thelephoricola were sequenced (Fig. 1a). Six of them, compounds 1−6, are 11-residue sequences displaying the classical building scheme of subfamily 4 (SF4) peptaibols (Chugh and Wallace 2001; Degenkolb et al. 2012; Röhrich

et al. 2013b). Compound 1 is new, whereas compounds 2−6 are likely to represent 11-residue peptaibols, which have been described before (Tables 4 and 5, Table S1a and S1b). Compounds 7−10 are new PD0332991 purchase 18-residue peptaibols, named thelephoricolins 1−4 sharing some structural similarity (N-terminal dipeptide, [Gln]6/[Aib]7, C-terminal heptapeptide) with trichotoxins A-50H and A-50-J5 (Brückner and Przybylski 1984). The plate culture produced predominantly 11-residue SF4-peptaibols (compounds 1, 2, 5, find more 6, 11−13), but only two 18-residue peptaibols, thelephoricolins 2 and 3 (Fig. 1b). Fig. 1 Base-peak chromatograms (BPCs) analysed with the micrOTOF-Q II. a specimen of H. thelephoricola; b plate culture of H. thelephoricola on PDA. †, non-peptaibiotic Ilomastat clinical trial metabolite(s); ‡, co-eluting peptaibiotics, not sequenced. The y-axis of all BPC chromatograms in this publication refers to relative ion intensities Table 4 Sequences of 11- and 18-residue peptaibiotics detected in the specimen of Hypocrea thelephoricola

No. tR [min] [M + H]+   Residuea 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 1 37.6–37.9 1161.7527 Ac Aib Gln Vxx Lxx Aib Pro Vxx Lxx Aib Pro Lxxol               2 37.6–37.9 1161.7527 Ac Aib Gln Vxx Vxx Aib Pro Lxx Lxx Aib Pro Lxxol               3 39.3–39.5 1175.7712 Ac Aib Gln Vxx Lxx Aib Pro Lxx Lxx Aib Pro Lxxol               4 39.7 –40.0 1175.7712 Ac Aib Gln Lxx Lxx Aib Pro Vitamin B12 Vxx Lxx Aib Pro Lxxol               5 41.5–41.7 1189.7836 Ac Aib Gln Lxx Lxx Aib Pro Lxx Lxx Aib Pro Lxxol               6 42.9–43.0 1203.7981 Ac Vxx Gln Lxx Lxx Aib Pro Lxx Lxx Aib Pro Lxxol               7 44.2–44.5 1732.0673 Ac Aib Ala Aib Ala Vxx Gln Aib Vxx Aib Gly Lxx Aib Pro Lxx Aib Vxx Gln Vxxol 8 44.8–45.0 1746.0866 Ac Aib Ala Aib Ala Vxx Gln Aib Lxx Aib Gly Lxx Aib

Pro Lxx Aib Vxx Gln Vxxol 9 45.2–46.0 1760.1035 Ac Aib Ala Vxx Ala Vxx Gln Aib Lxx Aib Gly Lxx Aib Pro Lxx Aib Vxx Gln Vxxol 10 47.5–47.8 1774.1161 Ac Aib Ala Vxx Ala Vxx Gln Aib Lxx Aib Gly Lxx Aib Pro Lxx Aib Vxx Gln Lxxol No. Compound identical or positionally isomeric with Ref.                                       1 New                                       2 Trichorovins: IIIa, IVa Wada et al. 1995                                         Hypomurocin A-1 Becker et al. 1997                                         Trichobrachins III: 5, 9b Krause et al. 2007                                         Tv-29-11-III g Mukherjee et al. 2011                                         Hypojecorin A: 8 Degenkolb et al. 2012                                       3 Trichobrachins III: 10a, 12a, 15b Krause et al. 2007                                         Trichorovins: VIII, IXa Wada et al. 1995                                         Hypomurocin A-3 Becker et al.