Selective ESI-MS detection of carbonyl containing compounds by aminooxyacetic acid immobilized on a resin.

Autor: Kijewska M; Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383, Wrocław, Poland. Electronic address: monika.kijewska@chem.uni.wroc.pl., Koch T; Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383, Wrocław, Poland., Waliczek M; Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383, Wrocław, Poland., Konieczny A; Department of Nephrology and Transplantation Medicine, Wrocław Medical University, Borowska 213, 50-556, Wrocław, Poland., Stefanowicz P; Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383, Wrocław, Poland., Szewczuk Z; Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383, Wrocław, Poland.
Jazyk: angličtina
Zdroj: Analytica chimica acta [Anal Chim Acta] 2021 Sep 01; Vol. 1176, pp. 338767. Date of Electronic Publication: 2021 Jun 16.
DOI: 10.1016/j.aca.2021.338767
Abstrakt: There are numerous examples of bioactive compounds containing carbonyl groups including modified proteins with oxidation of side chain of amino acid residues to aldehyde/ketone groups which are frequently considered as markers of oxidative stress. The carbonyl unit can be also distinguished as a substructure in many illegal drugs including anabolic steroids as well as cations derivatives. Based on chemoselective formation of oximes by solid phase immobilized hydroxylamine derivatives we proposed the protocol for derivatization and selective detection of carbonylated compounds in human serum albumin hydrolysate as a complex peptide mixture and of testosterone in urine samples. This allowed for the removal of the matrix and the qualitative and quantitative analysis of the derivatized analyte by LC-MS/MS (or LC-MRM). Herein we report the preparation and chemical characterization of a novel, ChemMatrix - based resin functionalized with aminooxyacetic acid (AOA). The hydroxylamine moiety in this resin is combined with a peptide linker (GRG) containing an arginine residue to enhance the ionization efficiency. Application of an isotopically labeled carbonylated peptide ((H-Leu-Val-Thr(O)-Asp-Leu-Thr-Lys [ 13 C 6 , 15 N 2 ]-OH and testosterone-d 3 allowed us to carry out quantitative analyses of detected compounds. Our method is general and may be applied for analysis of carbonylated compounds in biological samples. Our method based on application of functionalized resin allowed to quantify the level of free testosterone in small sample (0.5 mL) of urine, while the non-derivatized testosterone from urine sample was not detected during direct LC-MRM analysis.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2021 Elsevier B.V. All rights reserved.)
Databáze: MEDLINE
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