Moreno-González David, Pérez-Ortega Patricia, Gilbert-López Bienvenida, Molina-Díaz Antonio, García-Reyes Juan F, Fernández-Alba Amadeo R
Analytical Chemistry Research Group, Department of Physical and Analytical Chemistry, University of Jaén, 23071, Jaén, Spain.
Analytical Chemistry Research Group, Department of Physical and Analytical Chemistry, University of Jaén, 23071, Jaén, Spain; Center for Advanced Studies in Olives Grove and Olive Oils (CEAOAO), Science and Technology park GEOLIT, E-23620, Mengíbar, Spain.
J Chromatogr A. 2017 Aug 25;1512:78-87. doi: 10.1016/j.chroma.2017.07.019. Epub 2017 Jul 8.
This article reports on the evaluation of nanoflow liquid chromatography-mass spectrometry (LC-MS) for pesticide residue analysis in food. The approach is based on the use of reversed-phase C18nano columns with an integrated emitter, so that separation, ionization and detection are performed minimizing dead volumes. The use of nanoflow not only increases ionization efficiency and minimizes ionization suppression but also boost sensitivity compared to analytical-scale LC-MS methods. The nanoflow LC system was combined with full-scan high resolution mass spectrometry using a Q-Exactive Orbitrap instrument. The analytical performance was assessed for over 60 representative pesticides in five representative commodities (tomato, baby food, orange, fruit-based jam and olive oil). The sensitivity achieved with this configuration enables the implementation of high dilution factors (eg. 1:20, 1:50 or beyond) in pesticide residue workflows without compromising sensitivity, featuring limits of quantitation in the low ng kg range. Using this dilution factors, signal suppression was found negligible in most cases (<10% in most cases, especially with 1:50 dilution), so that matrix-matched standards may be skipped, thus simplifying laboratory workflows. The robustness of the nanoflow LC system and its capability to withstand long analytical runs was also evaluated. Appropriate precision in terms of peak area and retention time was obtained at different concentration levels for over 125 injections without any instrument servicing. The main benefits of the nanoflow liquid chromatography approach are the high sensitivity gain and the outstanding reduction in matrix effects thanks to the high sample dilution factors that can be implemented, along with the substantial reduction in solvent usage.
本文报道了采用纳流液相色谱 - 质谱联用(LC - MS)技术对食品中农药残留进行分析的评估。该方法基于使用带有集成发射器的反相C18纳流柱,从而在尽量减小死体积的情况下进行分离、电离和检测。与分析规模的LC - MS方法相比,纳流的使用不仅提高了电离效率并使电离抑制最小化,还提高了灵敏度。纳流LC系统与使用Q - Exactive Orbitrap仪器的全扫描高分辨率质谱联用。对五种代表性商品(番茄、婴儿食品、橙子、水果果酱和橄榄油)中的60多种代表性农药的分析性能进行了评估。这种配置所实现的灵敏度使得在农药残留分析流程中能够采用高稀释倍数(例如1:20、1:50或更高)而不影响灵敏度,定量限在低ng/kg范围内。使用这些稀释倍数时,在大多数情况下信号抑制可忽略不计(大多数情况下<10%,尤其是1:50稀释时),因此可以跳过基质匹配标准品,从而简化实验室分析流程。还评估了纳流LC系统的稳健性及其承受长时间分析运行的能力。在不同浓度水平下,经过超过125次进样,无需任何仪器维护即可获得峰面积和保留时间方面的适当精密度。纳流液相色谱方法的主要优点是灵敏度显著提高,由于可以采用高样品稀释倍数,基质效应显著降低,同时溶剂用量大幅减少。