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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》2013年第1期内容摘要
《色谱》2013年第1期内容摘要
2013年1月23日 来源:中国色谱网 责编:李华静

 

1~3

DOI: 10.3724/SP.J.1123.2013.01001

收稿日期: 2013-01-05

 

蛋白质组磷酸化和糖基化分析的新趋势

叶明亮

(中国科学院大连化学物理研究所, 中国科学院分离分析重点实验室, 辽宁 大连 116023)

 

1磷酸肽富集的新材料与新机理

磷酸肽的选择性富集是蛋白质组磷酸化分析是否成功的关键步骤。金属氧化物亲和色谱是富集磷酸肽的一类重要方法,一系列的过渡金属氧化物(如二氧化钛、二氧化锆等)被用于磷酸钛的选择性富集。最近,表面涂有三氧化二镧的硅胶复合材料被用于磷酸肽的富集[1]。Jabeen等利用标准蛋白质酶解液考察了该方法的富集效果,发现在两个标准磷酸化蛋白质α-酪蛋白和β-酪蛋白与非磷酸化蛋白质牛血清白蛋白的物质的量比为1∶1∶100时仍能检测到3个磷酸肽,说明该方法有较好的富集选择性。固定金属离子亲和色谱是另外一类重要的磷酸肽富集方法。传统的固定金属离子亲和色谱主要以亚氨基二乙酸、次氨基三乙酸等配合基团固定铁离子、镓离子等金属离子,在磷酸肽的富集中具有悠久的历史。但是该方法的主要缺点是特异性不高,在富集磷酸肽的同时酸性肽段也会被富集,因此效果不好。中国科学院大连化学物理研究所的邹汉法课题组[2,3]发展了一种以磷酸基团为配合基团的新一代固定金属离子亲和色谱。在该方法中,磷酸基团以共价键连接到固相载体上,而后利用钛离子、锆离子与磷酸基团之间强的相互作用将钛离子、锆离子固载在固相载体表面。被固定的钛离子、锆离子上剩余的配合位点可以选择性地将磷酸肽富集。该方法已经被证明具有非常优越的富集性能,比传统的固定金属离子亲和色谱、金属氧化物亲和色谱等方法具有更好的富集特异性。目前该方法已经引起国内外的广泛关注。在最近一期的Nature Protocols中将有这种新型富集材料的合成与应用的详细介绍[4]。

 

2激酶特异性磷酸肽的选择性富集技术

蛋白质磷酸化的规模化分析对于揭示疾病发生和发展过程中信号通路的调控机制具有重要的作用。邹汉法课题组[5]将基于高、低pH值不同的反相-反相多维液相色谱系统用于人肝组织中磷酸化位点的大规模鉴定,结合基于分类筛选策略的磷酸化蛋白质组学数据平台,最终在人肝组织中鉴定到9719个磷酸化位点和2998个磷酸化蛋白质,成为目前已报道的世界上最大的人类肝脏磷酸化蛋白质组学数据集。采用新开发的生物信息学软件iGPS构建人肝磷酸化蛋白质信号网络,对于系统、深入地了解磷酸化在研究人类肝脏相关功能的调控方面具有重要的意义。

尽管蛋白质磷酸化的规模化分析可以鉴定上万个磷酸化位点,但是在一些低丰度磷酸化位点的鉴定方面还存在一定的局限性。除了磷酸化蛋白质组的整体性分析外,最近另外一个研究发展趋势是对某一类激酶底物肽段的选择性分析。激酶是使蛋白质发生磷酸化的一类酶。丝氨酸/苏氨酸蛋白质激酶可以分成脯氨酸导向、嗜酸性、嗜碱性3大类。由于酪蛋白激酶2(casein kinase 2, CK2)等嗜酸性激酶一直保持活性,因此它们的底物特别多。嗜碱性激酶具有调控作用,其底物丰度相对比较低。目前规模化磷酸化分析一般针对所有蛋白质磷酸化进行分析,因此主要鉴定到的是嗜酸性和脯氨酸导向激酶的底物。为了提高鉴定嗜碱性磷酸化位点的灵敏度,目前出现了两种不同的富集方法。第一种方法是正向富集方法,利用强阳离子交换色谱富集碱性磷酸肽[6]。但是由于碱性模体(motif)会被胰蛋白酶剪切,因此在蛋白质酶解液中具有碱性模体序列的磷酸肽很少,故这种正向富集方法只能富集部分含嗜碱性磷酸化位点的肽段。另外一种方法是反向富集方法,通过选择性排除富集来自嗜碱性激酶底物的磷酸肽[7]。在实验中,先用固定金属离子亲和色谱富集蛋白质酶解液中的磷酸肽,而后利用强阴离子交换色谱将酸性磷酸肽选择性去除,从而实现嗜碱性激酶底物的选择性鉴定。经过这样处理后,嗜碱性激酶底物被鉴定的比例明显增加,如预测为蛋白激酶A(protein kinase A, PKA)的底物增加了62%。

3糖蛋白质组分析中样品预处理步骤的集成

在糖基化蛋白质组学的分析中,样品的预处理一般包括蛋白质酶解、糖基化多肽富集和糖基化多肽的去糖基化等步骤。传统的处理方法是将这3个步骤逐一进行。但由于3个处理步骤中所用的缓冲液各不相同,因此往往在一个步骤结束后需要进行除盐冻干。而过多的除盐冻干及样品转移操作会带来严重的样品损失,使得最终的鉴定灵敏度降低。这种方法的整个过程费时费力,往往需要花费2~3 d的时间才能完成整个处理过程。为了克服这一缺陷,最近出现了一种集成式的微反应系统,将3步样品预处理过程集成在一个系统中进行,避免了除盐冻干和样品转移等操作,因此特别适合对微量生物样品的处理[8]。在该系统中,利用乙腈辅助酶解的方法对蛋白质样品进行酶解,然后使用亲水色谱对糖基化多肽进行富集,最后加入酶对富集后的糖基化多肽进行去糖基化处理。整个过程均在微反应系统中进行,而且不需要任何除盐冻干和样品转移等操作,从而避免了样品的损失。利用标准糖基化蛋白IgG(免疫球蛋白G)对该系统进行考察,结果显示,该系统对IgG分析的定量限为30 fmol,灵敏度比传统方法的定量限(150 fmol)提高了约5倍。将该系统用于复杂样品人血清的分析,在100 nL血清中鉴定到了80个糖基化蛋白质和178个糖基化位点。

4糖肽的固相富集与标记

使用稳定同位素标记是目前蛋白质组定量分析的主要方法。化学标记一般在溶液中进行,因此需要进行溶液交换、脱盐等步骤。这些额外的步骤可能会导致样品的损失,从而影响定量准确性,降低检测灵敏度。对于基于固相的化学标记反应,则可以通过简单的离心实现溶液交换。将翻译后修饰的富集过程与化学标记过程组合起来,可以简化样品的制备步骤,在翻译后修饰的定量分析中具有很大的应用潜力。二甲基标记方法是一种基于靶向N末端以及赖氨酸侧链的还原胺化反应的方法,使用的标记试剂是便宜、易得的甲醛以及同位素甲醛,反应过程简单、迅速,而且标记后肽段的电荷状态以及离子化效率不会发生显著变化。最近邹汉法课题组[9]将富集糖肽特异性高达90%的肼化学方法与二甲基同位素标记方法联用,建立了一个在肼微球上固相富集和二甲基标记糖肽的一体化定量分析方法。使用标准糖蛋白混合物对该一体化定量分析方法的准确性、线性、回收率以及灵敏度进行了系统的研究。使用等量实际样品人血清分别做重同位素与轻同位素标记,97%被定量到的位点的重同位素与轻同位素标记之比在1左右(相对标准偏差(RSD)<50%),说明该方法有很高的准确性。实验结果表明该方法在两个数量级内保持良好的线性。通过与基于溶液的标记方法比较,这种方法具有良好的富集回收率和灵敏度,特别适合微量样品的标记定量。

5糖链结构的分析鉴定

糖蛋白及其糖链结构的改变能够体现特定的生理或病理状态改变。目前已知的多种疾病标志性分子如对前列腺癌有提示作用的前列腺特异性抗原、肿瘤抗原CA125等都是糖蛋白。因此,分析和研究糖链将有助于发现疾病标志性分子,从而提高疾病的预警和诊断能力。Anal Chem在2012年10月的一期杂志中发表了两篇关于糖链结构分析的论文。其中一篇论文是通过靶上衍生,在负离子模式下将衍生后的糖链在基质辅助激光解吸飞行时间串联质谱(MALDI-TOF-MS/MS)中进行分析[10]。该工作的特色是衍生试剂与MALDI基体为相同试剂,因此衍生后的试剂不需要洗去,从而具有快速、方便、灵敏的特点。另一篇论文是利用亚大气压电喷雾离子化分析糖链,发现比常规的电喷雾离子化技术具有更高的覆盖率[11]。这种仅分析糖链结构的研究也被称为糖组学,但由于没有蛋白质骨架的信息,糖链的位点不能确定。目前的糖基化蛋白质组学一般只分析去掉糖链的糖肽,因此没有糖链的结构信息。如何同时通量化地鉴定糖蛋白及其糖链结构和位点是目前蛋白质糖基化分析面临的一个挑战,也是今后的研究发展趋势。

 

 

4~9

DOI: 10.3724/SP.J.1123.2012.09011

*通讯联系人.Tel: (0592)2184530,E-mail: xichen@xmu.edu.cn.

基金项目: 国家自然科学基金项目(21105084);福建省自然科学基金项目(2009J01042);福建省科技重大专项专题项目(2011YZ0001-1).

收稿日期: 2012-09-07

 

耐压多样品微量衍生反应装置在气相色谱-质谱联用法分析极性杂环胺中的应用

王翊如1, 陈方翔1, 施雅梅2, TAN Connieal1, 陈曦1*

(1. 厦门大学化学化工学院化学系 分析科学重点实验室, 福建 厦门 361005; 2. 厦门出入境检验检疫局检验检疫技术中心, 福建 厦门 361012)

摘要: 设计并制作了耐压多样品微量衍生反应装置。在该装置中采用N-(叔丁基二甲基硅烷基)-N-甲基三氟乙酰胺(MTBSTFA,含1%叔丁基二甲基氯硅烷)硅烷化试剂高温衍生极性杂环胺,衍生产物可以直接在气相色谱-质谱联用仪上分析。使用该装置,既可以在比试剂沸点高的温度下实现衍生反应,也可以实现多个微量样品的同时衍生。着重考察了衍生化过程中反应瓶的顶空体积、试剂蒸发面积、温度、时间等实验条件的影响。结果表明,在90 ℃衍生时,与普通衍生装置相比,使用耐压衍生装置可以有效地减小挥发损失,显著增大衍生产量;在150 ℃衍生时,由于试剂挥发损失严重导致普通衍生装置无法使用,而采用耐压衍生装置却可以实现定量衍生,但通过加温加压方式来加快衍生反应速率的效果并不十分明显。

关键词: 衍生|耐压装置|气相色谱-质谱法|极性杂环胺

文章编号: 1000-8713(2013)01-0004-06

 

Applications of multi-micro-volume pressure-assisted derivatization reaction device for analysis of polar heterocyclic aromatic amines by gas chromatography-mass spectrometry

WANG Yiru1, CHEN Fangxiang1, SHI Yamei2, TAN Connieal1, CHEN Xi1*

(1. Department of Chemistry & Key Laboratory of Analytical Science, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China; 2. Inspection and Quarantine Technology Center, Xiamen Entry-Exit Inspection and Quarantine Bureau, Xiamen 361012, China)

Abstract: A multi-micro-volume pressure-assisted derivatization reaction device has been designed and made for the silylation derivatization of polar heterocyclic aromatic amines by N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) with 1% catalyst tert-butyldimethylchlorosilane (TBDMCS) at a high temperature. The tert-butyldimethylsilyl derivatives then could be automatically analyzed by gas chromatography-mass spectrometry. Using the pressure-assisted device, the silylation reaction may occur at a temperature higher than the boiling points of the reagents, and several micro-volume samples can be simultaneously pretreated in the same device to shorten the sample-preparation time and to improve the repeatability. The derivatization conditions including the headspace volume of the vial, the evaporative surface area of the reagent, derivatization temperature and time have been discussed for the use of the pressure-assisted device. The experimental results proved that the device is an effective way for the simultaneous derivatization of several micro-volume samples at a high temperature. Compared with a common device, the derivative amounts were obviously increased when using the pressure-assisted device at 90 ℃. Quantitative derivatization can be achieved even at 150 ℃ while there was no common device could be applied at such a high temperature due to the heavy losses of reagents by evaporation. However, no obviously higher reaction speed has been observed in such a circumstance with a higher temperature and a higher pressure using the pressure-assisted device.

Key words: derivatization| pressure-assisted device| gas chromatography-mass spectrometry (GC-MS)| polar heterocyclic aromatic amines

 

10~14

DOI: 10.3724/SP.J.1123.2012.08007

*通讯联系人.E-mail: tanganna@nankai.edu.cn.

基金项目: “973”计划项目(2011CB707703);国家自然科学基金项目(21275081,21005054);高校基本科研业务经费.

收稿日期: 2012-08-09

 

分子印迹聚合物颗粒在毛细管电色谱中的应用

岳春月1, 丁国生2, 唐安娜1*

(1. 南开大学化学学院分析科学研究中心, 天津 300071; 2. 天津大学分析测试中心, 天津 300072)

摘要: 依据分子印迹技术(MIT)制备的分子印迹聚合物(MIP)颗粒对模板分子及其结构类似物具有特异性识别和选择性吸附作用,同时具有较大的比表面积和快速的传质动力学特性,因而被广泛用作液相色谱固定相和固相萃取材料。将MIP颗粒作为固定相应用于毛细管电色谱(CEC),结合了CEC的快速、高效和MIP的高亲和性、高选择性的特点,成为分析科学领域最具有发展前景的分离技术之一。MIP颗粒在CEC领域有几种不同的应用形式: 作为填充材料填充到毛细管柱中;作为嵌入材料嵌入到毛细管柱内部不同基质的骨架中;作为准固定相添加到CEC运行缓冲溶液中。本文综述了近几年MIP颗粒在CEC领域应用的发展,对该领域今后的发展前景进行了展望。

关键词: 分子印迹聚合物颗粒|毛细管电色谱|固定相|综述

文章编号: 1000-8713(2013)01-0010-05

 

Application of molecularly imprinted polymer particles in capillary electrochromatography

YUE Chunyue1, DING Guosheng2, TANG Anna1*

(1. Research Center for Analytical Science, College of Chemistry, Nankai University, Tianjin 300071, China; 2. Analysis Center, Tianjin University, Tianjin 300072, China)

Abstract: Molecularly imprinted polymer (MIP) particles prepared by molecular imprinting technique (MIT) possess the ability of specific identification and selective affinity towards template molecules and their structural analogues. They also have a large specific surface area and rapid mass transfer kinetics, thus they have been widely used as stationary phases in liquid chromatography and matrixes in solid phase extraction. Using MIP particles as capillary electrochromatography (CEC) stationary phase, which combines the high speed and efficiency of CEC with the high affinity and selectivity of MIP, has become one of the most promising separation technique in analytical science. There are several different strategies of MIP particles applied in CEC: as packing materials packed into a capillary column; as entrapping materials entrapped into different matrix frameworks inside a capillary column; as pseudostationary phases (PSPs) added into the running buffer of CEC. This review focuses on the recent developments of MIP particles in CEC and prospects the future developments in this field.

Key words: molecularly imprinted polymer (MIP) particles| capillary electrochromatography (CEC)| stationary phases| review

 

15~21

DOI: 10.3724/SP.J.1123.2012.09015

*通讯联系人.E-mail: chen_hong@zju.edu.cn.

基金项目: 浙江省科技厅公益技术研究社会发展项目(2012C23043).

收稿日期: 2012-09-10

 

超高效液相色谱-串联质谱法同时检测地表水中18种药物与个人护理品的残留量

朱赛嫦1, 王静2, 邵卫伟2, 陈红1*

(1. 浙江大学环境与资源学院环境工程系, 浙江 杭州 310058; 2. 浙江省环境监测中心, 浙江 杭州 310058)

摘要: 采用固相萃取对水样进行预处理,建立了同时检测地表水中包括抗生素、β-阻滞剂、驱蚊剂、抗癫痫药、中枢神经兴奋剂、血脂调节剂、非甾体抗炎药、杀菌消毒剂在内的18种药物与个人护理品的超高效液相色谱-串联质谱分析方法。采用中性条件萃取水样,控制上样流速为2 mL/min,用甲醇-乙腈(1:1, v/v)溶液洗脱。纯水中的平均加标回收率为53.9%~112%,相对标准偏差为2.6%~15.3%(n=6);以地表水样加标100 ng/L为样品,目标分析物平均回收率为45.1%~156.6%,相对标准偏差为2.4%~15.7%(n=6)。结果表明,本方法可同时精确检测地表水样中的18种分析物,方法验证结果表明所建立的方法可靠。用该方法分析杭州余杭塘河水,结果检出9种分析物,其中咖啡因平均质量浓度达550.7 ng/L。结果表明该方法可靠。

关键词: 固相萃取|超高效液相色谱-串联质谱|药物与个人护理品|地表水

文章编号: 1000-8713(2013)01-0015-07

 

Simultaneous determination of 18 pharmaceuticals and personal care products in surface water by ultra-high performance liquid chromatography-tandem mass spectrometry

ZHU Saichang1, WANG Jing2, SHAO Weiwei2, CHEN Hong1*

(1. Department of Environmental Engineering, College of Environmental and Resource Science of Zhejiang University, Hangzhou 310058, China; 2. Zhejiang Environmental Monitoring Center, Hangzhou 310058, China)

Abstract: An analytical method has been developed and validated for the simultaneous determination of 18 pharmaceuticals and personal care products (PPCPs), including antibiotics (trimethoprim, erythromycin·2H2O, norfloxacin, ofloxacin, pencilline G, penicillin V potassium salt, cephalexin and sulfamethoxazole), β-bloker (atenolol), anophelifuge (N,N-diethyl-3-methylbenzoylamide, DEET), antiepileptics (carbamazepine), central nervous system stimulant (caffeine), lipid modifying agent (clofibric acid), non-steroidal anti-inflammatory drugs (ibuprofen, naproxen and diclofenac sodium salt) and antimicrobial agents (triclosan and triclocarban). The detection and qualification of the target compounds were performed by ultra-high performance liquid chromatography-tandem mass spectrometry. The optimized mobile phases were methanol as organic phase, 0.3% (v/v) formic acid-5 mmol/L ammonium acetate for positive electrospray ionization (ESI+) and 5 mmol/L ammonium acetate for ESI- as inorganic phase. Water samples were concentrated by solid phase extraction at 2 mL/min, and all the target PPCPs were efficiently extracted at pH 7. The extracted PPCPs were eluted by the mixture of methanol and acetonitrile (1:1, v/v). The average recoveries of the target compounds in the spiked pure water samples ranged from 53.9%-112%. The average recoveries of the target compounds ranged from 45.1%-156.6% with the relative standard deviations ranged from 2.4%-15.7%, in the surface water samples spiked at 100 ng/L. The surface water samples collected from Yu Hangtang River in Hangzhou were detected. The results showed that nine PPCPs were detected including caffeine that reached a maximum concentration of 550.7 ng/L. It proved that this analytical method is reliable and acceptable.

Key words: solid phase extraction (SPE); ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)| pharmaceuticals and personal care products| surface water

 

22~26

DOI: 10.3724/SP.J.1123.2012.07039

*通讯联系人.Tel: (025)52345193,E-mail: liuhan1982@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);科技部科技支撑项目(2011BAK10B04).

收稿日期: 2012-07-26

 

高效液相色谱-串联质谱法测定芽苗类蔬菜及其来源豆类中4种非法添加物的残留量

柳菡*, 吴斌, 殷耀, 许蔚, 桂茜雯, 余可垚, 龚玉霞, 赵增运, 林宏, 沈伟健, 沈崇钰, 张睿

(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)

摘要: 建立了芽苗类蔬菜及其来源豆类中对氯苯氧乙酸、6-苄基腺嘌呤、恩诺沙星和诺氟沙星残留量的反相高效液相色谱-串联质谱(LC-MS/MS)检测方法。样品经含0.1%冰醋酸的乙腈提取、浓缩后,以C18为分析色谱柱,甲醇和0.1%甲酸水溶液作为流动相进行梯度洗脱分离。质谱采用电喷雾方式电离,正、负离子分段扫描,测定上述4种非法添加物。选择确定对氯苯氧乙酸、6-苄基腺嘌呤、恩诺沙星和诺氟沙星的母离子依次为m/z 189.9、226.1、359.9和320.1,定量子离子依次为m/z 127.0、91.2、315.9和276.2。4种药物在5~200 μg/L范围内线性关系良好(r2> 0.995)。选取了绿豆芽和绿豆作为代表性基质进行添加回收试验,4种药物的检出限和定量限分别为1 μg/kg和5 μg/kg;在5.0、10.0、20.0 μg/kg 3个添加水平下,4种药物的回收率为70%~91%,相对标准偏差(RSD)小于14%。方法准确、灵敏、简便,适用于芽苗类蔬菜及其来源豆类中4种非法添加物残留的同时测定。

关键词: 液相色谱-串联质谱|非法添加物|芽苗类蔬菜|豆类|残留

文章编号: 1000-8713(2013)01-0022-05

 

Determination of four kinds of illegal additive residues in sprouts and source beans by high performance liquid chromatography-tandem mass spectrometry

LIU Han*, WU Bin, YIN Yao, XU Wei, GUI Qianwen, YU Keyao, GONG Yuxia, ZHAO Zengyun, LIN Hong, SHEN Weijian, SHEN Chongyu, ZHANG Rui

(Animal, Plant and Food Inspection Center of Jiangsu Entry-Exit Inspection and Quarantine Bureau, Nanjing 210001, China)

Abstract: A reversed-phase high performance liquid chromatography coupled with tandem mass spectrometric (LC-MS/MS) method was developed for the determination of 4-chlorophenoxyacetic acid, 6-benzylaminopurine, enrofloxacin and norfloxacin residues in sprouts and source beans. The sample was extracted by acetonitrile containing 0.1% acetic acid and concentrated. The chromatographic analysis was carried out on a C18 column with methanol and 0.1% formic acid solution as the mobile phases in gradient elution program. The MS analysis was set in electrospray ionization mode and separated to two segments of positive and negative modes. The precursor ions were m/z 189.9, 226.1, 359.9 and 320.1, while the product ions for quantification were m/z 127.0, 91.2, 315.9 and 276.2 for 4-chlorophenoxyacetic acid, 6-benzylaminopurine, enrofloxacin and norfloxacin, respectively. The calibration curves showed good linearity in the range of 5-200 μg/L with correlation coefficients more than 0.995. The limits of detection (LODs) were 1 μg/kg and the limits of quantification (LOQs) were 5 μg/kg for the four compounds spiked in mung bean sprouts and mung beans. The recoveries of the four compounds spiked at three levels of 5.0, 10.0 and 20.0 μg/kg ranged from 70% to 91%, with the relative standard deviations (RSDs) less than 14%. The method established is accurate, sensitive, simple, and has considerable advantages in the analysis of the four kinds of illegal additive residues in sprouts and beans simultaneously.

Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS)| illegal additives| sprouts| beans| residues

 

27~32

DOI: 10.3724/SP.J.1123.2012.08009

*通讯联系人.Tel: (0532)80885735,E-mail: cuishuh@163.com.

基金项目: 国家认证认可监督管理委员会标准修订(2008B266r).

收稿日期: 2012-08-13

 

高效液相色谱-串联质谱法快速测定食品中的抗倒胺残留量

许美玲1, 崔淑华2*, 刘同英1, 钱家亮1, 张立东1, 段浩1, 刘冰1

(1. 临沂出入境检验检疫局检验检疫技术中心, 山东 临沂 276034; 2. 山东出入境检验检疫局食品农产品检测中心, 山东 青岛 266002)

摘要: 建立了水果、蔬菜、茶叶、蜂蜜、粮谷和动物源性食品中抗倒胺残留的高效液相色谱-串联质谱(HPLC-MS/MS)分析方法。样品经乙腈提取,混合使用乙二胺-N-丙基硅烷和十八烷基硅烷键合相基质分散净化后,用HPLC-MS/MS检测和确证,外标法定量。质谱分析采用电喷雾电离,正离子扫描,多反应监测模式。该方法通过建立基质标准曲线消除基质效应,抗倒胺在1~100 μg/kg范围内具有良好的线性关系,相关系数在0.998~0.999之间;样品中添加5、10、50 μg/kg的标准品,其添加回收率在85.2%~112.4%之间,相对标准偏差均小于8.5%;检出限(LOD)在0.08~1.64 μg/kg之间,定量限(LOQ)在0.30~5.48 μg/kg之间。实验结果表明,该方法提取效果好,具有良好的灵敏度、回收率和重复性。

关键词: 高效液相色谱-串联质谱|抗倒胺|残留|食品

文章编号: 1000-8713(2013)01-0027-06

 

Determination of inabenfide residue in food by high performance liquid chromatography-tandem mass spectrometry

XU Meiling1, CUI Shuhua2*, LIU Tongying1, QIAN Jialiang1, ZHANG Lidong1, DUAN Hao1, LIU Bing1

(1. Inspection and Quarantine Technology Center, Linyi Entry-Exit Inspection and Quarantine Bureau, Linyi 276034, China; 2. Food and Agricultural Products Testing Agency, Shandong Entry-Exit Inspection and Quarantine Bureau, Qingdao 266002, China)

Abstract: A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was established for the determination of inabenfide in fruits, vegetables, tea, honey, cereals and animal-derived foods. The food samples were extracted with acetonitrile, then purified by dispersion solid phase extraction using primary secondary amine (PSA) and C18 as solid phase. The residue was determined and confirmed by HPLC-MS/MS and quantified by external standard method. The mass spectrometric detection was operated with electrospray in positive ionization mode and inabenfide was identified in multiple reaction monitoring (MRM) mode. The interference of matrix was reduced by the matrix-matched calibration standard curves. The linear range of the method was 1-100 μg/kg, with the correlation coefficients (r2) of 0.998-0.999. The recoveries of inabenfide spiked in food samples were 85.2%-112.4% at the spiked levels of 5, 10, 50 μg/kg. The relative standard deviations (RSDs) were less than 8.5%. The limits of detection (LODs) were 0.08-1.64 μg/kg, and the limits of quantification (LOQs) were 0.30-5.48 μg/kg. The results showed that the proposed method is sensitive and accurate for the determination of inabenfide in foodstuffs.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)| inabenfide| residue| foodstuffs

 

33~37

DOI: 10.3724/SP.J.1123.2012.09004

*通讯联系人.E-mail: wumaple@vip.sina.com.

收稿日期: 2012-09-02

 

高效液相色谱-串联质谱法测定葡萄果实中的乙酰辅酶A

杨艳, 吴广枫*

(中国农业大学食品科学与营养工程学院, 北京 100083)

摘要: 建立了高效液相色谱-三重串联四极杆质谱法(HPLC-MS/MS)测定葡萄果实中重要中间代谢产物乙酰辅酶A的分析方法。样品用纯水提取后离心,经C18固相萃取小柱净化,以5 mmol/L甲酸铵和乙腈(20:80,v/v)为流动相等度洗脱,经C18柱分离后,在电喷雾正离子化(ESI+)模式下,通过多反应监测(MRM)模式进行定性,以n-丙酰辅酶A为内标进行定量。该方法在1~2000 μg/L范围内线性关系良好,相关系数大于0.99,检出限(以信噪比(S/N)为3计)为0.1 μg/L,定量限(以S/N=10计)为0.5 μg/L;添加水平分别为50、500、1000 μg/L的3个样品的加标回收率为82.87%~89.67%,相对标准偏差均小于10%。该方法简便、快速、灵敏,可明显减少乙酰辅酶A在实验过程中的损失,适用于葡萄果实中乙酰辅酶A的检测分析。

关键词: 高效液相色谱-串联质谱法|乙酰辅酶A|葡萄果实

文章编号: 1000-8713(2013)01-0033-05

 

Determination of acetyl coenzyme A in grape berries by high performance liquid chromatography-tandem mass spectrometry

YANG Yan, WU Guangfeng*

(College of Food Science and Nutritional Engineering, China Agricultural University, Beijing 100083, China)

Abstract: A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for the determination of acetyl coenzyme A in grape berries using n-propionyl coenzyme A as an internal standard (IS). The sample was extracted with water and then centrifuged for 5 min at 10000 r/min on a centrifuge at 4 ℃, and cleaned-up with a C18 solid phase extraction cartridge. The identification and quantification were carried out by using electrospray ionization in positive ion mode (ESI+) with multiple reaction monitoring (MRM). The total run time was 1 min and the elution of both acetyl coenzyme A and n-propionyl coenzyme A occurred at about 0.45 min. This was achieved with a mobile phase consisting of 5 mmol/L ammonium formate-acetonitrile (20:80, v/v) at a flow rate of 0.4 mL/min on a C18 column. A linear response function was established for the concentration range of 1-2000 μg/L for acetyl coenzyme A and the correlation coefficient was more than 0.99. The limit of detection of acetyl coenzyme A was 0.1 μg/L. The spiked recoveries at 50, 500, 1000 μg/L ranged from 82.87%-89.67% with the relative standard deviations less than 10%. This method is simple, rapid, sensitive and can significantly reduce the loss of acetyl coenzyme A during the experiment. It is suitable for the determination of acetyl coenzyme A in grape berries.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)| acetyl coenzyme A| grape berries

 

38~45

DOI: 10.3724/SP.J.1123.2012.10028

*通讯联系人.E-mail: wangjianling@yahoo.com.cn.

基金项目: 国家质检总局科技计划项目(2005IK173).

收稿日期: 2012-10-31

 

高效液相色谱-串联质谱法快速测定水基食品模拟物中28种受限芳香族伯胺的迁移量

肖晓峰, 王建玲*, 杨娟娟, 刘艇飞, 陈彤, 何军, 邓弘毅, 高启燕

(台州出入境检验检疫局, 浙江 台州 318000)

摘要: 建立了高效液相色谱-串联质谱(HPLC-MS/MS)联用方法用于快速测定水基食品模拟物(10%乙醇、30 g/L乙酸和20%乙醇)中28种芳香族伯胺的迁移量。用水基食品模拟物浸泡待测样品中一定时间(在100 ℃条件下)后,冷却至室温并混匀,所得浸泡液经亲水性聚四氟乙烯针头式过滤器过滤后,直接进行HPLC-MS/MS测定。采用Agilent Zorbax SB-Phenyl柱,以水和0.1%甲酸-25%乙腈-甲醇溶液为流动相进行梯度洗脱分离;质谱具电喷雾离子源,在正离子和分段式多反应监测(MRM)模式下检测。结果表明,方法定量限为0.002~10 μg/L,在5~100 μg/L或10~100 μg/L范围内线性关系良好(r2>0.995);在10、20、40 μg/L水平的加标回收率为76.6%~114%,相对标准偏差为1.53%~8.97%。该方法样品前处理简单快速,色谱分离效果和线性关系好,检出限较低、回收率和准确度高,且完全满足欧盟(EU)No 10/2011法规中对芳香族伯胺特定迁移量的限量要求。该方法已成功应用于30批次出口欧盟的食品接触材料相关制品中芳香族伯胺特定迁移量的检测。

关键词: 液相色谱-串联质谱|水基食品模拟物|芳香族伯胺|迁移量|食品接触材料

文章编号: 1000-8713(2013)01-0038-08

 

Rapid analysis of 28 primary aromatic amines in aqueous food simulants by high performance liquid chromatography-tandem mass spectrometry

XIAO Xiaofeng, WANG Jianling*, YANG Juanjuan, LIU Tingfei, CHEN Tong, HE Jun, DENG Hongyi, GAO Qiyan

(Taizhou Entry-Exit Inspection and Quarantine Bureau, Taizhou 318000, China)

Abstract: A novel method for rapid analysis of the migration amounts of 28 primary aromatic amines (PAAs) in aqueous food simulants (10% ethanol, 30 g/L acetic acid and 20% ethanol aqueous solution) was developed using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). After the migration test, the soaking solution was cooled down from 100 ℃, vortexed, filtered through a hydrophilic polytetrafluoroethylene filter with a disposable syringe, and then the filtrate was analyzed by HPLC-MS/MS. A Zorbax SB-Phenyl column (250 mm×4.6 mm, 5 μm) was selected for chromatography. The mobile phase consisted of water and 0.1% formic acid-25% acetonitrile-methanol solution with gradient elution. The 28 PAAs in aqueous food simulants were detected by tandem mass spectrometer operated in positive electrospray ionization (ESI+)and multiple reaction monitoring (MRM) mode. The limits of quantification for the 28 PAAs were between 0.002 μg/L and 10 μg/L. The linearity of the method was good with correlation coefficients (r2) greater than 0.995 over the concentration range from 5 μg/L or 10 μg/L to 100 μg/L. The average recoveries of the 28 PAAs were between 76.6% and 114% with the relative standard deviations between 1.53% and 8.97% at the levels of 10, 20, and 40 μg/L. The method shows rapid pretreatment, the lower limits of quantification, good recoveries and accuracies, and meets the requirement of European Union (EU)No 10/2011 regulation for the specific migration of PAAs. The method has been applied to analyze the 28 PAAs in different aqueous food simulants from the migration test of 30 batches of food contact material samples exported to EU.

Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS)| aqueous food simulants| primary aromatic amines| migration amount| food contact material

 

46~52

DOI: 10.3724/SP.J.1123.2012.08055

*通讯联系人.Tel: (0755)83886193,E-mail: ccibly@126.com.

基金项目: 科技部科技支撑计划项目(2011BAK10B05-03).

收稿日期: 2012-08-30

 

气相色谱-质谱法同时测定塑料食品接触材料中25种芳香族伯胺的迁移量

李英1*, 李成发1, 肖道清2, 梁烽1, 陈枝楠1, 陈旭辉1, 孙小颖1, 李泳涛1

(1. 深圳出入境检验检疫局, 广东 深圳 518045; 2. 宁波出入境检验检疫局, 浙江 宁波 315012)

摘要: 采用固相萃取前处理技术,结合气相色谱-质谱法对食品接触材料中25种芳香族伯胺的迁移量进行了同时测定。样品中25种目标物分别用蒸馏水和30 g/L醋酸浸出后,用氨水调节浸泡液至pH 8~10,经固相萃取小柱富集净化,再用体积比为1:1的叔丁基甲醚和乙醇混合液洗脱定容后用气相色谱-质谱仪测定。不同芳香族伯胺的检出限略有差异,在0.4~2.0 μg/kg的范围内。加标水平在10 μg/kg时,除2,4-二氨基苯甲醚在酸性模拟物中的回收率较低外,其他芳香族伯胺的回收率均在51.6%~118.4%之间,相对标准偏差(n=7)为0.5%~9.8%。同时探讨了不同实验条件如叔丁基甲醚和乙醇的体积比、pH值等条件对25种芳香族伯胺回收率的影响。结果表明,该方法准确、稳定,完全满足欧盟指令No 10/2011对食品接触塑料材料及制品中芳香族伯胺特定迁移量的限量要求,可用于食品接触材料中芳香族伯胺的实际检验。

关键词: 气相色谱-质谱法|固相萃取|芳香族伯胺|食品接触材料|特定迁移量

文章编号: 1000-8713(2013)01-0046-07

 

Determination of migration of 25 primary aromatic amines from food contact plastic materials by gas chromatography-mass spectrometry

LI Ying1*, LI Chengfa1, XIAO Daoqing2, LIANG Feng1, CHEN Zhinan1, CHEN Xuhui1, SUN Xiaoying1, LI Yongtao1

(1. Shenzhen Entry-Exit Inspection and Quarantine Bureau, Shenzhen 518045, China; 2. Ningbo Entry-Exit Inspection and Quarantine Bureau, Ningbo 315012, China)

Abstract: A solid phase extraction (SPE) combination with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of the migration of 25 primary aromatic amines (PAAs) from food contact plastic materials and articles. The samples were extracted by deionized water and 30 g/L acetic acid, and the pH value of the solution was adjusted to 8-10 with ammonia. The extracts were cleaned up and concentrated on an SPE column, then eluted by equal volume of methyl-tert-butyl ether and ethanol. The analysis of the target compounds was performed by GC-MS. The results indicated that the limits of detection were in the range of 0.4-2.0 μg/kg for different PAAs. The recoveries and relative standard deviations (n=7) of 10 μg/kg PAAs ranged from 51.6%-118.4% and 0.5%-9.8%, respectively, except the 2,4-diaminoanisole in the acid simulant. The effects of different experimental conditions such as the pH value and volume ratio of methyl-tert-butyl ether and ethanol were studied. The results showed that the method is accurate and stable, and could meet the requirement of the European Commission Regulation (EU) No 10/2011 for the determination of primary aromatic amines. It can be applied in the analysis of the primary aromatic amines in real food contact plastic material and article samples.

Key words: gas chromatography-mass spectrometry (GC-MS)| solid phase extraction (SPE)| primary aromatic amines| food contact materials| specific migration limits

 

53~58

DOI: 10.3724/SP.J.1123.2012.08013

*通讯联系人.Tel: (0571)88982729,E-mail: yzwang@zju.edu.cn.

基金项目: 现代农业产业技术体系建设专项资金(CARS-36).

收稿日期: 2012-08-14

 

气相色谱-质谱联用同时分析新型细菌多糖中的单糖和糖醛酸

王凤芹, 杨航仙, 汪以真*

(浙江大学饲料科学研究所, 农业部华东动物营养与饲料重点实验室, 浙江省饲料及动物营养研究实验室, 浙江 杭州 310058)

摘要: 对纯化的新型细菌多糖进行酸水解,用乙硫醇-三氟乙酸和醋酐-吡啶体系先后对酸水解物进行衍生,与之前报道不同的是糖醛酸得到有效衍生化。以木糖为内标,采用气相色谱-质谱联用(GC-MS)定量分析该多糖酸水解物中单糖和糖醛酸衍生物发现,该多糖的糖链由岩藻糖、葡萄糖、葡萄糖醛酸和半乳糖组成,其相对物质的量比为1.50:1.0:0.79:2.06;中性糖比例与糖醇乙酸酯化分析岩藻糖、葡萄糖和半乳糖的相对物质的量比(1.76:1.0:1.98)接近;糖醛酸咔唑法与该方法分析葡萄糖醛酸的含量分别为16.19%和14.85%。以上结果表明所建立的衍生化方法及GC-MS同时定量分析多糖酸水解物中单糖和糖醛酸的方法可行。此外还对葡萄糖醛酸的质谱裂解机理进行了阐述。

关键词: 气相色谱-质谱联用|糖醛酸|衍生化|裂解机理|细菌多糖

文章编号: 1000-8713(2013)01-0053-06

 

Simultaneous determination of neutral sugars and uronic acid constituents in a novel bacterial polysaccharide using gas chromatography-mass spectrometry

WANG Fengqin, YANG Hangxian, WANG Yizhen*

(Feed Science Institute of Zhejiang University, Key Laboratory of Animal Nutrition and Feed Science, Ministry of Agriculture (East China), Zhejiang Provincial Laboratory of Feed and Animal Nutrition, Hangzhou 310058, China)

Abstract: The purified novel bacterial polysaccharide was acid-hydrolyzed, followed by the subsequent derivatization using ethanethiol-trifluoroacetic acid and acetic anhydride-pyridine systems sequentially. Our findings differ from the previous reports in that the glucuronic acid was obtained through effective derivatization. The neutral sugars and glucuronic acid were analyzed using gas chromatography-mass spectrometry (GC-MS) with xylose as an internal standard. The polysaccharide was found to be composed of fucose, glucose, glucuronic acid and galactose, with the relative molar ratio of 1.50:1.0:0.79:2.06. The neutral sugars ratio was similar to the relative molar ratio for fucose, glucose and galactose of 1.76:1.0:1.98 through alditol acetates determined by GC. The percentages of glucuronic acid analyzed using either the carbazole and sulfuric acid method or the above method were 16.19% and 14.85%, respectively. These results indicate that it is practicable to use the derivatization method and GC-MS to quantitatively analyze neutral sugars and glucuronic acid simultaneously in polysaccharide. For GC-MS analysis, the procedure was developed for the simultaneous determination of the derivatives in 25 min, and was performed using an HP-5MS column. Molecular ion peaks were observed in the electron ionization (EI) mass spectra. The fragmentation mechanism for glucuronic acid derivative is discussed in detail.

Key words: gas chromatography-mass spectrometry (GC-MS)| uronic acid| derivatization| fragmentation mechanism| bacterial polysaccharide

 

59~63

DOI: 10.3724/SP.J.1123.2012.07041

*通讯联系人.E-mail: zgb858@163.com.

基金项目: 安徽省高等学校自然科学研究基金项目(KJ2007B022);皖南医学院中青年科研基金项目(WK201208).

收稿日期: 2012-07-21

 

毛细管区带电泳分析五步蛇毒蛋白C激活剂和蛋白C的相互作用

孙瑶1,2, 包鹏举3, 张根葆1,2*

(1. 皖南医学院蛇毒研究所, 安徽 芜湖 241002; 2. 皖南医学院病理生理学教研室, 安徽 芜湖 241002; 3. 皖南医学院生理学教研室, 安徽 芜湖 241002)

摘要: 建立了毛细管区带电泳分析五步蛇毒蛋白C激活剂(protein C activator, PCA)与血浆蛋白C(protein C, PC)的相互作用。以未涂层毛细管(60.2 cm(有效长度50 cm)×75 μm)为分离柱,50 mmol/L Tris-HCl(pH 7.4)为运行缓冲液,于198 nm波长下检测。对影响五步蛇毒PCA分离的因素(如缓冲液、离子浓度)及在37.5 ℃下孵育不同时间的五步蛇毒PCA与PC的相互作用进行考察。方法的检出限(以信噪比为3计)为3 mg/L,线性范围为10~300 mg/L。五步蛇毒PCA迁移时间和峰面积的相对标准偏差分别为0.56%和3.8%(n=6)。等体积的五步蛇毒PCA(200 mg/L)与PC(60 mg/L)孵育5 min,其结合率达到最大,且谱图中未见有PC水解的肽链。该五步蛇毒PCA可改变PC空间构象直接激活PC。该方法简单,灵敏度和分辨率高,分析结果为今后快速检测五步蛇毒PCA及其活性提供了重要的理论依据。

关键词: 毛细管区带电泳|蛋白C激活剂|蛋白C|相互作用|五步蛇毒

文章编号: 1000-8713(2013)01-0059-05

 

Application of capillary zone electrophoresis in the interaction analysis of protein C with protein C activator from Agkistrodon acutus venom

SUN Yao1,2, BAO Pengju3, ZHANG Genbao1,2*

(1. Institute of Snake Venom of Wannan Medical College, Wuhu 241002, China; 2. Department of Pathophysiology of Wannan Medical College, Wuhu 241002, China; 3. Department of Physiology of Wannan Medical College, Wuhu 241002, China)

Abstract: A new capillary zone electrophoresis method (CZE) has been established for the interaction analysis of protein C (PC) with a protein C activator (PCA) from Agkistrodon acutus venom. The analysis was performed on an uncoated fused-silica capillary with 75 μm i.d. and a total length of 60.2 cm (50 cm to the detector) with a buffer solution of 50 mmol/L Tris-HCl (pH 7.4) and 198 nm of wavelength. The factors which influence the separation of the PCA, such as buffer solution and ion concentration, and the interaction between the PCA and PC incubated for different times at 37.5 ℃ were studied. The linear range was from 10 to 300 mg/L. The limit of detection was 3 mg/L (S/N=3). The relative standard deviation (RSD) for the migration time of the PCA was 0.56%. The RSD for the peak area was 3.8% (n=6). The equal volumes of the PCA (200 mg/L) and PC (60 mg/L) were incubated for five minutes, at which their binding rate reached the maximum. And no hydrolyzed peptide chain from PC was found in the electropherogram. The PCA from Agkistrodon acutus venom could activate PC directly through changing the space conformation of PC. The method is simple, and highly sensitive with high resolution, and will provide important theoretical basis for the rapid detection of venom proteins and their activities in the future.

Key words: capillary zone electrophoresis (CZE)| protein C activator (PCA)| protein C (PC)| interaction| Agkistrodon acutus venom

 

64~70

DOI: 10.3724/SP.J.1123.2012.08046

*通讯联系人.E-mail: dingxiaojing@gmail.com(丁晓静);E-mail: wangzhi@hebau.edu.cn(王 志).

收稿日期: 2012-08-27

 

胶束电动毛细管色谱法同时测定复方化学消毒剂及日化产品中邻苯二甲醛、对氯间二甲基苯酚及三氯生

解娜1,2, 丁晓静2,3*, 宋宝花1,2, 李佳2,3, 王志1*

(1. 河北农业大学理学院, 河北 保定 071001; 2. 北京市疾病预防控制中心, 北京 100013; 3. 首都医科大学公共卫生与家庭医学学院, 北京 100069)

摘要: 建立了邻苯二甲醛(OPA)、对氯间二甲基苯酚(PCMX)和三氯生3种杀菌剂同时分离测定的胶束电动毛细管色谱(MEKC)新方法。详细研究了影响上述3种杀菌剂同时分离与准确定量的因素: 如分离缓冲溶液的浓度及pH,十二烷基硫酸钠(SDS)浓度、样品缓冲溶液等。以40.2 cm (有效长度: 30 cm)×50 μm未涂层熔融石英毛细管为分离柱,20 mmol/L硼砂-80 mmol/L SDS(无需调pH)为分离缓冲溶液,2 mmol/L硼砂-8 mmol/L SDS (含体积分数为10%甲醇)为样品缓冲溶液,检测波长为214 nm。3种杀菌剂的校正峰面积的相对标准偏差(RSD)在1.1%~ 3.8%范围内,迁移时间的RSD均小于0.9%, OPA、PCMX和三氯生的检出限(LOD,信噪比为3)分别为4.0、0.4、0.4 mg/L,定量限(LOQ,信噪比为10)分别为12、1.2、1.2 mg/L,校正峰面积与相应的质量浓度分别在12~2 000 mg/L、1.2~200 mg/L和1.2~200 mg/L范围内具有良好的线性关系,相关系数分别为0.9994、0.9993和0.9995。该法前处理简单,可快速、准确地同时测定3种组分,非常适合常规实验室分析。

关键词: 胶束电动毛细管色谱|邻苯二甲醛|对氯间二甲基苯酚|三氯生|杀菌剂|消毒剂|日用化学品

文章编号: 1000-8713(2013)01-0064-07

 

Simultaneous determination of o-phthalaldehyde, p-chloro-m-xylenol and triclosan in compound chemical disinfectants and daily chemicals by micellar electrokinetic chromatography

XIE Na1,2, DING Xiaojing2,3*, SONG Baohua1,2, LI Jia2,3, WANG Zhi1*

(1. College of Sciences, Agricultural University of Hebei, Baoding 071001, China; 2. Beijing Center for Diseases Control and Prevention, Beijing 100013, China; 3. College of Public Health and Domestic Medicine, Capital Medical University, Beijing 100069, China)

Abstract: A novel method for the separation and determination of o-phthalaldehyde (OPA), p-chloro-m-xylenol (PCMX) and triclosan in daily chemicals and compound chemical disinfectants in a single run by micellar electrokinetic chromatography (MEKC) was established. The factors such as the buffer concentration and pH, the concentration of sodium dodecyl sulfate (SDS), and the sample buffer, were investigated in detail. The analysis was carried out using a 50 μm uncoated capillary of 40.2 cm in total length (effective length: 30 cm). The running buffer was 20 mmol/L Na2B4O7 and 80 mmol/L SDS. The sample buffer was 2 mmol/L Na2B4O7-8 mmol/L SDS (without pH adjustment) containing 10% (v/v) methanol. The detection wavelength was 214 nm. The relative standard deviations (RSDs) of the corrected peak areas of the three components were in the range of 1.1%-3.8%, and the RSDs of migration times were less than 0.9%. The limits of detection (LODs, S/N=3) were 4.0, 0.4 and 0.4 mg/L, and the limits of quantification (LOQs, S/N=10) were 12, 1.2, and 1.2 mg/L for OPA, PCMX and triclosan, respectively. The corrected peak areas and the concentrations of the three components showed good linear relationship within the ranges of 12-2 000 mg/L, 1.2-200 mg/L and 1.2-200 mg/L with the correlation coefficients of 0.9994, 0.9993 and 0.9995 for OPA, PCMX and triclosan, respectively. The method was used for the determination of the three components in compound chemical disinfectants, hand washing liquids, soaps and a toothpaste. The results showed that the three components could be assayed in a single run with simple sample pretreatment, rapidity, accuracy and low cost, and the method is convenient for routine analysis.

Key words: micellar electrokinetic chromatography (MEKC)| o-phthalaldehyde (OPA)| p-chloro-m-xylenol (PCMX)| triclosan| bactericides| disinfectant| daily chemical

 

71~78

DOI: 10.3724/SP.J.1123.2012.07033

*通讯联系人.Tel: (010)82109532,E-mail: liusu@mail.caas.net.cn.

基金项目: 中央级公益性科研院所基本科研业务费专项(2012ZL023);农业部园艺作物生物学与种质创制重点实验室项目.

收稿日期: 2012-07-18

 

超快速液相色谱-串联质谱法快速筛查蔬菜中176种农药的残留量

郑姝宁1, 李凌云1, 林桓1, 赵文1, 张延国1, 姚周麟2, 刘肃1*

(1. 中国农业科学院蔬菜花卉研究所, 农业部蔬菜品质监督检验测试中心, 北京 100081; 2. 浙江省柑橘研究所, 浙江 台州 318020)

摘要: 采用超快速液相色谱-串联质谱(UFLC-MS/MS)技术建立了蔬菜中176种农药残留快速筛查的分析方法。蔬菜样品采用乙腈提取,盐析后无需净化。采用多反应监测-信息关联采集-增强子离子扫描(MRM-IDA-EPI)的复合扫描模式,利用基于EPI谱图和色谱峰峰面积的谱库检索技术,完成了蔬菜中176种农药残留的定性定量分析。所有农药在各自的线性范围内线性关系良好(r>0.99),除了丁硫克百威和灭蝇胺在3个添加水平下的平均回收率分别为46.8%和53.1%,其余174种农药的平均回收率范围为72.4%~126.4%,相对标准偏差范围为1.0%~18.7%,方法的检出限和定量限范围分别为0.005~2.0 μg/kg和0.1~10 μg/kg。该方法具有快速、灵敏度高、准确度高等优点,适合于蔬菜样品中农药多残留的快速筛查分析。

关键词: 超快速液相色谱-串联质谱|谱库检索|农药残留|蔬菜|筛查

文章编号: 1000-8713(2013)01-0071-08

 

Rapid screening of 176 pesticide residues in vegetables by ultra fast liquid chromatography-tandem mass spectrometry

ZHENG Shuning1, LI Lingyun1, LIN Huan1, ZHAO Wen1, ZHANG Yanguo1, YAO Zhoulin2, LIU Su1*

(1. Institute of Vegetables and Flowers, Chinese Academy of Agricultural Sciences, Supervision and Testing Center for Vegetable Quality, Ministry of Agriculture, Beijing 100081, China; 2. Zhejiang Citrus Research Institute, Taizhou 318020, China)

Abstract: A multiresidue analytical method for rapid screening of 176 pesticide residues in vegetables was developed by using ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS). The vegetable samples were extracted by acetonitrile. It is not necessary for the extract to make a further purification after salting out. Multiple reaction monitoring with information-dependent acquisition of enhanced product ion (MRM-IDA-EPI) was used for the analysis. Based on EPI spectra and chromatographic peak area, identification and quantification of the 176 pesticide residues in vegetables were carried out by using library search technique. All the pesticides had the good linearity within their respective linear ranges (r>0.99). The average recoveries of the 174 pesticides except for carbosulfan and cyromazine were in the range of 72.4% to 126.4% with the relative standard deviations (RSDs) from 1.0% to 18.7%. The limits of detection and quantification of the method were 0.005-2.0 μg/kg and 0.1-10 μg/kg, respectively. The results demonstrated that the method has distinct advantages of rapid speed, high sensitivity and good accuracy. Therefore, this method is suitable for the rapid screening of pesticide residues in vegetables.

Key words: ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS)| library search| pesticide residues| vegetables| screening

 

79~82

DOI: 10.3724/SP.J.1123.2012.08038

*通讯联系人.E-mail: zhanghua@dlut.edu.cn(张 华);E-mail: guozhimou@dicp.ac.cn(郭志谋).

基金项目: 国家杰出青年基金项目(20825518);国家自然科学基金项目(21005077).

收稿日期: 2012-08-22

 

高效液相色谱法定量测定中药千层塔提取物中的石杉碱甲

张敬彩1, 魏杰2, 钟虹敏1, 郭志谋2*, 张华1*

(1. 大连理工大学化学学院, 辽宁 大连 116023; 2. 中国科学院大连化学物理研究所, 辽宁 大连 116023)

摘要: 建立了高效液相色谱快速定量测定中药千层塔提取物中石杉碱甲含量的分析方法。千层塔提取物经甲醇/水/甲酸(10/90/0.2, v/v/v)提取并定容后,过滤膜后直接分析。色谱分离选用XCharge C18色谱柱(150 mm×4.6 mm, 5 μm),以水(含0.1%三氟乙酸)和乙腈(含0.09%三氟乙酸)为流动相进行梯度洗脱,流速为2 mL/min,于310 nm波长下检测,可在10 min内完成石杉碱甲的快速分离分析。结果表明,石杉碱甲在2.12~106 mg/L范围内线性关系良好(相关系数为0.9999);平均加标回收率为102.34%,相对标准偏差(RSD)为0.46%;日内及日间精密度均小于2%,满足定量要求。该方法简便、快速,结果可靠,重现性好,可作为千层塔提取物质量评价的依据。

关键词: 高效液相色谱法|生物碱|石杉碱甲|千层塔|中草药

文章编号: 1000-8713(2013)01-0079-04

 

Determination of Huperzine A in the extract of Huperzia serrata by high performance liquid chromatography

ZHANG Jingcai1, WEI Jie2, ZHONG Hongmin1, GUO Zhimou2*, ZHANG Hua1*

(1. College of Chemistry, Dalian University of Technology, Dalian 116023, China; 2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China)

Abstract: A high performance liquid chromatographic (HPLC) method was established to determine the Huperzine A in the extract of Huperzia serrata. After extracted by methanol/water/formic acid (10/90/0.2, v/v/v), the sample was filtered for HPLC analysis. The separation was performed on an XCharge C18 column (150 mm×4.6 mm, 5 μm) by gradient elution with water (containing 0.1% (v/v) trifluoroacetic acid) and acetonitrile (containing 0.09%(v/v) trifluoroacetic acid) as the mobile phases. Rapid separation was achieved within 10 min at a flow rate of 2 mL/min with ultraviolet absorption detection at a wavelength of 310 nm. Under the optimized conditions, good linearity was obtained in the range of 2.12-106 mg/L with the correlation coefficient (R2) of about 0.9999. The average recovery was 102.34% with the relative standard deviation (RSD) of 0.46%. The intraday and interday precisions were all below 2%. The results demonstrate that this method is simple, rapid and accurate with good reproducibility, and can be used to evaluate the quality of Huperzia serrata.

Key words: high performance liquid chromatography (HPLC)| alkaloid| Huperzine A| Huperzia serrata| Chinese medicinal herb

 

83~87

DOI: 10.3724/SP.J.1123.2012.08050

*通讯联系人.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: 2012-08-29

 

高效液相色谱-荧光检测法测定食品接触材料塑料制品中荧光增白剂

焦艳娜1,2, 丁利1, 朱绍华1, 傅善良1, 龚强1, 李晖2, 王利兵1*

(1. 湖南出入境检验检疫局技术中心, 湖南 长沙 410004; 2. 四川大学化学工程学院, 四川 成都 610065)

摘要: 建立了同时测定食品接触材料塑料制品(食品包装袋)中荧光增白剂的高效液相色谱-荧光检测法。样品用20 mL三氯甲烷作提取剂,超声提取30 min,提取温度为40 ℃,用高效液相色谱进行定性定量分析。采用Eclipse XDB-C18(250 mm×4.6 mm, 5 μm)为分析柱,以5 mmol/L乙酸铵溶液和乙腈为流动相,梯度洗脱,荧光激发波长为350 nm,发射波长为430 nm。结果显示,4种荧光增白剂4,4′-双[2-(邻氰苯基)乙烯基]苯(1,4-bis(4-cyanostyryl)benzene, C.I. 199)、1,4-双(2-苯并恶唑)萘(1,4-bis (2-benzoxazolyl)naphthalene, C.I. 367)、4,4′-双(2-甲氧苯乙烯基)联苯(4,4′-bis(2-methoxystyryl)biphenyl, C.I. 378)和2,5-双(5-叔丁基-2-苯并恶唑基)噻吩(2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole), C.I. 184)可以较好地分离;检出限(S/N=3)分别为0.3、0.1、0.05、0.14 mg/L,定量限(S/N=10)分别为1.0、0.4、0.2、0.5 mg/L,回收率范围为78.9%~101.1%,相对标准偏差小于10%,线性关系良好。该法简便、结果准确、灵敏度高,能够满足进出口食品包装材料塑料制品中荧光增白剂的日常检测。

关键词: 高效液相色谱|荧光检测|荧光增白剂|食品接触材料;塑料制品

文章编号: 1000-8713(2013)01-0083-05

 

Determination of fluorescent whitening agents in plastic food contact materials by high performance liquid chromatography with fluorescence detector

JIAO Yanna1,2, DING Li1, ZHU Shaohua1, FU Shanliang1, GONG Qiang1, LI Hui2, WANG Libing1*

(1. Technology Center of Hunan Entry-Exit Inspection and Quarantine Bureau, Changsha 410004, China; 2. School of Chemical Engineering, Sichuan University, Chengdu 610065, China)

Abstract: A method for the determination of fluorescent whitening agents in plastic food contact materials by high performance liquid chromatography (HPLC) with fluorescence detector was developed. The samples were extracted with trichloromethane by sonication for 30 min at 40 ℃. The HPLC method was performed on a column of Eclipse XDB-C18 (250 mm×4.6 mm, 5 μm) by gradient elution using 5 mmol/L ammonium acetate and acetonitrile as the mobile phases, and detected by the fluorescence detector at an excitation wavelength of 350 nm and an emission wavelength of 430 nm. The experimental results indicated that the four fluorescent whitening agents were separated well. The limits of detection (LOD) (S/N=3) were 0.3, 0.1, 0.05, 0.14 mg/L, and the limits of quantification (LOQ) (S/N=10) were 1.0, 0.4, 0.2, 0.5 mg/L for 1,4-bis(4-cyanostyryl)benzene (C.I. 199), 1,4-bis(2-benzoxazolyl)naphthalene (C.I. 367), 4,4′-bis(2-methoxystyryl)biphenyl (C.I. 378) and 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole) (C.I. 184), respectively. Good linearities with correlation coefficients (r2) not less than 0.991 were obtained. The proposed method is simple, accurate, sensitive and can meet the requirements of the routine determination of fluorescent whitening agents in entry-exit products.

Key words: high performance liquid chromatography (HPLC)| fluorescence detection| fluorescent whitening agents (FWAs)| food contact materials| plastic

 

88~91

DOI: 10.3724/SP.J.1123.2012.08001

*通讯联系人.Tel: (021)58957001,E-mail: njuttingting@163.com.

基金项目: 浙江省省级公益性技术应用研究计划项目(2012C37038).

收稿日期: 2012-08-01

 

阀切换-离子色谱法测定分析纯硫酸钠中痕量氯离子

张婷婷1*, 王娜妮2, 叶明立1, 胡忠阳1, 潘广文1

(1. 赛默飞世尔科技有限公司上海实验室, 上海 201203; 2. 浙江大学化学系, 浙江 杭州 310028)

摘要: 建立了阀切换-离子色谱法测定分析纯硫酸钠固体中痕量氯离子含量的方法。ICS-2100离子色谱系统,配置十通阀,用IonPac AS18色谱柱将硫酸钠固体样品中的氯离子和硫酸根离子预分离后,以IonPac TAC-ULP1为富集柱,将氯离子富集后在相同的IonPac AS18色谱柱上进行定量分析。同时以淋洗液发生器产生的不同浓度的KOH作为淋洗液,以抑制型电导检测器测定氯离子的含量。结果表明,阀切换-离子色谱法测定分析纯硫酸钠固体中的痕量氯离子,检出限为10 μg/L,线性相关系数(r2)大于0.999,实际样品的加标回收率为98.0%~103.0%,具有分离度和灵敏度高,选择性好,操作简单等特点。该方法能够准确测定硫酸钠固体中痕量氯离子的含量,适用于高纯化学试剂中痕量氯离子的分离测定。

关键词: 离子色谱|阀切换|氯离子|分析纯硫酸钠

文章编号: 1000-8713(2013)01-0088-04

 

Determination of trace chloride in sodium sulfate of analytical reagent-grade by valve-switching ion chromatography

ZHANG Tingting1*, WANG Nani2, YE Mingli1, HU Zhongyang1, PAN Guangwen1

(1. Shanghai Lab, Thermo Fisher Scientific Inc., Shanghai 201203, China; 2. Department of Chemistry, Zhejiang University, Hangzhou 310028, China)

Abstract: A valve-switching ion chromatography system was developed for the determination of trace chloride in sodium sulfate using a single pump, a suppressor, two valves and three columns. Using this technique, the trace chloride was eluted from the concentrator column (IonPac TAC-ULP1, 23 mm×5 mm) to the analytical column (IonPac AS18, 250 mm×4 mm), and the sulfate flowed to the waste. Under the optimized separation conditions, the method showed good linearity (r2>0.999) in the range of 0.03-1 mg/L and the average recoveries of chloride were 98.0%-103.0% with the relative standard deviation less than 2%. The limit of detection was 0.01 mg/L (S/N=3). The results demonstrated that this system has the advantages of high sensitivity, facile automation and simple sample pretreatment, which might be a promising approach for the determination of trace chloride in high-purity reagents.

Key words: ion chromatography (IC)| valve-switching| chloride| sodium sulfate of analytical reagent-grade

 

 


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