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Identification of (−)-β-Caryophyllene as a Gender-Specific Terpene Produced by the Multicolored Asian Lady Beetle

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Abstract

This work reports the development and use of techniques for characterizing volatile chemicals emitted by the multicolored Asian lady beetle, Harmonia axyridis (Pallas) (Coleoptera: Coccinellidae), in an effort to identify the semiochemicals involved in establishment and persistence of overwintering beetle aggregations. Volatiles emitted from live beetles were detected by using whole-air sampling and solid-phase microextraction (SPME). Adsorbed volatiles were thermally desorbed and identified with gas chromatography-mass spectrometry (GC/MS). By comparing the chromatograms of volatiles emitted from live male and female beetles, a sesquiterpene, (−)-β-caryophyllene, was found only in the females. The identity of (−)-β-caryophyllene was confirmed by using NIST Library searches, comparing retention times with those of known standards, and by using higher-resolution GC/MS above bench top capability. Although SPME trapping detected a wider array of compounds compared to whole-air sampling, the latter method is better suited for automation. Unattended automated sampling is required for the continuous measurement of targeted compounds under dynamically changing incubation conditions. These conditions, mimicking natural overwintering conditions, are essential to our long-term goal of using this technology to detect and identify the aggregation pheromone of H. axyridis.

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References

  • Agelopoulos, N. G. and Pickett, J. A. 1998. Headspace analysis in chemical ecology: Effects of different sampling methods on ratios of volatile compounds present in headspace samples. J. Chem. Ecol. 24:1161–1172.

    Article  CAS  Google Scholar 

  • Al Abassi, S. A., Birkett, M. A., Pettersson, J., Pickett, J. A., and Woodcock, C. M. 1998. Ladybird beetle odor identified and found to be responsible for attraction between adults. Cell. Mol. Life Sci. 54:876–879.

    Article  CAS  Google Scholar 

  • Al Abassi, S. A., Birkett, M. A., Pettersson, J., Pickett, J. A., Wadhams, L. J., and Woodcock, C. M. 2000. Response of the seven-spot ladybird to an aphid pheromone inhibitor is mediated by paired olfactory cells. J. Chem. Ecol. 26:1765–1771.

    Article  Google Scholar 

  • Arthur, C. L. and Pawliszyn, J. 1990. Solid phase microextraction with thermal desorption using fused silica optical fibers. Anal. Chem. 62:2145–2148.

    Article  CAS  Google Scholar 

  • Birkett, M. A. and Pickett, J. A. 2003. Aphid sex pheromones: From discovery to commercial production. Phytochemistry 62:651–656.

    Article  PubMed  CAS  Google Scholar 

  • Brown, M. W. 2004. Role of the aphid predator guild in controlling spirea aphid populations on apple in West Virginia, USA. Biol. Control 29:189–198.

    Article  Google Scholar 

  • Brown, M. W. and Miller, S. S. 1998. Coccinellidae (Coleoptera) in apple orchards of eastern West Virginia and the impact of invasion by Harmonia axyridis. Entomol. News 109:136–142.

    Google Scholar 

  • Campbell, C. A. M., Petterson, J., Pickett, J. A., Wadhams, L. J., and Woodcock, C. M. 1993. Spring migration of damson hop aphid, Phorodon humuli (Homoptera, Aphididae), and summer host plant derived semiochemicals released on feeding. J. Chem. Ecol. 19:1569–1576.

    Article  CAS  Google Scholar 

  • Cudjoe, E., Wiederkehr, T. B., and Brindle, I. D. 2005. Headspace gas chromatography-mass spectrometry: A fast approach to the identification and determination of 2-alkyl-3-methoxypyrazine pheromones in ladybugs. Analyst 130:152–155.

    Article  PubMed  CAS  Google Scholar 

  • Environmental Protection Agency (EPA). 1989. Compendium of methods for the determination of toxic organic compounds in ambient air. Method TO-14. EPA 600/4-89-018.

  • Flint, H. M., Salter, S. S., and Walters, S. 1979. Caryophyllene: An attractant for the green lacewing. Environ. Entomol. 8:1123–1125.

    CAS  Google Scholar 

  • Fricke, C., Rieck, A., Hardt, I. H., Konig, W. A., and Muhle, H. 1995. Identification of (+)-beta-caryophyllene in essential oils of liverworts by enantioselective gas chromatography. Phytochemistry 39:1119–1121.

    Article  CAS  Google Scholar 

  • Greenwood, J. M., Solomon, M. D., Sutherland, J. K., and Torre, A. 1968. A cyclisation of humulene. J. Chem. Soc., C 1968:3004–3008.

    Article  Google Scholar 

  • Guerin, P. M., Stadler, E., and Buser, H. R. 1983. Identification of host plant attractants for the carrot fly, Psila rosae. J. Chem. Ecol. 9:843–861.

    Article  CAS  Google Scholar 

  • Hedin, P. A., Thompson, A. C., and Gueldner, R. C. 1973. The boll weevil–cotton plant complex. Toxicol. Environ. Chem. Rev. 1:291–351.

    Article  CAS  Google Scholar 

  • Khalilova, A. Z., Paramonov, E. A., Odinokov, V. N., and Khalilov, L. M. 1998. Identification and biological activity of volatile organic substances emitted by plants and insects. 1. Components of the native scents of Leptinotarsa decemlineata and Solanum tuberosum. Chem. Nat. Compd. 34:647–649.

    Article  CAS  Google Scholar 

  • King, A. G. and Meinwald, J. 1996. Review of defensive chemistry of Coccinellidae. Chem. Rev. 96:1105–1122.

    Article  CAS  Google Scholar 

  • Laurent, P., Brackman, J. C., Daloze, D., and Pasteels, J. M. 2002. In vitro production of adaline and coccinelline, two defensive alkaloids from ladybird beetles (Coleoptera: Coccinellidae). Insect Biochem. Mol. Biol. 32:1017–1023.

    Article  PubMed  CAS  Google Scholar 

  • Malosse, C., Ramirez-Lucas, P., Rochat, D., and Morin, J. 1995. Solid-phase microextraction, an alternative method for the study of airborne insect pheromones (Metamasius hemipterus, Coleoptera, Curculionidae). J. High Resolut. Chromatogr. 18:669–670.

    Article  CAS  Google Scholar 

  • Michaud, J. P. 2002. Invasion of the Florida citrus ecosystem by Harmonia axyridis (Coleoptera: Coccinellidae) and asymmetric competition with a native species, Cycloneda sanguinea. Environ. Entomol. 31:827–835.

    Article  Google Scholar 

  • Minyard, J. P., Hardee, D. D., Gueldner, R. C., Thompson, A. C., Wiygul, G., and Hedin, P. A. 1969. Compounds attractive to the boll weevil. J. Agric. Food Chem. 17:1093–1097.

    Article  CAS  Google Scholar 

  • Nalepa, C. A., Kidd, K. A., and Ahlstrom, K. R. 1996. Biology of Harmonia axyridis (Coleoptera: Coccinellidae) in winter aggregations. Ann. Entomol. Soc. Am. 89:681–685.

    Google Scholar 

  • Nazaruk, J., Gora, J., Majda, T., and Gudej, J. 2002. Investigation of essential oil from Cirsium rivulare (Jacq.) All. flowers. Herba Pol. 48:193–197.

    CAS  Google Scholar 

  • Pickering, G., Lin, J., Riesen, R., Reynolds, A., Brindle, I., and Soleas, G. 2004. Influence of Harmonia axyridis on the sensory properties of white wine and red wine. Am. J. Enol. Vitic. 55:153–159.

    Google Scholar 

  • Pickering, G., Lin, J., Reynolds, A., Soleas, G., Riesen, R., and Brindle, I. 2005. The influence of Harmonia axyridis on wine composition and aging. J. Food Sci. 70:S128–S135.

    Article  CAS  Google Scholar 

  • Ray, J. N. and Pence, H. L. 2004. Ladybug hypersensitivity: Report of a case and review of literature. Allergy Asthma Proc. 25:133–136.

    PubMed  Google Scholar 

  • Riddick, E. W. and Aldrich, J. R. 2004. Search for repellents, attractants and pheromones of the multicolored Asian lady beetle. Instant Symposium—Multicolored Asian lady beetles in agriculture and the urban environments. Am. Entomol. 50:167–168.

    Google Scholar 

  • Riddick, E. W., Aldrich, J. R., De Milo, A., and Davis, J. C. 2000. Potential for modifying the behavior of the multicolored Asian lady beetle (Coleoptera: Coccinellidae) with plant-derived natural products. Ann. Entomol. Soc. Am. 93:1314–1321.

    Article  Google Scholar 

  • Robbins, P. S., Crocker, R. L., Nojima, S., Morris, B. D., Roelofs, W. L., and Villani, M. G. 2003. Methyl-2-(methylthio) benzoate: The unique sulfur-containing sex pheromone of Phyllophaga crinita. Naturwissenschaften 90:517–520.

    Article  PubMed  CAS  Google Scholar 

  • Schaefer, P. W. 2003. Winter aggregation of Harmonia axyridis (Coleoptera: Coccinellidae) in a concrete observation tower. Entomol. News 114:23–28.

    Google Scholar 

  • Tedders, W. L. and Schaefer, P. W. 1994. Release and establishment of Harmonia axyridis (Coleoptera Coccinellidae) in the southeastern United States. Entomol. News 105:228–243.

    Google Scholar 

  • Tumlinson, J. H., Hardee, D. D., Gueldner, R. C., Thompson, A. C., Hedin, P. A., and Minyard, J. P. 1969. Sex pheromones produced by the male boll weevils: Isolation, identification, and synthesis. Science 166:1010–1012.

    Article  CAS  PubMed  Google Scholar 

  • Yarbrough, J. A., Armstrong, J. L., Blumberg, M. Z., Phillips, A. E., McGahee, E., and Dolen, W. K. 1999. Allergic rhinoconjunctivitis caused by Harmonia axyridis (Asian lady beetle, Japanese lady beetle, lady bug). J. Allergy Clin. Immunol. 104:704–705.

    Article  PubMed  CAS  Google Scholar 

  • Zhang, Q. H. and Aldrich, J. R. 2003. Male-produced anti-sex pheromone in a plant bug. Naturwissenschaften 90:505–508.

    Article  PubMed  CAS  Google Scholar 

  • Zhang, Z. and Pawliszyn, J. 1993. Headspace solid-phase microextraction. Anal. Chem. 65:1843–1852.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Ralph Dollar, Rezwan Hague, Mary Catherine Tate, Elizabeth Wray, and Bart H.J. van den Berg provided technical assistance in the laboratory. We thank Jim Oliver (retired, USDA-ARS) for help with the organic synthesis, and Steven Grossman and Thomas Nebeker for reviewing an earlier version of the manuscript.

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Correspondence to Eric W. Riddick.

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The United States Government has the right to retain a nonexclusive, royalty-free license in and to any copyright of this article. This article reports the results of research only. Mention of a commercial or proprietary product does not constitute an endorsement of the product by the USDA.

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Brown, A.E., Riddick, E.W., Aldrich, J.R. et al. Identification of (−)-β-Caryophyllene as a Gender-Specific Terpene Produced by the Multicolored Asian Lady Beetle. J Chem Ecol 32, 2489–2499 (2006). https://doi.org/10.1007/s10886-006-9158-0

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