title: Metabolism of glucosinolate-derived isothiocyanates to glutathione conjugates in generalist lepidopteran herbivores.
abstract: The defensive properties of the glucosinolate-myrosinase system in plants of the order Brassicales have been attributed to the formation of toxic isothiocyanates generated upon tissue damage. Lepidopteran herbivores specialised on brassicaceous plants have been shown to possess biochemical mechanisms preventing the formation of isothiocyanates. Yet, no such mechanisms are known for generalist lepidopterans which also occasionally but successfully feed on plants of the Brassicales. After feeding on Arabidopsis thaliana plants, faeces of Spodoptera littoralis larvae contained glutathione conjugate derivatives (cysteinylglycine- and cysteinyl-isothiocyanate-conjugates) of the plant's major glucosinolate hydrolysis product, 4-methylsulfinylbutyl isothiocyanate. When caterpillars fed on leaves of A. thaliana containing [¹⁴C]₄-methylsulfinylbutyl glucosinolate, more than half of the ingested radioactivity was excreted as the unmetabolised corresponding isothiocyanate, and only 11% as glutathione conjugate derivatives. However, these conjugates were demonstrated to be the major metabolites of isothiocyanates in S. littoralis, and their abundance was shown to correlate with the amount of isothiocyanates ingested. Analysis of larval faeces from several species of generalist lepidopterans (Spodoptera exigua, S. littoralis, Mamestra brassicae, Trichoplusia ni and Helicoverpa armigera) fed on different Brassicaceae revealed that glutathione conjugates arise from a variety of aliphatic and aromatic isothiocyanates derived from dietary glucosinolates.
authors.affiliation: Max Planck Institute for Chemical Ecology, Hans-Knoell-Str. 8, 07745 Jena, Germany. kschramm@ice.mpg.de
authors.forename: Katharina
authors.initials: K
authors.lastname: Schramm
authors.forename: Daniel Giddings
authors.initials: DG
authors.lastname: Vassão
authors.forename: Michael
authors.initials: M
authors.lastname: Reichelt
authors.forename: Jonathan
authors.initials: J
authors.lastname: Gershenzon
authors.forename: Ute
authors.initials: U
authors.lastname: Wittstock
mesh_terms: D000818:Animals; D017360:Arabidopsis; D002250:Carbon Radioisotopes / Q000032:analysis; D005243:Feces / Q000737:chemistry; D005961:Glucosinolates / Q000378:metabolism*; D005978:Glutathione / Q000378:metabolism*; D060434:Herbivory; D017879:Isothiocyanates / Q000378:metabolism*; D007814:Larva / Q000378:metabolism; D018411:Spodoptera / Q000378:metabolism*
chemical_list: D002250:Carbon Radioisotopes; D005961:Glucosinolates; D017879:Isothiocyanates; D005978:Glutathione