Fast Quantitation of Target Analytes in Small Volumes of Complex Samples by Matrix‐Compatible Solid‐Phase Microextraction Devices

Abstract

Abstract:The current study reports the development of solid phase microextraction (SPME) devices designed to perform fast extraction/enrichment of target analytes present in small volumes of complex matrices (i.e. V ≤ 10 μL). Micro-sampling was performed with the use of etched metal tips coated with a thin layer of biocompatible nano-structured polypyrrole (PPy (tip diameter ≤ 10 µm), or by using coated blade spray (CBS) devices with an extraction phase thickness ≤ 10 µm, facilitating rapid extraction. These devices can be coupled either to liquid chromatography (LC), or directly to mass spectrometry (MS) via dedicated interfaces. The reported results demonstrated that the whole analytical procedure can be carried out within a few minutes (tanalysis ≤ 7 min) with high sensitivity and quantitation precision, and can be used to sample from various biological matrices such as blood, plasma, and urine, towards the analysis of therapeutics, pesticides, and controlled substances as model analytes. As a proof-of-concept, the analysis and quantification of target compounds present in single cells of Allium cepa L was demonstrated.

Quantitative analysis of biofluid spots by coated blade spray mass spectrometry, a new approach to rapid screening

“…1 ) 18 , 19 . Unlike classical microsampling devices or PS, CBS functions by extracting/enriching analytes of interest from a given sample, rather than through a collection of dried sample spots 20 . Certainly, extracting analytes on a selective adsorbent—rather than collecting analyte-matrix on a non-selective substrate—is more advantageous because it safeguards against the presence of other matrix components, such as enzymes, that can facilitate the conversion/degradation of the target compound.…”

“…Contrary to general assumptions 21 – 23 , CBS has been shown to handle a broad range of sample volumes ( i.e . µL to L) 17 , 20 , 24 . Herein, having accepted the challenge of employing CBS towards analysis of minimum amounts of sample (≤10 µL), we present a thorough validation of the quantitation capabilities of CBS for analysis of broad range of analytes in small volumes of biofluids.…”

Development of a solid‐phase microextraction LC–MS/MS method for determination of oxidative stress biomarkers in biofluids

“…Furthermore, SPME can take any shape based on the demands of the study. Up to date, it has been prepared in fiber [31], micro‐tip [32], arrow [33], coated mesh [34], coated blades [35, 36], flexible self‐supported membranes [37], or membranes on support [38]. Also, it has been utilized for numerous applications where standard sample preparation approaches cannot be used [39, 40].…”

In-capillary microextraction for direct mass spectrometry analysis of biological samples

“…Sample processing can be minimized for analysis of complex samples using an effective ambient ionization method[2]. Some successful applications have also been demonstrated by Laser ablation electrospray ionization,[10] electrochemical electrospray ionization[11], coated blade spray[12,13], electrospray-assisted laser desorption ionization[14], paper spray[15] and extraction spray[16]. These achievements suggest a promising direction in technical development for direct MS analysis of complex samples.…”