Chapter 1 Polyamine Toxins from Spiders and Wasps

Tandem mass spectrometric investigation of acylpolyamines of spider venoms and their 15N-labeled derivatives

“…The detailed knowledge of acylpentamine fragmentation mechanisms is essential for the correct characterization of isomeric compounds, particularly for coeluting compounds within complex mixtures such as spider venoms. P olyamines and polyamine-containing alkaloids are widely found throughout the plant and animal kingdom [1,2]. Over the past decades, spider venoms, particularly their fractions containing acylpolyamine derivatives [1,3,4], have increasingly attracted the attention of scientists.…”

“…P olyamines and polyamine-containing alkaloids are widely found throughout the plant and animal kingdom [1,2]. Over the past decades, spider venoms, particularly their fractions containing acylpolyamine derivatives [1,3,4], have increasingly attracted the attention of scientists. With the advent of more sensitive and selective analytical methods-in particular of the modern mass spectrometric approaches-not only the major but also minor constituents of such trace toxin sources became amenable to detection and structural elucidation.…”

Efficient and Flexible Solid‐Phase Synthesis of N‐Hydroxypolyamine Derivatives

“…the N-hydroxylated spider toxins Agel 448 and Agel 452 of Agelenopsis aperta, Figure 1). [14] In connection with our ongoing studies in the isolation and analysis of spider toxins, we were interested in extending our solid-phase strategy for the preparation of N-hydroxylated polyamine derivatives, too. We were confident that the Cope elimination provided an efficient transformation for the concurrent introduction of the desired N-hydroxy functionality and the cleavage of the final products from the resin.…”

Structure Determination of a Tetrahydro-?-carboline of Arthropod Origin: A Novel Alkaloid-Toxin Subclass from the Web of SpiderNephila clavipes

“…In the last decade, insecticide toxins from arthropod venoms have been the subjects of considerable emphasis [2]. Spider venoms generally are constituted of complex mixtures of biologically active substances [3], which may be grouped into three major classes of compounds according to their chemical nature: high-molecular-mass proteins (M r > 10 kDa), peptides (M r 3 ± 10 kDa), and low-molecular-mass compounds (M r < 1 kDa) [4]. The latter class, in turn, can be subdivided into other chemical subclasses, according to the chemical nature of these toxins.…”

“…The subclass of the acylpolyamines, is well-characterized both in spiders and solitary wasp venoms [3] [5 ± 8]. Spider polyamines are formed by a hydrophobic moiety ((hydroxyphenyl)acetic acid, indole acetic acid, or (hydroxyindole) acetic acid) linked to a polyamine ± amide backbone constituted of putrescyl or cadaveryl units, condensed to some amino acid residues such as glycine, alanine, arginine, and asparagine.…”