Skip to main content
Log in

Enantiodifferentiation of 1,2-propanediol in various wines as phenylboronate ester with multidimensional gas chromatography-mass spectrometry

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


Native concentrations and enantiomeric distribution of 1,2-propanediol in various wines were studied in order to evaluate its merits as a potential marker for aroma adulteration in wine. Heart-cut multidimensional gas chromatography coupled to mass spectrometry was applied to analyze 1,2-propanediol after salting-out of the polar phase, derivatization with phenyl boronic acid, and extraction with cyclohexane. The enantiomeric separation of the derivative was achieved with heptakis-(6-O-tert. butyl dimethylsilyl-2,3-di-O-acetyl)-β-cyclodextrin as the chiral selector. In all authentic wines studied, 1,2-propanediol showed a high enantiomeric ratio in favor of the (R)-enantiomer, proving its potential as a marker for the adulteration with flavor extracts based on industrial 1,2-propandiol as solvent. Usually, concentrations varied between 15 and 100 mg/L. Higher values (up to 170 mg/L) were found in wines made with high amounts of dry berries. However, despite the higher concentrations of 1,2-propanediol in such wines, no apparent influence on the enantiomeric distribution could be detected.

Detection of fraudulent aromatization of wines by enantiodifferentiation of 1,2-propanediol as its phenylboronate ester

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

Access this article

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

Instant access to the full article PDF.

Scheme 1
Fig 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others


  1. Regulation (EC) No 1333/2008 of the European parliament and of the council of 16 December 2008 on food additives. Offic J Eur Union. 2008;L354:16–33.

  2. Regulation (EC) No 606/2009 of July 2009 laying down certain detailed rules for implementing Council Regulation (EC) No 479/2008 as regards the categories of grapevine products, oenological practices and the applicable restrictions. Offic J Euro Union. 2009;L193:1–59.

  3. Wagner S, Jakob L, Rapp A, Niebergall H. Native content of polyols in wine and the possible influence of the technology of wine-making. Wein-Wissenschaft. 1994;49(6):247–253.

    CAS  Google Scholar 

  4. Wagner K, Kreutzer P. The content of 1,2-propanediol in wine. Wein-Wissenschaft. 2000;55(1):41–44.

    CAS  Google Scholar 

  5. de Revel G, Martin N, Pripis-Nicolau L, Lonvaud-Funel A, Bertrand A. Contribution to the knowledge of malolactic fermentation. Influence on wine aroma. J Agric Food Chem. 1999;47(10):4003–4008.

    Article  Google Scholar 

  6. Di Stefano R, Borsa D, Moruno EG. Glycols naturally present in wines. Vini d'Italia. 1988;30(5):39–44.

    Google Scholar 

  7. Sponholz WR, Dittrich HH, Muno H. Diole in Wein. Wein-Wissenschaft. 1994;49(1):23–26.

    CAS  Google Scholar 

  8. Girard B, Yuksel D, Cliff MA, Delaquis P, Reynolds AG. Vinification effects on the sensory, colour, and GC profiles of Pinot Noir wines from British Columbia. Food Res Int. 2001;34(6):483–499.

    Article  CAS  Google Scholar 

  9. Herzberger E, Kapol R, Pfeiffer P, Radler F. Degradation of diols and formation of ethylene glycol by different yeast species. Z Lebensm-Unters Forsch. 1989;188(4):309–313.

    Article  CAS  Google Scholar 

  10. Suzuki T, Onishi H. Aerobic dissimilation of L-rhamnose and the production of l-rhamnonic acid and 1,2-propanediol by yeasts. Agric Biol Chem. 1968;32(7):888–893.

    Article  CAS  Google Scholar 

  11. Schütz H, Radler F. Anaerobic reduction of glycerol to propanediol-1,3 by Lactobacillus brevis and Lactobacillus buchneri. Syst Appl Microbiol. 1984;5(2):169–178.

    Article  Google Scholar 

  12. Bennett GN, San KY. Microbial formation, biotechnological production, and applications of 1,2-propanediol. Appl Microbiol Biotechnol. 2001;55(1):1–9.

    Article  CAS  Google Scholar 

  13. Mochizuki N, Kikuchi K, Ikeda M. Determination of enantiomers of 1,2-propanediol in beer by gas chromatography. Seibutsu Kogaku Kaishi. 1997;75(5):339–334.

    CAS  Google Scholar 

  14. Hartlieb A. Enantioselektivität und Isotopendiskriminierung zur Analytik von 1,2-Propandiol und 4-Hydroxy-2,5-dimethyl-3(2H)-furanon (Furaneol®), Ph.D. thesis, Fakultät für Chemie und Pharmazie, Julius-Maximilians-Universität Würzburg, 2009

  15. Bandion F, Valenta M, Kohlmann H. Detection of extract-increasing additions in wine. Mitt Klosterneuburg. 1985;35(3):89–92.

    CAS  Google Scholar 

  16. Kaiser RE, Rieder RI. Diethylene glycol in wine. HRC & CC. J High Resol Chromatogr Chromatogr Commun. 1985;8(12):863–865.

    Article  CAS  Google Scholar 

  17. Rapp A, Engel L, Ullemeyer H. Determination of mono- and diethylene glycol in wine by two-dimensional gas chromatography. Z Lebensm-Unters Forsch. 1986;182(6):498–500.

    Article  CAS  Google Scholar 

  18. Conte L, Minguzzi A, Natali N. Determination of diethylene glycol in wines: comparison of several methods of analysis. Vignevini. 1986;13(3):49–53.

    CAS  Google Scholar 

  19. Kaiser RE, Rieder RI. Native ethylene glycol in wine: application of a dead volume free, very fast 'Deans heart-cut' system on-line with multi-chromatography. HRC & CC. J High Resol Chromatogr Chromatogr Commun. 1987;10:240–243.

    Article  CAS  Google Scholar 

  20. Bollani T. Determination of diethylene glycol in wine. Laboratorio 2000. 1991;5(4):24–26.

    CAS  Google Scholar 

  21. Method OIV-MA-AS315-15 : R2007. Determination of 3-methoxypropane-1,2-diol and cyclic diglycerols (by-products of technical glycerol) in wine by GC-MS - description of the method and collaborative study. In: Compendium of international methods of wine and must analysis. International Organisation of Vine and Wine – OIV, Paris, 2013.

  22. Woidich H, Pfannhauser W. Anreicherung und quantitative Bestimmung von Inhaltsstoffen alkoholischer Getränke. Dtsch Lebensm-Rundsch. 1978;74:397–400.

  23. Haase-Aschoff K, Haase-Aschoff I. Bestimmung von Diethylenglycol (DEG) durch Kapillar-Gaschromatographie. Weinwirtschaft Technik. 1985;9:266–267.

  24. Sugihara JM, Bowman CM. Cyclic benzeneboronate esters. J Am Chem Soc. 1958;80:2443–2446.

  25. Luong J, Gras R, Cortes HJ, Shellie RA. Determination of trace ethylene glycol in industrial solvents and lubricants using phenyl boronic acid derivatization and multidimensional gas chromatography. Anal Chim Acta. 2013;805:101–106.

    Article  CAS  Google Scholar 

  26. Divinova V, Svejkovska B, Dolezal M, Velisek J. Determination of free and bound 3-chloropropane-1,2-diol by gas chromatography with mass spectrometric detectio using deuterated 3-chloropropane-1,2-diol as internal standard. Czech J Food Sci. 2004;22(5):182–189.

    CAS  Google Scholar 

  27. Kusters M, Bimber U, Ossenbrueggen A, Reeser S, Gallitzendoerfer R, Gerhartz M. Rapid and simple micromethod for the simultaneous determination of 3-MCPD and 3-MCPD esters in different foodstuffs. J Agric Food Chem. 2010;58(11):6570–6577.

    Article  CAS  Google Scholar 

  28. Schmarr H-G, Mosandl A, Kaunzinger A. Influence of derivatization on the chiral selectivity of cyclodextrins: alkylated/acylated cyclodextrins and γ-/δ-lactones as an example. J Microcolumn Sep. 1991;3(5):395–402.

    Article  CAS  Google Scholar 

  29. Bruche G, Schmarr H-G, Bauer A, Mosandl A, Rapp A, Engel L. Stereoisomere Aromastoffe LI: Stereodifferenzierung chiraler Furanone Möglichkeiten und Grenzen der herkunftsspezifischen Aromastoff-Analyse. Z Lebensm-Unters Forsch. 1991;193(2):115–118.

  30. Odom JD, Moore TF, Goetze R, Noeth H, Wrackmeyer B. Nuclear magnetic resonance studies of boron compounds. XVI. Carbon-13 studies of organoboranes: phenylboranes and boron-substituted aromatic heterocycles. J Organomet Chem. 1979;173(1):15–32.

    Article  CAS  Google Scholar 

  31. Schmarr H-G, Ganß S, Sang W, Potouridis T. Analysis of 2-aminoacetophenone in wine using a stable isotope dilution assay and multidimensional gas chromatography-mass spectrometry. J Chromatogr A. 2007;1150(1/2):78–84.

    Article  CAS  Google Scholar 

  32. Schmarr H-G, Slabizki P, Legrum C. Optimization in multidimensional gas chromatography applying quantitative analysis via a stable isotope dilution assay. Anal Bioanal Chem. 2013;405(20):6589–6593.

    Article  CAS  Google Scholar 

  33. Mosandl A, Hener U, Fuchs S. Natürliche Duft- und Aromastoffe — Echtheitsbewertung mittels enantioselektiver Kapillar-GC und/oder Isotopenverhältnis-massenspektrometrie. In: Günzler H, Bahadir AM, Danzer K, Engewald W, Fresenius W, Galensa R et al., editors. Analytiker-Taschenbuch. Berlin, Heidelberg: Springer; 2000. p. 37–63.

  34. Jimenez-Marti E, Gomar-Alba M, Palacios A, Ortiz-Julien A, del Olmo M-l. Towards an understanding of the adaptation of wine yeasts to must: relevance of the osmotic stress response. Appl Microbiol Biotechnol. 2011;89(5):1551–1561.

    Article  CAS  Google Scholar 

  35. Fernandes L, Relva AM, Gomes da Silva MDR, Costa Freitas AM. Different multidimensional chromatographic approaches applied to the study of wine malolactic fermentation. J Chromatogr A. 2003;995(1/2):161–169.

    Article  CAS  Google Scholar 

Download references


The authors are particularly thankful to Supelco (Sigma-Aldrich) for the supply of the ionic liquid GC column. They thank the donating institutions for reference wine samples (Staatsweingut mit Johannitergut, Neustadt an der Weinstraße, Germany; Haute école de viticulture et oenologie, Changins, Switzerland). The authors are thankful for wine samples from food and wine control authorities of the state of Rheinland-Pfalz, Germany. They also appreciate the support and fruitful discussions from colleagues, particularly Patricia Golombek, Harald Kelm (TU Kaiserslautern, Germany), and Reinhard Meusinger (TU Darmstadt, Germany). Furthermore, the financial support from the Ministerium für Umwelt, Landwirtschaft, Ernährung, Weinbau und Forsten (Rheinland-Pfalz, Germany) is gratefully acknowledged.

Author information

Authors and Affiliations


Corresponding author

Correspondence to Hans-Georg Schmarr.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.


(PDF 232 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Langen, J., Fischer, U., Cavalar, M. et al. Enantiodifferentiation of 1,2-propanediol in various wines as phenylboronate ester with multidimensional gas chromatography-mass spectrometry. Anal Bioanal Chem 408, 2425–2439 (2016).

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: