Quantitative determination of pesticides in human plasma using bio-SPME-LC–MS/MS: a robust tool to assess occupational exposure to pesticides

Matrix effects demystified: Strategies for resolving challenges in analytical separations of complex samples

“…Recently, alternative sorbents have been developed to enhance the efficiency of the cleanup process of QuECh-ERS. The development of new advanced sorbent materials involves zirconia-based sorbents, organic polymers, natural polymers such as chitosan, multiwalled carbon nanotubes, graphene, molecularly imprinted polymers, alumina, zirconia-based sorbents, and florisil [83][84][85][86][87]. A major limitation of improving the cleanup step for multiresidue analysis is the potential loss of analytes during this step due to their polarity, molecular weight, and functional group matching with interferences.…”

“…Highly complex matrices, such as food samples, are often challenging when developing DI-SPME techniques because DI of the fiber may cause fouling of the extraction phase, which can lead to MEs, reduced extraction efficiency, and a lifetime of the device [87][88][89]. Thus, dilution of very complex samples before SPME extraction can be a critical step necessary to avoid interference and significant fouling of the extraction phase and to obtain reproducible results.…”

“…plasma) with targeted analytes before analysis on LC-MS. An alternative way to calculate MEs is to compare the analyte response in the desorption solution spiked post-extraction in a complex sample, with a desorption solution spiked post-extraction in ultrapure water and phosphate buffer saline, to evaluate potential interferences from leachates. Absolute ME can then be calculated where 100% indicates no MEs for analyte response, > 100% indicates response enhancement, and < 100% indicates response suppression [87,94]. Olomukoro et al evaluated the performance of the HLB-weak anion exchange/PAN SPME device for extraction of poly-and perfluoro alkyl substances in varied matrices such as seawater, melted snow, and human plasma.…”

“…By contrast, exhaustive sampling methods such as LLE and QuEChERS are less selective extraction techniques, and thus matrix constituents are extracted [59]. To mitigate ME in biofluids, sample preparation techniques such as SPE and QuEChERS have been extensively validated and adopted for biofluid analysis [87]. However, these techniques have drawbacks such as the potential clogging of the SPE cartridge due to the complex matrix present in biofluids.…”

“…However, these techniques have drawbacks such as the potential clogging of the SPE cartridge due to the complex matrix present in biofluids. To overcome these limitations, SPME with biocompatible extraction phases is a promising alternative as it enables the DI of the extraction phase into biofluids whilst bypassing the issue of biofouling caused by matrix constituents [87,90]. In fact, Godage et al demonstrated the effectiveness of biocompatible SPME coatings in mitigating ME versus QuEChERS, for the quantification of pesticides at ultra-trace levels through analysis with LC-MS [87].…”