Silphiperfolene-Type Terpenoids and Other Metabolites from Cultures of the Tropical Ascomycete Hypoxylon rickii(Xylariaceae)

A culture isolated from ascospores of Hypoxylon rickii,a xylariaceous ascomycete collected in Martinique,had yielded botryane,noreremophilane and abietane-type terpenoids in a preceding study,but additional metabolites were detected by extensive HPLC–MS analysis in other fractions.Herein we report the further isolation of four new sesquiterpenoids with a silphiperfol-6-ene skeleton from extracts of H.rickii.The planar structures were elucidated by NMR and HRMS data as 13-hydroxysilphiperfol-6-ene(1),9-hydroxysilphiperfol-6-en-13-oic acid(2),2-hydroxysilphiperfol-6-en-13-oic acid(3)and 15-hydroxysilphiperfol-6-en-13-oic acid(4).For compounds 2–4 we propose the trivial names rickinic acids A–C.Their stereochemistry was assigned by ROESY correlations as well as by the specific optical rotation.Additionally,the known compounds,botryenanol,dehydrobotrydienol,cyclo(Phe-Pro),cyclo(Pro-Leu),(?)-ramulosin and aeleostearic acid were isolated.The antimicrobial and cytotoxic activities of the new compounds are also reported.

A new endophytic insect-associated Daldinia species, recognised from a comparison of secondary metabolite profiles and molecular phylogeny

Xylariaceous endophytes are commonly encountered in plants,and it has recently been found out that insect vectors play a major role in their life cycle,as well as in the apparent host-specificity of the fungal stromata.In this study,a new insect-associated,endophytic anamorph species of Daldinia is recognised from a comparison of (a)morphological and ecological data;(b)molecular phylogenetic data based on rDNA,alpha-actin and beta-tubulin genes;and (c)secondary metabolite profiles based on high performance liquid chromatography/diode array/mass spectrometry(HPLC-DAD/MS)and gas chromatography/mass spectrometry(GC-MS)in comparison with authentic strains of Daldinia and other Xylariaceae.The new species,Daldinia hawksworthii,is a symbiont of the willow woodwasp,Xiphydria prolongata,which is in turn preferentially associated with Salix.A comparison of HPLCDAD/MS profiles from standardised cultures revealed the presence of a specific compound,which was not encountered in any of the ca.250 Daldinia strains studied for comparison.This compound was isolated after fermentation of the fungus in 10 l scale by preparative chromatography.Structure elucidation by NMR spectroscopy revealed a novel pyrone,for which the name dalsymbiopyrone is proposed.The compound showed weak antimicrobial and cytotoxic effects and might be a signal molecule involved in the trilateral ecological interaction between the host plant,the insect,and its fungal symbiont.

Lenormandins A—G,new azaphilones from Hypoxylon lenormandii and Hypoxylon jaklitschii sp.nov.,recognised by chemotaxonomic data

Seven new azaphilone pigments named lenormandins A–G were isolated from stromata(fruiting bodies)of the xylariaceous fungus,Hypoxylon lenormandii using preparative High Performance Liquid Chromatography(HPLC)and their structures were elucidated by NMR spectroscopy,high resolution mass spectrometry and other spectral methods.Their occurrence in herbarium specimens(including various type materials collected in the 19th and early 20th century)and several fresh collections was studied by analytical HPLC with diode array and mass spectrometric detection(HPLC-DAD/MS),revealing that this group of pigments is specific for Hypoxylon lenormandii from various geographic regions and otherwise only occurs in closely related taxa,i.e.H.sublenormandii and an undescribed fungus from Sri Lanka,for which we propose the name H.jaklitschii.The status of the new species was established by using molecular phylogenetic data based on ITS and partial beta-tubulin sequences,and by detailed morphological studies.

Identification of fungal fossils and novel azaphilone pigments in ancient carbonised specimens of Hypoxylon fragiforme from forest soils of Chatillon-sur-Seine(Burgundy)

Fungal stromata were recently discovered in association with charcoal and burnt soil aggregates during an archaeological survey in the Chaˆtillon-sur-Seine forest massif.The wood and soil in the samples were dated to the medieval period(between 738 and 1411 AD).Light microscopy and scanning electron microscopy revealed that a few of the stromatal fragments still contained ascospores.Their macromorphological characters were described and secondary metabolite profiles were generated using high performance liquid chromatography with diode array and mass spectrometric detection(HPLC–DAD/MS).The combination of these two data lines then allowed species identification.Most of the fragments were assigned to Hypoxylon fragiforme,the type species of the Hypoxylaceae(Xylariales).Two further species whose stromata grew on the fossil charcoal could be tentatively identified as Jackrogersella cohaerens and(more tentatively)as Hypoxylon vogesiacum.These three species are still commonly encountered in the forests of Central Europe today.Furthermore,the HPLC-HRMS data of H.fragiforme suggested the presence of unknown azaphilone dimers and of further new pigments.These archaeological compounds were compared to fresh stromata of H.fragiforme collected in Germany and subjected to the same analytical protocol.While the major components in both samples were identified as the known mitorubrin type azaphilones and orsellinic acid,the chemical structures of seven novel complex azaphilone pigments,for which we propose the trivial names rutilins C-D and fragirubrins A-E,were elucidated using spectral methods(NMR and CD spectroscopy,high resolution mass spectrometry).It appears that these pigments had indeed persisted for millennia in the fossil stromata.

Ten decadal advances in fungal biology leading towards human well‑being

Fungi are an understudied resource possessing huge potential for developing products that can greatly improve human well-being.In the current paper,we highlight some important discoveries and developments in applied mycology and interdisciplinary Life Science research.These examples concern recently introduced drugs for the treatment of infections and neurological diseases;application of–OMICS techniques and genetic tools in medical mycology and the regulation of mycotoxin production;as well as some highlights of mushroom cultivaton in Asia.Examples for new diagnostic tools in medical mycology and the exploitation of new candidates for therapeutic drugs,are also given.In addition,two entries illustrating the latest developments in the use of fungi for biodegradation and fungal biomaterial production are provided.Some other areas where there have been and/or will be significant developments are also included.It is our hope that this paper will help realise the importance of fungi as a potential industrial resource and see the next two decades bring forward many new fungal and fungus-derived products.