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Hypomiltin, a novel azaphilone from Hypoxylon hypomiltum, and chemotypes in Hypoxylon sect. Hypoxylon as inferred from analytical HPLC profiling

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Abstract

A novel azaphilone named hypomiltin was isolated by preparative reversed phase HPLC from the stromatal extract of the xylariaceous ascomycete Hypoxylon hypomiltum. Its chemical structure was determined by mass spectrometry and 2D nuclear magnetic resonance spectroscopy. Analytical HPLC profiling of stromatal crude extracts, using UV/visual (diode array) and mass spectrometric detection based on electrospray ionisation, revealed the presence of hypomiltin also in Hypoxylon intermedium, H. perforatum, H. trugodes, and Pulveria porrecta. In contrast, this compound was found neither in type material of H. hypomiltum var. lavandulocinereum nor in several further Hypoxylon species. Despite being chemically related to mitorubrin, hypomiltin never co-occurred with the latter compound and its derivatives. Characteristic secondary metabolite profiles of several further Hypoxylon species are correlated with the colours of their taxonomically significant KOH-extractable pigments. These species are divided into chemotypes, based on analytical HPLC data. The results point toward an extraordinary diversity of secondary metabolites in Hypoxylon.

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References

  • Bills GF, Polishook JD, Goetz MA, Sullivan RF, White Jr. JF (2002) Chaunopycnis pustulata sp. nov., a new claviciptalean anamorph producing metabolites that modulate potassium ion channels. — Mycological Progress 1: 3–17.

    Google Scholar 

  • Casser I (1983) Isolierung und Strukturaufklärung von Farbstoffen aus holzbewohnenden Pilzen. Doctoral thesis. University of Bonn, Germany.

    Google Scholar 

  • Gill M, Steglich W (1987) Pigments of fungi (Macromycetes). In Herz W, Grisebach H, Kirby GW, Tamm C (eds) Progress in the chemistry of organic natural products, vol. 51, Springer Verlag Berlin, Heidelberg, New York.

    Google Scholar 

  • Granmo A (1999) Morphotaxonomy and chorology of the genus Hypoxylon (Xylariaceae) in Norway. — Sommerfeltia 26: 1–81.

    Google Scholar 

  • Greenhalgh GN, Chesters CGC (1968) Conidiophore morphology in some British members of the Xylariaceae. — Transactions of the British Mycological Society 51: 57–82.

    Google Scholar 

  • Greenhalgh, GN, Whalley AJS (1970) Stromal pigments of some species of Hypoxylon. — Transactions of the British Mycological Society 55: 89–96.

    Google Scholar 

  • Hashimoto T, Tahara S, Takaoka S, Tori M, Asakawa Y (1994) Structures of Daldinins A-C, three novel azaphilone derivatives from ascomycetous fungus Daldinia concentrica. — Chemical and Pharmaceutical Bulletin 42: 2397–2399.

    CAS  Google Scholar 

  • Hashimoto T, Asakawa Y (1998) Biologically active substances of Japanese inedible mushrooms. — Heterocycles 47: 1067–1110.

    CAS  Google Scholar 

  • Johannesson H (2001) Ecology of Daldinia spp. with special emphasis on Daldinia loculata. PhD Thesis. Swedish University of Agricultural Sciences, Uppsala, Sweden.

    Google Scholar 

  • Jong SC, Rogers JD (1972) Illustrations and descriptions of conidial states of some Hypoxylon species. Washington State Agricultural Experimental Station Bulletin, No. 71.

  • Ju YM, Rogers JD (1996) A revision of the genus Hypoxylon. Mycologia Memoir no. 20. APS Press, St. Paul, MN., USA.

    Google Scholar 

  • Ju Y-M, Rogers JD (2002) The genus Nemania (Xylariaceae). — Nova Hedwigia 74: 75–120.

    Article  Google Scholar 

  • Ju YM, Rogers JD, San Martín F (1997) A revision of the genus Daldinia. — Mycotaxon 61: 243–293.

    Google Scholar 

  • Ju Y-M, Rogers JD, San Martín F, Granmo A (1998) The genus Biscogniauxia. — Mycotaxon 66: 1–98.

    Google Scholar 

  • Ju Y-M, Rogers JD & Hsieh HM (2004) New Hypoxylon species and notes on some names associated with or related to Hypoxylon. — Mycologia 96: 154–161.

    Google Scholar 

  • Laessøe T, Rogers JD, Whalley AJS (1989) Camillea, Jongiella and light-spored species of Hypoxylon. — Mycological Research 93: 121–155.

    Google Scholar 

  • Malloch D, Rogerson CT (1977) Pulveria, a new genus of Xylariaceae (Ascomycetes). — Canadian Journal of Botany 55: 1505–1509.

    Google Scholar 

  • Martin P (1968) Studies in the Xylariaceae: IV. Hypoxylon, sections Papillata and Annulata. — South African Journal of Botany 34: 303–330.

    Google Scholar 

  • Martin P (1969) Studies in the Xylariaceae: V. Euhypoxylon. — South African Journal of Botany 35: 149–206.

    Google Scholar 

  • Miller JH (1961) A monograph of the world species of Hypoxylon. Univ. Georgia Press, Athens, Georgia, USA.

    Google Scholar 

  • Mühlbauer A, Triebel D, Persoh D, Wollweber H, Seip S, Stadler M (2002) Macrocarpones, novel metabolites from stromata of Hypoxylon macrocarpum and new evidence on the chemotaxonomy of Hypoxylon. — Mycological Progress 1: 235–248.

    Google Scholar 

  • Nielsen KF, Smedsgaard J (2003) Fungal metabolite screening: database of 474 mycotoxins and fungal metabolites for dereplication by standardised liquid chromatography—UV-mass spectrometry methodology. — Journal of Chromatography 1002A: 111–136.

    Google Scholar 

  • Ogasawara N, Kawai K (1998) Hydrogenated azaphilones from Emericella falconensis and E. fruticulosa. — Phytochemistry 47: 1131–1135.

    Article  CAS  Google Scholar 

  • Parenicova L, Skouboe P, Frisvad JC, Samson RA, Rossen L, ten Hoor-Suykerbuyk M, Visser J (2001) Combined molecular and biochemical approach identifies Aspergillus japonicus and Aspergillus aculeatus as two species. — Applied and Environmental Microbiology 67: 521–527

    Article  CAS  PubMed  Google Scholar 

  • Petch T (1924) Xylariaceae Zeylanicae. — Annuals of the Royal Botanical Garden (Peradeniya) 8: 119–166.

    Google Scholar 

  • Petrini, LE, Müller E (1986) Haupt-und Nebenfruchtformen europäischer Hypoxylon-Arten (Xylariaceae, Sphaeriales) und verwandter Pilze. — Mycologia Helvetica 1: 501–627.

    Google Scholar 

  • Polishook JD, Ondeyka JB, Dombrowski AW, Peláez F, Platas G, Teran AM (2001). Biogeography and relatedness of Nodulisporium strains producing nodulisporic acid. — Mycologia 93: 1125–1137.

    CAS  Google Scholar 

  • Pouzar Z (1972) Hypoxylon fraxinophilum spec. nov. and H. moravicum spec. nov., two interesting species found on Fraxinus angustifolia. — Ceská Mykologia 26: 129–137.

    Google Scholar 

  • Quang DN, Hashimoto T, Tanaka M, Baumgartner M, Stadler M, Asakawa Y (2002) Chemical constituents of the ascomycete Daldinia concentrica. — Journal of Natural Products 65: 1869–1874.

    Article  CAS  PubMed  Google Scholar 

  • Quang DN, Hashimoto T, Tanaka M, Stadler M, Asakawa Y (2004a) Cyclic azaphilones daldinins E and F from the ascomycete fungus Hypoxylon fuscum. — Phytochemistry 65: 469–473.

    CAS  PubMed  Google Scholar 

  • Quang DN, Hashimoto T, Stadler M, Asakawa Y (2004b) Chemical constituents of the inedible mushroom Hypoxylon rubignosum. — Journal of Natural Products 67: 1152–1155.

    CAS  PubMed  Google Scholar 

  • Rayner RW (1970) A mycological colour chart. Commonwealth Mycological Institute, Kew and British Mycological Society.

  • Rogers JD (1982) Entonaema liquescens: description of the anamorph and thoughts on its systematic position. — Mycotaxon 15: 500–506.

    Google Scholar 

  • Rogers JD (2000) Thoughts and musings about tropical Xylariaceae. — Mycological Research 104: 1412–1420.

    Article  Google Scholar 

  • Rogers JD, Ju Y-M (1998) The genus Kretzschmaria. — Mycotaxon 68: 345–393.

    Google Scholar 

  • Sánchez-Ballesteros J, González V, Salazar O, Acero J, Portal MA, Julián M, Rubio V, Bills GF, Polishook JD, Platas G, Mochales S, Peláez F (2000) Phylogenetic study of Hypoxylon and related genera based on ribosomal ITS sequences. — Mycologia 92: 964–977.

    Google Scholar 

  • Stadler M, Anke H, Dekermendijan K, Reiss R, Sterner O, Witt M.R. (1995) New azaphilones from fruit-bodies and mycelial cultures of the ascomycete Bulgaria inquinans. — Natural Product Letter 7: 7–14.

    CAS  Google Scholar 

  • Stadler M, Baumgartner M, Grothe T, Mühlbauer A, Seip S, Wollweber H (2001c) Concentricol, a taxonomically significant triterpenoid from Daldinia concentrica. — Phytochemistry 56: 787–793.

    Article  CAS  PubMed  Google Scholar 

  • Stadler M, Baumgartner M, Wollweber H. (2001d) Three new Daldinia species with yellow stromatal pigments. — Mycotaxon 80: 179–196.

    Google Scholar 

  • Stadler M, Ju YM, Rogers JD (2004a) Chemotaxonomy of Entonaema, Rhopalostroma and other Xylariaceae. — Mycological Research 108: 239–256.

    PubMed  Google Scholar 

  • Stadler M, Tichy HV, Katsiou E, Hellwig V (2003) Chemotaxonomy of Pochonia and other conidial fungi with Verticillium-like anamorphs. — Mycological Progress 2: 95–122.

    Google Scholar 

  • Stadler M, Wollweber H, Baumgartner M, Ju YM, Rogers JD (2001e) Daldinia decipiens sp. nov. and notes on further Daldinia spp. inhabiting Betulaceae in Europe. — Mycotaxon 80: 167–176.

    Google Scholar 

  • Stadler M, Wollweber H, Fournier J (2004b) A host-specific species of Hypoxylon from France, and notes on the chemotaxonomy of the ‘Hypoxylon rubiginosum complex’. — Mycotaxon 90: 187–211.

    Google Scholar 

  • Stadler M, Wollweber H, Mühlbauer A, Asakawa Y, Hashimoto T, Rogers JD, Ju YM, Wetzstein HG, Tichy HV (2001b) Molecular chemotaxonomy of Daldinia and other Xylariaceae. — Mycological Research 105: 1191–1205.

    CAS  Google Scholar 

  • Stadler M, Wollweber H, Mühlbauer A, Henkel T, Wollweber H, Asakawa Y, Hashimoto T, Rogers JD, Ju YM, Wetzstein HG, Tichy HV (2001a) Secondary metabolite profiles, genetic fingerprints and taxonomy of Daldinia and allies. — Mycotaxon 77: 379–429.

    Google Scholar 

  • Steglich W, Klaar M, Furtner W (1974) (−)-Mitorubrin derivatives from Hypoxylon fragiforme. — Phytochemistry 13: 2874–2875.

    Article  CAS  Google Scholar 

  • Suzuki S, Hosoe T, Nozawa K, Yaguchi T, Udagawa S, Kawai K (1999) Mitorubrin derivatives on ascomata of some Talaromyces species of ascomyceteous fungi. — Journal of Natural Products 62: 1329–1329.

    Article  Google Scholar 

  • Thines E, Anke H, Sterner O (1998) Trichoflectin, a bioactive azaphilone from the ascomycete Trichopezizella nidulus. — Journal of Natural Products 61: 306–308.

    Article  CAS  PubMed  Google Scholar 

  • Triebel D, Persoh D, Wollweber, H & Stadler M (2005) Phylogenetic relationships among Daldinia, Entonaema, and Hypoxylon as inferred from ITS nrDNA analyses of Xylariales. — Nova Hedwigia 80: 25–43.

    Article  Google Scholar 

  • Tuthill DE, Frisvad JC, Christensen M (2001) Systematics of Penicillium simplicissimum based on rDNA sequences, morphology and secondary metabolites. — Mycologia 93: 298–308.

    CAS  Google Scholar 

  • Whalley AJS, Edwards RL (1995) Secondary metabolites and systematic arrangement within the Xylariaceae. — Canadian Journal of Botany 73Suppl.1: S802–S810.

    CAS  Google Scholar 

  • Whalley AJS, Edwards RL (1998) The Xylariaceae: A study in biological and chemical diversity. — Pure and Applied Chemistry 70: 2123, and concurrent pdf download available from the Internet: http://www.iupac.org/symposia/proceedings/phuket97/whalley.pdf

    Google Scholar 

  • Whalley AJS, Greenhalgh GN (1971) Chemical races of Hypoxylon rubiginosum. — Transactions of the British Mycological Society 57: 161–164.

    Google Scholar 

  • Whalley AJS, Whalley MA (1977) Stromal pigments and taxonomy of Hypoxylon. — Mycopathologia 61: 99–103.

    Article  Google Scholar 

  • Wollweber H, Stadler M (2001) Zur Kenntnis der Gattung Daldinia in Deutschland und Europa. — Zeitschrift für Mykologie 67: 3–51.

    Google Scholar 

  • Yasukawa K, Takahashi M, Natori S, Kawai K, Yamazaki M, Takeuchi M, Takido M (1994) Azaphilones inhibit tumor promotion by 12-O-tetradecanoyl-phorbol-13-acetate in two-stage carcinogenesis in mice. — Oncology 51: 108–112.

    CAS  PubMed  Google Scholar 

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Authors and Affiliations

  1. PH-R&D EU-ET Natural Products Research, Bayer Health Care, P.O.B. 101709, D-42096, Wuppertal, Germany

    Veronika Hellwig & Marc Stadler

  2. Institute of Botany, Academia Sinica, Nankang, Taipei, 11529, Taiwan

    Yu-Ming Ju

  3. Dept. Plant Pathology, Washington State University, Pullman, WA, 99164-6430, USA

    Jack D. Rogers

  4. Las Muros, F-09420, Rimont, France

    Jacques Fournier

  5. Naturwissenschaftlicher Verein Wuppertal (Mykologische Sektion) und Mykologisches Herbarium des Fuhlrott-Museums, Wuppertal, Germany

    Marc Stadler

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  1. Veronika Hellwig
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  2. Yu-Ming Ju
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  3. Jack D. Rogers
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  4. Jacques Fournier
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  5. Marc Stadler
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Correspondence to Marc Stadler.

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Dedicated to Timm Anke, Kaiserslautern, on the occasion of his 60th birthday

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Hellwig, V., Ju, YM., Rogers, J.D. et al. Hypomiltin, a novel azaphilone from Hypoxylon hypomiltum, and chemotypes in Hypoxylon sect. Hypoxylon as inferred from analytical HPLC profiling. Mycol Progress 4, 39–54 (2005). https://doi.org/10.1007/s11557-006-0108-6

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