Department of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR ESPCI-ParisTech-UPMC-CNRS 7195 PECSA, Paris, France.
J Chromatogr B Analyt Technol Biomed Life Sci. 2012 Jul 1;900:48-58. doi: 10.1016/j.jchromb.2012.05.029. Epub 2012 Jun 2.
Degradation products of chemical warfare agents are considered as important environmental and biological markers of chemical attacks. Alkyl methylphosphonic acids (AMPAs), resulting from the fast hydrolysis of nerve agents, such as sarin and soman, and the methylphosphonic acid (MPA), final degradation product of AMPAs, were determined from complex matrices by using an emergent and miniaturized extraction technique, the hollow fiber liquid-phase microextraction (HF-LPME), before their analysis by liquid chromatography coupled to mass spectrometry (LC-MS). After studying different conditions of separation in the reversed phase LC-MS analysis, the sample treatment method was set up. The three-phase HF-LPME was carried out by using a porous polypropylene (PP) hollow fiber impregnated with 1-octanol that separates the donor and acceptor aqueous media. Various extraction parameters were evaluated such as the volume of the sample, the effect of the pH and the salt addition to the sample, the pH of the acceptor phase, the extraction temperature, the stirring speed of the sample, the immersion time in the organic solvent and the time of extraction. The optimum conditions were applied to the determination of MPA and five AMPAs in real samples, such as surface waters and urine. Compounds were extracted from a 3 mL acidified sample into only 6 μL of alkaline water without any other pretreatment of the complex matrices. Enrichment factors (EFs) higher than 170 were obtained for three less polar AMPAs. Limits of quantification (LOQs) in the 0.013-5.3 ng mL(-1) range were obtained after microextraction of AMPAs from river water and in the range of 0.056-4.8 ng mL(-1) from urine samples with RSD values between 1 and 9%.
化学战剂的降解产物被认为是化学袭击的重要环境和生物标志物。烷基甲基膦酸（AMPA）是神经毒剂（如沙林和梭曼）快速水解的产物，甲基膦酸（MPA）是 AMPA 的最终降解产物，通过一种新兴的微型提取技术——中空纤维液相微萃取（HF-LPME），从复杂基质中提取，然后进行液相色谱-质谱联用（LC-MS）分析。在研究了反相 LC-MS 分析中的不同分离条件后，建立了样品处理方法。采用多孔聚丙烯（PP）中空纤维进行三相 HF-LPME，该纤维中浸渍有 1-辛醇，可将供体和受体水相分离。评估了各种萃取参数，如样品体积、pH 值和盐对样品的影响、受体相的 pH 值、萃取温度、样品搅拌速度、有机溶剂浸渍时间和萃取时间。将最佳条件应用于实际样品（如地表水和尿液）中 MPA 和五种 AMPA 的测定。将 3 mL 酸化样品直接萃取到 6 μL 碱性水中，无需对复杂基质进行任何预处理。对于三种极性较小的 AMPA，可获得大于 170 的富集因子（EF）。从河水微萃取 AMPA 后，在 0.013-5.3ngmL-1范围内可获得定量限（LOQ），从尿液样品中微萃取 AMPA 后，在 0.056-4.8ngmL-1范围内可获得定量限，相对标准偏差（RSD）在 1-9%之间。
