Analytical and Bioanalytical Chemistry

, Volume 403, Issue 10, pp 2923–2931 | Cite as

Identification and quantification of six major α-dicarbonyl process contaminants in high-fructose corn syrup

  • Sabrina Gensberger
  • Stefan Mittelmaier
  • Marcus A. Glomb
  • Monika Pischetsrieder
Original Paper

Abstract

High-fructose corn syrup (HFCS) is a widely used liquid sweetener produced from corn starch by hydrolysis and partial isomerization of glucose to fructose. During these processing steps, sugars can be considerably degraded, leading, for example, to the formation of reactive α-dicarbonyl compounds (α-DCs). The present study performed targeted screening to identify the major α-DCs in HFCS. For this purpose, α-DCs were selectively converted with o-phenylendiamine to the corresponding quinoxaline derivatives, which were analyzed by liquid chromatography with hyphenated diode array–tandem mass spectrometry (LC-DAD-MS/MS) detection. 3-Deoxy-d-erythro-hexos-2-ulose (3-deoxyglucosone), d-lyxo-hexos-2-ulose (glucosone), 3-deoxy-d-threo-hexos-2-ulose (3-deoxygalactosone), 1-deoxy-d-erythro-hexos-2,3-diulose (1-deoxyglucosone), 3,4-dideoxyglucosone-3-ene, methylglyoxal, and glyoxal were identified by enhanced mass spectra as well as MS/MS product ion spectra using the synthesized standards as reference. Addition of diethylene triamine pentaacetic acid and adjustment of the derivatization conditions ensured complete derivatization without de novo formation for all identified α-DCs in HFCS matrix except for glyoxal. Subsequently, a ultra-high performance LC-DAD-MS/MS method was established to quantify 3-deoxyglucosone, glucosone, 3-deoxygalactosone, 1-deoxyglucosone, 3,4-dideoxyglucosone-3-ene, and methylglyoxal in HFCS. Depending on the α-DC compound and concentration, the recovery ranged between 89.2% and 105.8% with a relative standard deviation between 1.9% and 6.5%. Subsequently, the α-DC profiles of 14 commercial HFCS samples were recorded. 3-Deoxyglucosone was identified as the major α-DC with concentrations up to 730 μg/mL HFCS. The total α-DC content ranged from 293 μg/mL to 1,130 μg/mL HFCS. Significantly different α-DC levels were not detected between different HFCS specifications, but between samples of various manufacturers indicating that the α-DC load is influenced by the production procedures.

Keywords

High-fructose corn syrup (HFCS) Sugar degradation products α-Dicarbonyl compound (α-DC) o-Phenylenediamine (OPD) Quinoxaline derivatives Ultra high-performance liquid chromatography (UHPLC) 

Notes

Acknowledgment

We thank the Deutsche Forschungsgemeinschaft for their contribution to the applied UHPLC-MS/MS unit.

Supplementary material

216_2012_5817_MOESM1_ESM.pdf (754 kb)
ESM 1 (PDF 753 kb)

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Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Sabrina Gensberger
    • 1
  • Stefan Mittelmaier
    • 1
  • Marcus A. Glomb
    • 2
  • Monika Pischetsrieder
    • 1
  1. 1.Department of Chemistry and Pharmacy, Food Chemistry, Emil Fischer CenterUniversity of Erlangen-NurembergErlangenGermany
  2. 2.Institute of Chemistry, Food Chemistry and Environmental ChemistryMartin-Luther-University Halle-WittenbergHalleGermany

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