Sequences of Tolypins, Insecticidal Efrapeptin-Type Peptaibiotics from Species of the Fungal GenusTolypocladium
Sequences of Tolypins, Insecticidal Efrapeptin-Type Peptaibiotics from Species of the Fungal GenusTolypocladium
复制标题
DOI：
10.1002/cbdv.202000276
复制
发表时间：
2020-06-23
影响因子：
2.9
通讯作者：
Degenkolb, Thomas
中科院分区：
文献类型：
--
作者：
Brueckner, Hans;Degenkolb, Thomas
A peptide mixture named tolypin, originally isolated from species of the fungal genusTolypocladium, was structurally characterised and sequences compared to those reported for efrapeptins isolated from strains ofTolypocladium inflatum. Chiral amino acid analysis, direct infusion, and online HPLC electrospray ionization tandem mass spectrometry provided composition, molecular weights of peptides, and series of diagnostic fragment ions. Sequences deduced from ESI-MS revealed that tolypins C-G are identical to efrapeptins C-G. The results were corroborated by ESI-MS and HPLC of an authentic efrapeptin sample fromEli Lilly Research Laboratories(USA). Comparison of the HPLC elution profiles of efrapeptin and tolypin indicated a pronounced microheterogeneity of the former. A high-resolution HPLC of authentic efrapeptin has not been published before. Close relationship and partial identity of sequences of tolypins and efrapeptins, which had previously been postulated, were definitely proven. The geographical origin of the two most importantT. inflatumstrains used for sequencing of efrapeptins/tolypins could unambiguously be clarified. A new minor compound, designated tolypin H1, was sequenced. High proportions of helicogenic Aib (alpha-aminoisobutyric acid) andl-isovaline,N-terminal acetyl-l-pipecolic acid and the unusual, amide-boundC-terminal residue, named (S)-2-amino-1-(1,5-diazabicyclo[4.3.0]non-5-ene-5-ylium)-4-methylpentane corresponding to 1-[(2S)-2-amino-4-methylpentyl]-2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidin-1-ium, define these peptides as linear, cationic peptaibiotics.
