Abstract
In addition to pure synthetic fragrance materials several natural extracts are still in use in the perfume industry. Among them oak moss absolute, prepared from the lichen Evernia prunastri (L.) Arch., is considered a major contact sensitizer and is therefore included in the fragrance mix used for diagnosing perfume allergy. The process of preparing oak moss absolute has changed during recent years and, even though several potential sensitizers have been identified from former benzene extracts, its present constituents and their allergenic status are not clear. In the study reported here, we applied a method developed for the identification of contact allergens present in natural complex mixtures to oak moss absolute. The method is based on the combination of bioassay-guided chemical fractionation, gas chromatography-mass spectrometry analysis and structure-activity relationship studies. Our first results showed that atranol and chloroatranol, formed by transesterification and decarboxylation of the lichen depsides, atranorin and chloroatranorin, during the preparation of oak moss absolute, are strong elicitants in most patients sensitized to oak moss. Methyl-β-orcinol carboxylate, a depside degradation product and the most important monoaryl derivative of oak moss from an olfactory standpoint, was also found to elicit a reaction in most patients.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Actander S (1960) Oak moss. In: Perfume and flavor materials of natural origin. Elisabeth, NJ, pp 446–456
Johansen JD, Menné T (1995) The fragrance mix and its constituents: a 14-year material. Contact Dermatitis 32:18–23
Johansen JD, Heydorn S, Menné T (2002) Oak moss extracts in the diagnosis of fragrance contact allergy. Contact Dermatitis 46:157–161
Gavin J, Tabacchi R (1975) Isolement et identification de composés phénoliques et monoterpéniques de la mousse de chêne (Evernia prunastri (L.) Ach.). Helv Chim Acta 58:190–194
Gavin J, Nicollier G, Tabacchi R (1978) Composants volatils de la mousse de chêne (Evernia prunastri (L.) Ach.). Helv Chim Acta 61:352–357
Schulz H, Albroscheit G (1989) Characterization of oak moss products used in perfumery by high-performance liquid chromatography. J Chromatogr 466:301–306
Hiserodt RD, Swijter DFH, Mussinan CJ (2000) Identification of atranorin and related potential allergens in oak moss absolute by high-performance liquid chromatography-tandem mass spectrometry using negative ion atmospheric pressure chemical ionization. J Chromatogr A 888:103–111
Dahlquist I, Fregert S (1980) Contact allergy to atranorin in lichens and perfumes. Contact Dermatitis 6:111–119
Thune P, Solberg Y, McFadden N, Staerfelt F, Sandberg M (1982) Perfume allergy due to oak moss and other lichens. Contact Dermatitis 8:396–400
Sandberg M, Thune P (1984) The sensitizing capacity of atranorin. Contact Dermatitis 11:168–173
Gonçalo S, Cabral F, Gonçalo M (1988) Contact sensitivity to oak moss. Contact Dermatitis 19:355–357
Terajima Y, Ichikawa H, Tokuda K, Nakamura S (1988) Quantitative analysis of oak moss oil. In: Lawrence BM, Mookerjee BD, Willis BJ (eds) Flavors and fragrances: a world perspective. Elsevier Science, Amsterdam, pp 685–695
Buckley DA, Wakelin SH, Seed PT, Holloway D, Rycroft RJG, White IR, McFadden JP (2000) The frequency of fragrance allergy in a patch test population over 17 years. Br J Dermatol 142:279–283
Mutterer V, Giménez Arnau E, Lepoittevin J-P, Johansen JD, Frosch PJ, Menné T, Andersen KE, Bruze M, Rastogi SC, White IR (1999) Identification of coumarin as the sensitizer in a patient sensitive to her own perfume but negative to the fragrance mix. Contact Dermatitis 40:196–199
Giménez Arnau E, Andersen KE, Bruze M, Frosch PJ, Johansen JD, Menné T, Rastogi SC, White IR, Lepoittevin J-P (2000) Identification of Lilial as a fragrance sensitizer in a perfume by bioassay-guided chemical fractionation and structure-activity relationships. Contact Dermatitis 43:351–358
Lepoittevin J-P, Meschkat E, Huygens S, Goosens A (2000) Presence of resin acids in "Oakmoss" patch test material: a source of misdiagnosis? J Invest Dermatol 115:129–130
Ter Heide R, Provatoroff N, Traas PC, De Valois PJ, Wobben HJ, Timmer R (1975) Qualitative analysis of the odoriferous fraction of oakmoss (Evernia prunastri (L.) Arch.). J Agric Food Chem 23:950–957
Boelens MH (1993) Formation of volatile compounds from oakmoss. Perfumer Flavorist 18:27–30
Bauer K, Garbe D, Surburg H (1997) Common fragrance and flavor materials: preparation, properties and uses, 3rd edn. Wiley-VCH Verlag, Weinheim
Rustemeyer T, Van Hoogstrate IMW, Von Blomberg BME, Scheper RJ (2001) Mechanisms in allergic contact dermatitis. In: Rycroft RJG, Menné T, Frosch PJ, Lepoittevin J-P (eds) Textbook of contact dermatitis, 3rd edn. Springer, Berlin Heidelberg, pp 13–58
Smith CK, Hotchkiss SAM (2001) Xenobiotics as skin sensitizers: metabolic activation and detoxication, and protein-binding mechanisms. In: Smith CK, Hotchkiss SAM (eds) Allergic contact dermatitis: chemical and metabolic mechanisms. Taylor & Francis, London, pp 119–205
Acknowledgements
The assistance of Mireille Huel for the synthesis of atranol and chloroatranol is gratefully acknowledged. This work was financially supported by the Fifth Framework Programme of the European Commission, under the Quality of Life and Management of Living Resources thematic programme, key action Environment and Health (Contract QLK4-CT-1999-01558: "Fragrance chemical allergy: a major environmental and consumer health problem in Europe"). Research participants: Jean-Pierre Lepoittevin, Elena Giménez-Arnau and Guillaume Bernard, University Louis Pasteur, Strasbourg, France; Ann-Therese Karlberg, Mihaly Matura, Anna Börje and Maria Sköld, National Institute for Working Life, Stockholm, Sweden; David Basketter and Grace Patlewicz, SEAC, Unilever Research, Bedford, UK; Torkil Menné, Jeanne Duus Johansen and Siri Heydorn, Department of Dermatology, Gentofte Hospital, University of Copenhagen, Denmark; Peter J. Frosch, Department of Dermatology and University of Witten/Herdecke, Dortmund, Germany; Ian White, Department of Contact Dermatitis and Occupational Dermatology, St. John's Institute of Dermatology, St. Thomas' Hospital, London, UK; Suresh Rastogi, National Environmental Research Institute, Roskilde, Denmark; Klaus E. Andersen, Department of Dermatology, Odense University Hospital, Denmark; Magnus Bruze and Cecilia Svedman, Department of Occupational Dermatology, University Hospital Malmö, Sweden; and An Goossens, Department of Dermatology, University Hospital KU Leuven, Belgium.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Bernard, G., Giménez-Arnau, E., Rastogi, S.C. et al. Contact allergy to oak moss: search for sensitizing molecules using combined bioassay-guided chemical fractionation, GC-MS, and structure-activity relationship analysis. Arch Dermatol Res 295, 229–235 (2003). https://doi.org/10.1007/s00403-003-0426-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00403-003-0426-3