Skip to main content
Log in

Photo-protective effects of furocoumarins on terpenes in lime, lemon and bergamot essential oils upon UV light irradiation

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

Abstract

The impact of naturally occurring furocoumarins on essential agrumen oils, namely bergamot, lime and, lemon, was investigated upon exposure to UV-A light. For this purpose, the oils were initially freed from furocoumarins and coumarins by precipitation in cold hexane. Such pretreated oils, as well as samples of these oils spiked with separated furocoumarins were irradiated for up to 10 days. All essential oils devoid of furocoumarins showed a massive degradation of the predominant terpenes R-(+)-limonene and γ-terpinene. For lime and lemon essential oils 10% and 7.5% of the initial R-(+)-limonene amount was degraded within 10 days, respectively. In addition, a noticeable hydroperoxide formation was observed. For γ-terpinene, this effect was even more pronounced and in both, lime and lemon essential oil samples, the terpene was entirely converted into p-cymene after 6 days. In comparison, addition of 5% furocoumarins to the essential oils decelerated the photo degradation of R-(+)-limonene and γ-terpinene by up to one order of magnitude. The protective effect of furocoumarins, presumably due to bathochromic shifts of emitted light to less harmful longer wavelengths, also improved the olfactory quality. The results demonstrate that blends of non-volatile furocoumarins and volatile terpenes extend the shelf-life of light-sensitive agrumen oils.

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.

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

Similar content being viewed by others

References

  1. Teuscher E (2018) Gewürze und Küchenkräuter: Gewinnung, Inhaltsstoffe, Wirkungen, Verwendung. Wissenschaftliche Verlagsgesellschaft, Stuttgart

    Google Scholar 

  2. Agustí M, Mesejo C, Reig C, Martínez-Fuentes A (2014) Citrus production. In: Dixon GR, Aldous DE (eds) Horticulture: plants for people and places, volume 1: production horticulture. Springer, Netherlands, Dordrecht, pp 159–195

    Google Scholar 

  3. Hung W-L, Suh JH, Wang Y (2017) Chemistry and health effects of furanocoumarins in grapefruit. J Food Drug Anal 25:71–83. https://doi.org/10.1016/j.jfda.2016.11.008

    Article  CAS  PubMed  Google Scholar 

  4. Arce A, Soto A (2008) Citrus essential oils: extraction and deterpenation. Tree and Forestry Science and Biotechnology. Global Science Books, Santiago de Compostela, Spain

  5. Russo M, Rigano F, Arigò A, Dugo P, Mondello L (2021) Coumarins, psoralens and polymethoxyflavones in cold-pressed citrus essential oils: a review. J Essent Oil Res 33:221–239. https://doi.org/10.1080/10412905.2020.1857855

    Article  CAS  Google Scholar 

  6. Crozier A, Clifford MN, Ashihara H (2008) Plant secondary metabolites: occurrence, structure and role in the human diet. Wiley, Hoboken

    Google Scholar 

  7. Frérot E, Decorzant E (2004) Quantification of total furocoumarins in citrus oils by HPLC coupled with UV, fluorescence, and mass detection. J Agric Food Chem 52:6879–6886. https://doi.org/10.1021/jf040164p

    Article  CAS  PubMed  Google Scholar 

  8. Peroutka R, Schulzová V, Botek P, Hajšlová J (2007) Analysis of furanocoumarins in vegetables (Apiaceae) and citrus fruits (Rutaceae). J Sci Food Agric 87:2152–2163. https://doi.org/10.1002/jsfa.2979

    Article  CAS  Google Scholar 

  9. Stringlis IA, de Jonge R, Pieterse CMJ (2019) The age of coumarins in plant-microbe interactions. Plant Cell Physiol 60:1405–1419. https://doi.org/10.1093/pcp/pcz076

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Eisenbrand G (2007) Toxicological assessment of furocoumarins in foodstuffs. Mol Nutr Food Res 51:367–373. https://doi.org/10.1002/mnfr.200600270

    Article  CAS  Google Scholar 

  11. Melough MM, Cho E, Chun OK (2018) Furocoumarins: a review of biochemical activities, dietary sources and intake, and potential health risks. Food Chem Toxicol 113:99–107. https://doi.org/10.1016/j.fct.2018.01.030

    Article  CAS  PubMed  Google Scholar 

  12. Regulation (EC) No 1223/2009 (2009) of the European Parliament and of the Council of 30 November 2009 on cosmetic products

  13. Costa R, Dugo P, Navarra M, Raymo V, Dugo G, Mondello L (2010) Study on the chemical composition variability of some processed bergamot (Citrus bergamia) essential oils. Flavour Fragr J 25:4–12. https://doi.org/10.1002/ffj.1949

    Article  CAS  Google Scholar 

  14. Musajo L, Rodighiero G (1962) The skin-photosensitizing furocoumarins. Experientia 18:153–161. https://doi.org/10.1007/BF02151700

    Article  CAS  PubMed  Google Scholar 

  15. Naganuma M, Hirose S, Nakayama Y, Nakajima K, Someya T (1985) A study of the phototoxicity of lemon oil. Arch Dermatol Res 278:31–36. https://doi.org/10.1007/BF00412492

    Article  CAS  PubMed  Google Scholar 

  16. Zaynoun ST, Johnson BE, Frain-Bell W (1977) A study of oil of bergamot and its importance as a phototoxic agent. Contact Dermatitis 3:225–239. https://doi.org/10.1111/j.1600-0536.1977.tb03667.x

    Article  CAS  PubMed  Google Scholar 

  17. Scott BR, Pathak MA, Mohn GR (1976) Molecular and genetic basis of furocoumarin reactions. Mutat Res Genet Toxicol 39:29–74. https://doi.org/10.1016/0165-1110(76)90012-9

    Article  CAS  Google Scholar 

  18. Bitterling H, Lorenz P, Vetter W, Kammerer DR, Stintzing FC (2022) Photo-protective effects of selected furocoumarins on β-pinene, R-(+)-limonene and γ-terpinene upon UV-A irradiation. J Photochem Photobiol Chem. 424 (2022) 113623. https://doi.org/10.1016/j.jphotochem.2021.113623

    Article  Google Scholar 

  19. Verhoeven JW (1996) Glossary of terms used in photochemistry (IUPAC Recommendations 1996). Pure Appl Chem 68:2223–2286. https://doi.org/10.1351/pac199668122223

    Article  CAS  Google Scholar 

  20. Hammond GS, Stout CA, Lamola AA (1964) Mechanisms of photochemical reactions in solution. XXV. The photodimerization of coumarin. J Am Chem Soc 86:3103–3106. https://doi.org/10.1021/ja01069a026

    Article  CAS  Google Scholar 

  21. Bitterling H, Lorenz P, Vetter W, Kammerer DR, Stintzing FC (2020) Rapid spectrophotometric method for assessing hydroperoxide formation from terpenes in essential oils upon oxidative conditions. J Agric Food Chem 68:9576–9584. https://doi.org/10.1021/acs.jafc.0c03981

    Article  CAS  PubMed  Google Scholar 

  22. Van Den Dool H, Dec. Kratz P (1963) A generalization of the retention index system including linear temperature programmed gas-liquid partition chromatography. J Chromatogr A 11:463–471. https://doi.org/10.1016/S0021-9673(01)80947-X

    Article  Google Scholar 

  23. Scheel LD, Perone VB, Larkin RL, Kupel RE (1963) The isolation and characterization of two phototoxic furanocoumarins (psoralens) from diseased celery. Biochemistry 2:1127–1131. https://doi.org/10.1021/bi00905a038

    Article  CAS  PubMed  Google Scholar 

  24. Feger W, Brandauer H, Gabris P, Ziegler H (2006) Nonvolatiles of commercial lime and grapefruit oils separated by high-speed countercurrent chromatography. J Agric Food Chem 54:2242–2252. https://doi.org/10.1021/jf052267t

    Article  CAS  PubMed  Google Scholar 

  25. Jungen M, Lotz P, Patz C-D, Steingass CB, Schweiggert R (2021) Coumarins, psoralens, and quantitative 1H-NMR spectroscopy for authentication of lemon (Citrus limon [L.] Burm.f.) and Persian lime (Citrus × latifolia [Yu.Tanaka] Tanaka) juices. Food Chem 359:129804. https://doi.org/10.1016/j.foodchem.2021.129804

    Article  CAS  PubMed  Google Scholar 

  26. Ziegler H, Spiteller G (1992) Coumarins and psoralens from sicilian lemon oil (Citrus limon (L.) Burm. f.). Flavour Fragr J 7:129–139. https://doi.org/10.1002/ffj.2730070307

    Article  CAS  Google Scholar 

  27. Mondello L, d’Alcontres IS, Duce RD, Crispo F (1993) On the genuineness of citrus essential oils. Part XL. The composition of the coumarins and psoralens of Calabrian bergamot essential oil (Citrus bergamia Risso). Flavour Fragr J 8:17–24. https://doi.org/10.1002/ffj.2730080105

    Article  CAS  Google Scholar 

  28. Spadaro F, Costa R, Circosta C, Occhiuto F (2012) Volatile composition and biological activity of key lime Citrus aurantifolia essential oil. Nat Prod Commun 7:1523–1526

    CAS  PubMed  Google Scholar 

  29. Erasto P, Viljoen AM (2008) Limonene—a review: biosynthetic, ecological and pharmacological relevance. Nat Prod Commun. https://doi.org/10.1177/1934578X0800300728

    Article  Google Scholar 

  30. Ravichandran C, Badgujar PC, Gundev P, Upadhyay A (2018) Review of toxicological assessment of d-limonene, a food and cosmetics additive. Food Chem Toxicol 120:668–680. https://doi.org/10.1016/j.fct.2018.07.052

    Article  CAS  PubMed  Google Scholar 

  31. Karlberg A-T, Magnusson K, Nilsson U (1992) Air oxidation of d-limonene (the citrus solvent) creates potent allergens. Contact Dermatitis 26:332–340. https://doi.org/10.1111/j.1600-0536.1992.tb00129.x

    Article  CAS  PubMed  Google Scholar 

  32. Christensson JB, Johansson S, Hagvall L, Jonsson C, Börje A, Karlberg A-T (2008) Limonene hydroperoxide analogues differ in allergenic activity. Contact Dermatitis 59:344–352. https://doi.org/10.1111/j.1600-0536.2008.01442.x

    Article  CAS  PubMed  Google Scholar 

  33. Asikainen M, Jauhiainen O, Aaltonen O, Harlin A (2013) Continuous catalyst-free aromatization of γ-terpinene using air as an oxidant. Green Chem 15:3230–3235. https://doi.org/10.1039/C3GC41224E

    Article  CAS  Google Scholar 

  34. Dugo P, Mondello L, Lamonica G, Dugo G (1997) Characterization of cold-pressed key and persian lime oils by gas chromatography, gas chromatography/mass spectroscopy, high-performance liquid chromatography, and physicochemical indices. J Agric Food Chem 45:3608–3616. https://doi.org/10.1021/jf960932f

    Article  CAS  Google Scholar 

  35. Nguyen H, Campi EM, Roy Jackson W, Patti AF (2009) Effect of oxidative deterioration on flavour and aroma components of lemon oil. Food Chem 112:388–393. https://doi.org/10.1016/j.foodchem.2008.05.090

    Article  CAS  Google Scholar 

  36. Bitterling H, Lorenz P, Vetter W, Kammerer DR, Stintzing FC (2021) Storage-related changes of terpene constituents in caraway (Carum carvi L.) under real-time storage conditions. Ind Crops Prod 170:113782. https://doi.org/10.1016/j.indcrop.2021.113782

    Article  CAS  Google Scholar 

  37. Serrano-Pérez JJ, González-Luque R, Merchán M, Serrano-Andrés L (2008) The family of furocoumarins: looking for the best photosensitizer for phototherapy. J Photochem Photobiol Chem 199:34–41. https://doi.org/10.1016/j.jphotochem.2008.04.013

    Article  CAS  Google Scholar 

  38. Kitamura N, Kohtani S, Nakagaki R (2005) Molecular aspects of furocoumarin reactions: photophysics, photochemistry, photobiology, and structural analysis. J Photochem Photobiol C Photochem Rev 6:168–185. https://doi.org/10.1016/j.jphotochemrev.2005.08.002

    Article  CAS  Google Scholar 

  39. Pathak MA, Allen B, Ingram DJE, Fellman JH (1961) Photosensitization and the effect of ultraviolet radiation on the production of unpaired electrons in the presence of furocoumarins (psoralens). Biochim Biophys Acta 54:506–515. https://doi.org/10.1016/0006-3002(61)90091-9

    Article  CAS  PubMed  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Florian C. Stintzing.

Ethics declarations

Conflict of interest

The work was supported by WALA Heilmittel GmbH, Dorfstraße 1, D-73087, Bad Boll/Eckwälden.

Compliance with ethics requirements

The study does not contain any studies with human participants or animals performed by any one of the authors.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bitterling, H., Mailänder, L., Vetter, W. et al. Photo-protective effects of furocoumarins on terpenes in lime, lemon and bergamot essential oils upon UV light irradiation. Eur Food Res Technol 248, 1049–1057 (2022). https://doi.org/10.1007/s00217-021-03945-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00217-021-03945-1

Keywords

Navigation