AbstractSubmerged cultures of the edible mushrooms Phlebopus portentosus and Phlebopus spongiosus were screened for their secondary metabolites by HPLC-UV/Vis and HR-LC-ESI-MS. Two new compounds, 9′-hydroxyphenyl pulvinone (1), containing an unusual pulvinone structure, and phlebopyron (2), together with the seven known pigments, atromentic acid (3), xerocomic acid (4), variegatic acid (5), methyl atromentate (6), methyl isoxerocomate (7), methyl variegatate (8), and variegatorubin (9) were isolated from the cultures. Their structures were assigned on the basis of extensive 1D/2D NMR spectroscopic analyses, as well as HR-ESI-MS, and HR-ESI-MS/MS measurements. Furthermore, the isolated compounds were evaluated for their antimicrobial and cytotoxic properties. 9′-hydroxyphenyl pulvinone (1), xerocomic acid (4), and methyl variegatate (8) exhibited weak to moderate cytotoxic activities against several tumor cell lines. The present paper provides a comprehensive characterization of pigments from the class of pulvinic acids that are present in the basidiomes of many edible bolete species.

Based on comparison of molecular, morphological and ecological data, we propose that Hybogaster giganteus Singer, a parasitic basidiomycete on stem bases and coarse roots of Nothofagus in Chile, is conspecifically related to the sympatric Bondarzewia guaitecasensis. According to our concept, H. giganteus is representing a sequestrate form of the latter and is hence recombined and formally described as Bondarzewia guaitecasensis f. gigantea; we further discuss the evidence that its sequestrate morphology may provide higher resistance to drought stress in early autumn, extending the sporulation season of the species.

A mesomeric form of quaternary indoloquinazoline alkaloid, soyauxinium chloride (1) was obtained through the chemical investigation of stem bark and roots of Araliopsis soyauxii Engl. [syn. Vepris soyauxii (Engl.) Mziray] (Rutaceae) together with fifteen known compounds, including three furoquinoline alkaloids, three 2-quinolones, two limonoids, two triterpenes, two steroids, a coumarin, an acridone alkaloid, and a flavonoid glycoside. Their structures were established by comprehensive spectroscopic and spectrometric analyses (1D and 2D NMR, ESI-HR-MS) and by comparison with previously reported data. 13C NMR data of araliopsinine are also reported here for the first time. The isolated compounds were screened in vitro for their effects on the viability of two different human cancer cell lines, namely prostate PC-3 adenocarcinoma cells and colorectal HT-29 adenocarcinoma cells. However, none of the tested compounds exhibited strong anti-proliferative or cytotoxic activities, to either prostate PC-3 cells or colon HT-29 cells. At 100 μM, the furoquinoline maculine showed a slightly increased anti-proliferative effect, however, exclusively on HT-29 cells. The chemotaxonomic significance of the isolated compounds has also been discussed.

This  paper describes  the isolation and comparative studies on NMR spectra of cardenolide glycosides from Streptocaulon tomentosum Wight & Arnott (Asclepiadaceae).  Nine cardenolides were isolated from the roots of Streptocaulon tomentosum. by column chromatography and identified by NMR spectroscopy. They are 17α-H-periplogenin, 17α-H-periplogenin-β-D digitoxose,17α-H-periplogenin-β-D cymarose, 17α-H-periplogenin-β-glucosyl-(1-4)-2-O-acetyl-digitalose, 17β-H-periplogenin, 17β-H-periplogenin-β-D digitoxose, 17β-H-periplogenin-β-D cymarose, 17α -H-digitoxigenin, and 17 α-H-digitoxigenin-β-D-digitoxoside. Comparative studies on NMR spectra of cardenolide glycosides were carried out. Six cardenolides isolated from Streptocaulon tomentosum were tested for their antiproliferative activity in vitro against MCF-7 (human breast cancer cell line) and L 929 (mouse fibroblast cell line). Among these six cardenolides, 17α-H-periplogenin-3-O-β-D-digitoxoside and 17α-H-periplogenin-3-O-β-D-cymaroside exhibit significant antiproliferative activity (IC50 values, < 1μM) against MCF-7. Four cardenolides  were examined for their cellular viability in the tumor cell and  U 937  (human leukemic cell line) at concentrations 100 μM, 10 μM, and 1 μM. All these four cardenolides  show the induction of apoptosis at 100 μM and 10 μM in both cell lines.

High-performance thin-layer chromatography (HPTLC) coupled with negative ion desorption electrospray ionization high-resolution mass spectrometry (DESI-HRMS) was used for the analysis of anthraquinones in complex crude extracts of Chilean dermocyboid Cortinarii. For this proof-of-concept study, the known anthraquinones emodin, physcion, endocrocin, dermolutein, hypericin, and skyrin were identified by their elemental composition. HRMS also allowed the differentiation of the investigated anthraquinones from accompanying compounds with the same nominal mass in the crude extracts. An investigation of the characteristic fragmentation pattern of skyrin in comparison with a reference compound showed, exemplarily, the feasibility of the method for the determination of these coloring, bioactive and chemotaxonomically important marker compounds. Accordingly, we demonstrate that the coupling of HPTLC with DESI-HRMS represents an advanced and efficient technique for the detection of anthraquinones in complex matrices. This analytical approach may be applied in the field of anthraquinone-containing food and plants such as Rheum spp. (rhubarb), Aloe spp., Morinda spp., Cassia spp. and others. Furthermore, the described method can be suitable for the analysis of anthraquinone-based colorants and dyes, which are used in the food, cosmetic, and pharmaceutical industry.

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