Skip to main content
SpringerLink
Log in

Analysis and stereodifferentiation of linalool in Theobroma cacao and cocoa products using enantioselective multidimensional gas chromatography

  • Original Paper
  • Published:
European Food Research and Technology Aims and scope Submit manuscript

Abstract

Contents and enantiomeric distributions of linalool (3,7-dimethyl-1,6-octadien-3-ol) were investigated in raw and roasted cocoa beans (seeds of Theobroma cacao) of defined origin as well as in commercial products, such as cocoa powders or chocolates. The stereodifferentiation of linalool was achieved by enantioselective multidimensional gas chromatography using heptakis (2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as chiral stationary phase. Simultaneous steam distillation–extraction at pH 7 allowed sample preparation without racemization of linalool. Cocoa beans contain linalool primarily as (S)-enantiomer. Model experiments and analyses of commercial products such as cocoa powders and chocolates revealed that technological procedures employed in the manufacturing of cocoa products do not result in significant changes of the original enantiomeric distribution of linalool.

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.

Institutional subscriptions

Fig. 1

Similar content being viewed by others

References

  1. Biehl B, Meursing EH (1993) Cocoa—production, products and uses. In: Macrae R, Robinson RK, Sadler MJ (eds) Enzyclopedia of food science, food technology and nutrition, vol 2. Academic Press, London, pp 1083–1097

    Google Scholar 

  2. Biehl B, Ziegleder G (1993) Cocoa—chemistry of processing. In: Macrae R, Robinson RK, Sadler MJ (eds) Enzyclopedia of food science, food technology and nutrition, vol 2. Academic Press, London, pp 1073–1083

    Google Scholar 

  3. Bainbridge JS, Davies SH (1912) The essential oil of cocoa. J Chem Soc Trans 101:2209–2221

    Article  CAS  Google Scholar 

  4. Nijssen LM, Visscher CA, Maarse H, Willemsens L (1996) Cocoa. Volatile compounds in foods. Qualitative and quantitative data. TNO, Zeist

    Google Scholar 

  5. Schnermann P, Schieberle P (1997) Evaluation of key odorants in milk chocolate and cocoa mass by aroma extract dilution analyses. J Agric Food Chem 45:867–872

    Article  CAS  Google Scholar 

  6. Frauendorfer F, Schieberle P (2006) Identification of the key aroma compounds in cocoa powder based on molecular sensory correlations. J Agric Food Chem 54:5521–5529

    Article  CAS  Google Scholar 

  7. Stark T, Bareuther S, Hofmann T (2006) Molecular definition of the taste of roasted cocoa nibs (Theobroma cacao) by means of quantitative studies and sensory experiments. J Agric Food Chem 54:5530–5539

    Article  CAS  Google Scholar 

  8. Frauendorfer F, Schieberle P (2008) Changes in key aroma compounds of criollo cocoa beans during roasting. J Agric Food Chem 56:10244–10251

    Article  CAS  Google Scholar 

  9. Ziegleder G (1990) Linalool contents as characteristic of some flavor grade cocoas. Z Lebensm-Unters Forsch 191:306–309

    Article  CAS  Google Scholar 

  10. Pino JA, Roncal E (1992) Linalool content in roasted cocoa butter as a characteristic of several flavour grade cocoas. Nahrung 36:299–301

    Article  CAS  Google Scholar 

  11. Ziegleder K (1991) Fortschritte in der analytischen Aromakontrolle von Schokoladen. Suesswaren 35:343–345

    Google Scholar 

  12. Mosandl A, Schubert V (1990) Stereoisomere Aromastoffe. XXXIX. Chirale Inhaltsstoffe ätherischer Öle. (I). Stereodifferenzierung des Linalylacetats—ein neuer Weg zur Qualitätsbeurteilung des Lavendelöls. Z Lebensm-Unters Forsch 190:506–510

    Article  CAS  Google Scholar 

  13. Hener U, Braunsdorf R, Kreis P, Dietrich A, Maas B, Euler E, Schlag B, Mosandl A (1992) Chiral compounds of essential oils. X. The role of linalool in the origin evaluation of essential oils. Chemie Mikrobiol Technol Lebensm 14:129–133

    CAS  Google Scholar 

  14. Full G, Winterhalter P, Schmidt G, Herion P, Schreier P (1993) MDGC-MS: a powerful tool for enantioselective flavor analysis. J High Resolut Chromatogr 16:642–644

    Article  CAS  Google Scholar 

  15. Mosandl A (1995) Enantioselective capillary gas chromatography and stable isotope mass spectrometry in the authenticity control of flavours and essential oils. Food Rev Int 11:597–664

    Article  CAS  Google Scholar 

  16. Werkhoff P, Brennecke S, Bretschneider W, Guentert M, Hopp R, Surburg H (1993) Chirospecific analysis in essential oil, fragrance and flavour research. Z Lebensm-Unters Forsch 196:307–328

    Article  CAS  Google Scholar 

  17. Bernreuther A, Epperlein U, Koppenhoefer B (1997) Enantiomers: why they are important and how to resolve them. In: Marsili R (ed) Techniques for analyzing food aroma. Food Science and Technology. Marcel Dekker, New York, pp 143–207

    Google Scholar 

  18. Boelens MH, van GLJ (1993) Sensory properties of optical isomers. Perfumer Flavor 18:1, 3–6, 8–10, 12–14, 16

  19. Ohloff G, Klein E (1962) Die absolute Konfiguration des Linalools durch Verknüpfung mit dem Pinansystem. Tetrahedron 18:37–42

    Article  CAS  Google Scholar 

  20. Padrayuttawat A, Yoshizawa T, Tamura H, Tokunaga T (1997) Optical isomers and odor thresholds of volatile constituents in Citrus sudachi. Food Sci Technol Int Tokyo 3:402–408

    Article  CAS  Google Scholar 

  21. Fritsch HT, Schieberle P (2005) Identification based on quantitative measurements and aroma recombination of the character impact odorants in a Bavarian Pilsner-type beer. J Agric Food Chem 53:7544–7551

    Article  CAS  Google Scholar 

  22. Schuh C, Schieberle P (2006) Characterization of the key aroma compounds in the beverage prepared from Darjeeling black tea: quantitative differences between tea leaves and infusion. J Agric Food Chem 54:916–924

    Article  CAS  Google Scholar 

  23. Czerny M, Christlbauer M, Christlbauer M, Fischer A, Granvogl M, Hammer M, Hartl C, Hernandez NM, Schieberle P (2008) Re-investigation on odour thresholds of key food aroma compounds and development of an aroma language based on odour qualities of defined aqueous odorant solutions. Eur Food Res Technol 228:265–273

    Article  CAS  Google Scholar 

  24. Dugo G, Verzera A, Cotroneo A, Stagno d’Alcontres I, Mondello L, Bartle KD (1994) Automated HPLC-HRGC: a powerful method for essential oil analysis. II. Determination of the enantiomeric distribution of linalool in sweet orange, bitter orange and mandarin essential oils. Flavour Fragr J 9:99–104

    Article  CAS  Google Scholar 

  25. Bernreuther A, Schreier P (1991) Multidimensional gas chromatography/mass spectrometry: a powerful tool for the direct chiral evaluation of aroma compounds in plant tissues. II. Linalool in essential oils and fruits. Phytochem Anal 2:167–170

    Article  CAS  Google Scholar 

  26. Schubert V, Mosandl A (1991) Chiral compounds of essential oils. VIII: stereodifferentiation of linalool using multidimensional gas chromatography. Phytochem Anal 2:171–174

    Article  CAS  Google Scholar 

  27. Marriott PJ, Chin S-T, Maikhunthod B, Schmarr H-G, Bieri S (2012) Multidimensional gas chromatography. TrAC, Trends Anal Chem 34:1–21

    Article  CAS  Google Scholar 

  28. Kawakami M, Ganguly SN, Banerjee J, Kobayashi A (1995) Aroma composition of oolong tea and black tea by brewed extraction method and characterizing compounds of Darjeeling tea aroma. J Agric Food Chem 43:200–207

    Article  CAS  Google Scholar 

  29. Wang D, Ando K, Morita K, Kubota K, Kobayashi A (1994) Optical isomers of linalool and linalool oxides in tea aroma. Biosci Biotechnol Biochem 58:2050–2053

    Article  CAS  Google Scholar 

  30. Askari C, Hener U, Schmarr H-G, Rapp A, Monsandl A (1991) Stereodifferentiation of some chiral monoterpenes using multidimensional gas chromatography. Fresenius’ J Anal Chem 340:768–772

    Article  CAS  Google Scholar 

  31. Schmaus G, Kubeczka KH (1985) The influence of isolation conditions on the composition of essential oils containing linalool and linalyl acetate. In: Baerheim-Svendsen A, Scheffer JJC (eds) Essential oils and aromatic plants. Nijhoff/Junk, Dordrecht, pp 127–136

    Chapter  Google Scholar 

  32. Baxter RL, Laurie WA, McHale D (1978) Transformations of monoterpenoids in aqueous acids. Tetrahedron 34:2195–2199

    Article  CAS  Google Scholar 

  33. Weinreich B, Nitz S (1992) Influences of processing on the enantiomeric distribution of chiral flavour compounds. I. Linalyl acetate and terpene alcohols. Chem Mikrobiol Technol Lebensm 14:117–124

    CAS  Google Scholar 

  34. Krysiak W (2006) Influence of roasting conditions on coloration of roasted cocoa beans. J Food Eng 77:449–453

    Article  CAS  Google Scholar 

  35. Wieland T, Mayer C (1972) Gattermann-Wieland, Die Praxis des organischen Chemikers, Teil 1. Allgemeine Arbeitsanweisungen. Walter de Gruyter & Co., Berlin

    Google Scholar 

  36. Schultz TH, Flath RA, Mon TR, Eggling SB, Teranishi R (1977) Isolation of volatile components from a model system. J Agric Food Chem 25:446–449

    Article  CAS  Google Scholar 

  37. Sulzbach H (1996) Multidimensionale Kapillarsäulen-Gaschromatographie. GIT Fachz Lab 40:131

    Google Scholar 

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

    Article  CAS  Google Scholar 

  39. Grob K (1986) Making and manipulating capillary columns for gas chromatography. Huethig, Heidelberg

    Google Scholar 

  40. Schmarr H-G (1992) Beiträge zur on-line LC-GC Kopplung und modifizierte Cyclodextrine als chirale stationäre Phasen in der Kapillar-GC. Johann Wolfgang Goethe University, Frankfurt am Main

    Google Scholar 

  41. Dietrich A, Maas B, Messer W, Bruche G, Karl V, Kaunzinger A, Mosandl A (1992) Stereoisomeric flavor compounds, part LVIII: the use of heptakis (2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as a chiral stationary phase in flavor analysis. J High Resolut Chromatogr 15:590–593

    Article  CAS  Google Scholar 

  42. Bonvehi JS (2005) Investigation of aromatic compounds in roasted cocoa powder. Eur Food Res Technol 221:19–29

    Article  CAS  Google Scholar 

  43. Cori O, Chayet L, Perez LM, Bunton CA, Hachey D (1986) Rearrangement of linalool, geraniol, and nerol and their derivatives. J Org Chem 51:1310–1316

    Article  CAS  Google Scholar 

  44. Mosandl A, Juchelka D (1997) Advances in the authenticity assessment of citrus oils. J Essent Oil Res 9:5–12

    Article  CAS  Google Scholar 

  45. Williams PJ, Strauss CR, Wilson B, Massy-Westropp RA (1982) Studies on the hydrolysis of Vitis vinifera monoterpene precursor compounds and model monoterpene β-d glucosides rationalizing the monoterpene composition of grapes. J Agric Food Chem 30:1219–1223

    Article  CAS  Google Scholar 

  46. Schmid W, Grosch W (1986) Quantitative analyse flüchtiger Aromastoffe mit hohen Aromawerten in Sauerkirschen (Prunus cerasus L.), Süßkirschen (Prunus avium L.) und Kirschkonfitüren. Z Lebensm-Unters Forsch 183(1):39–44

  47. Counet C, Callemien D, Ouwerx C, Collin S (2002) Use of gas chromatography-olfactometry to identify key odorant compounds in dark chocolate. Comparison of samples before and after conching. J Agric Food Chem 50:2385–2391

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge Claudia Preis, Carsten Stein, and Lilian Simões dos Santos for their contribution and technical assistance in this work. We also thank the “Fraunhofer Institut für Lebensmitteltechnologie und Verpackung” (Freising, Germany), the “Bundesverband der Deutschen Süßwarenindustrie e.V.” (Köln, Germany), HACHEZ (Bremen, Germany), Kraft Jacobs Suchard R&D, Inc. (München, Germany), as well as the “Verein der am Rohkakaohandel beteiligten Firmen e.V.” (Hamburg, Germany) for donating defined cocoa samples.

Author information

Authors and Affiliations

  1. Dienstleistungszentrum Ländlicher Raum Rheinpfalz, Kompetenzzentrum Weinforschung, Breitenweg 71, 67435, Neustadt an der Weinstraße, Germany

    Hans-Georg Schmarr

  2. Technische Universität München, Lehrstuhl für Allgemeine Lebensmitteltechnologie, Maximus-von-Imhof-Forum 2, 85350, Freising-Weihenstephan, Germany

    Hans-Georg Schmarr & Karl-Heinz Engel

Authors
  1. Hans-Georg Schmarr
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Karl-Heinz Engel
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hans-Georg Schmarr.

Additional information

This paper is dedicated to Prof. Dr. Armin Mosandl (Dettelbach) on the occasion of his 70th birthday.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Schmarr, HG., Engel, KH. Analysis and stereodifferentiation of linalool in Theobroma cacao and cocoa products using enantioselective multidimensional gas chromatography. Eur Food Res Technol 235, 827–834 (2012). https://doi.org/10.1007/s00217-012-1812-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00217-012-1812-x

Keywords

Search

Navigation