Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties

Solid-phase microextraction (SPME) has evolved significantly since its inception, yet challenges remain in developing coatings fully compatible with LC-MS that combine broad polarity coverage with biocompatibility for complex matrices. This study evaluates mixed-mode C18-SCX (strong cation exchange)...

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Main Authors: Marcos Tascon, Ezel Boyaci, Nathaly Reyes-Garcés, Janusz Pawliszyn
Format: Article
Language:English
Published: Elsevier 2025-08-01
Series:Advances in Sample Preparation
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Online Access:http://www.sciencedirect.com/science/article/pii/S2772582025000488
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author Marcos Tascon
Ezel Boyaci
Nathaly Reyes-Garcés
Janusz Pawliszyn
author_facet Marcos Tascon
Ezel Boyaci
Nathaly Reyes-Garcés
Janusz Pawliszyn
author_sort Marcos Tascon
collection DOAJ
description Solid-phase microextraction (SPME) has evolved significantly since its inception, yet challenges remain in developing coatings fully compatible with LC-MS that combine broad polarity coverage with biocompatibility for complex matrices. This study evaluates mixed-mode C18-SCX (strong cation exchange) SPME fibers designed to extract analytes of a wide range of physicochemical properties, addressing limitations in current methodologies. The fibers were tested for extraction efficiency, reproducibility, and matrix compatibility using a group of model compounds with different physicochemical properties, namely, codeine (logP=1.19), carbamazepine (logP=2.45), diazepam (logP=2.82), and propranolol (logP=3.47). Furthermore, the biocompatibility was tested in diverse matrices, such as PBS, blood, plasma, urine, and grape juice.Results demonstrated exceptional inter-fiber reproducibility (RSD ≤ 15 %, n = 96 fibers) and robust performance in biomatrices, with relative matrix effects primarily governed by analyte binding affinities to matrix macromolecules rather than coating fouling. Absolute matrix effects were negligible (93–111 %), underscoring the fibers’ ability to deliver clean extracts for LC-MS analysis. Fiber reusability was validated over three consecutive extractions (RSD ≤ 10 %), and morphological integrity was preserved post-extraction, even in challenging matrices like whole blood. This work represents the versatility of mixed-mode SPME fibers for high-throughput bioanalysis, offering a significant advancement for in vivo and in vitro targeted and untargeted applications.
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spelling doaj-art-28f497dbf74f4beb8b416ffbbfc3a0e12025-08-20T02:44:49ZengElsevierAdvances in Sample Preparation2772-58202025-08-011510019510.1016/j.sampre.2025.100195Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical propertiesMarcos Tascon0Ezel Boyaci1Nathaly Reyes-Garcés2Janusz Pawliszyn3Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada; Instituto de Investigación e Ingeniería Ambiental (IIIA-CONICET), Universidad Nacional de San Martín (UNSAM), San Martín, 1650, Buenos Aires, Argentina; Centro de Estudios sobre Patrimonios y Ambiente (Escuela de Hábitat y Sostenibilidad -Escuela de Arte y Patrimonio), Universidad Nacional de San Martín (UNSAM), San Martín, 1650, Buenos Aires, ArgentinaDepartment of Chemistry, University of Waterloo, Waterloo, Ontario, Canada; Department of Chemistry, Middle East Technical University, Ankara, 06800, TürkiyeDepartment of Chemistry, University of Waterloo, Waterloo, Ontario, Canada; Present address: Integrated Bioanalysis, Clinical Pharmacology and Safety Sciences, R&D, AstraZeneca, Gaithersburg, MD, USADepartment of Chemistry, University of Waterloo, Waterloo, Ontario, Canada; Corresponding author.Solid-phase microextraction (SPME) has evolved significantly since its inception, yet challenges remain in developing coatings fully compatible with LC-MS that combine broad polarity coverage with biocompatibility for complex matrices. This study evaluates mixed-mode C18-SCX (strong cation exchange) SPME fibers designed to extract analytes of a wide range of physicochemical properties, addressing limitations in current methodologies. The fibers were tested for extraction efficiency, reproducibility, and matrix compatibility using a group of model compounds with different physicochemical properties, namely, codeine (logP=1.19), carbamazepine (logP=2.45), diazepam (logP=2.82), and propranolol (logP=3.47). Furthermore, the biocompatibility was tested in diverse matrices, such as PBS, blood, plasma, urine, and grape juice.Results demonstrated exceptional inter-fiber reproducibility (RSD ≤ 15 %, n = 96 fibers) and robust performance in biomatrices, with relative matrix effects primarily governed by analyte binding affinities to matrix macromolecules rather than coating fouling. Absolute matrix effects were negligible (93–111 %), underscoring the fibers’ ability to deliver clean extracts for LC-MS analysis. Fiber reusability was validated over three consecutive extractions (RSD ≤ 10 %), and morphological integrity was preserved post-extraction, even in challenging matrices like whole blood. This work represents the versatility of mixed-mode SPME fibers for high-throughput bioanalysis, offering a significant advancement for in vivo and in vitro targeted and untargeted applications.http://www.sciencedirect.com/science/article/pii/S2772582025000488BioanalysisLiquid chromatographyMass spectrometryMixed-mode fibersSPME LC-tips
spellingShingle Marcos Tascon
Ezel Boyaci
Nathaly Reyes-Garcés
Janusz Pawliszyn
Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties
Advances in Sample Preparation
Bioanalysis
Liquid chromatography
Mass spectrometry
Mixed-mode fibers
SPME LC-tips
title Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties
title_full Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties
title_fullStr Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties
title_full_unstemmed Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties
title_short Evaluation of performance and matrix compatibility of mixed mode C18-SCX SPME fibers for compounds with different physicochemical properties
title_sort evaluation of performance and matrix compatibility of mixed mode c18 scx spme fibers for compounds with different physicochemical properties
topic Bioanalysis
Liquid chromatography
Mass spectrometry
Mixed-mode fibers
SPME LC-tips
url http://www.sciencedirect.com/science/article/pii/S2772582025000488
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AT nathalyreyesgarces evaluationofperformanceandmatrixcompatibilityofmixedmodec18scxspmefibersforcompoundswithdifferentphysicochemicalproperties
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