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Glöckler, D.* ; Harir, M. ; Schmitt-Kopplin, P. ; Elsner, M.* ; Bakkour, R.*

Selectivity of β-cyclodextrin polymer toward aquatic contaminants: Insights from ultrahigh-resolution mass spectrometry of dissolved organic matter.

Anal. Chem. 95, 15505-15513 (2023)

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Open Access Green as soon as Postprint is submitted to ZB.

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Selectivity in solid-phase extraction (SPE) materials has become increasingly important for analyte enrichment in sensitive analytical workflows to alleviate detrimental matrix effects. Molecular-level investigation of matrix constituents, which are preferentially extracted or excluded, can provide the analytical chemist with valuable information to learn about their control on sorbent selectivity. In this work, we employ nontargeted Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to elucidate the molecular chemodiversity of freshwater-derived dissolved organic matter (DOM) extracted by the selective model sorbent β-cyclodextrin polymer (β-CDP) in comparison to conventional, universal SPE sorbents (i.e., Oasis HLB, Supel-Select HLB, and LiChrolut EN). Statistical analysis of MS data corroborated the highly selective nature of β-CDP by revealing the extracted DOM spectra that are most dissimilar to original compositions. We found that its selectivity was characterized by pronounced discrimination against highly oxygenated and unsaturated DOM compounds, which were associated with the classes of lignin-like, tannin-like, and carboxylic-rich alicyclic molecules. In contrast, conventional sorbents excluded less highly oxygenated compounds and showed a more universal extraction behavior for a wide range of DOM compositional space. We lay these findings in a larger context that aids the analyst in obtaining an a priori estimate of sorbent selectivity toward any target analyte of interest serving thereby an optimization of sample preparation. This study highlights the great value of nontargeted ultrahigh-resolution MS for better understanding of targeted analytics and provides new insights into the selective sorption behavior of novel sorbents.

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Publication type Article: Journal article

Document type Scientific Article

Corresponding Author

Keywords Solid-phase Extraction; Molecular Characterization; Suwannee River; Pesticide-residues; Gas-chromatography; Optical-properties; Sample Preparation; Lake-superior; Electrospray; Liquid

ISSN (print) / ISBN 0003-2700

e-ISSN 1520-6882

Journal Analytical Chemistry

Quellenangaben Volume: 95, Issue: 42, Pages: 15505-15513

Publisher American Chemical Society (ACS)

Publishing Place 1155 16th St, Nw, Washington, Dc 20036 Usa

Non-patent literature Publications

Reviewing status Peer reviewed

Institute(s) Research Unit Analytical BioGeoChemistry (BGC)

Grants German Research Foundation (DFG)