Academic Journal
Novel Strongly Basic Molecularly Imprinted Solid-Phase Extraction Sorbent for Simultaneous Determination of Catecholamines and Their Metabolites in Urine.
| Τίτλος: | Novel Strongly Basic Molecularly Imprinted Solid-Phase Extraction Sorbent for Simultaneous Determination of Catecholamines and Their Metabolites in Urine. |
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| Συγγραφείς: | Šilaks A; Faculty of Medicine and Life Sciences, University of Latvia, Riga, Latvia., Podjava A; Faculty of Medicine and Life Sciences, University of Latvia, Riga, Latvia., Bernāte L; Faculty of Medicine and Life Sciences, University of Latvia, Riga, Latvia., Grebnevs V; Faculty of Medicine and Life Sciences, University of Latvia, Riga, Latvia.; Faculty of Chemistry, Silesian University of Technology, Gliwice, Poland., Maciej A; Faculty of Chemistry, Silesian University of Technology, Gliwice, Poland. |
| Πηγή: | Journal of separation science [J Sep Sci] 2026 Jun; Vol. 49 (6), pp. e70467. |
| Τύπος έκδοσης: | Journal Article |
| Γλώσσα: | English |
| Στοιχεία περιοδικού: | Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 101088554 Publication Model: Print Cited Medium: Internet ISSN: 1615-9314 (Electronic) Linking ISSN: 16159306 NLM ISO Abbreviation: J Sep Sci Subsets: MEDLINE |
| Imprint Name(s): | Original Publication: Weinheim, Germany : Wiley-VCH, c2001- |
| Ιατρικοί όροι (MeSH): | Solid Phase Extraction*/instrumentation , Solid Phase Extraction*/methods , Catecholamines*/urine , Catecholamines*/metabolism , Catecholamines*/isolation & purification , Molecularly Imprinted Polymers*/chemistry , Molecularly Imprinted Polymers*/chemical synthesis , Molecular Imprinting*, Polymers/chemistry ; Polymers/chemical synthesis ; Humans ; Adsorption ; Chromatography, High Pressure Liquid |
| Περίληψη: | Catecholamines are important hormones and neuromediators in the human body. Simultaneous determination of both catecholamines and catecholamine metabolites in bodily fluids can help accurately diagnose dangerous health conditions like adrenal tumors. However, the biggest obstacle is the selective separation of these compounds from the biological matrix. In this work, we propose a novel, dual-recognition, non-covalent molecularly-imprinted polymer that utilizes strong anion exchange as the source of sorbent-analyte interaction. (4-Vinylbenzyl)trimethylammonium-homovanillyl alcohol anion salt and (4-vinylbenzyl)trimethylammonium-homoveratric acid anion salt served as template/functional monomer complexes for catecholamines and acidic metabolites, respectively. The sorbent was synthesized using precipitation polymerization and studied with batch adsorption experiments, scanning electron microscopy, Fourier-transform infrared spectroscopy, and Brunauer-Emmett-Teller surface area and pore size analysis. The polymer was loaded into cartridges and tested with acidified urine samples. The analytes are deprotonated and adsorbed via sorbent's tetraalkylammonium moiety in hydroxide form, which also neutralizes excess acid, removing the need for pH readjustment (which is often necessary for urine analysis). The imprinted sorbent can also be reused at least four times without performance deterioration. Norepinephrine, epinephrine, dopamine, normetanephrine, metanephrine, vanillylmandelic acid, and homovanillic acid were separated and analyzed in a single run using molecularly imprinted solid-phase extraction combined with liquid chromatography-tandem mass spectrometry (MISPE-LC-MS/MS), with recoveries ranging from 69% (epinephrine) to 97% (homovanillic acid). Method's limits of detection, limits of quantitation, linearity, repeatability, trueness, and intermediate precision were evaluated. Limits of quantitation ranged from 0.7 to 6.5 µg/L (for catecholamines and metanephrines) and from 0.12 to 0.2 mg/L (for acidic metabolites). Compared to commercially available weak-cation exchange and hydrophilic-lipophilic balance cartridges, the imprinted sorbent produced stronger catecholamine signals with minimal volume of urine (25 µL). This study successfully demonstrated molecularly imprinted solid-phase extraction workflow for simultaneous separation and quantitation of urinary catecholamines and their basic and acidic metabolites, proving its compatibility with bioanalysis. (© 2026 The Author(s). Journal of Separation Science published by Wiley‐VCH GmbH.) |
| References: | E. C. Y. Chan and P. C. L. Ho, “Chromatographic Measurements of Catecholamines and Metanephrines,” in Chromatographic Methods in Clinical Chemistry and Toxicology (Wiley, 2007), 101–126, https://doi.org/10.1002/9780470023129. C. Lv, Q. Li, X. Liu, et al., “Determination of Catecholamines and Their Metabolites in Rat Urine by Ultra‐Performance Liquid Chromatography–Tandem Mass Spectrometry for the Study of Identifying Potential Markers for Alzheimer's Disease,” Journal of Mass Spectrometry 50 (2015): 354–363, https://doi.org/10.1002/jms.3536. N. Shi, X. Bu, M. Zhang, et al., “Current Sample Preparation Methodologies for Determination of Catecholamines and Their Metabolites,” Molecules 27 (2022): 2702, https://doi.org/10.3390/molecules27092702. A. Němečková‐Makrlíková, F. Matysik, T. Navrátil, J. Barek, and V. Vyskočil, “Determination of Three Tumor Biomarkers (Homovanillic Acid, Vanillylmandelic Acid, and 5‐Hydroxyindole‐3‐Acetic Acid) Using Flow Injection Analysis With Amperometric Detection,” Electroanalysis 31 (2019): 303–308, https://doi.org/10.1002/elan.201800540. I. R. N. Verly, A. B. P. van Kuilenburg, N. G. G. M. Abeling, et al., “Catecholamines Profiles at Diagnosis: Increased Diagnostic Sensitivity and Correlation With Biological and Clinical Features in Neuroblastoma Patients,” European Journal of Cancer 72 (2017): 235–243, https://doi.org/10.1016/j.ejca.2016.12.002. E. Rezkallah, A. Elsaify, R. Hanna, and W. Elsaify, “Correlation Between the Size of Pheochromocytoma and the Level of Metanephrines,” Endocrine Regulations 57 (2023): 183–190, https://doi.org/10.2478/enr‐2023‐0022. G. Eisenhofer, S. Brown, M. Peitzsch, et al., “Levodopa Therapy in Parkinson's Disease: Influence on Liquid Chromatographic Tandem Mass Spectrometric‐Based Measurements of Plasma and Urinary Normetanephrine, Metanephrine and Methoxytyramine,” Annals of Clinical Biochemistry 51 (2014): 38–46, https://doi.org/10.1177/0004563213487894. T. Afroz, R. Ferdous, and M. A. Rahman, “The Safety and Efficacy of Labetalol vs. Methyldopa in Treatment of Pregnancy Induced Hypertension,” International Journal of Gynaecology and Obstetrics Sciences 6 (2024): 38–42, https://doi.org/10.33545/26649004.2024.v6.i1a.28. M. Peitzsch, J. E. Adaway, and G. Eisenhofer, “Interference From 3‐O‐Methyldopa With Ultra–High Performance LC‐MS/MS Measurements of Plasma Metanephrines: Chromatographic Separation Remains Important,” Clinical Chemistry 61 (2015): 993–996, https://doi.org/10.1373/clinchem.2015.239962. M. L. Bergmann and A. Schmedes, “Highly Sensitive LC‐MS/MS Analysis of Catecholamines in Plasma,” Clinical Biochemistry 82 (2020): 51–57, https://doi.org/10.1016/j.clinbiochem.2020.03.006. B. M. Fonseca, M. Rodrigues, A. C. Cristóvão, et al., “Determination of Catecholamines and Endogenous Related Compounds in Rat Brain Tissue Exploring Their Native Fluorescence and Liquid Chromatography,” Journal of Chromatography B 1049–1050 (2017): 51–59, https://doi.org/10.1016/j.jchromb.2017.02.028. J. Jiang, M. Zhang, Z. Xu, et al., “Recent Advances in Catecholamines Analytical Detection Methods and Their Pretreatment Technologies,” Critical Reviews in Analytical Chemistry 55, no. 1 (2025): 1–20, https://doi.org/10.1080/10408347.2023.2258982. S. M. M. Morsi, M. M. Morsi, and M. E. Abd El‐Aziz, “Advances in Molecularly Imprinted Synthetic Polymers: From Structural Principles to Functional Technologies,” European Polymer Journal 245 (2026): 114542, https://doi.org/10.1016/j.eurpolymj.2026.114542. M. Sobiech and P. Luliński, “Molecularly Imprinted Solid Phase Extraction—Recent Strategies, Future Prospects and Forthcoming Challenges in Complex Sample Pretreatment Process,” TrAC Trends in Analytical Chemistry 174 (2025): 117695, https://doi.org/10.1016/j.trac.2024.117695. M. Bouri, M. J. Lerma‐García, R. Salghi, M. Zougagh, and A. Ríos, “Selective Extraction and Determination of Catecholamines in Urine Samples by Using a Dopamine Magnetic Molecularly Imprinted Polymer and Capillary Electrophoresis,” Talanta 99 (2012): 897–903, https://doi.org/10.1016/j.talanta.2012.07.053. S. Deng, Y. Wang, X. Huang, et al., “Automated Online Solid‐Phase Extraction‐Tandem Mass Spectrometry Detection for Simultaneous Analysis of Acidic and Alkaline Catecholamines and Their Metabolites in Human Urine,” Journal of Pharmaceutical and Biomedical Analysis 248 (2024): 116292, https://doi.org/10.1016/j.jpba.2024.116292. Q. Li, J. Lin, C. Tang, et al., “Simultaneous Quantification of Catecholamine and Their Metabolites in Urine via Mixed‐Mode Magnetic Bead‐Based Extraction Coupled With ID‐LC‐MS/MS: A Robust Tool for Diagnosing Catecholamine‐Secreting Tumors,” Journal of Chromatography A 1764 (2025): 466468, https://doi.org/10.1016/j.chroma.2025.466468. A. Podjava and A. Šilaks, “Synthesis and Sorptive Properties of Molecularly Imprinted Polymer for Simultaneous Isolation of Catecholamines and Their Metabolites From Biological Fluids,” Journal of Liquid Chromatography & Related Technologies 44 (2021): 181–188, https://doi.org/10.1080/10826076.2021.1874980. A. Podjava and A. Šilaks, “Study of Chromatographic Properties of Catecholamines and Their Acidic Metabolites Using Novel Molecularly Imprinted Polymers as Stationary Phases,” Key Engineering Materials 903 (2021): 15–21, https://doi.org/10.4028/www.scientific.net/KEM.903.15. S. Vikingsson, T. Rautio, J. Wallgren, et al., “LC‐QTOF‐MS Identification of Major Urinary Cyclopropylfentanyl Metabolites Using Synthesized Standards,” Journal of Analytical Toxicology 43 (2019): 607–614, https://doi.org/10.1093/jat/bkz057. S. Cardinal, J. Azelmat, D. Grenier, and N. Voyer, “Anti‐Inflammatory Properties of Quebecol and Its Derivatives,” Bioorganic & Medicinal Chemistry Letters 26 (2016): 440–444, https://doi.org/10.1016/j.bmcl.2015.11.096. A. Zagorodni, Ion Exchange Materials: Properties and Applications (Elsevier, 2007), 87. R. Umpleby, S. Baxter, A. Rampey, G. Rushton, Y. Chen, and K. Shimizu, “Characterization of the Heterogeneous Binding Site Affinity Distributions in Molecularly Imprinted Polymers,” Journal of Chromatography B 804 (2004): 141–149, https://doi.org/10.1016/j.jchromb.2004.01.064. Y. Shen, L. Cheng, Q. Guan, H. Li, J. Lu, and X. Wang, “Development and Validation of a Liquid Chromatography Tandem Mass Spectrometry Method for the Measurement of Urinary Catecholamines in Diagnosis of Pheochromocytoma,” Biomedical Chromatography 31, no. 11 (2017): e4003, https://doi.org/10.1002/bmc.4003. T. Hu, Q. Zhao, M. Wang, K. Zhou, Z. Xia, and Y. Huang, “Improved Selectivity of Molecularly Imprinted Polymers Based on the Synergistic Action of Hydrogen Bond and Electrostatic Interaction,” Journal of Molecular Recognition 36, no. 7 (2023): e3024, https://doi.org/10.1002/jmr.3024. R. F. Jameson, G. Hunter, and T. Kiss, “A 1H Nuclear Magnetic Resonance Study of the Deprotonation of L‐Dopa and Adrenaline,” Journal of the Chemical Society Perkin Transactions 2 (1980): 1105, https://doi.org/10.1039/p29800001105. F. Mack and H. Bönisch, “Dissociation Constants and Lipophilicity of Catecholamines and Related Compounds,” Naunyn‐Schmiedebergs Archives of Pharmacology 310 (1979): 1–9, https://doi.org/10.1007/BF00499868. E. W. Grant and W. W. Hilty, “The Separation of Morphine From Codeine by Means of Ion Exchange,” Journal of the American Pharmaceutical Association 42 (1953): 150–152, https://doi.org/10.1002/jps.3030420309. S. Chu and R. J. Letcher, “Halogenated Phenolic Compound Determination in Plasma and Serum by Solid Phase Extraction, Dansylation Derivatization and Liquid Chromatography–Positive Electrospray Ionization–Tandem Quadrupole Mass Spectrometry,” Journal of Chromatography A 1320 (2013): 111–117, https://doi.org/10.1016/j.chroma.2013.10.068. D. A. Spivak, “Optimization, Evaluation, and Characterization of Molecularly Imprinted Polymers,” Advanced Drug Delivery Reviews 57 (2005): 1779–1794, https://doi.org/10.1016/j.addr.2005.07.012, Erratum in Adv. Drug Deliv. Rev. 2006, 58, 116. J. Bicker, A. Fortuna, G. Alves, and A. Falcão, “Liquid Chromatographic Methods for the Quantification of Catecholamines and Their Metabolites in Several Biological Samples—A Review,” Analytica Chimica Acta 768 (2013): 12–34, https://doi.org/10.1016/j.aca.2012.12.030. A. M. Maes, T. P. Pandey, M. A. Vandiver, et al., “Preparation and Characterization of an Alkaline Anion Exchange Membrane From Chlorinated Poly(Propylene) Aminated With Branched Poly(Ethyleneimine),” Electrochimica Acta 110 (2013): 260–266, https://doi.org/10.1016/j.electacta.2013.04.033. K. Farrington, E. Magner, and F. Regan, “Predicting the Performance of Molecularly Imprinted Polymers: Selective Extraction of Caffeine by Molecularly Imprinted Solid Phase Extraction,” Analytica Chimica Acta 556, no. 1 (2006): 60–68, https://doi.org/10.1016/j.aca.2006.02.057. M. Khalikova, K. Faistauerová, and M. Lísa, “Current Trends in Sample Preparation for Liquid Chromatography—Mass Spectrometry Analysis of Catecholamines and Their Metabolites in Biological Samples,” Talanta 298 (2026): 128837, https://doi.org/10.1016/j.talanta.2025.128837. S. Rufolo, A. C. Balsamo, F. Parisi, A. Coglianese, B. Charlier, and V. Izzo, “Catecholamines and Metanephrines: Quantification in the Diagnosis of Pheochromocytoma and Paraganglioma, Considerations and Critical Issues,” Diagnostics 16, no. 9 (2026): 1263, https://doi.org/10.3390/diagnostics16091263. J. G. Boyle, D. F. Davidson, C. G. Perry, and J. M. C. Connell, “Comparison of Diagnostic Accuracy of Urinary Free Metanephrines, Vanillyl Mandelic Acid, and Catecholamines and Plasma Catecholamines for Diagnosis of Pheochromocytoma,” Journal of Clinical Endocrinology and Metabolism 92, no. 12 (2007): 4602–4608, https://doi.org/10.1210/jc.2005‐2668. |
| Grant Information: | lzp-2022/1-0141 Fundamental and Applied Research Project (Latvian Scientific Council) |
| Contributed Indexing: | Keywords: catecholamines; molecularly‐imprinted polymers; non‐covalent imprinting; solid‐phase extraction; strong anion exchange |
| Substance Nomenclature: | 0 (Catecholamines) 0 (Molecularly Imprinted Polymers) 0 (Polymers) |
| Entry Date(s): | Date Created: 20260615 Date Completed: 20260615 Latest Revision: 20260726 |
| Update Code: | 20260726 |
| PubMed Central ID: | PMC13266282 |
| DOI: | 10.1002/jssc.70467 |
| PMID: | 42290105 |
| Βάση Δεδομένων: | MEDLINE |
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