Skip to main content
SpringerLink
Log in

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

  • Original Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Hanover LM, White JS (1993) Manufacturing, composition, and applications of fructose. Am J Clin Nutr 58(5 Suppl):724S–732S

    CAS  Google Scholar 

  2. Vuilleumier S (1993) Worldwide production of high-fructose syrup and crystalline fructose. Am J Clin Nutr 58(5 Suppl):733S–736S

    CAS  Google Scholar 

  3. Putnam J, Allshouse J, Kantor LS (2002) U.S. per capita food supply trends: more calories, refined carbohydrates, and fats. Food Rev 25:2–15

    Google Scholar 

  4. White JS (2009) Misconceptions about high-fructose corn syrup: is it uniquely responsible for obesity, reactive dicarbonyl compounds, and advanced glycation endproducts? J Nutr 139(6):1219S–1227S

    Article  CAS  Google Scholar 

  5. Anet EFLJ (1964) 3-Deoxyglycosuloses (3-deoxyglycosones) and the degradation of carbohydrates. Advan Carbohydr Chem 19:181–218

    Article  CAS  Google Scholar 

  6. Wolff SP, Dean RT (1987) Glucose autoxidation and protein modification. The potential role of ‘autoxidative glycosylation’ in diabetes. Biochem J 245(1):243–250

    CAS  Google Scholar 

  7. Gobert J, Glomb MA (2009) Degradation of glucose: reinvestigation of reactive alpha-dicarbonyl compounds. J Agric Food Chem 57(18):8591–8597

    Article  CAS  Google Scholar 

  8. Usui T, Yanagisawa S, Ohguchi M, Yoshino M, Kawabata R, Kishimoto J, Arai Y, Aida K, Watanabe H, Hayase F (2007) Identification and determination of alpha-dicarbonyl compounds formed in the degradation of sugars. Biosci Biotechnol Biochem 71(10):2465–2472

    Article  CAS  Google Scholar 

  9. Pfeifer YV, Kroh LW (2010) Investigation of reactive alpha-dicarbonyl compounds generated from the Maillard reactions of l-methionine with reducing sugars via their stable quinoxaline derivatives. J Agric Food Chem 58(14):8293–8299

    Article  CAS  Google Scholar 

  10. Tauer A, Knerr T, Niwa T, Schaub TP, Lage C, Passlick-Deetjen J, Pischetsrieder M (2001) In vitro formation of N[epsilon]-(carboxymethyl)lysine and imidazolones under conditions similar to continuous ambulatory peritoneal dialysis. Biochem Biophys Res Commun 280(5):1408–1414

    Article  CAS  Google Scholar 

  11. Mittelmaier S, Pischetsrieder M (2011) Multistep ultrahigh performance liquid chromatography/tandem mass spectrometry analysis for untargeted quantification of glycating activity and identification of most relevant glycation products. Anal Chem 83(24):9660–9668

    Article  CAS  Google Scholar 

  12. Linden T, Cohen A, Deppisch R, Kjellstrand P, Wieslander A (2002) 3,4-Dideoxyglucosone-3-ene (3,4-DGE): a cytotoxic glucose degradation product in fluids for peritoneal dialysis. Kidney Int 62(2):697–703

    Article  CAS  Google Scholar 

  13. Niwa T (1999) 3-Deoxyglucosone: metabolism, analysis, biological activity, and clinical implication. J Chromatogr B Biomed Sci Appl 731(1):23–36

    Article  CAS  Google Scholar 

  14. Mittelmaier S, Funfrocken M, Fenn D, Berlich R, Pischetsrieder M (2011) Quantification of the six major alpha-dicarbonyl contaminants in peritoneal dialysis fluids by UHPLC/DAD/MSMS. Anal Bioanal Chem 401(4):1183–1193

    Article  CAS  Google Scholar 

  15. Bryland A, Broman M, Erixon M, Klarin B, Linden T, Friberg H, Wieslander A, Kjellstrand P, Ronco C, Carlsson O, Godaly G (2010) Infusion fluids contain harmful glucose degradation products. Intensive Care Med 36(7):1213–1220

    Article  CAS  Google Scholar 

  16. Hellwig M, Degen J, Henle T (2010) 3-Deoxygalactosone, a “new” 1,2-dicarbonyl compound in milk products. J Agric Food Chem 58(19):10752–10760

    Article  CAS  Google Scholar 

  17. Bravo A, Herrera JC, Scherer E, Ju-Nam Y, Rubsam H, Madrid J, Zufall C, Rangel-Aldao R (2008) Formation of alpha-dicarbonyl compounds in beer during storage of Pilsner. J Agric Food Chem 56(11):4134–4144

    Article  CAS  Google Scholar 

  18. Marceau E, Yaylayan VA (2009) Profiling of alpha-dicarbonyl content of commercial honeys from different botanical origins: identification of 3,4-dideoxyglucoson-3-ene (3,4-DGE) and related compounds. J Agric Food Chem 57(22):10837–10844

    Article  CAS  Google Scholar 

  19. Daglia M, Papetti A, Aceti C, Sordelli B, Spini V, Gazzani G (2007) Isolation and determination of alpha-dicarbonyl compounds by RP-HPLC-DAD in green and roasted coffee. J Agric Food Chem 55(22):8877–8882

    Article  CAS  Google Scholar 

  20. Lo C-Y, Li S, Wang Y, Tan D, Pan M-H, Sang S, Ho C-T (2008) Reactive dicarbonyl compounds and 5-hydroxymethylfurfural in carbonated beverages containing high fructose corn syrup. Food Chem 107:1099–1105

    Article  CAS  Google Scholar 

  21. Thornalley PJ, Rabbani N (2010) Dicarbonyls in cola drinks sweetened with sucrose or high fructose corn syrup. In: Thomas M, Forbes J (eds) The Maillard reaction: interface between aging, nutrition and metabolism. Royal Society of Chemistry, Cambridge, pp 158–163

    Google Scholar 

  22. de Revel G, Pripis-Nicolau L, Barbe J-C, Bertrand A (2000) The detection of [α]−dicarbonyl compounds in wine by formation of quinoxaline derivatives. J Sci Food Agric 80:102–108

    Article  Google Scholar 

  23. Mittelmaier S, Funfrocken M, Fenn D, Fichert T, Pischetsrieder M (2010) Identification and quantification of the glucose degradation product glucosone in peritoneal dialysis fluids by HPLC/DAD/MSMS. J Chromatogr B Analyt Technol Biomed Life Sci 878(11–12):877–882

    CAS  Google Scholar 

  24. Mittelmaier S, Funfrocken M, Fenn D, Pischetsrieder M (2011) 3-Deoxygalactosone, a new glucose degradation product in peritoneal dialysis fluids: identification, quantification by HPLC/DAD/MSMS and its pathway of formation. Anal Bioanal Chem 399(4):1689–1697

    Article  CAS  Google Scholar 

  25. Madson MA, Feather MS (1981) An improved preparation of 3-deoxy–erythro-hexos-2-ulose via the bis(benzoylhydrazone) and some related constitutional studies. Carbohydr Res 94(2):183–191

    Article  CAS  Google Scholar 

  26. Glomb MA, Pfahler C (2000) Synthesis of 1-deoxy-d-erythro-hexo-2,3-diulose, a major Maillard intermediate. Carbohydr Res 329(3):515–523

    Article  CAS  Google Scholar 

  27. Glomb MA, Tschirnich R (2001) Detection of alpha-dicarbonyl compounds in Maillard reaction systems and in vivo. J Agric Food Chem 49(11):5543–5550

    Article  CAS  Google Scholar 

  28. Beck J, Ledl F, Severin T (1988) Formation of 1-deoxy-d-erythro-2,3-hexodiulose from Amadori compounds. Carbohydr Res 177:240–243

    Article  CAS  Google Scholar 

  29. Hollnagel A, Kroh LW (1998) Formation of α-dicarbonyl fragments from mono- and disaccharides under caramelization and Maillard reaction conditions. Z Lebensm Unters Forsch A 207:50–54

    Article  CAS  Google Scholar 

  30. Ledl F, Schleicher ED (1990) New aspects of the Maillard reaction in foods and in the human body. Angew Chem Int Ed Engl 29:565–594

    Article  Google Scholar 

  31. Anet EFLJ (1963) Degradation of carbohydrates. Unsaturated hexones. Aust J Chem 15:503–509

    Article  Google Scholar 

  32. Frischmann M, Spitzer J, Funfrocken M, Mittelmaier S, Deckert M, Fichert T, Pischetsrieder M (2009) Development and validation of an HPLC method to quantify 3,4-dideoxyglucosone-3-ene in peritoneal dialysis fluids. Biomed Chromatogr 23(8):843–851

    Article  CAS  Google Scholar 

Download references

Acknowledgment

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

Author information

Authors and Affiliations

  1. Department of Chemistry and Pharmacy, Food Chemistry, Emil Fischer Center, University of Erlangen-Nuremberg, Schuhstr. 19, 91052, Erlangen, Germany

    Sabrina Gensberger, Stefan Mittelmaier & Monika Pischetsrieder

  2. Institute of Chemistry, Food Chemistry and Environmental Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes-Str. 2, 06120, Halle, Germany

    Marcus A. Glomb

Authors
  1. Sabrina Gensberger
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Stefan Mittelmaier
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Marcus A. Glomb
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Monika Pischetsrieder
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Monika Pischetsrieder.

Additional information

Published in the special paper collection Recent Advances in Food Analysis with guest editors J. Hajslova, R. Krska, M. Nielen.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 753 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gensberger, S., Mittelmaier, S., Glomb, M.A. et al. Identification and quantification of six major α-dicarbonyl process contaminants in high-fructose corn syrup. Anal Bioanal Chem 403, 2923–2931 (2012). https://doi.org/10.1007/s00216-012-5817-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-012-5817-x

Keywords

Search

Navigation