Compound identical or positionally isomeric with Ref.                                         64 Minutisporin-9 (pos. 1, 6–10, 12–19; [Pro]2 → [Ala]2, [Aib]11 → [Lxx]11 and deletion of [Aib]5: cf. stilboflavin B-5) Jaworski and Brückner 2001b                                 65 Minutisporin-10 (positional

isomer of 64: [Ala]4 → [Gly]4, [Aib]16 → [Vxx]16)                                           66 Minutisporin-11 (positional isomer of 57: [Lxx]11 → [Vxx]11, [Aib]16 → [Vxx]16)                                           57 Minutisporin-2                                           67 Minutisporin-12 (positional isomer of 57: [Gln]17 → [Glu]17 and of 56: [Ala]4 → [Gly]4, [Aib]16 → [Vxx]16)                                           59 Minutisporin-4                                           60 Minutisporin-5                               JQ-EZ-05             68 Luminespib Minutisporin-13 (positional isomer of 61: [Aib]5 → [Vxx]5)                                           61 Minutisporin-6                                           aVariable residues are underlined in the table header. Minor sequence variants are underlined in the sequences. This applies to all sequence tables Fig. 5 Base-peak chromatograms (BPCs) analysed with the micrOTOF-Q II. a specimen of H. minutispora; b plate culture of H. minutispora on PDA. †, non-peptaibiotic metabolite(s); ‡, co-eluting

Combretastatin A4 peptaibiotics, not sequenced Screening of Hypocrea citrina. The specimen of H. citrina was shown to be a prolific producer of 19-residue peptaibols, compounds 69−78, of which seven are new, viz. compounds 69, 70, 72−74, 76, and 78. The names hypocitrins 1−7 were selected in order to avoid possible confusion with the mycotoxin citrinin and its derivatives. The remaining three were identified as hypophellin-15, −18, and −20, respectively (Röhrich et al. 2013a). Notably,

compound 69, hypocitrin-1, exhibits a C-terminal substituent, which is novel to peptaibiotics, dihydroxyphenylalaninol (Table 12 and Table S5; Fig. 6). Compound 70, hypocitrin-2, a homologue of hypophellin-15 (compound 73), also terminates in Tyrol (Fig. 4). Due to exceptionally high background noise of unknown origin, the methanolic extract of the well-grown H. citrina plate culture could not be interpreted appropriately. Table 12 Sequences C59 mouse of 19-residue peptaibiotics detected in the specimen of Hypocrea citrina No. tR [min] [M + H]+   Residuea 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 69 31.6–31.7 1926.1036 Ac Aib Ala Aib Ala Aib Gln Aib Lxx Aib Gly Lxx Aib Pro Vxx Aib Vxx Gln Gln di-OH-Pheol 70 32.0–32.1 1896.0937 Ac Aib Ala Aib Ala Aib Gln Aib Lxx Aib Gly Lxx Aib Pro Vxx Aib Aib Gln Gln Tyrol 71 32.9–33.1 1910.1084 Ac Aib Ala Aib Ala Aib Gln Aib Lxx Aib Gly Lxx Aib Pro Vxx Aib Vxx Gln Gln Tyrol 72 33.6–33.9 1880.0971 Ac Aib Ala Aib Gly Aib Gln Aib Lxx Aib Gly Lxx Aib Pro Vxx Aib Vxx Gln Gln Pheol 73 34.6–34.7 1880.