance liquid chromatography with tandem mass spectrometry

QIN Sha1,2, WANG Jin2, XU Yuanjin1,2*

(1. State Key Laboratory of Conservation and Utilization of Subtropical Agro-bioresources, Guangxi University, Nanning 530004, China; 2. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China)

Abstract: A method for the simultaneous determination of paeoniflorin, tetrahydropalmatine, jatrorrhizine, berberine, palmatine, evodiamine, saikosaponin C, saikosaponin A and saikosaponin D in Jiaweizuojin Pills was established by ultra performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS). The UPLC separation was performed on a Zorbax RRHD Eclipse Plus C18 column (50 mm×2.1 mm, 1.8 μm) by using 0.2% (v/v) formic acid aqueous solution and methanol as mobile phases with the gradient elution at a flow rate of 0.4 mL/min. The analytes were detected by tandem mass spectrometry under the positive ion mode with the electrospray ionization (ESI) source and in the multiple reaction monitoring (MRM) mode. Under the optimized conditions, the calibration curves were linear in the ranges of 0.025~5.0 mg/L for paeoniflorin, 0.0010~2.0 mg/L for tetrahydropalmatine, 0.0023~7.2 mg/L for jatrorrhizine, 0.0027~28.9 mg/L for berberine, 0.0023~9.1 mg/L for palmatine, 0.0050~1.0 mg/L for evodiamine, 0.050~10 mg/L for saikosaponin C, 0.0050~1.0 mg/L for saikosaponin A and 0.0075~1.5 mg/L for saikosaponin D with the detection limits of 5.0, 0.20, 0.45, 0.54, 0.45, 1.0, 10, 1.0, 1.5 μg/L, respectively. The average recoveries of the nine effective components were between 99.3% and 105% with the relative standard deviations not more than 2.6%. The developed method is simple, rapid and accurate, and suitable for the quality control of the nine effective components in Jiaweizuojin Pills.

Key words: ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)| effective components| Jiaweizuojin Pills| Chinese patent drug

 

1159-1165

DOI: 10.3724/SP.J.1123.2012.06033

*通讯联系人: 伊雄海,博士,工程师,研究方向为食品安全. E-mail: yixh@shciq.gov.cn.

基金项目: 国家质量监督检验检疫总局科技计划项目(2011IK233)、上海检验检疫局专项(HK005-2011)和质检公益行业科研专项(201110019-04).

收稿日期: 2012-06-24

 

亚临界水萃取及气相色谱-串联质谱法检测红茶中多种农药残留

潘煜辰1, 伊雄海2*, 邓晓军2, 赵善贞2, 陈舜胜1, 杨惠琴2, 韩丽2, 朱坚2

(1. 上海海洋大学, 上海 201306; 2. 上海出入境检验检疫局, 上海 200135)

摘要: 建立了亚临界水萃取及气相色谱-串联质谱(GC-MS/MS)检测红茶中21种有机氯和拟除虫菊酯农药残留的方法。在萃取压力为5 MPa条件下,样品经150 ℃的亚临界水提取15 min后,将目标物转移至丙酮-正己烷(1:1, v/v)中,经ENVI-Carb固相萃取净化小柱净化,DB-5毛细管气相色谱柱分离,在多反应监测(MRM)模式下进行MS/MS检测,基质匹配溶液内标法定量。各目标物在5.0-320.0 μg/L范围内线性关系良好,相关系数均大于0.99,其定量限(信噪比(S/N)>10)为50 ng/g,检出限(S/N>3)为10 ng/g。茶叶基质中添加50、100和200 ng/g的标准品时,21种农药的回收率为70.18%-119.98%,相对标准偏差(RSD)为5.01%-11.76%。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求,适用于红茶中有机氯和拟除虫菊酯农药残留的检测。

关键词: 亚临界水萃取|气相色谱-串联质谱|有机氯农药|拟除虫菊酯农药|红茶

文章编号: 1000-8713(2012)11-1159-07

 

Determination of multi-pesticides in black tea by subcritical water extraction and gas chromatography-tandem mass spectrometry

PAN Yuchen1, YI Xionghai2*, DENG Xiaojun2, ZHAO Shanzhen2, CHEN Shunsheng1, YANG Huiqin2, HAN Li2, ZHU Jian2

(1. Shanghai Ocean University, Shanghai 201306, China; 2. Shanghai Entry-Exit Inspection and Quarantine Bureau, Shanghai 200135, China)

Abstract: A gas chromatography-tandem mass spectrometry (GC-MS/MS) method with subcritical water extraction was developed for the determination of 21 organochlorine and pyrethroid pesticides in black tea. Under the extraction pressure of 5 MPa, the target compounds were extracted with subcritical water at the temperature of 150 ℃ for 15 min, transferred into acetone-n-hexane (1:1, v/v), and cleaned-up by an ENVI-Carb solid phase extraction (SPE) column. The GC separation was performed on a DB-5 capillary column. The pesticides were determined by MS/MS in multiple reaction monitoring (MRM) mode and quantified by matrix-matched internal standard method. The calibration curves showed good linearities in the range of 5.0~320.0 μg/L with the correlation coefficients greater than 0.99. The limit of quantification (S/N>10) was 50 ng/g, and the limit of detection (S/N>3) was 10 ng/g. The recoveries of pesticides spiked in the tea at three levels of 50, 100 and 200 ng/g were ranged from 70.18% to 119.98% with the relative standard deviations (RSDs) of 5.01%~11.76%. The sensitivity, accuracy and precision of the method meet the technical standard of the pesticide determination. The method can be applied to the determination of organochlorine and pyrethroid pesticides in black tea.

Key words: subcritical water extraction| gas chromatography-tandem mass spectrometry (GC-MS/MS)| organochlorine pesticides| pyrethroid pesticides| black tea

 

1166-1171

DOI: 10.3724/SP.J.1123.2012.06041

*通讯联系人: 潘家荣,博士,教授,研究方向为食品安全. E-mail: panjr@263.net.

基金项目: 国家科技支撑计划课题(2011BAK10B04).

收稿日期: 2012-06-28

 

全二维气相色谱-四极杆质谱法检测植物油脂中脂肪酸

郑月明1,2, 冯峰2, 国伟2, 储晓刚2, 潘家荣1,3*, 贾玮2

(1. 中国农业科学院农产品加工研究所, 北京 100193; 2. 中国检验检疫科学研究院, 北京 100123; 3. 中国计量学院, 浙江 杭州 310018)

摘要: 建立了植物油脂中31种脂肪酸成分的全二维气相色谱-四极杆质谱(GC×GC-qMS)分析方法。样品经甲酯化衍生后,以DB-1柱(30 m×0.25 mm×0.25 μm)作为一维柱、DB-Wax柱(3.2 m×0.1 mm×0.1 μm)作为二维柱组成柱系统进行分离,在调制周期为3.5 s、四极杆质量扫描范围为m/z 40-350的条件下,植物油脂中31种脂肪酸成分可以在50 min内得到准确和灵敏的检测。将本方法应用于实际样品的分析,灵敏度较传统的气相色谱-质谱法提高了100倍以上,一些植物油中微量的脂肪酸成分也因此被检出。该研究不仅为植物油中脂肪酸成分的分析提供了新的技术手段,同时对于确保食用植物油的质量安全、消除食用植物油的掺假伪劣等均有重要意义。

关键词: 全二维气相色谱-四极杆质谱|脂肪酸|植物油

文章编号: 1000-8713(2012)11-1166-06

 

Determination of fatty acids in vegetable oils using comprehensive two-dimensional gas chromatography coupled to quadropole mass spectrometry

ZHENG Yueming1,2, FENG Feng2, GUO Wei2, CHU Xiaogang2, PAN Jiarong1,3*, JIA Wei2

(1. Institute of Agro-Food Product Processing Science and Technology, Chinese Academy of Agricultural Science, Beijing 100193, China; 2. Chinese Academy of Inspection and Quarantine, Beijing 100123, China; 3. China Jiliang University, Hangzhou 310018, China)

Abstract: Comprehensive two-dimensional gas chromatography with quadropole mass spectrometry (GC×GC-qMS) was applied to the detection of 31 fatty acids in vegetable oils. The sets of columns, modulation period, scan range of quadropole mass spectrometer were optimized. The results demonstrated that the separation was achieved in 50 min with the column set of DB-1 (30 m×0.25 mm×0.25 μm) as the 1st column and DB-Wax (3.2 m×0.1 mm×0.1 μm) as the 2nd column. All fatty acids were accurately and sensitively determined while the modulation period was 3.5 s and the scan range of quadropole MS was m/z 40~350. Most of the fatty acids were identified by NIST library spectra search, the other fatty acid isomers were identified by single standard injection analysis. When applying this method to the real vegetable oil samples, not only the sensitivities were 100 times higher than those obtained with GC-qMS methods, but also some minor fatty acids were identified. This work suggested a new technical approach in analyzing fatty acid components in vegetable oils, which is meaningful to prohibit adulteration and ensuring the quality safety of edible vegetable oils.

Key words: comprehensive two-dimensional gas chromatography-quadropole mass spectrometry (GC×GC-qMS)| fatty acids| vegetable oils

 

1172-1177

DOI: 10.3724/SP.J.1123.2012.07044

*通讯联系人: 沈伟健,高级工程师. Tel: (025)52345193, E-mail: swj9722418@yahoo.com.cn.

基金项目: 国家质量监督检验检疫总局科技计划项目(2011KJ39, 2012KJ31)和科技部科技支撑项目(2011BAK10B04).

收稿日期: 2012-07-26

 

气相色谱-负化学源质谱法测定蔬菜中17种拟除虫菊酯类农药残留量

沈伟健1*, 曹孝文2, 刘一军1, 张睿1, 范欣1, 赵增运1, 沈崇钰1, 吴斌1

(1. 江苏出入境检验检疫局食品实验室, 江苏 南京 210001; 2. 常州出入境检验检疫局, 江苏 常州 213022)

摘要: 建立了气相色谱-负化学源质谱检测蔬菜中17种拟除虫菊酯类农药残留量的方法。样品中的目标物经乙腈提取后,用乙二胺-N-丙基甲硅烷(PSA)和石墨化炭黑填料进行分散固相萃取净化,气相色谱-负化学源质谱选择离子监测模式测定,同位素内标法定量。在甜豌豆、绿花菜和大葱基质中均未见干扰所有农药测定的现象。17种拟除虫菊酯类农药的定量限均为0.02-5 μg/kg。在10、20、30和100 μg/kg等4个添加水平下,所有农药的回收率均为71.0%-139.0%,相对标准偏差≤12.8%。该方法可作为蔬菜中17种菊酯类农残检测的确证方法。

关键词: 气相色谱|负化学离子源质谱|拟除虫菊酯类农药|蔬菜

文章编号: 1000-8713(2012)11-1172-06

 

Determination of 17 pyrethroid pesticide residues in vegetables by gas chromatography-mass spectrometry with negative chemical ionization

SHEN Weijian1*, CAO Xiaowen2, LIU Yijun1, ZHANG Rui1, FAN Xin1, ZHAO Zengyun1, SHEN Chongyu1, WU Bin1

(1. Jiangsu Entry-Exit Inspection and Quarantine Bureau, Nanjing 210001, China; 2. Changzhou Entry-Exit Inspection and Quarantine Bureau, Changzhou 213022, China)

Abstract: A method was established for the determination of 17 pyrethroid pesticide residues in vegetables using QuEChERS (quick, easy, cheap, effective, rugged and safe) clean-up method and gas chromatography-mass spectrometry (GC-MS) with negative chemical ionization (NCI). The pyrethroid pesticides in the sample were extracted with acetonitrile. After QuEChERS clean-up with a mixture of primary secondary amine and graphitized carbon black packings, the extract was analyzed by GC-NCI-MS in selected ion monitoring (SIM) mode. An isotope internal standard of cypermethrin was employed to the quantification. The limits of quantification ranged from 0.02 to 5 μg/kg. The recoveries of the pyrethroid pesticides spiked in three different matrixes (peas, broccoli and Chinese onion green) at four spiked levels of 10, 20, 30 and 100 μg/kg were from 71.0% to 139.0%, and the relative standard deviations were less than 12.8%. This method can be used as a conclusive evidence method of the 17 pyrethroid pesticide residues in vegetables.

Key words: gas chromatography (GC)| negative chemical ionization mass spectrometry (NCI-MS)| pyrethroid pesticides| vegetables

 

1178-1182

DOI: 10.3724/SP.J.1123.2012.07003

*通讯联系人: 王征,博士研究生,主要从事食品安全分析. Tel: (0591)83762000, E-mail: syymwan@sina.com.

基金项目: 国家质量监督检验检疫总局科技计划项目(2011QK180, 2010QK025).

收稿日期: 2012-07-02

 

气相色谱-负化学源-三重四极杆质谱法测定化妆品中的硝基麝香类化合物

王征*

(福建省产品质量检验研究院, 国家加工食品质量监督检验中心, 福建 福州 350002)

摘要: 建立了一种用于不同化妆品中5种硝基麝香含量的气相色谱-负化学离子源三重四极杆质谱联用(GC-MS/MS)检测方法。采用丙酮/正己烷混合溶液超声提取化妆品中的硝基麝香,将提取液浓缩,以CNWBOND Si固相萃取柱净化。再由GC-MS/MS检测,氘代二甲苯麝香内标法定量。该方法对化妆品中5种硝基麝香的加标回收率为85.81%-103.77%,相对标准偏差(RSD)不大于5.32%,灵敏度高,定量限为50.0-500 ng/kg;选择性好,能有效消除复杂基体干扰。可作为常见化妆品中硝基麝香类化合物含量检测的确证方法。

关键词: 气相色谱|负化学离子源三重四极杆质谱|硝基麝香|化妆品

文章编号: 1000-8713(2012)11-1178-05

 

Determination of synthetic nitro-musks in cosmetics by gas chromatography coupled with negative chemical ionization-triple quadrupole mass spectrometry

WANG Zheng*

(Fujian Inspection and Research Institute for Product Quality, National Quality Supervision and Testing Center for Processed Food, Fuzhou 350002, China)

Abstract: A confirmatory method is presented for the determination of five nitro-musks (musk ambrette, musk xylene, musk moskene, musk tibeten and musk ketone) in different cosmetics by gas chromatography coupled with negative chemical ionization (NCI)-triple quadrupole mass spectrometry (GC-MS/MS). The samples were extracted under ultrasonication using a mixture of acetone and hexane. The extract was concentrated and then cleaned up by CNWBOND Si solid phase extraction cartridge. Five different instrument parameters such as the temperature programmed, ion source temperature, reagent gas pressure, collision energy, monitoring ion pairs were optimized for higher sensitivity. Then the analytes were qualitatively and quantitatively analyzed under the multiple reaction monitoring (MRM) mode after the chromatographic separation on an HP-5MS capillary column (30 m×0.25 mm, 0.25 μm), and employing d15-musk xylene as internal standard. The mixed standards were spiked in the blank cosmetics samples (each nitro-musk was about 500 ng/kg), and the recoveries were in the range of 85.81%~103.77% with the relative standard deviations (RSDs) not more than 5.32%. The limits of quantification of the method were about 50.0~500 ng/kg. The method is accurate, rapid, sensitive and can be used in the inspection of the five nitro-musks in cosmetics.

Key words: gas chromatography (GC)| negative chemical ionization-triple quadrupole mass spectrometry| nitro-musks| cosmetics

 

1183-1187

DOI: 10.3724/SP.J.1123.2012.06039

*通讯联系人: 伍海涛,博士,研究方向为临床药理和眼科药理. Tel: (020)36585405, E-mail: znwht@sina.com.cn.

基金项目: 广东省“211工程”三期重点学科建设项目(粤发改社[2009]972号)、广东省建设中医药强省课题(2010373)、广东省自然科学基金项目(S2011040003546)和广东省科技计划项目(2011B031700069).

收稿日期: 2012-06-28

 

高效液相色谱法同时测定离体角膜灌流液中8个普萘洛尔衍生物

伍海涛1*, 陈传兵2, 王宁生1, 宓穗卿1, 廖南英1

(1. 广州中医药大学临床药理研究所, 广东 广州 510405; 2. 广州中医药大学中药学院, 广东 广州 510405)

摘要: 为了解促渗透剂对不同物质的促渗透能力,建立了采用高效液相色谱分离测定8个普萘洛尔衍生物的分析方法。采用盒式给药技术在离体角膜上皮侧给予普萘洛尔衍生物,内皮侧接收灌流液,用甲醇沉淀蛋白、高速离心后进样,采用Agilent Zorbax Extend色谱柱,以乙腈(A)-0.03%(v/v)磷酸水溶液(B)为流动相,在3%A-20%A间梯度洗脱,柱温30 ℃,检测波长205 nm。结果表明,该方法可在31 min内实现离体角膜灌流液中8个衍生物的完全分离和定量,线性范围为0.2(0.1)-40.0 μmol/L,线性关系良好,相关系数均不小于0.9970。其加样回收率为91.12%-105.73%,日内精密度(相对标准偏差(RSD))为1.00%-11.63%,日间精密度为1.18%-18.58%,样本冻存、冻融稳定性良好。该法适用于离体角膜灌流、细胞小室培养等跨膜吸收研究中普萘洛尔衍生物的检测。

关键词: 高效液相色谱|普萘洛尔|衍生物|角膜

文章编号: 1000-8713(2012)11-1183-05

 

Simultaneous determination of eight derivatives of propranolol in cornea perfusate in vitro by high performance liquid chromatography

WU Haitao1*, CHEN Chuanbing2, WANG Ningsheng1, MI Suiqing1, LIAO Nanying1

(1. Institute of Clinical Pharmacology, Guangzhou University of Chinese Medicine, Guangzhou 510405, China; 2. School of Chinese Pharmaceutical Science, Guangzhou University of Chinese Medicine, Guangzhou 510405, China)

Abstract: A high performance liquid chromatographic method was developed for the simultaneous determination of eight derivatives of propranolol. Cassette dosing method was used in the epithelium side of cornea in vitro to get the effect of penetrant, and the perfusate was collected in the side of endothelium. The protein in the sample was precipitated and discarded by high speed centrifugation before injection. An Agilent Zorbax Extend column (150 mm×3 mm, 5 μm) was used at 30 ℃. The mobile phase system contained acetonitrile and 0.03% (v/v) phosphoric acid aqueous solution and the percentage of acetonitrile changed between 3% and 20% (v/v) in a linear gradient elution. The samples were detected by an ultraviolet (UV) detector at 205 nm. The results showed that the eight derivatives of propranolol were completely separated and determined in 31 min. The correlation coefficients were above 0.9970 and good linear relationships were obtained in the range of 0.2(0.1)~40.0 μmol/L. Under the optimized conditions, the recoveries of the derivatives were in the range of 91.12%~105.73%. The intra-day relative standard deviations (RSDs) were in the range of 1.00%~11.63%, and the inter-day RSDs were in the range of 1.18%~18.58%. The sample showed stability under room temperature, freeze and three cycles of freeze-thaw conditions. This method is fast and accurate for the quantitative analysis of the derivatives of propranolol in transmembrane absorption such as cornea perfusion in vitro or transwell cell system.

Key words: high performance liquid chromatography (HPLC)| propranolol| derivatives| cornea

 

1188-1193

DOI: 10.3724/SP.J.1123.2012.07011

*通讯联系人: 郭志谋,博士,副研究员,主要研究方向为新型分离材料和分离技术. E-mail: guozhimou@dicp.ac.cn.

基金项目: 国家杰出青年科学基金项目(20825518).

收稿日期: 2012-07-09

 

β-环糊精键合手性固定相分离苯并恶嗪类对映体

徐雪峰, 郭志谋*, 梁鑫淼

(中国科学院大连化学物理研究所, 辽宁 大连 116023)

摘要: 研究了在反相高效液相色谱模式下,基于点击化学的β-环糊精手性固定相对苯并恶嗪类对映体的手性分离情况。考察了流动相中有机改性剂的类型和比例、缓冲盐的浓度和pH值对分离的影响。考察结果表明: 乙腈作为有机改性剂比甲醇更有利于苯并恶嗪对映体的分离;乙酸三乙胺缓冲盐体积分数从0.1%增大到1.0%时,苯并恶嗪对映体的保留时间和分离度都随之减小,在pH 4.1时苯并恶嗪对映体具有最大分离度。因此确定乙腈和体积分数为0.1%的乙酸三乙胺缓冲盐流动相(pH 4.1)为最佳分离条件。分离机理研究结果表明,固定相和样品之间的包容络合相互作用以及样品和固定相之间的氢键作用,是样品得以分离的基础。本研究为进一步深入研究β-环糊精固定相提供了实验基础,同时也证明了点击化学在手性环糊精固定相制备中具有极大潜力。

关键词: 苯并恶嗪对映体|手性分离|点击化学|β-环糊精手性固定相

文章编号: 1000-8713(2012)11-1188-06

 

Separation of benzoxazine enantiomers on β-cyclodextrin bonded chiral stationary phases

XU Xuefeng, GUO Zhimou*, LIANG Xinmiao

(Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China)

Abstract: Chiral separation of benzoxazine enantiomers was studied on click chemistry based beta-cyclodextrin stationary phases under reversed-phase high performance liquid chromatographic mode. The effects of the type and percentage of the organic modifier, the concentration of triethylammonium acetate buffer (TEAA), and pH on enantioselective separation were examined and studied. It was demonstrated that acetonitrile was better for the chiral separation of benzoxazine enantiomers than methanol. It was observed that the retention time and the resolution of benzoxazine enantiomers decreased with the increase of the volume ratio of TEAA from 0.1% to 1.0%. The separation of benzoxazine enantiomers was of the maximum resolution at pH 4.1. With the optimized mobile phase of the mixture of acetonitrile and 0.1% TEAA (pH 4.1), all the enantiomers were separated at the baseline. The chiral recognition mechanism is also discussed. The separation was probably based on the inclusion complex interaction and the hydrogen bonding between enantiomers and chiral stationary phases. This work provided the experience for the intensive study of click beta-cyclodextrin bonded stationary phases, and it also illustrated the potential of click chemistry in the preparation of beta-cyclodextrin based chiral stationary phase.

Key words: benzoxazine enantiomers| chiral separation| click chemistry| beta-cyclodextrin chiral stationary phases

 

1194-1202

DOI: 10.3724/SP.J.1123.2012.06007

*Corresponding author: André Moreni LOPES. Tel: +55-11-3091-3862, Fax: +55-11-3815-6386, E-mail: andreml@usp.br. #This author and the first author contributed equally to this work.Foundation item: This research was supported by grants from the Brazilian Agency Coordination of Graduate Level Training (CAPES, project 0366/09-9) and State of Sao Paulo Research Support Foundation (FAPESP-Brazil, project 2005/60159-7).Received date: 2012-06-06

 

Adsorption of endotoxins on Ca2+ iminodiacetic acid by metal ion affinity chromatography

André Moreni LOPES1*, Jorge Sánchez ROMEU2#, Rolando Páez MEIRELES2, Gabriel Marquez PERERA2, Rolando Perdomo MORALES3, Adalberto PESSOA Jr1, Lourdes Zumalacárregui CáRDENAS4

1. Department of Biochemical and Pharmaceutical Technology, School of Pharmaceutical Sciences, University of Sao Paulo (FCF/USP), 05508-000 Sao Paulo, Brazil; 2. Purification Development Department, Center for Genetic Engineering and Biotechnology (CIGB), Havana, Cuba; 3. Center for Pharmaceuticals Research and Development (CIDEM), Havana, Cuba; 4. Higher Polytechnic Institute José Antonio Echeverría (CUJAE), Havana, Cuba

Abstract: Endotoxins (also known as lipopolysaccharides (LPS)) are undesirable by products of recombinant proteins, purified from Escherichia coli. LPS can be considered stable under a wide range of temperature and pH, making their removal one of the most difficult tasks in downstream processes during protein purification. The inherent toxicity of LPS makes their removal an important step for the application of these proteins in several biological assays and for a safe parenteral administration. Immobilized metal affinity chromatography (IMAC) enables the affinity interactions between the metal ions (immobilized on the support through the chelating compound) and the target molecules, thus enabling high efficiency separation of the target molecules from other components present in a mixture. Affinity chromatography is applied with Ca2+iminodiacetic acid (IDA) to remove most of the LPS contaminants from the end product (more than 90%). In this study, the adsorption of LPS on an IDA-Ca2+was investigated. The adsorption Freundlich isotherm of LPS-IDA-Ca2+provides a theoretical basis for LPS removal. It was found that LPS is bound mainly by interactions between the phosphate group in LPS and Ca2+ligands on the beads. The factors such as pH (4.0 or 5.5) and ionic strength (1.0 mol/L) are essential to obtain effective removal of LPS for contaminant levels between endotoxin’ concentration values less than 100 EU/mL and 100000 EU/mL. This new protocol represents a substantial advantage in time, effort, and production costs.

 

Key words: immobilized metal affinity chromatography (IMAC) ; lipopolysaccharides (LPS) ; endotoxin removal; recombinant proteins; isotherms; protein purification

 

 

1203-1207

DOI: 10.3724/SP.J.1123.2012.07020

*通讯联系人: 黄娟,工程师,主要从事食品中添加剂、抗生素、真菌毒素类的残留检测. Tel: (025)52345187, E-mail: huang-juan@yeah.net.

基金项目: 江苏检验检疫局科研项目(2010KJ32).

收稿日期: 2012-07-11

 

固相萃取-高效液相色谱-串联质谱法检测粮食及其制品中的呕吐毒素

黄娟1*, 陈国松2, 张晓燕1, 沈崇钰1, 吕辰2, 吴斌1, 刘艳1, 陈惠兰1, 丁涛1

(1. 江苏出入境检验检疫局动植物与食品检测中心, , 江苏 南京 210001; 2. 南京工业大学理学院, 江苏 南京 210009)

摘要: 建立了粮食及其制品中呕吐毒素的高效液相色谱-串联质谱(HPLC-MS/MS)检测方法。样品经乙腈-水(84:16, v/v)溶液提取,HLB固相萃取柱富集净化,采用HPLC-MS/MS法对目标物进行定性确证和定量分析。在Phenomenex Kinetex C18柱(100 mm×4.6 mm, 2.6 μm)上以0.3‰氨水和乙腈为流动相进行梯度洗脱分离;质谱模式为电喷雾负离子监测模式。本方法的检出限(以信噪比(S/N)=3计)和定量限(以S/N=10计)分别为20 μg/kg和50 μg/kg;在20-1000 μg/L范围内呈现良好的线性关系,相关系数(r)大于0.99。对本底空白的面粉、大麦、大豆、大米、玉米粉、木薯干、小麦等7种代表性基质进行50、100、500 μg/kg 3个含量水平的添加试验,回收率范围为75.6%-111.0%,精密度(以相对标准偏差(RSD)计)不大于13.0%。本方法准确可靠,灵敏度高,经济实用,可替代较为昂贵的免疫亲和柱和多功能净化柱,较大地降低检测成本。

关键词: 固相萃取|高效液相色谱-串联质谱|呕吐毒素|粮食|粮食制品

文章编号: 1000-8713(2012)11-1203-05

 

Determination of deoxynivalenol in grain and its products by solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry

HUANG Juan1*, CHEN Guosong2, ZHANG Xiaoyan1, SHEN Chongyu1, L Chen2, WU Bin1, LIU Yan1, CHEN Huilan1, DING Tao1

(1. Animal, Plant and Food Inspection Center of Jiangsu Entry-Exit Inspection and Quarantine Bureau, Nanjing 210001, China; 2. College of Science, Nanjing University of Technology, Nanjing 210009, China)

Abstract: A method was established for the determination of deoxynivalenol (vomitoxin) in grain and its products based on solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The sample was firstly extracted by acetonitrile-water (84:16, v/v). The extract was then cleaned-up by an HLB solid phase extraction cartridge. The separation was carried out on a Phenomenex Kinetex C18 column (100 mm×4.6 mm, 2.6 μm) with a gradient elution using 0.3‰ ammonia solution-acetonitrile as mobile phases. The analysis of deoxynivalenol was performed under electrospray negative ionization mode. The limit of detection (LOD, S/N=3) and the limit of quantification (LOQ, S/N=10) were 20 μg/kg and 50 μg/kg, respectively. A good linearity (r >0.99) was achieved for the target compound over the range of 20~1000 μg/L. The recoveries at the three spiked levels (50, 100, 500 μg/kg) in the blank matrices such as flour, barley, soybean, rice, cornmeal, cassava and wheat, were varied from 75.6% to 111.0% with the relative standard deviations no more than 13.0%. The method is accurate, efficient, sensitive and practical. The cost of pretreatment is obviously reduced by replacing immunoaffinity columns and Mycosep columns with HLB columns which have the same purification effect.

Key words: solid-phase extraction (SPE)| high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)| deoxynivalenol| grain| grain products

 


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