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Thermally Accelerated Oxidative Degradation of Quercetin Using Continuous Flow Kinetic Electrospray-Ion Trap-Time of Flight Mass Spectrometry

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

Thermally accelerated oxidative degradation of aqueous quercetin at pH 5.9 and 7.4 was kinetically measured using an in-house built online continuous flow device made of concentric capillary tubes, modified to fit to the inlet of an electrospray ionization-ion trap-time-of-flight-mass spectrometer (ESI-IT-TOF-MS). Time-resolved mass spectral measurements ranging from 2 to 21 min were performed in the negative mode to track intermediate degradation products and to evaluate the degradation rate of the deprotonated quercetin ion, [Q-H]–. Upon heating solutions in the presence of dissolved oxygen, degradation of [Q-H]– was observed and was accelerated by an increase in pH and temperature. Regardless of the condition, the same degradation pathways were observed. Degradation mechanisms and structures were determined using higher order tandem mass spectrometry (up to MS3) and high mass accuracy. The observed degradation mechanisms included oxidation, hydroxylation, and ring-cleavage by nucleophilic attack. A chalcan-trione structure formed by C-ring opening after hydroxylation at C2 was believed to be a precursor for other degradation products, formed by hydroxylation at the C2, C3, and C4 carbons from attack by nucleophilic species. This resulted in A-type and B-type ions after cross-ring cleavage of the C-ring. Based on time of appearance and signal intensity, nucleophilic attack at C3 was the preferred degradation pathway, which generated 2,4,6-trihydroxymandelate and 2,4,6-trihydroxyphenylglyoxylate ions. Overall, 23 quercetin-related ions were observed.

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Acknowledgments

The authors gratefully acknowledge Shimadzu Scientific Instruments, Inc. for their support of instrumentation through the Shimadzu Equipment Grants for Research Program.

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  1. Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX, 76019-0065, USA

    Jeremy S. Barnes, Frank W. Foss Jr. & Kevin A. Schug

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  1. Jeremy S. Barnes
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  2. Frank W. Foss Jr.
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  3. Kevin A. Schug
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Correspondence to Kevin A. Schug.

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Barnes, J.S., Foss , F.W. & Schug, K.A. Thermally Accelerated Oxidative Degradation of Quercetin Using Continuous Flow Kinetic Electrospray-Ion Trap-Time of Flight Mass Spectrometry. J. Am. Soc. Mass Spectrom. 24, 1513–1522 (2013). https://doi.org/10.1007/s13361-013-0698-6

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