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Application of LC and GC hyphenated with mass spectrometry as tool for characterization of unknown derivatives of isoflavonoids

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Abstract

Polyphenols belonging to the class of secondary metabolites of plants and microorganisms play an important role as bioactive food constituents as well as contaminants. Structure elucidation of polyphenols in plant extracts or polyphenol metabolites, especially those arising during biotransformation, still represents a challenge for analytical chemistry. Various approaches have been proposed to utilize fragmentation reactions in connection with mass spectrometry (MS) for structural considerations on polyphenolic targets. We compiled and applied specific liquid chromatography (LC)–electrospray ionization in positive mode [ESI(+)]–tandem MS (MS/MS) and gas chromatography (GC)–(electron impact, EI)–MS/MS fragmentation reactions with a special focus on the analysis of isoflavones, whereby this technique was also found to be extendable to determine further polyphenols. For ESI(+)-MS the basic retro-Diels–Alder (rDA) fragmentation offers information about the substitution pattern in the A- and B-rings of flavonoids and the elimination of a protonated 4-methylenecyclohexa-2,5-dienone (m/z = 107) fragment can be used as a diagnostic tool for many isoflavanones. For GC-(EI)-MS/MS analysis after derivatization of the analytes to their trimethylsilyl ethers, the elimination of methyl radicals, tetramethylsilane groups or the combined loss of two methyl groups can be shown to be specific for certain substitution patterns in polyphenols. The applicability of the fragmentation reactions presented is demonstrated exemplarily for three derivatives of the isoflavone irilone. With the help of these fragmentation reactions of the two MS techniques combined, a reliable identification of polyphenols is possible. Especially in such cases where NMR cannot be utilized owing to low analyte amounts being available or prior to purification, valuable information can be obtained.

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Abbreviations

AOH:

alternariol

BIOA:

biochanin A

BSTFA:

N,O-bis(trimethylsilyl)trifluoroacetamide

DAI:

daidzein

DHD:

dihydrodaidzein

DHG:

dihydrogenistein

EI:

electron impact

ESI:

electrospray ionization

ESI(+):

electrospray ionization in positive mode

ESI(−):

electrospray ionization in negative mode

FORM:

formononetin

GC:

gas chromatography

GEN:

genistein

GLY:

glycitein

HFM:

human fecal microflora

IRI:

irilone

IFA:

isoflavane

IFAO:

isoflavanone

IF:

isoflavone

LC:

liquid chromatography

MS:

mass spectrometry

PRUN:

prunetin

rDA:

retro Diels–Alder

TMS:

trimethylsilyl

ZAL:

zearalanol

ZAN:

zearalanone

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Acknowledgements

We acknowledge the financial support of the Studienstiftung des deutschen Volkes (Bonn, Germany) in form of a Ph.D. scholarship for N.H.S. Further we would like to thank A. Braune at the Deutsches Institut für Ernährungsforschung Potsdam-Rehbrücke for carrying out the HFM incubations and initial cleanup.

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Authors and Affiliations

  1. Institut für Biochemie und Lebensmittelchemie, Universität Hamburg, Grindelallee 117, 20146, Hamburg, Germany

    Ronald Maul

  2. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 30, 48149, Münster, Germany

    Nils Helge Schebb

  3. Lehrstuhl für Lebensmittelchemie, Universität Potsdam, Arthur-Scheunert-Allee 114-116, 14558, Nuthetal, Germany

    Sabine E. Kulling

Authors
  1. Ronald Maul
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  2. Nils Helge Schebb
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  3. Sabine E. Kulling
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Correspondence to Sabine E. Kulling.

Additional information

Ronald Maul and Nils Helge Schebb contributed equally to this work.

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Maul, R., Schebb, N.H. & Kulling, S.E. Application of LC and GC hyphenated with mass spectrometry as tool for characterization of unknown derivatives of isoflavonoids. Anal Bioanal Chem 391, 239–250 (2008). https://doi.org/10.1007/s00216-008-1884-4

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