In continuation of previous studies on glandular exudates of Primula. we analyzed eleven so far unstudied species and several populations for exudate composition. Unsubstituted flavone and unusually substituted flavones, normally predominant in Primula exudates, were not detected in all of the analyzed samples. Instead, some species exhibited regular substituted flavonoids, and in some cases, no flavonoids could be detected at all. The detection of a diterpene (1) in P. minima exudates is new to Primula. On basis of MS and NMR, 1 was structurally characterized as ent-kaur-16-en-19-oic acid. Comparative profiling of exudates as performed by HPLC and TLC against authentic markers indicated further the presence of the benzoquinone primin and derivatives in some exudates. Thus, exudates of newly studied species contrast markedly with those analyzed so far. The significance of observed exudate diversification is discussed in view of the phylogeny of derived lineages in European alpine regions.
FicoG., RodondiG., FlaminiG., PassarellaD., ToméF. (2007) Comparative phytochemical and morphological analyses of three Italian Primula species. Phytochemistry, 68, 1683–1691.
9.
IsshikiR., GalisI., TanakamaruS. (2014) Farinose flavonoids are associated with high freezing tolerance in fairy primrose (Primula malacoides) plants. Journal of Integrative Plant Biology, 56, 181–188.
10.
ZhangL-B, KadereitJ.W. (2004) Classification of Primula sect. Auricula (Primulaceae) based on two molecular data sets (ITS, AFLPs), morphology and geographical distribution. Botanical Journal of the Linnean Society, 146, 1–26.
11.
MastA.R., KelsoS., RichardsA.J., LangD.J., FellerD.M.S., ContiE. (2001) Phylogenetic relationships in Primula L. and related genera (Primulaceae) based on noncoding chloroplast DNA. International Journal of Plant Sciences, 162, 1381–1400.
12.
GuggisbergA., MansionG., KelsoS., ContiE. (2006) Evolution of biogeographic patterns, ploidy levels, and breeding systems in a diploid-polyploid species complex of Primula.New Phytologist, 171, 617–632.
13.
RichardsJ. (2002) Primula.Batsford, London.
14.
ChristensenL.P., LarsenE. (2000) Direct emission of the allergen primin from intact Primula obconica plants. Contact Dermatitis, 149–153.
15.
WollenweberE., MarxD., Favre-BonvinJ., BrassyC. (1983) Ent-Kaurenoic Acid: A Diterpene as Frond Exudate on Ferns of the Genus Notholaena.Zeitschrift für Naturforschung, 38, 146–147.
16.
MendozaL., WilkensM., UrzúaA. (1997) Antimicrobial study of the resinous exudates and of diterpenoids and flavonoids isolated from some Chilean Pseudognaphalium (Asteraceae). Journal of Ethnopharmacology, 58, 85–88.
17.
ChangF-R, YangP-Y, LinJ-Y, LeeK-H, WuY-C. (1998) Bioactive kaurane diterpenoids from Annona glabra.Journal of Natural Products, 61, 437–439.
18.
Coll AráozM.V., MercadoM.I., GrauA., CatalánC.A.N. (2010) Ent-kaurane derivatives from the root cortex of yacon and other three Smallanthus species (Heliantheae, Asteraceae). Biochemical Systematics and Ecology, 38, 1042–1048.
19.
PadlaE.P., SolisL.T., RagasaC.Y. (2012) Antibacterial and antifungal properties of ent-kaurenoic acid from Smallanthus sonchifolius.Chinese Journal of Natural Medicines, 10, 408–414.
20.
LangeB.M. (2015) The evolution of plant secretory structures and emergence of terpenoid chemical diversity. Annual Review of Plant Biology, 66, 139–159.
21.
RobienW. (2009) Do high-quality 13C-NMR spectral data really come from journals with high Impact Factors?Trends in Analytical Chemistry, 28, 914–922.
22.
SilvaE.A., TakahashiJ.A., BoaventuraM.A.D., OliveiraA.B. (1999) The biotransformation of ent-kaur-16-en-19-oic acid by Rhizopus stolonifer.Phytochemistry, 52, 397–400.
23.
HorperW., MarnerF-J. (1996) Biosynthesis of primin and its derivatives. Phytochemistry, 41, 451–456.
24.
FischerM.A., OswaldK., AlderW. (2008) Exkusionsflora für Österreich, Liechtenstein und Südtirol, Biologiezentrum der Oberösterreichischen Landesmuseen.
25.
Schmidt-LebuhnA.N., de VosJ.M., KellerB., ContiE. (2012) Phylogenetic analysis of Primula section Primula reveals rampant non-monophyly among morphologically distinct species. Molecular Phylogenetics and Evolution, 65, 23–34.
26.
BrunswikH. (1922) Die Mikrochemie der Flavonexkrete bei den Primulinae.Hölder-Pichler-Tempsky.
27.
RyanK.G., SwinnyE.E., MarkhamK.R., WinefieldC. (2002) Flavonoid gene expression and UV photoprotection in transgenic and mutant Petunia leaves. Phytochemistry, 59, 23–32.
28.
TokalovS.V., KindB., WollenweberE., GutzeitH.O. (2004) Biological Effects of Epicuticular Flavonoids from Primula denticulata on Human Leukemia Cells. Journal of Agricultural and Food Chemistry, 52, 239–245.
