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离子液体辅助液相色谱-氢化物发生原子荧光光谱法分离测定食品和饮料样品中的硒形态

Ionic liquid-assisted separation and determination of selenium species in food and beverage samples by liquid chromatography coupled to hydride generation atomic fluorescence spectrometry.

作者信息

Castro Grijalba Alexander, Fiorentini Emiliano F, Wuilloud Rodolfo G

机构信息

Laboratory of Analytical Chemistry for Research and Development (QUIANID), Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Cuyo, Padre J. Contreras 1300, 5500 Mendoza, Argentina; Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Argentina.

Laboratory of Analytical Chemistry for Research and Development (QUIANID), Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Cuyo, Padre J. Contreras 1300, 5500 Mendoza, Argentina; Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Argentina.

出版信息

J Chromatogr A. 2017 Mar 31;1491:117-125. doi: 10.1016/j.chroma.2017.02.045. Epub 2017 Feb 22.

Abstract

Different ionic liquids (ILs) were assayed as mobile phase modifiers for the separation and determination of selenite [Se(IV)], selenate [Se(VI)], selenomethionine (SeMet) and Se-methylselenocysteine (SeMeSeCys) by reversed-phase high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry (RP-HPLC-HG-AFS). The use of several ILs: 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride ([Cmim]Cl), 1-octyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium bromide, 1-hexadecyl-3-methylimidazolium bromide and tributyl(methyl)phosphonium methylsulphate was evaluated. Also, the effect of pH, buffer type and IL concentration on the separation of Se species was studied. Complete separation was attained within 12min using a C column and a gradient performed with a mobile phase containing 0.1% (v/v) [Cmim]Cl at pH 6.0. The proposed method allows the separation of inorganic and organic Se species in a single chromatographic run, adding further benefits over already reported methods based on RP-HPLC. In addition, the influence of ILs on the AFS signals of each Se species was evaluated and a multivariate methodology was used for optimization of AFS sensitivity. The limits of detection were 0.92, 0.86, 1.41 and 1.19μgL for Se(IV), Se(VI), SeMet and SeMeSeCys, respectively. The method was successfully applied for speciation analysis of Se in complex samples, such as wine, beer, yeast and garlic.

摘要

采用反相高效液相色谱-氢化物发生原子荧光光谱法(RP-HPLC-HG-AFS),测定了不同离子液体(ILs)作为流动相改性剂对亚硒酸盐[Se(IV)]、硒酸盐[Se(VI)]、硒代蛋氨酸(SeMet)和硒甲基硒代半胱氨酸(SeMeSeCys)的分离效果。评估了几种离子液体的使用情况:1-丁基-3-甲基咪唑氯盐、1-己基-3-甲基咪唑氯盐([Cmim]Cl)、1-辛基-3-甲基咪唑氯盐、1-十二烷基-3-甲基咪唑溴盐、1-十六烷基-3-甲基咪唑溴盐和三丁基(甲基)硫酸氢膦。此外,还研究了pH值、缓冲液类型和离子液体浓度对硒形态分离的影响。使用C柱和在pH 6.0条件下含0.1%(v/v)[Cmim]Cl的流动相进行梯度洗脱,12分钟内实现了完全分离。所提出的方法能够在一次色谱运行中分离无机和有机硒形态,比已报道的基于RP-HPLC的方法具有更多优势。此外,评估了离子液体对每种硒形态原子荧光光谱信号的影响,并采用多元方法优化原子荧光光谱的灵敏度。Se(IV)、Se(VI)、SeMet和SeMeSeCys的检测限分别为0.92、0.86、1.41和1.19μg/L。该方法成功应用于葡萄酒、啤酒、酵母和大蒜等复杂样品中硒的形态分析。

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