Cortinarius hinnuleus (Earthy Webcap), a common mycorrhizal mushroom in Central Europe, is characterized by a mouldy earthy odour. The relevant volatile compounds were detected by gas chromatography-mass spectrometry using headspace-solid phase microextraction technology and identified as geosmin, ß-caryophyllene and ß-barbatene together with the C8-volatiles 1-octen-3-ol, 1-octen-3-one, octan-3-ol, octan-3-one, and 2-octen-1-ol.

Hydnora abyssinica A.Br. (Hydnoraceae), a holoparasitic herb, is for the first time recorded for Abyan governorate of South Yemen. Flowers of this species were studied for their ethnobotanical, biological and chemical properties for the first time. In South Yemen, they are traditionally used as wild food and to cure stomach diseases, gastric ulcer and cancer. Phytochemical analysis of the extracts showed the presence of terpenes, tannins, phenols, and flavonoids. The volatile components of the air-dried powdered flowers were identified using a static headspace GC/MS analysis as acetic acid, ethyl acetate, sabinene, α-terpinene, (+)-D-limonene and γ-terpinene. These volatile compounds that characterize the odor and taste of the flowers were detected for the first time in a species of the family Hydnoraceae. The flowers were extracted by n-hexane, dichlormethane, ethyl acetate, ethanol, methanol and water. With exception of the water extract all extracts demonstrated activities against Gram-positive bacteria as well as remarkable radical scavenging activities in DPPH assay. Ethyl acetate, methanol and water extracts exhibited good antifungal activities. The cytotoxic activity of the extracts against FL cells, measured in neutral red assay, was only weak (IC50 > 500 μg /mL). The results justify the traditional use of the flowers of Hydnora abyssinica in South Yemen.

Four new 19-residue peptaibols, named tulasporins A–D (1–4), were isolated from the semi-solid cultures of Sepedonium tulasneanum. Their structures were elucidated on the basis of extensive ESI-HRMSn fragmentation studies as well as 1H NMR spectroscopic analyses. Interestingly, the structures of tulasporins A–D (1–4) resemble those of chrysospermins isolated earlier from cultures of S. chrysospermum. Previously, it was hypothesized that the peptaibol production by Sepedonium species correlates with the morphology of the aleurioconidia, as exclusively round-shaped aleurioconidia forming species produced peptaibols. Since the investigated Sepedonium tulasneanum produces oval aleurioconidia, this study can be considered as the first report of peptaibols from a Sepedonium strain with oval-shaped aleurioconidia. Thus, it could be demonstrated that both round as well as oval aleurioconidia forming Sepedonium species are able to produce peptaibols. Tulasporins A-D (1–4), when tested against phytopathogenic fungi, exhibited good growth inhibitory activity against both Botrytis cinerea and Phytophthora infestans, while they were devoid of significant activity against Septoria tritici.

Pseudohygrophorones A(12) (1) and B(12) (2), the first naturally occurring alkyl cyclohexenones from a fungal source, and the recently reported hygrophorone B(12) (3) have been isolated from fruiting bodies of the basidiomycete Hygrophorus abieticola Krieglst. ex Gröger & Bresinsky. Their structures were assigned on the basis of extensive one- and two-dimensional NMR spectroscopic analysis as well as ESI-HRMS measurements. The absolute configuration of the three stereogenic centers in the diastereomeric compounds 1 and 2 was established with the aid of (3)JH,H and (4)JH,H coupling constants, NOE interactions, and conformational analysis in conjunction with quantum chemical CD calculations. It was concluded that pseudohygrophorone A(12) (1) is 4S,5S,6S configured, while pseudohygrophorone B(12) (2) was identified as the C-6 epimer of 1, corresponding to the absolute configuration 4S,5S,6R. In addition, the mass spectrometric fragmentation behavior of 1-3 obtained by the higher energy collisional dissociation method allows a clear distinction between the pseudohygrophorones (1 and 2) and hygrophorone B(12) (3). The isolated compounds 1-3 exhibited pronounced activity against phytopathogenic organisms.

The Chilean Sepedonium aff. chalcipori strain KSH 883, isolated from the endemic Boletus loyo Philippi, was studied in a polythetic approach based on chemical, molecular, and biological data. A taxonomic study of the strain using molecular data of the ITS, EF1-α, and RPB2 barcoding genes confirmed the position of the isolated strain within the S. chalcipori clade, but also suggested the separation of this clade into three different species. Two new linear 15-residue peptaibols, named chilenopeptins A (1) and B (2), together with the known peptaibols tylopeptins A (3) and B (4) were isolated from the semisolid culture of strain KSH 883. The structures of 1 and 2 were elucidated on the basis of HRESIMS(n) experiments in conjunction with comprehensive 1D and 2D NMR analysis. Thus, the sequence of chilenopeptin A (1) was identified as Ac-Aib(1)-Ser(2)-Trp(3)-Aib(4)-Pro(5)-Leu(6)-Aib(7)-Aib(8)-Gln(9)-Aib(10)-Aib(11)-Gln(12)-Aib(13)-Leu(14)-Pheol(15), while chilenopeptin B (2) differs from 1 by the replacement of Trp(3) by Phe(3). Additionally, the total synthesis of 1 and 2 was accomplished by a solid-phase approach, confirming the absolute configuration of all chiral amino acids as l. Both the chilenopeptins (1 and 2) and tylopeptins (3 and 4) were evaluated for their potential to inhibit the growth of phytopathogenic organisms.

Representative compounds with a 1,3‐dihydroxybenzene substructure belonging to different important polyphenol classes (stilbenes, flavones, isoflavones, flavonols, flavanones, flavanols, phloroglucinols, anthraquinones and bisanthraquinones) were investigated based on detailed high‐resolution tandem mass spectrometry measurements with an Orbitrap system under negative ion electrospray conditions. The mass spectral behaviour of these compound classes was compared among each other not only with respect to previously described losses of CO, CH2CO and C3O2 but also concerning the loss of CO2 and successive specific fragmentations. Furthermore, some unusual fragmentations such as the loss of a methyl radical during mass spectral decomposition are discussed. The obtained results demonstrate both similarities and differences in their mass spectral fragmentation under MSn conditions, allowing a characterization of the corresponding compound type.

Pyrofomins A-D, four polyoxygenated sesquiterpenoids have been isolated from the methanolic extract of the fruit bodies of Pyrofomes demidoffii. Their structures are elucidated by IR, HR-FTICR-MS, and 2D NMR spectroscopy. Furthermore, the cedrane carbon skeleton of pyrofomin A (1) is confirmed by X-ray crystallographic analysis. The sesquiterpenoids 1–4 show neither cytotoxicity against KB cells nor antimicrobial activity.