Investigation on Some Compounds Biosynthesized by Fruitbodies of Naematoloma Fasciculare/Huds. Ex Fr./P. Karst

Abstract

The chromatographic analysis of ethanolic extract from N a e m a t o 1 o m a f a s c i c u 1 a r e fruitbodies indicated 20 nitrogen compounds (4 liquid amines, 4 volatile amines, 10 amino acids, 2 purines) 5 sugars, 4 sterols. Ergosterol, ergosterol peroxide, cerevisterol were separated by column chromatography and crystallized.Naematoloma fasciculare HUDS. ex Fr. P. KARST* a representative of xylophilous Basidiomycetes beIongs to the family Strophariaceae [9, 171. Ethanolic extract of N. fasciculare shows diuretic and parasymphathetic action in rats after ip administration [15]. Herbich et al. [6] reported that the fatal poisonings of men with fruitbodies of N. fasciculare were connected with necrosis of the liver, damage of the cardiac muscle and brain cells. The previously described*:-investigations on mycelial cultures (surface and submerged) obtained from the explantats of N. fasciculare fruitbodies and analyzed compounds biosynthesized in vitro.The aim of the present study was a phytochemical analysis of the constituents occuring in ethanolic extract of N. fasciculare fruitbodies collected in the natural habitats. ExperimentalGeneral: The infrared spectra were taken in KBr pellets on a Digilap. Mod. FTS-20 spectrometer. The mass spectra were measured with a LKB 9000s in the Regional Laboratory of Physicochemical Analysis and Structural Research in Krak6w. The melting points were determined on a Boetius hot stage microscope and are uncorrected. * synonym: Hypholorna fasciculare (FR.) QUEL. :' * J. DIAK: POI.Abreviations used: Be = benzene, n-BuOH = n-butanol, EtOAc = ethyl acetate, He = heksane, HOAc = acetic acid, M,Co = acetone, MeCOEt = ethylmethyl ketone, MeOH = methanol, PhOH = phenol, iso-PrOH = iso-propanol, Pyr = pyridine.Plant material: The well developed (open hats) fruitbodies of N. fasciculare were collected in the natural habitats in 1973-1975.Extraction methods: The fresh fruitbodies were washed in runnig water and homogenized with ethanol. After centrifugation of the precipitate, ethanolic extract was analyzed acc. to the scheme in Fig. 1.Paper chromatography: For separation of nitrogen compounds and sugars,

A new look into the reaction between ergosterol and singlet oxygen in vitro

“…Thus, when ERGO was irradiated according to the general method with rose Bengal in MTBE and with eosine in MTBE independently, the comparative chromatographic analysis (TLC) of both irradiated solutions showed similar mixture of products formed during the irradiations. The TLC spots observed for each irradiated solution showed R f values corresponding to authentic EEP, KE, DHE, EEP9 (11) and DHOE together with nonconverted ERGO and two new products whose spots had not been previously detected during the irradiation of ERGO in Py and in EtOH solution. After the products were isolated and purified, EEP, KE, EEP9 (11) and DHOE were characterized by comparison of R f (TLC) and 1 H-NMR spectra with authentic samples that we had previously fully characterized (see Experimental section).…”

“…The TLC spots observed for each irradiated solution showed R f values corresponding to authentic EEP, KE, DHE, EEP9 (11) and DHOE together with nonconverted ERGO and two new products whose spots had not been previously detected during the irradiation of ERGO in Py and in EtOH solution. After the products were isolated and purified, EEP, KE, EEP9 (11) and DHOE were characterized by comparison of R f (TLC) and 1 H-NMR spectra with authentic samples that we had previously fully characterized (see Experimental section). DHE co-migrates in TLC analysis of the photolyzed mixtures with the authentic sample, although it could not been isolated from these reaction mixtures by column chromatography because it was present as trace.…”

“…On the contrary, together with EEP and non-converted ERGO, three new products were observed which had not been previously detected by TLC analysis when irradiations were performed in Py. After the work-up of the reaction mixture, according to the general method described in Experimental section, EEP in 47% yield together with (22E )-ergosta-6,9,22triene-3β-,5α,8α-triol (DHOE) in 24% yield and (22E )-5α,8αepidioxyergosta-6,9,22-trien-3β-ol (EEP9 (11)) in 8% yield were obtained. The fourth compound isolated in trace amount (yield < 0.5%) was characterized as 9(11)-dehydroergosterol (DHE).…”

“…5 These endoperoxides are relatively stable and are easily purified by column 6 or by preparative thin-layer adsorption chromatography. 7 Furthermore, sterols with the 5,8-ring-bridging endoperoxide group (5,8-epidioxy sterols) are widespread in nature, and are found in sponges, 7-9 tunicates, 9 coral, 10 the sea hare, 9 fungi 6, 11 and lichens. 7,12 The (22E )-5α,8α-epidioxyergosta-6,22-dien-3β-ol (EEP) has been described as the main product obtained by reaction of singlet oxygen with ergosterol in vivo and in vitro.…”