采用低相变温度混合物的分散液液微萃取及尿液样品中农药的液相色谱-质谱分析。
Dispersive liquid-liquid microextraction using a low transition temperature mixture and liquid chromatography-mass spectrometry analysis of pesticides in urine samples.
机构信息
Department of Chemistry, Sapienza University, P.le Aldo Moro 5, 00185, Rome Italy.
INAIL- DiMEILA, Chemical Risk Laboratory, Monte Porzio Catone Research Center, Rome.
出版信息
J Chromatogr A. 2021 Apr 12;1642:462036. doi: 10.1016/j.chroma.2021.462036. Epub 2021 Mar 4.
Biomonitoring is a potent tool to control the health risk of people occupationally and non-occupationally exposed. The latest trend in bioanalytical chemistry is to develop quick, cheap, easy, safe and reliable green analytical procedures to analyse a large number of chemicals in easily accessible biomatrices such as urine. In this paper, a new dispersive liquid-liquid microextraction (DLLME) procedure, conceived to treat urine samples and based on the use of a low transition temperature mixture (LTTM), was developed and validated to analyse twenty pesticides commonly used in farm practises. The LTTM was composed of choline chloride and sesamol in molar ratio 1:3 (ChCl:Ses 1:3); its characterization via differential scanning calorimetry identified it as an LTTM and not as a deep eutectic solvent due to the occurrence of a glass transition at -71 °C. The prepared mixture was used as the extraction solvent in the DLLME procedure, while ethyl acetate as the dispersing solvent. The salting out effect (50 mg mL of NaCl in a diluted urine sample) improved the separation phase and the analyte transfer to the extractant. Due to the high ionic strength and despite the density of ChCl:Ses 1:3 (1.25 g mL), the LTTM layer floated on the top of the sample solution after centrifugation. All extracts were analysed by high-performance liquid chromatography coupled to mass spectrometry. After optimization and validation of the whole method, lower limits of quantitation were in the range of 0.02 - 0.76 µg L. Extraction recoveries spanned from 50 to 101 % depending on the spike level and analytes. Precision and accuracy ranges were 3-18% and 5-20%, respectively. The extraction procedure was also compared with other methods, showing to be advantageous for rapidity, simplicity, efficiency, and low cost. Finally, urine samples from ten volunteers were effectively analysed using the developed method.
生物监测是控制职业和非职业暴露人群健康风险的有效工具。生物分析化学的最新趋势是开发快速、廉价、简单、安全和可靠的绿色分析程序，以分析尿液等易于获取的生物基质中的大量化学物质。本文提出了一种新的分散液 - 液微萃取（DLLME）方法，该方法旨在处理尿液样本，并基于使用低转变温度混合物（LTTM），开发并验证了该方法来分析在农业实践中常用的二十种农药。LTTM由氯化胆碱和芝麻酚以摩尔比 1:3 组成（ChCl:Ses 1:3）；通过差示扫描量热法对其进行的表征表明，由于在-71°C 处发生玻璃化转变，它是一种 LTTM，而不是深共晶溶剂。制备的混合物用作 DLLME 方法中的萃取溶剂，而乙酸乙酯用作分散溶剂。盐析效应（在稀释的尿液样品中加入 50mgmL 的 NaCl）改善了分离相和分析物向萃取剂的转移。由于离子强度高，尽管 ChCl:Ses 1:3 的密度为 1.25 g mL，但 LTTM 层在离心后仍浮在样品溶液的顶部。所有提取物均通过高效液相色谱-质谱联用进行分析。在对整个方法进行优化和验证后，定量下限范围在 0.02-0.76µg L 之间。根据加标水平和分析物的不同，萃取回收率在 50-101%之间。精密度和准确度范围分别为 3-18%和 5-20%。该萃取程序还与其他方法进行了比较，结果表明该方法具有快速、简单、高效和低成本的优势。最后，使用开发的方法有效地分析了十个志愿者的尿液样本。
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