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

Alam, Md. Nazmul; Pawliszyn, Janusz

doi:10.1021/acs.analchem.7b05436

Cited by 39 publications

(22 citation statements)

References 23 publications

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“…A theoretical approach based on Langmuir's theory for the extraction kinetics of solid coating SPME has been previously addressed in the literature. 28,34 In brief, the amount of extract on the solid coating at equilibrium cs eq (mol•m −2 ) is given by…”

Section: ■ Theoretical Considerationsmentioning

confidence: 99%

“…26 In addition to the use of experimental techniques, mathematical modelling has been demonstrated as an excellent tool to determine the kinetics of SPME extraction in the presence of a binding matrix, as it allows for better predictions of results while minimizing the number of experiments that must be carried out during method development and routine analysis. 17,27,28 Alam et al first demonstrated the effects of a binding matrix on the extraction kinetics of SPME liquid coatings via development of a 2D model in COMSOL Multiphysics. 17 Gorecki et al and Zhou et al, in turn, demonstrated the extraction kinetics of solid coatings with the use of Langmuir's isotherms, which assumes isotropy of the fiber surface.…”

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confidence: 99%

“…26 In addition to the use of experimental techniques, mathematical modeling has been demonstrated as an excellent tool to determine the kinetics of SPME extraction in the presence of a binding matrix, as it allows for better predictions of results while minimizing the number of experiments that must be carried out during method development and routine analysis. 17,27,28 Since the site of action of DOX is intracellular and it enters into the cell through passive diffusion like other small molecules, the drug has been commonly administered intravenously (IV). 31,32 Pharmacokinetic studies have shown that DOX has a plasma half-life of 3−5 min, and a tissue halflife of 24−36 h. This indicates rapid uptake of DOX by tissue matrix.…”

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confidence: 99%

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Measurement of Free Drug Concentration from Biological Tissue by Solid-Phase Microextraction: In Silico and Experimental Study

et al. 2019

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In this article, the use of an SPME technique is reported for the first time for direct measurement of free drug concentration in solid tissue. In our investigations, we considered doxorubicin (DOX) spiked in homogenized tissue matrix at transient and equilibrium extraction conditions, with subsequent assessment of obtained experimental results by an in-silico approach using mathematical models developed in COMSOL Multyphysics. In-silico studies were performed based on transported diluted species (tds) and reaction engineering (re) modules from COMSOL Multiphysics, using the same conditions as those used to attain experimental results. To determine the apparent binding affinity of DOX to the tissue matrix which contains multiple binding species, the experimentally determined binding affinity of DOX with human serum albumin (HSA) was considered to simplify the mathematical calculations. Here, the value of the binding affinity was considered for single binding site and adjusted by fitting the experimental results with the mathematical model. Bovine lung tissue homogenate was selected as a surrogate matrix, and a biocompatible C-8 commercial SPME fiber was used for extraction of DOX. In total, four mathematical models were herein developed to describe the mass transfer kinetics of solid coatings: in agar gel at static conditions, in PBS solution with agitated conditions, extraction in PBS solution in the presence of an HSA binding matrix, and static extraction in homogenized lung tissue. For all conditions, simulated results were in good agreement with experimental results. The developed mathematical model allows for measurements of free drug concentrations inside tissue matrix, and facilitates calculations of local depletion of DOX by a solid SPME coating. Results of the investigations indicate that local depletion of the free form of DOX, even at the kinetic stage, is negligible for tissue extraction, as the release of the heavily bound analyte (over 99% binding to tissue matrix) is very rapid, thus easily compensating for the loss of the drug to the SPME coating. This indicates that the dissociation rate constant of DOX from lung tissue components is very rapid; therefore, the mass transfer of drug to the fiber coating via free from is very efficient. Our results also indicate that thin coating SPME fibers provide a good way to measure drug distribution after dosing, as extractions via thin coating SPME fibers do not affect the free concentration of the drug, which is responsible for drug distribution in tissue.

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Section: ■ Theoretical Considerationsmentioning

confidence: 99%

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confidence: 99%

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Measurement of Free Drug Concentration from Biological Tissue by Solid-Phase Microextraction: In Silico and Experimental Study

et al. 2019

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“…These molecules, having a moderate to high affinity constant towards the extraction phase, usually take several hours to reach equilibrium. 32 Therefore, in this section, the profiling of phosphopeptides from beta casein is used as a proof of concept. Beta casein is phosphorylated at five different serine residues: S-15, S-17, S-18, S-19, and S-36.…”

Section: Figurementioning

confidence: 99%

Direct Coupling of Dispersive Extractions with Magnetic Particles to Mass Spectrometry via Microfluidic Open Interface

et al. 2019

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Microextraction coupled to MS has great potential in analytical chemistry laboratories operating in a variety of fields. Indeed, microextraction methods directly coupled to MS can be of large value given that they can provide not only analyte extraction and enrichment, but also effective sample cleanup. In recent years, the practicality in handling, high active surface area, versatility, and environmentally friendly features of magnetic dispersive microextraction technologies have contributed to an explosion in the number of methods and technologies reported in the literature for a wide range of applications. However, to the best of our knowledge, no technology to date has been capable of efficiently merging these two rising concepts in a simple and integrated analytical workflow. In this context, the microfluidic open interface is presented for the direct coupling of dispersive magnetic extraction to mass spectrometry. This technology operates under the concept of a flow-isolated desorption volume, which generates a stagnant droplet open to ambient while continuously feeding with solvent the ionization source by means of the self-aspiration process intrinsic of the ESI interface. To improve the efficiency of the final analytical workflow, a novel dispersive magnetic micro-and nanoparticle extraction protocol for biofluid droplets was developed. The final methodology entailed the dispersion of a small amount of magnetic particles (20-70 µg) in a droplet of biofluid (≤ 40 µL) for extraction, followed by a particle collection step using a home-made 3D-printed holder containing an embedded rare-earth magnet. In the final step, the holder is set on top of the MOI for desorption in the isolated droplet. By switching the valve, the desorbed analytes are transferred to the ESI source in less than 5 sec. As proof of concept, the completely new setup was applied to the determination of prohibited substances from PBS and human urine using Fe2O3 magnetic nanoparticles (50 nm) functionalized with C18. The LOQs obtained were in the low-ppb range in all cases, and acceptable precision (≤20%) and accuracy (80-120%) were attained. Also, taking advantage of the fast extraction kinetics provided by the radial diffusion associated with small particles, the methodology was employed for the selective extraction of phosphopeptides from 40 µL of tryptic β-casein digest using 70 µg of magnetic Ti-IMAC microparticles. To conclude, the technology and methodology herein presented provided excellent capabilities comparable to other SPME-MS approaches while dramatically minimizing the amount of sample and sorbent required per analysis, as well as affording significantly fast extraction times due to the enhanced kinetics of extraction.

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“…It is based on the sorption of analytes directly from the sample in one-step extraction and preconcentration of analytes [18,20]. The SPME has demonstrated its simplicity, usefulness, selectivity, and efficiency in the analysis of a broad range of compounds in several matrixes without requiring sample pretreatment [21].…”

Section: Introductionmentioning

confidence: 99%

Occurrence of Selected Known or Suspected Endocrine-Disrupting Pesticides in Portuguese Surface Waters Using SPME-GC-IT/MS

et al. 2021

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A multiresidue analytical methodology based on a solid-phase microextraction (SPME), followed by gas chromatography-ion trap mass spectrometry (GC–IT/MS), has been developed for trace analysis of 20 known or suspected endocrine-disrupting pesticides. The SPME conditions are optimized considering several key parameters to obtain the maximum sensitivity. After the optimization, the method validation is performed, and the limits of detection (ranged from 2–150 ng/L) and the coefficient of determination (above 0.990) of studied compounds are determined for all the analytes. A robust sampling of twenty sampling points of surface water samples from the north and center of Portugal is performed, and the validated methodology is applied. In total, 20 compounds from four chemical families (13 organochlorine, 1 organophosphorus, 2 dicarboximide, and 4 pyrethroids) are studied, and the pesticides most frequently detected are eight organochlorine pesticides (α-, β-HCHs, lindane, HCB, o,p′-DDT, p,p′-DDE, p,p′-DDD, α-endosulfan), cypermethrin, and vinclozolin.

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

Cited by 39 publications

References 23 publications

Measurement of Free Drug Concentration from Biological Tissue by Solid-Phase Microextraction: In Silico and Experimental Study

Measurement of Free Drug Concentration from Biological Tissue by Solid-Phase Microextraction: In Silico and Experimental Study

Direct Coupling of Dispersive Extractions with Magnetic Particles to Mass Spectrometry via Microfluidic Open Interface

Occurrence of Selected Known or Suspected Endocrine-Disrupting Pesticides in Portuguese Surface Waters Using SPME-GC-IT/MS

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