Solid-Phase Microextraction in Targeted and Nontargeted Analysis: Displacement and Desorption Effects

An aqueous multicomponent mixture containing a wide range of volatility and polarity compounds (log <i>K</i>_ow range 1.26–8.72) was used to clearly define the capabilities and limitations of headspace solid-phase microextraction in quantification of multicomponent complex samples. Commercially available fiber coatings were evaluated by investigating the extraction efficiency and desorption carryover. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry was selected to map out the differences between the coatings. The investigated components were chosen to represent several homologous groups of metabolites most frequently present in complex food and environmental samples, including straight-chain hydrocarbons, primary alcohols, secondary alcohols, 2-ketones, aldehydes, ethyl esters, and terpenes. Particular emphasis was placed on examination of coating saturation and interanalyte displacements. These effects were assessed by evaluating the linear dynamic range obtained for spiked aqueous samples with divinylbenzene/Carboxen/poly­(dimethylsiloxane) fiber. This coating was found to provide the optimum extraction coverage and sensitivity for the widest range of analytes. Displacement investigations were extended to apple homogenate characterized by high chemical diversity. The results indicate that interanalyte displacements are infrequent in the naturally occurring samples considered in this study. When displacements take place, they tend to occur for analytes characterized by small distribution constants, and they can be effectively detected by adding such compounds to the sample and corrected by selecting a shorter extraction time

Effect of Binding Components in Complex Sample Matrices on Recovery in Direct Immersion Solid-Phase Microextraction: Friends or Foe?

The development of matrix compatible coatings for solid-phase microextraction (SPME) has enabled direct extraction of analytes from complex sample matrices. The direct immersion (DI) mode of SPME when utilized in conjunction with such extraction phases facilitates extraction of a wide range of analytes from complex matrices without the incurrence of fouling or coating saturation. In this work, mathematical models and computational simulations were employed to investigate the effect of binding components present in complex samples on the recovery of small molecules varying in logP for extractions carried out using the direct immersion approach. The presented findings corroborate that the studied approach indeed enables the extraction of both polar and nonpolar analytes from complex matrices, provided a suitable sorbent is employed. Further results indicated that, in certain cases, the kinetics of extraction of a given analyte in its free form might be dependent on the desorption kinetics of their bound form from matrix components, which might lower total recoveries of analytes with high affinity for the matrix. However, the binding of analytes to matrix components also enables SPME to extract a balanced quantity of different logP analytes, facilitated by multiphase equilibria, with a single extraction device

Preparation of a Particle-Loaded Membrane for Trace Gas Sampling

A divinylbenzene (DVB) particle-loaded membrane with high extraction capacity was prepared using the bar coating method. The prepared membrane was evaluated in terms of morphology, effect of particle ratio, and membrane size on extraction efficiency, as well as linear calibration curve and limit of detection. The SEM (scanning electron microscope) images showed that the DVB particles were uniformly distributed in the PDMS base, ensuring the repeatability of the membranes. The extraction amount was quantified by gas chromatography–mass spectrometry coupled with a thermal desorption unit. Results showed that the extraction efficiency of the prepared membrane increased about 2 orders of magnitude for benzene sampling as the particle ratio increased from 0% to 30%, and the extraction amount was linearly proportional to the size of the membrane. A comparison with a pure PDMS membrane and DVB/PDMS fiber for outdoor air sampling showed that the extraction efficiency of the DVB/PDMS membrane was significantly enhanced, especially for volatile and polar compounds. The limit of detection was about 0.03 ng/mL for benzene in air, and the linear dynamic range extended to 100 ng/mL. An equilibrium calibration method was proposed for low-level air pollutant sampling using this high capacity membrane, and a displacement effect was not observed. To demonstrate the power of the technique, the developed approach was applied to monitor both spot and time weighted average (TWA) concentrations of benzene in outdoor air. A high spot concentration of benzene was observed in morning and afternoon rush hours, with TWA concentrations of 10.7 ng/L measured over the 11-h monitoring period

Reusable Solid-Phase Microextraction Coating for Direct Immersion Whole-Blood Analysis and Extracted Blood Spot Sampling Coupled with Liquid Chromatography–Tandem Mass Spectrometry and Direct Analysis in Real Time–Tandem Mass Spectrometry

Three different biocompatible polymers were tested and evaluated in order to improve the whole-blood biocompatibility of previously developed C18–polyacrylonitrile (C18–PAN) thin-film solid-phase microextraction (SPME) coating. Among all methods of modification, UV-dried thin PAN-over C18–PAN provided the best results. This coating presented reusable properties and reproducible extraction efficiency for at least 30 direct extractions of diazepam from whole blood [relative standard deviation (RSD) = 12% using external calibration and 4% using isotope dilution calibration]. The amount of absolute recovery for direct immersion analysis and based on the free concentration of diazepam in blood matrix was about 4.8% (desorption efficiency = 98%). The limit of quantitation (LOQ) for the developed solid-phase microextraction liquid chromatography–tandem mass spectrometry (SPME-LC–MS/MS) method for direct whole-blood analysis was 0.5 ng/mL. The optimized modification of the coating was then used for an extracted blood spot (EBS) sampling approach, a new sampling method which is introduced to address the limitations of dried blood spot sampling. EBS was evaluated using LC–MS/MS and direct analysis in real time (DART)–MS/MS, where, for a 5 μL blood spot, LOQs of 0.2 and 1 μg/mL, respectively, were achieved for extraction of diazepam

Sorbent Coated Glass Wool Fabric as a Thin Film Microextraction Device

A new approach for thin film microextraction (TFME) with mixed-phase sorptive coating is presented. Carboxen/polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) TFME samplers were prepared using spin coating and glass wool fabric mesh as substrate. The samplers were easily tailored in size and shape by cutting tools. Good durability and flat-shape stability were observed during extraction, stirring in water, and thermal desorption. The latter characteristic obviates the need for an extra framed holder for rapid TFME and makes the samplers more robust and easier to deploy. The samplers combine the advantages of adsorptive solid-phase microextraction (SPME) and TFME, including one-step solvent-free extraction and preconcentration, direct thermal desorption, and enhanced sensitivity without sacrificing analysis time due to thin film geometry. The analytical performance of these new devices was demonstrated using water samples spiked with N-nitrosamines (NAs) as model compounds. Over an order of magnitude enhancement of extraction efficiencies was obtained for the model compounds compared with the SPME fibers of similar coatings and PDMS thin film membrane. The results of this study indicate that these novel thin film devices are promising for rapid and efficient microextraction of polar analytes in water

Optimization of Fiber Coating Structure Enables Direct Immersion Solid Phase Microextraction and High-Throughput Determination of Complex Samples

This study presents a new approach for improving the structure, and hence the robustness, of the SPME fiber coating applied for gas chromatography (GC) analysis. It involves application of an external layer of poly­(dimethyl siloxane) (PDMS) over the commercial PDMS/divinyl benzene (DVB) extraction phase. The fiber provided extraction capabilities similar to that exhibited by the original PDMS/DVB fiber toward triazole pesticides from water samples. Furthermore, the fiber could be utilized for over 100 extractions in direct contact with a complex food matrix such as whole grape pulp, with no sample pretreatment required. The amount of extracted pesticides from whole grape pulp had RSD values below 20% throughout 130 extraction/desorption/conditioning cycles, which is a dramatic improvement when compared to commercial PDMS/DVB fiber coating applied in food analysis facilitating high-throughput automation

Direct Immersion Solid-Phase Microextraction with Matrix-Compatible Fiber Coating for Multiresidue Pesticide Analysis of Grapes by Gas Chromatography–Time-of-Flight Mass Spectrometry (DI-SPME-GC-ToFMS)

A fast and sensitive direct immersion–solid-phase microextraction–gas chromatography–time-of-flight mass spectrometry (DI-SPME-GC-ToFMS) method for the determination of multiresidue pesticides in grapes employing a PDMS-modified PDMS/DVB coating was developed utilizing multivariate approaches for optimization of the most important factors affecting SPME performance. A comprehensive investigation of appropriate internal standards using a bottom-up approach led to the selection of suitable compounds that adequately covered a range of 40 pesticides pertaining to various classes. The validated method yielded good accuracy, precision, and sensitivity and has been successfully applied to the analysis of commercial samples. With regard to the limitations of the proposed method, the DI-SPME method did not provide a satisfactory performance toward more polar pesticides (e.g., acephate, omethoate, dimethoate) and highly hydrophobic pesticides, such as pyrethroids. Despite the challenges and limitations encountered by this method, the practical aspects of the PDMS-modified coating demonstrated here create new opportunities for SPME applied in food analysis

Headspace versus Direct Immersion Solid Phase Microextraction in Complex Matrixes: Investigation of Analyte Behavior in Multicomponent Mixtures

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, <i>ex vivo</i> and <i>in vivo</i> 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 <i>in vivo</i> applications. These findings shed light into the implementation of <i>in vivo</i> SPME strategies in quantitative metabolomics studies of complex plant-based systems

Development of a Carbon Mesh Supported Thin Film Microextraction Membrane As a Means to Lower the Detection Limits of Benchtop and Portable GC/MS Instrumentation

In this work, a durable and easy to handle thin film microextraction (TFME) device is reported. The membrane is comprised of poly­(divinylbenzene) (DVB) resin particles suspended in a high-density polydimethylsiloxane (PDMS) glue, which is spread onto a carbon fiber mesh. The currently presented membrane was shown to exhibit a substantially lesser amount of siloxane bleed during thermal desorption, while providing a statistically similar extraction efficiency toward a broad spectrum of analytes varying in polarity when compared to an unsupported DVB/PDMS membrane of similar shape and size which was prepared with previously published methods. With the use of hand-portable GC-TMS instrumentation, membranes cut with dimensions 40 mm long by 4.85 mm wide and 40 ± 5 μm thick (per side) were shown to extract 21.2, 19.8, 18.5, 18,4, 26.8, and 23.7 times the amount of 2,4 dichlorophenol, 2,4,6 trichlorophenol, phorate D10, fonofos, chloropyrifos, and parathion, respectively, within 15 min from a 10 ppb aqueous solution as compared to a 65 μm DVB/PDMS solid phase microextraction (SPME) fiber. A portable high volume desorption module prototype was also evaluated and shown to be appropriate for the desorption of analytes with a volatility equal to or lesser than benzene when employed in conjunction with TFME membranes. Indeed, the coupling of these TFME devices to hand-portable gas chromatography toroidial ion trap mass spectrometry (GC-TMS) instrumentation was shown to push detection limits for these pesticides down to the hundreds of ppt levels, nearing that which can be achieved with benchtop instrumentation. Where these membranes can also be coupled to benchtop instrumentation it is reasonable to assume that detection limits could be pushed down even further. As a final proof of the concept, the first ever, entirely on-site TFME-GC-TMS analysis was performed at a construction impacted lake. Results had indicated the presence of contaminants such as toluene, ethylbenzene, xylene, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and tris­(1-chloro-2-propyl)­phosphate, which stood out from other naturally occurring compounds detected

Development of a Biocompatible In-Tube Solid-Phase Microextraction Device: A Sensitive Approach for Direct Analysis of Single Drops of Complex Matrixes

The aim of the current study is to develop a sensitive solid-phase microextraction (SPME) device for direct and rapid analysis of untreated complex matrixes (i.e., single drop of the samples, <i>V</i> ≤ 2 μL). A thin layer of a biocompatible nanostructured polypyrrole (PPy) was electrochemically deposited inside a medical grade spinal needle, minimizing the matrix effect. Microsampling was facilitated by loading the sample inside the in-tube SPME device (withdraw of sample via plunger), where extraction was performed under static conditions. Two strategies were used for analysis of the compounds including offline desorption and running the extract to the liquid chromatograph–tandem mass spectrometer (LC–MS/MS) or direct coupling of the in-tube SPME device to the MS. Given the high surface-area-to-volume ratio of the coating, a short equilibrium time (i.e., <i>t</i> ≤ 2 min) was obtained. The whole analytical procedure (i.e., extraction, rinsing, desorption, and LC–MS/MS analysis) was performed within 10 min by LC–MS/MS, and 3 min by in-tube–MS/MS. Possible matrix effects for the prepared device were evaluated in whole blood samples at three levels of concentration, and encouraging results were achieved in the range of 83–120%. The obtained results, no matrix effect, are attributed to the smooth surface and small pore size of the biocompatible PPy coating, which was prepared in the presence of cetyltrimethylammonium bromide (CTAB) surfactant. The in-tube SPME device was shown to be very sensitive, with high total recoveries obtained for all compounds in phosphate-buffered saline (PBS) and urine samples owing to the large volume and capacity of the coating. Subnanogram per milliliter levels of detection were achieved for urine samples, and low nanogram per milliliter levels were found in whole blood samples for all studied compounds with a high protein binding index. Rapid analysis of whole blood samples was achieved without need of any pretreatment or manipulation of sample, revealing the developed in-tube SPME device as an ideal probe for forensic application, drug monitoring, and point-of care-diagnosis