Headspace versus Direct Immersion Solid Phase Microextraction in Complex Matrixes: Investigation of Analyte Behavior in Multicomponent Mixtures
Headspace versus Direct Immersion Solid Phase Microextraction in Complex Matrixes: Investigation of Analyte Behavior in Multicomponent Mixtures
复制标题
DOI：
10.1021/acs.analchem.5b01850
复制
发表时间：
2015-08-18
影响因子：
7.4
通讯作者：
Pawliszyn, Janusz
中科院分区：
文献类型：
--
作者：
Gionfriddo, Emanuela;Souza-Silva, Erica A.;Pawliszyn, Janusz
本工作旨在研究固相微萃取（SPME）在复杂混合物和基质中分析物的行为。考虑了影响分析物吸收的各种因素，如涂层化学、提取模式、分析物的理化性质和基质复杂性。首先，通过使用市售的液体和固体多孔涂层研究了含有具有不同疏水性、分子量和化学官能度的分析物的水性体系。传质机制的差异导致顶空模式中发生更明显的涂层饱和。此外，直接浸没浸提最大限度地减少了与涂层饱和度相关的伪影的发生，并提供了极性化合物的增强浸提。此外，基质相容的PDMS改性的固体涂料，其特征在于一个新的形态，避免涂层污垢，进行了比较，其未改性的类似物。所获得的结果表明，PDMS改性的涂层减少了与涂层饱和度相关的伪影，即使在顶空模式下。这一因素，再加上他们的基质相容性，使直接SPME的使用非常实用的定量方法和代谢组学研究的最佳选择，其中广泛的覆盖范围是打算。为了进一步了解对分析物摄取的影响，在系统中，由于基质组分，离体和体内采样条件进行了模拟，使用淀粉基质模型，模拟植物来源的材料的目的发生额外的相互作用。我们的研究结果证实了这样一个事实，即基质处理可以影响分析物/基质平衡，从而释放高浓度的先前结合的疏水化合物，可能导致涂层饱和。直接浸没SPME限制了伪影的发生，这证实了SPME适用于体内应用。这些发现揭示了在体内SPME策略的实施在复杂的植物为基础的系统的定量代谢组学研究。
This work aims to investigate the behavior of analytes in complex mixtures and matrixes with the use of solid-phase microextraction (SPME). Various factors that influence analyte uptake such as coating chemistry, extraction mode, the physicochemical properties of analytes, and matrix complexity were considered. At first, an aqueous system containing analytes bearing different hydrophobicities, molecular weights, and chemical functionalities was investigated by using commercially available liquid and solid porous coatings. The differences in the mass transfer mechanisms resulted in a more pronounced occurrence of coating saturation in headspace mode. Contrariwise, direct immersion extraction minimizes the occurrence of artifacts related to coating saturation and provides enhanced extraction of polar compounds. In addition, matrix-compatible PDMS-modified solid coatings, characterized by a new morphology that avoids coating fouling, were compared to their nonmodified analogues. The obtained results indicate that PDMS-modified coatings reduce artifacts associated with coating saturation, even in headspace mode. This factor, coupled to their matrix compatibility, make the use of direct SPME very practical as a quantification approach and the best choice for metabolomics studies where wide coverage is intended. To further understand the influence on analyte uptake on a system where additional interactions occur due to matrix components, ex vivo and in vivo sampling conditions were simulated using a starch matrix model, with the aim of mimicking plant-derived materials. Our results corroborate the fact that matrix handling can affect analyte/matrix equilibria, with consequent release of high concentrations of previously bound hydrophobic compounds, potentially leading to coating saturation. Direct immersion SPME limited the occurrence of the artifacts, which confirms the suitability of SPME for in vivo applications. These findings shed light into the implementation of in vivo SPME strategies in quantitative metabolomics studies of complex plant-based systems.