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Authentication of a Flavoring Substance: The Vanillin Case

Contact Author Corine Cochennec, Solvay Vanil’Expert Center EMEA & Global Formulations Manager and Corinne Duffy, Technical Marketing Manager, Solvay Aroma Performance
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Vanilla beans

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Vanilla is, and will certainly remain, one of the most appreciated flavors in the world. Grown in tropical areas around the world, vanilla is mainly grown in Madagascar. Its supply is subject to variability in availability, price and quality. In recent years, vanilla beans prices have increased greatly due to climate issues and speculation, alongside with a decrease of quality. The large demand for vanilla in sweet flavors cannot be met by the limited amount of cultivated vanilla beans.

Vanillin (4-hydroxy-3-methoxybenzaldehyde) is the main organoleptic characteristic aroma component, naturally occurring in cured vanilla beans between 1-2% of the dry matter. In order to satisfy the increasing global demand for this highly favored flavor, ingredients suppliers have developed several types of vanillins identical to the one present in vanilla beans, meeting different labels, either synthetic or more recently natural to meet the increasing natural trend market demand (see T-1).

Overview of industrial synthetic and natural pathways to obtain vanillins

The current offer for vanillin is quite vast; F-1 gives a large and comprehensive landscape of vanillins available on the market.

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Originally, vanillin came from vanilla beans where it is present as glucovanillin, linked to a carbohydrate moiety and released by the curing process. Vanillins can now be largely grouped into three categories:

  • Synthetic vanillins: Nowadays, the very large majority of vanillin used in the flavor and food and beverage industry are synthetic vanillin. Most of the synthetic vanillins are produced from catechol by a first step of methylation leading to synthetic guaiacol, followed by formylation with glyoxylic acid. Other types of synthetic vanillin are produced by chemical oxidation of the sulfitic waste, namely the brown liquor, of the paper industry leading to vanillin from lignin.
  • EU natural vanillins: Driven by consumer demand for natural flavors in the 90’s, a growing interest to produce natural vanillin through bioconversion from sources other than the vanilla bean was observed. One of the most intensively studied processes to produce natural vanillin is the bioconversion of ferulic acid, naturally occurring in the cell walls of plants such as rice or maize.3-9, 22,23 Vanillin obtained from ferulic acid, available on the market since the 2000’s10, strictly meets the EU and U.S. regulations on natural flavors.
  • U.S. natural vanillins: Eugenol is naturally occurring in clove. Because eugenol is an antiseptic compound, the biotransformation of eugenol to vanillin is difficult.10-16

The vanillin ex-eugenol available on the market is produced by conversion of eugenol to isoeugenol followed by catalytic oxidation,17,18 process conditions not meeting the definition of natural process according to EU regulation and accepted as natural in the U.S. market.

Curcumin naturally occurring in curcuma is another natural precursor. Though described in the literature, the bioconversion of curcumin to vanillin is tedious19 and ex-curcumin vanillin available on the market is mainly produced by the Mallinkrodt process,20, at high temperature (> 250°C) and high pressure (> 100 mbar). These process conditions do not fulfill the definition of natural process stated in Regulation (EC) N° 1334/2008.

Guaiacol is a naturally-occurring molecule that can be derived from guaiacum or wood creosote. Nowadays, natural guaiacol is sustainably obtained from renewable wood such as beech, pine or oak. Guaiacol itself is a flavoring substance (FEMA# 2532) displaying a smoky, bacon note contributing to the flavor of many substances such as whiskey and roasted coffee.

U.S. natural vanillin was recently produced by Solvay at industrial scale from natural guaiacol by a process compliant with the FDA regulation in force. Rhovanil US Nat from natural guaiacol displays a pure vanillin profile, making it the perfect substitute to synthetic vanillin for US natural flavors, unlike other US natural vanillin, such as ex-eugenol vanillin displaying unpleasant spicy, smoky and eugenol facets. As prices can vary greatly depending on availability, processes and labeling, it is key to rely on authentication methods to guarantee transparency to customers.

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T-1. Regulations on natural flavoring substances in force

T-1. Regulations on natural flavoring substances in force

T-1.

F-1. Available vanillin pathways in the market

F-1. Available vanillin pathways in the market

F-1.

References

References

  1. EC 1334/2008: REGULATION (EC) No 1334/2008 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 16 December 2008 on flavorings and certain food ingredients with flavoring properties for use in and on foods and amending Council Regulation (EEC) No 1601/91, Regulations (EC) No 2232/96 and (EC) No 110/2008 and Directive 2000/13/EC
  2. US FDA 21CFR101.22
  3. H Priefert, J Rabenhorst, A Steinbüchel, Biotechnological production of vanillin, Appl Microbiol Biotechnol, 56, 296-314 (2001)
  4. JB Sutherland, DL Crawford and AL Pometto, Metabolism of cinnamic, p-coumaric and ferulic acids by streptomyces setonii, Can.J. Microbiol., 29, 1253-1257 (1983)
  5. EP 885968, Process for production of vanillin, B Mueller, T Muench, A Muheim and M Welti (June 19, 1997) (to Givaudan)
  6. WO 9634971, Method for producing vanillin using the bioconversion of benzene precursors, B Audras and J More (May 5, 1995) (to Orsan)
  7. EP761817, Process for the preparation of vanillin and microorganisms suitable therefore, R Hopp and J Rabenhorst (September 1rst,1995) (to Symrise)
  8. EP 1240336, Enzyme and genes used for producing vanillin, J Rabenhorst, A Stein-Büchel, H Priefert and S Achterholt (December 14, 1999) (to Symrise)
  9. GB 2347424, Flavor/aroma materials and their preparation, PSJ Cheetham, ML Gradley and JT Sime (February 24, 1999) (to Zylepsis)
  10. JR Desmurs, D Giannotta, M Gelo-Pujic, C Role and P Lancelin, Synthesis and Authentication of Natural Vanillins Prepared by Fermentation, Perfumer & Flavorist, 29 (1) 32 (2004)
  11. “Biochemical process for preparing aromatic substances” – WO9622381- MANE-J. mane & J. Zucca.
  12. “process for the preparation of phenylaldehydes” – EP542348- QUEST – P.H. markus, R. Roos and A.L.J. Peters.
  13. “Production of vanillin and its related compounds by fermentation” – JP 5227980 – TAKASAGO – Y. Washisu, A. Tetsushi, N. Hashimoto and Y. Kanisawa.
  14. “Process for the preparation of vanillin” – Haarman & Reimer (Symrise) - US5017388 and EP405197 – J. Rabenhorst and R. Hopp.
  15. “Construction of production strains for producing substituted phenols by specifically incactivating genes of eugenol and ferulic acid catabolism” – EP1124947 – SYMRISE – J. Rabenhorst, A. Steinbüchel, H. Priefert and J. Overhage
  16. “Method for producing aromatic molecules in streptomyces” – WO2008/113936 – MANE FILS -
  17. A. Kadarohman – Sigmatropic rearrangement of cis-eugenol formation in isomerization reaction – Chemistry Education Department of Indonesia University of education.
  18. “Oxidation of isoeugenol to vanillin by the H2O2 vanadate pyrazine – carboxylic acid” reagent – Journal of molecular catalysis A :chemical - 363-364 (2012) 140-147
  19. “Biotransformation of curcumin to vanillin”, Indian Journal of Chemistry, vol 50B, august 2011, pp 1119-1122
  20. US4927805 (20/01/1989) – Mallinkrodt
  21. Corine Cochennec, Natural Vanillin Obtained by Means of Bioconversion, Perfumer & Flavorist, vol 38, 20 (2013)
  22. L Lesage-Meessen, A Lomascolo, E Bonnin, JF Thibault, A Buleon, M Roller, M Asther, E Record, B Colonna Ceccaldi and M Asther, A biotechnological Process Involving Filamentous Fungi to Produce Natural Crystalline Vanillin from Maize Bran, Applied Biochemistry and Biotechnology, 102-103, 141-153 (2002)
  23. AIR1-CT92-0026project continued by FAIR Consortium – FAIR-CT95-1099- - Final Report February 2000) (available in the web in 2006, not available anymore)
  24. ASTM D6866-16: Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis
  25. Hoffman PG, Salb M. Isolation and stable isotope ratio analysis of vanillin. J Agric Food Chem. 1979;27:352-355.
  26. Bricout J, Fontes JC, Merlivat L. Detection of synthetic vanillin in vanilla extracts by isotopic analysis. Creteil, France: Institut de Recherches Appliquées aux Boissons; 1974.
  27. “ L’Isotope : Traceur d’Origine. Distribution isotopique dans les composés naturels”. Article rédigé par Gérald Remaud et Serge Akoka (Professeurs, Laboratoire d’Analyse Isotopique et Electrochimique de Métabolismes, LAIEM - UMR-CNRS 6006, Faculté des Sciences et des Techniques de Nantes), relu par Guillaume Champion (professeur agrégé à l’ENS).
  28. Tenailleau EJ, Lancelin P, Robins RJ, Akoka S. Authentication of the origin of vanillin using quantitative natural abundance 13C NMR. J Agric Food Chem. 2004;52:7782-7787.
  29. Caytan E, Botosoa EP, Silvestre V, Robins RJ, Akoka S, Remaud GS. Accurate quantitative 13C NMR spectroscopy: repeatability over time of site-specific 13C isotope ratio determination. Anal Chem. 2007;79:8266-8269.
  30. Caytan E, Remaud GS, Tenailleau E, Akoka S. Precise and accurate quantitative 13C NMR with reduced experimental time. Talanta. 2007;71:1016-1021
  31. Tenailleau E, Lancelin P, Robins RJ, Akoka S. NMR approach to the quantification of nonstatistical 13C distribution in natural products: vanillin. Anal Chem. 2004;76:3818-3825.
  32. Alain Chaintreau, Wolfgang Fieber, Horst Sommer, Alexis Gilbert, Keita Yamada, Naohiro Yoshida, Alain Pagelot, Detlef Moskau, Aitor Moreno, Jürgen Schleucher, Fabiano Reniero, Margaret Holland, Claude Guillou, Virginie Sylvestre, Serge Aloka, Gérald S. Rémaud, Site –specific 3C content by quantitative isotopic 3C Nuclear magnetic Resonance spectrometry: a pilot interlaboratory study. Analytica Chemica Acta 788 (2013) 108-113
  33. Sophie Guyader, Freddy Thomas, Eric Jamin, Mathilde Grand, Serge Akoka, Virginie Silvestre, Gérald S. Remaud, Combination of 13C and 2 H SNIF-NMR isotopic fingerprints of vanillin to control its precursors. Flavour Fragr J. 2019;1–12

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