Analytical and Bioanalytical Chemistry

, Volume 391, Issue 1, pp 239–250

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

  • Ronald Maul
  • Nils Helge Schebb
  • Sabine E. Kulling
Original Paper

DOI: 10.1007/s00216-008-1884-4

Cite this article as:
Maul, R., Schebb, N.H. & Kulling, S.E. Anal Bioanal Chem (2008) 391: 239. doi:10.1007/s00216-008-1884-4

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.

Keywords

Fragmentation reactions Gas chromatography–mass spectrometry Irilone Isoflavonoides Liquid chromatography–mass spectrometry Structure analyses 

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

Supplementary material

216_2008_1884_MOESM1_ESM.pdf (123 kb)
ESM(PDF 122 KB)

Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  • Ronald Maul
    • 1
  • Nils Helge Schebb
    • 2
  • Sabine E. Kulling
    • 3
  1. 1.Institut für Biochemie und LebensmittelchemieUniversität HamburgHamburgGermany
  2. 2.Institut für Anorganische und Analytische ChemieWestfälische Wilhelms-Universität MünsterMünsterGermany
  3. 3.Lehrstuhl für LebensmittelchemieUniversität PotsdamNuthetalGermany

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