The spider Paracoelotes birulai: detection and structure elucidation of new acylpolyamines by on-line coupled HPLC-APCI-MS and HPLC-APCI-MS/MS

The lyophilized venom of the spider Paracoelotes birulai (Araneidae: Amaurobiidae) has been analyzed. A no. of acylpolyamines were found and sepd. By online coupled high-performance liq. chromatog. and atm.-pressure chem.-ionization mass spectrometry, the structures of the three most abundant compds. PB 490 (N-(16-guanidino-4-hydroxy-4,8,12-triazahexadecyl)-2-(4-hydroxyindol-3-yl)acetamide), PB 421 (N-(16-guanidino-4,8,12-triazahexadecyl)-4-hydroxybenzamide), and PB 448 (N-(16-amino-4-hydroxy4,8,12-triazahexadecyl)-2-(4-hydroxyindol-3-yl)acetamide) were elucidated. Two different types of polyamines were found in the ?-palutoxins and compared with acylpolyamines from the Agelenidae spider family. The results of this investigation will initiate further chemotaxonomical studies on spiders. Protoverbine, the parent member of a class of macrocyclic spermine alkaloids. Guggisberg, Armin; Drandarov, Konstantin; Hesse, Manfred Helv. Chim. Acta (2000), 83(11), 3035-3042 Abstract The 17-membered macrocyclic spermine alkaloids protoverbine (8S)-8-phenyl-1,5,9,13tetraazacycloheptadecan-6-one (I) and its N(9),N(13)-methylene-bridged deriv. protomethine (2S)-2phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one (II) were isolated from Verbascum pseudonobile Stoj. et Stef. (Scrophulariaceae) and characterized. The synthesis of their racemates is described. The possible role of I and II as precursors in the biogenesis of the whole class of N(1),N(9)and/or N(13)-substituted alkaloids, the groups of verbamethine, verbacine, incasine B'/verdoline, verbamedine, and verbascenine is discussed.The 17-membered macrocyclic spermine alkaloids protoverbine (8S)-8-phenyl-1,5,9,13tetraazacycloheptadecan-6-one (I) and its N(9),N(13)-methylene-bridged deriv. protomethine (2S)-2phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one (II) were isolated from Verbascum pseudonobile Stoj. et Stef. (Scrophulariaceae) and characterized. The synthesis of their racemates is described. The possible role of I and II as precursors in the biogenesis of the whole class of N(1),N(9)and/or N(13)-substituted alkaloids, the groups of verbamethine, verbacine, incasine B'/verdoline, verbamedine, and verbascenine is discussed.