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Chocolate and Cocoa Aroma

Chapter
Part of the Nutrition and Health book series (NH, volume 7)

Key Points

  • Chocolate- and cocoa-specific aroma is formed during roasting of fermented, but not of unfermented, cocoa beans.

  • Essential components of the chocolate- and cocoa-specific aroma are generated by heat-induced Maillard reactions of free amino acids and peptides with reducing sugars.

  • Essential aroma precursors are derived from the vicilin (7S)-class globular storage protein of the cocoa beans by acid-induced successive degradation by endogenous aspartic endoprotease and carboxypeptidase activities.

  • Effects of the time course of acidification and the final pH values of cocoa fermentations on the aroma potential of the resulting raw cocoa are due to the differential pH optima of the aspartic endoprotease and the carboxypeptidase of the cocoa beans.

  • Genotype-dependent differences in the aroma potential of cocoa clones are at least partly due to varying contents of the vicilin (7S)-class globular storage protein and/or the amounts and activities of the aspartic endoprotease and carboxypeptidase of the cocoa beans.

Keywords

Aroma components Aspartic endoprotease Carboxypeptidase Cocoa beans Free amino acids Maillard reactions Peptides Storage protein Vicilin (7S)-class globulin 

References

  1. 1.
    Clapperton JF. A review of research to identify the origins of cocoa flavour characteristics. Cocoa Growers Bull. 1994;48:7–16.Google Scholar
  2. 2.
    Beckett ST. Is the taste of British milk chocolate different? Int J Dairy Technol. 2003;56:138–42.CrossRefGoogle Scholar
  3. 3.
    Whitefield R. Making chocolates in the factory. London: Kennedy’s Publications Ltd; 2005.Google Scholar
  4. 4.
    Voigt J, Biehl B. Precursors of the cocoa specific aroma components are derived from the vicilin-class (7S) globulin of the cocoa seeds by proteolytic processing. Bot Acta. 1995;108:283–9.Google Scholar
  5. 5.
    Voigt J, Lieberei R. Biochemistry of cocoa fermentation. In: Schwan RF, Fleet GH, editors. Cocoa and coffee fermentations. Boca Raton: CRC Press; 2013.Google Scholar
  6. 6.
    Afoakwa EO, Paterson A, Fowler M, et al. Flavor formation and character in cocoa and chocolate: a critical review. Crit Rev Food Sci Nutr. 2008;48:840–57.PubMedCrossRefGoogle Scholar
  7. 7.
    Ziegleder G, Biehl B. Analysis of cocoa flavour components and flavour precursors. In: Linskens HF, Jackson JF, editors. Modern methods of plant analysis, New Series, vol. 8. New York: Springer; 1988. p. 321–93.Google Scholar
  8. 8.
    Bonvehí JS. Investigation of aromatic compounds in roasted cocoa powder. Eur Food Res Technol. 2005;221:19–29.CrossRefGoogle Scholar
  9. 9.
    Cerny C, Grosch W. Precursors of ethylpyrazine isomers and 2,3-diethyl-5-methylpyrazine formed in roasted beef. Z Lebensm Unters Forsch. 1994;198:210–4.CrossRefGoogle Scholar
  10. 10.
    Amrani-Hemaimi M, Cerny C, Fay LB. Mechanism of formation of alkylpyrazine in the Maillard reaction. J Agric Food Chem. 1995;43:2818–22.CrossRefGoogle Scholar
  11. 11.
    Schnermann P, Schieberle P. Evaluation of key odorants in milk chocolate and cocoa mass by aroma extract dilution analysis. J Agric Food Chem. 1997;45:867–72.CrossRefGoogle Scholar
  12. 12.
    Counet C, Callemien D, Ouwerx C, et al. Use of gas chromatography-olfactometry to identify key odorant compounds in dark chocolate. Comparison of samples before and after conching. J Agric Food Chem. 2002;50:2385–91.PubMedCrossRefGoogle Scholar
  13. 13.
    Taylor AJ. Food flavour technology. Sheffield: Sheffield Academic Press; 2002.Google Scholar
  14. 14.
    Taylor AJ, Roberts DD. Flavour perception. Oxford: Blackwell Publishing; 2004.CrossRefGoogle Scholar
  15. 15.
    Reineccius G. Flavour chemistry and technology. 2nd ed. Boca Raton: CRC Press; 2006.Google Scholar
  16. 16.
    Afoakwa EO, Paterson A, Fowler M, et al. Matrix effects on flavour volatiles release in dark chocolates varying in particle size distribution and fat content using GC-mass spectrometry and GC-olfactometry. Food Chem. 2009;113:208–15.CrossRefGoogle Scholar
  17. 17.
    Frauendorfer F, Schieberle P. Changes in key aroma compounds of Criollo cocoa beans during roasting. J Agric Food Chem. 2008;56:10244–51.PubMedCrossRefGoogle Scholar
  18. 18.
    Huang Y, Barringer SA. Alkylpyrazines and other volatiles in cocoa liquor at pH 5 to 8, by selected ion flow tube-mass spectrometry (SIFT-MS). J Food Sci. 2010;75:C121–7.PubMedCrossRefGoogle Scholar
  19. 19.
    Granvogel M, Bugan S, Schieberle P. Formation of amines and aldehydes from parent amino acids during thermal processing of cocoa and model systems: new insights into pathways of the Strecker reaction. J Agric Food Chem. 2006;54:1730–9.CrossRefGoogle Scholar
  20. 20.
    Ledl F, Schleicher E. New aspects of the Maillard reaction in foods and in the human body. Angew Chem Int Ed Engl. 1990;29:565–94.CrossRefGoogle Scholar
  21. 21.
    Rohan TA. The precursors of chocolate aroma: a comparative study of fermented and unfermented cocoa beans. J Sci Food Agric. 1964;29:456–9.Google Scholar
  22. 22.
    Ostovar K, Keeney PG. Isolation and characterization of microorganisms involved in the fermentation of Trinidad cocoa beans. J Food Sci. 1973;39:611–7.CrossRefGoogle Scholar
  23. 23.
    Biehl B, Brunner E, Passern D, et al. Acidification, proteolysis and flavour potential in fermenting cocoa beans. J Sci Food Agric. 1985;36:583–98.CrossRefGoogle Scholar
  24. 24.
    Schwan RF, Wheals AE. The microbiology of cocoa fermentation and its role in chocolate quality. Crit Rev Food Sci Nutr. 2004;44:205–21.PubMedCrossRefGoogle Scholar
  25. 25.
    Kirchhoff PM, Biehl B, Crone G. Peculiarity of the accumulation of free amino acids during cocoa fermentation. Food Chem. 1989;31:295–311.CrossRefGoogle Scholar
  26. 26.
    Kirchhoff PM, Biehl B, Ziegeler-Berghausen H, et al. Kinetics of the formation of free amino acids in cocoa seeds during fermentation. Food Chem. 1989;34:161–79.CrossRefGoogle Scholar
  27. 27.
    Rohsius C, Matissek R, Lieberei R. Free amino acid amounts in raw cocoas from different origins. Eur Food Res Technol. 2006;222:432–8.CrossRefGoogle Scholar
  28. 28.
    Voigt J, Biehl B, Heinrichs H, et al. In-vitro formation of cocoa-specific aroma precursors: aroma-related peptides generated from cocoa seed protein by co-operation of an aspartic endoprotease and a carboxypeptidase. Food Chem. 1994;49:173–80.CrossRefGoogle Scholar
  29. 29.
    Mohr W, Landschreiber E, Severin T. Zur Spezifität des Kakaoaromas. Fette Seifen Anstrichmittel. 1976;78:88–95.CrossRefGoogle Scholar
  30. 30.
    Biehl B, Heinrichs H, Ziegeler-Berghausen H, et al. The proteases of ungerminated cocoa seeds and their role in the fermentation process. Angew Bot. 1993;67:59–65.Google Scholar
  31. 31.
    Laloi M, McCarthy J, Morandi O, et al. Molecular and biochemical characterization of two proteinases TcAP1 and TcAP2 from Theobroma cacao seeds. Planta. 2002;215:754–62.PubMedCrossRefGoogle Scholar
  32. 32.
    Voigt J, Kamaruddin S, Heinrichs H, et al. Developmental stage-dependent variation of the levels of globular storage protein and aspartic endoprotease during ripening and germination of Theobroma cacao seeds. J Plant Physiol. 1995;145:299–307.CrossRefGoogle Scholar
  33. 33.
    Voigt G, Biehl B, Heinrichs H, et al. Aspartic proteinase levels in seeds of different angiosperms. Phytochemistry. 1997;44:389–92.CrossRefGoogle Scholar
  34. 34.
    Guilloteau M, Lalaoi M, Michaux S, et al. Identification and characterization of the major aspartic endoprotease activity in Theobroma cacao seeds. J Sci Food Agric. 2005;85:549–62.CrossRefGoogle Scholar
  35. 35.
    Hansen CE, del Olmo M, Burri C. Enzyme activities in cocoa beans during fermentation. J Sci Food Agric. 1998;77:273–81.CrossRefGoogle Scholar
  36. 36.
    Hansen CE, Manez A, Burri C, et al. Comparison of enzyme activities involved in flavour precursor formation in unfermented beans of different cocoa genotypes. J Sci Food Agric. 2000;80:1193–8.CrossRefGoogle Scholar
  37. 37.
    Bytof G, Biehl B, Heinrichs H, et al. Specificity and stability of the carboxypeptidase activity in ripe, ungerminated seeds of Theobroma cacao L. Food Chem. 1995;54:15–21.CrossRefGoogle Scholar
  38. 38.
    Neurath H. Carboxypeptidase A. In: Boyer PD, Lardy HA, Myrbäck K, editors. The enzymes, vol. 4. New York: Academic; 1960. p. 11–24.Google Scholar
  39. 39.
    Ambler RP. Enzymatic hydrolysis with carboxypeptidases. Methods Enzymol. 1972;25:143–54.CrossRefGoogle Scholar
  40. 40.
    Breddam K, Sœrensen SB, Svendson I. Primary structure and enzymatic properties of carboxypeptidase II from wheat bran. Carlsberg Res Commun. 1987;52:297–311.CrossRefGoogle Scholar
  41. 41.
    Spencer ME, Hodge R. Cloning and sequencing of the cDNA encoding the major albumin of Theobroma cacao. Planta. 1991;183:528–35.CrossRefGoogle Scholar
  42. 42.
    Tai H, McHenry L, Fritz PJ, et al. Nucleic acid sequence of a 21 kDa cocoa seed protein with homology to the soybean trypsin inhibitor (Kunitz) family of protease inhibitors. Plant Mol Biol. 1991;16:913–5.PubMedCrossRefGoogle Scholar
  43. 43.
    Voigt J, Biehl B, Kamaruddin S. The major seed proteins of Theobroma cacao L. Food Chem. 1993;47:145–51.CrossRefGoogle Scholar
  44. 44.
    Kochhar S, Gartenmann K, Juillerat MA. Primary structure of the abundant seed albumin of Theobroma cacao by mass spectrometry. J Agric Food Chem. 2000;48:5593–9.PubMedCrossRefGoogle Scholar
  45. 45.
    Kochhar S, Gartenmann K, Gilloteau M, et al. Isolation and characterization of 2 S cocoa seed albumin storage polypeptide and the corresponding cDNA. J Agric Food Chem. 2001;49:4470–7.PubMedCrossRefGoogle Scholar
  46. 46.
    Pettipher GL. The extraction and partial purification of cocoa storage proteins. Café Cacao Thé. 1999;34:23–6.Google Scholar
  47. 47.
    Spencer ME, Hodge R. Cloning and sequencing of a cDNA encoding the major storage proteins of Theobroma cacao. Identification of the proteins as members of the vicilin class of storage proteins. Planta. 1992;186:567–76.CrossRefGoogle Scholar
  48. 48.
    McHenry L, Fritz PJ. Comparison of the structure and nucleotide sequence of vicilin genes of cocoa and cotton raise questions about vicilin evolution. Plant Mol Biol. 1992;18:1173–6.PubMedCrossRefGoogle Scholar
  49. 49.
    Biehl B, Wewetzer C, Passern D. Vacuolar (storage) proteins and their degradation during germination and fermentation. J Sci Food Agric. 1982;33:1291–304.CrossRefGoogle Scholar
  50. 50.
    Voigt J, Heinrichs H, Voigt G, et al. Cocoa-specific aroma precursors are generated by proteolytic digestion of the vicilin-like globulin of the cocoa seeds. Food Chem. 1994;50:177–84.CrossRefGoogle Scholar
  51. 51.
    Voigt J, Wrann D, Heinrichs H, et al. The proteolytic formation of essential cocoa-specific aroma precursors depends on particular chemical structures of the vicilin-class globulin of the cocoa seeds lacking in the globular storage proteins of coconuts, hazelnuts, and sunflower seeds. Food Chem. 1994;51:197–205.CrossRefGoogle Scholar
  52. 52.
    Derbyshire E, Wright DJ, Boulter D. Legumin and vicilin, storage proteins of legume seeds. Phytochemistry. 1976;15:3–24.CrossRefGoogle Scholar
  53. 53.
    Borroto K, Dure L. The globulin seeds storage proteins of flowering plants are derived from two ancestral genes. Plant Mol Biol. 1987;8:113–31.CrossRefGoogle Scholar
  54. 54.
    Kratzer U, Frank R, Kalbacher H, et al. Subunit structure of the vicilin-like globular storage protein of cocoa seeds and the origin of cocoa- and chocolate-specific aroma precursors. Food Chem. 2009;113:903–13.CrossRefGoogle Scholar
  55. 55.
    Amin I, Jinap S, Jamilah B, et al. Analysis of vicilin (7S)-class globulin in cocoa cotyledons from various genetic origins. J Sci Food Agric. 2002;82:728–32.CrossRefGoogle Scholar
  56. 56.
    Vaintraub IA, Kotova LV, Shaha R. Protein deamidase from germinating wheat grains. FEBS Lett. 1992;302:169–71.PubMedCrossRefGoogle Scholar
  57. 57.
    Voigt J, Voigt G, Heinrichs H, et al. In vitro studies on the proteolytic formation of the characteristic aroma precursors of fermented cocoa seeds: the significance of endoprotease specificity. Food Chem. 1994;51:7–14.CrossRefGoogle Scholar
  58. 58.
    Heinzler M, Eichner KV. Verhalten von Amadori-Verbindungen während der Kakaoverarbeitung. Bildung von Aromastoffen unter Röstbedingungen. Z Lebensm Unters Forsch. 1991;192:445–50.CrossRefGoogle Scholar
  59. 59.
    Garbe LA, Wuertz A, Piechotta CT, et al. The peptide-catalyzed Maillard reaction. Characterization of 13°C reductones. Ann NY Acad Sci. 2008;1126:244–7.PubMedCrossRefGoogle Scholar
  60. 60.
    Van Lancker F, Adams A, De Kimpe N. Formation of pyrazines in Maillard model systems of lysine-containing dipeptides. J Agric Food Chem. 2010;58:2470–8.PubMedCrossRefGoogle Scholar
  61. 61.
    Voigt J, Kratzer U, Biehl B, et al. The origin of cocoa- and chocolate-specific aroma precursors. Malays Cocoa J. 2009;5:68–72.Google Scholar
  62. 62.
    Ploetz RC. Cacao diseases: important threats to chocolate production worldwide. Phytopathology. 2007;97:1634–9.PubMedCrossRefGoogle Scholar
  63. 63.
    Schnell RJ, Brown JS, Kuhn DN, et al. Development of a marker assisted selection program for cacao. Phytopathology. 2007;97:1664–9.PubMedCrossRefGoogle Scholar
  64. 64.
    Schnell RJ, Kuhn DN, Shapiro HY, et al. New tools to increase the efficiency of traditional cacao breeding. Malays Cocoa J. 2009;5:24–36.Google Scholar
  65. 65.
    Luna F, Crouzillat D, Cirou L, et al. Chemical composition and flavor of Ecuadorian cocoa liquor. J Agric Food Chem. 2002;50:3527–32.PubMedCrossRefGoogle Scholar
  66. 66.
    Counet C, Ouwerx C, Rosoux D, et al. Relationship between procyanidin and flavour contents of cocoa liquors from different origins. J Agric Food Chem. 2004;52:6243–9.PubMedCrossRefGoogle Scholar
  67. 67.
    Khairul Bariah S, Amin I, Furtek D. Correlation of cocoa flavor with the concentration of vicilin (7S)-class globulin in embryos. In: Proceedings of the 2007 Conference on Plantation Commodities; Kuala Lumpur; 2007. p. 55–58.Google Scholar
  68. 68.
    Pino J, Roncal E. Linalool content in roasted cocoa butter as characteristic of several flavour grade cocoas. Die Nahrung. 1992;36:299–301.CrossRefGoogle Scholar
  69. 69.
    Ziegleder G. Linalool contents as characteristic of some flavour grade cocoas. Z Lebensm Unters Forsch. 1990;191:306–9.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2013

Authors and Affiliations

  1. 1.Institute for BiochemistryCharité – University Medicine BerlinBerlinGermany

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