Fast-GC Quantification of Harmonine, the Major Defense Alkaloid of the Multicolored Asian Ladybird <i>Harmonia axyridis</i>(Pallas) — Oak Academic Publishing
Research ArticleOpen AccessGoogle Scholar indexed
Fast-GC Quantification of Harmonine, the Major Defense Alkaloid of the Multicolored Asian Ladybird <i>Harmonia axyridis</i>(Pallas)
These last few years the multicolored Asian ladybird, Harmonia axyridis (Pallas), previously introduced in Europe and North America as a biological control agent, has swiftly spread out on those territories and turns out to be a pest in several ways. In order to improve understanding of several key points of the biology of this ladybird, a novel fast-GC method of quantification of harmonine, the main defense alkaloid of H. axyridis, has been designed and validated using the accuracy profile concept for concentrations ranging from 13 to 264 μg/individual. This method allows quantifying harmonine in a single insect with a maximal error risk of 20%. For ladybirds collected in spring, mean harmonine concentration observed was 106.6 μg/individual with a very high standard deviation of 80.2 μg/individual, which can easily be explained by the strong asymmetry of the results distribution. Males and females seem equally chemically protected as the harmonine concentration did not significantly differ between sexes. This method is currently used to improve our comprehension of several key points of H. axyridis biology including aggregation behavior and aposematism.
R. L. Koch, “The Multicolored Asian Lady Beetle, Har- monia axyridis: A Review of Its Biology, Uses in Bio- logical Pest Control, and Non-Target Impacts,” Journal of Insect Science, Vol. 3, No. 32, 2003, pp. 16.
A. Pervez and Omkar, “Ecology and Biological Control Application of Multicoloured Asian Ladybird, Harmonia axyridis: A Review,” Biocontrol Science and Technology, Vol. 16, No. 2, 2006, pp. 111-128. doi:10.1080/09583150500335350
J. K. Pell, J. Baverstock, H. E. Roy, R. L. Ware and M. E. N. Majerus, “Intraguild Pre-dation Involving Harmonia axyridis: A Review of Current Knowledge and Future Perspectives,” Biomedical and Life Sciences, Vol. 53, No. 1, 2008, pp. 147-168.
L. Hautier, J.-C. Grégoire, J. de Schauwers, G. San Mar- tin, P. Callier, J.-P. Jansen and J.-C. de Biseau, “Intra- guild Predation by Harmonia axyridis on Coccinellids Revealed by Exogenous AlkaloidSequestration,” Che- moecology, Vol. 18, No. 3, 2008, pp. 191-196. doi:10.1007/s00049-008-0405-4
L. Cai, J. A. Koziel and M. E. O’Neal, “Determination of Characteristic Odorants from Harmonia axyridis Beetles Using in Vivo Solid-Phase Micro-extraction and Multidi- mensional Gas Chromatography-Mass Spectrometry-Ol- factometry,” Journal of Chromatography A, Vol. 1147, No.1 , 2007, pp. 66-78. doi:10.1016/j.chroma.2007.02.044
E. Cudjoe, T. B. Wie-derkehr and I. D. Brindle, “Head- space Gas Chromatogra-phy-Mass Spectrometry: A Fast Approach to the Identification and Determination of 2- alkyl-3-methoxypyrazine Pheromones in Ladybugs,” Ana- lyst, Vol. 130, No. 4, 2005, pp. 152-155. doi:10.1039/b410659h
C. Ross, H. Fergusson, M. Keller, D. Walsh, K. Weller and S. Spayd, “Determination of Or-tho-Nasal Aroma Thre- shold for Multicolored Asian Lady Beetle in a Concord Grape Juice,” Journal of Food Quality, Vol. 30, No. 6, 2007, pp. 855-863. doi:10.1111/j.1745-4557.2007.00135.x
P. Laurent, J.-C. Braekman and D. Daloze, “Insect Che- mical Defense,” Topics in Current Chemistry, Vol. 240, 2005, pp. 167-229.
P. Laurent, J.-C. Braekman, D. Daloze and J. M. Pasteels, “Bio-synthesis of Defensive Compounds from Beetles and Ants,” European Journal of Organic Chemistry, Vol. 2003, No. 15, 2003, pp. 2733-2743. doi:10.1002/ejoc.200300008
N. Alam, I. S. Choi, K.-S. Song, J. Hong, C. O. Lee and J. H. Jung, “A New Alkaloid from Two Coccinellid Beetles Harmonia axyridis and Aiolocaria hexaspilota,” Bull. Bulletin of the Korean Chemical Society, Vol. 23, No. 3, 2002, pp. 497-499.
T. Guilford, C. Nicol, M. Rothschild and B. P. Moore, “The Biological Roles of Pyrazines: Evidence for a Warning Odour Function,” Biological Journal of the Linnean Society, Vol. 31, No. 2, 1987, pp. 113-128. doi:10.1111/j.1095-8312.1987.tb01984.x
A. L. Bezzerides, K. J. McGraw, R. S. Parker and J. Hus- seini, “Elytra Color as a Signal of Chemical Defense in the Asian Ladybird Beetle Harmonia axyridis,” Behavioral Ecology and Sociobiology, Vol. 61, 2007, pp. 1401- 1408. doi:10.1007/s00265-007-0371-9
Y. Kajita, J. J. Obrycki, J. J. Sloggett and K. F. Haynes, “Intraspecific Alkaloid Variation in Ladybird Eggs and Its Effects on Con- and Hetero-Specific Intraguild Preda- tors,” Oecologia, Vol. 163, No. 2, 2010, pp. 313-322. doi:10.1007/s00442-009-1551-2
J. J. Sloggett, J. J. Ob-rycki and K. F. Haynes, “Identifica- tion and Quantification of Predation: Novel Use of Gas Chromatography-Mass Spectro-metric Analysis of Prey Alkaloid Markers,” Functional Ecology, Vol. 23, No. 2, 2009, pp. 416-426. doi:10.1111/j.1365-2435.2008.01492.x
E. Haulotte, “Biosynthèse D’Alcalo?des Défensifs de Co- ccinellidae,” PhD Dissertation, Université Libre de Bru- xelles, Bruxelles, 2007.
J. M. Pasteels, C. Deroe, B. Tursch, J.-C. Braekman, D. Daloze and C. Hootele, “Distribution et Activité des Al- calo?des Défensifs des Coccinellidae,” Journal of Insect Physiology, Vol. 19, No. 9, 1973, pp. 1771-1779. doi:10.1016/0022-1910(73)90046-2
M. Braconnier, J.-C. Braekman, D. Daloze and J. M. Pasteels, “(Z)-1,17-diaminooctadec-9-ene, a Novel Ali- phatic Diamine from Coccinellidae,” Cellular and Mo- lecular Life Sciences, Vol. 41, No. 4, 1984, pp. 519-520. doi:10.1007/BF01966179
G. C. Lognay, J.-L. Hemptinne, F. Y. Chan, C. Gaspar, M. Marlier, J.-C. Braekman, D. Daloze and J. M. Pasteels, “Adalinine, a New Piperidine Alkaloid from the Ladybird Beetles Adalia bipunctata and Adalia decem-punctata,” Journal of Natural Products, Vol. 59, No. 5, 1996, pp. 510-511. doi:10.1021/np960129f
P. Hubert, P. Chiap, J. Crommen, B. Boulanger, E. Chapuzet, N. Mercier, S. Ber-voas-Martin, P. Chevalier, D. Grandjean, P. Lagorce, M. Lallier, M. C. Laparra, M. Laurentie and J. C. Nivet, “The SFSTP Guide on the Va- lidation of Chromatographic Methods for Drug Bio- analysis: From the Washington Conference to the Labra- tory,” Analytica Chimica Acta, Vol. 391, No. 2, 1999, pp. 135-148. doi:10.1016/S0003-2670(99)00106-3
P. Hubert, J. Nguyen-Huu, B. Boulanger, E. Chapuzet, P. Chiap , N. Cohen, P. Compagnon, W. Dewe, M. Feinberg, M. Lallier, M. Laurentie, N. Mercier, G. Muzard, C. Nivet and L. Valat, “Validation des Procédures Analy- ti- ques Quantitatives: Harmonisation des Démarches,” STP Pharma Pratiques, Vol. 3, No. 13, 2003, pp. 101- 138.
P. Hubert, J. Nguyen-Huu, B. Boulanger, E. Chapuzet, P. Chiap , N. Cohen, P. Compagnon, W. Dewe, M. Feinberg, M. Laurentie, N. Mercier, G. Muzard and L. Valat, “Vali- dation des Procédures Analytiques Quantitatives: Harmo- nisation des Démarches. Partie II—Statistiques,” STP Pharma Pratiques, Vol. 1, No. 16, 2006, pp. 28-58.
E. Rozet, “Improvement of the Predictive Character of Test Results Issued from Analytical Methods Life Cycle,” PhD Dissertation, Université de Liège, Liège, 2008.
E. Rozet, A. Ceccato, C. Hubert, E. Ziemons, R. Oprean, S. Rudaz, B. Boulanger and P. Hubert, “Analysis of Re- cent Pharmaceutical Regulatory Documents on Analytical Method Validation,” Journal of Chromatography A, Vol. 1158, No. 1-2, 2007, pp. 111-125. doi:10.1016/j.chroma.2007.03.111
L. Roland, “Etapes de Validation d’une Méthode de Dosage de Résidus par CPG ou HPLC,” Application Pratique de la Procédure Validana.P01, BEAGx, Gembloux, 2002.
B. P. McCornack, R. L. Koch and D. W. Ragsdale, “A Simple Method for in-Field Sex De-termination of the Multicolored Asian Lady Beetle Harmonia axyridis,” Journal of Insect Science, Vol. 7, No. 10, 2006, p. 12.