Abstract.
The iridoid glycosides, methyl catalpol, asperuloside, verbenalin, cinnamoyl catalpol, catalpol and aucubin, were studied from both larvae and adults of butterfly Melitaea cinxia. Special emphasis in the study was put on finding a correlation between the iridoid glycoside content in butterflies and plants. An optimised partial filling micellar electrokinetic capillary chromatographic–electrospray ionisation mass spectrometric (PF-MECC-ESI-MS) method was employed for the separation and identification of the six iridoid glycosides. In this work, the isolation and determination of catalpol and aucubin from extracts of both larvae and adults of Melitaea cinxia butterflies is demonstrated. The PF-MECC-ESI-MS method, using the [M+Na]+, [M+Li]+ and/or [M+NH4]+ adducts in ESI-MS, was used for quantification of aucubin and catalpol in the insects. In addition, the identification of all analytes was attempted by direct infusion MS/MS analysis. LOQ values for the iridoid glycosides varied between 10 mg/l (for verbenalin) to 50 mg/l (for catalpol and aucubin) corresponding to 0.1% of the sample´s dry mass. A correlation was noticed between the concentrations of iridoid glycosides in plants and the concentrations in larvae feeding on them.
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References
Dyer LA, Bowers MD (1996) J Chem Ecol 22:1527–1539
Theodoratus DH, Bowers MD (1999) J Chem Ecol 25:283–295
Suomi J, Sirén H, Wiedmer SK, Riekkola M-L, (2001) Anal Chim Acta 429:91–99
Bowers MD, Puttick GM (1986) J Chem Ecol 12:169–178
Camara M.D (1997) J Chem Ecol 23:2093–2106
Mead EW, Foderaro TA, Gardner DR, Stermitz FR (1993) J Chem Ecol 19:1155–1166
Gardner DR, Stermitz FR (1988) J Chem Ecol 14:2147–2168
L'Empereur KM, Stermitz FR (1990) J Chem Ecol 16:1495–1506
González A, Rossini C, Eisner M, Eisner T (1999) Proc Natl Acad Sci (USA) 96:5570–5574.
Eisner T, Eisner M, Rossini C, Iyengar VK, Roach BL, Benedikt E, Meinwald J (2000) Proc Natl Acad Sci (USA) 97:1634–1639.
Suomi J, Sirén H, Hartonen K, Riekkola M-L (2000) J Chromatogr A 868:73–83
Suomi J, Wiedmer SK, Jussila M, Riekkola M-L (2001) Electrophoresis 22:2580–2587
Suomi J, Wiedmer SK, Jussila M and Riekkola M-L (2002) J Chromatogr A 970:287–296
Wu H-K, Chuang W-C, Sheu S-J (1998) J Chromatogr A 803:179–187
Li Y, Zou C, Liu H (1999) Chromatographia 50:358–362
Sturm S, Stuppner H (2001) Chromatographia 53:612–618
Gardner DR, Stermitz FR (1988) J Chem Ecol 14:2147–2168
Damtoft S, Franzyk H, Jensen SR (1997) Phytochemistry 45:743–750
Nieminen M, Suomi J, van Nouhuys S, Sauri P, Riekkola M-L (2003) J Chem Ecol 29:805–826 (in press)
Palmer J, Munro NJ, Landers JP (1999) Anal Chem 71:1679–1687
Liu Z, Sam P, Sirimanne SR, McClure PC, Grainger J, Patterson DG Jr (1994) J Chromatogr A 673:125–132
Quirino JP, Terabe S (1999) Anal Chem 71:1638–1644
Bianco A (1990) The chemistry of iridoids. In: Atta-ur-Rahman (ed) Studies in natural products chemistry. Elsevier, Amsterdam, 7:439–497
Madhusudanan KP, Raj K, Bhaduri AP (2000) J Mass Spectrom 35:901–911
Acknowledgements.
We wish to thank Heidi Adler (Laboratory of Analytical Chemistry, University of Helsinki) for help with the Pallas Chemical Software and Pentti Jyske (the same address) for help with the analysis instrument. HS and SKW acknowledge their financial supports of the Academy of Finland and JS that of the Alfred Kordelin Foundation.
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Suomi, J., Sirén, H., Jussila, M. et al. Determination of iridoid glycosides in larvae and adults of butterfly Melitaea cinxia by partial filling micellar electrokinetic capillary chromatography—electrospray ionisation mass spectrometry. Anal Bioanal Chem 376, 884–889 (2003). https://doi.org/10.1007/s00216-003-2003-1
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DOI: https://doi.org/10.1007/s00216-003-2003-1