Spectral Assignment in the [3 + 2] Cycloadditions of Methyl (2E)-3-(Acridin-4-yl)-prop-2-enoate and 4-[(E)-2-Phenylethenyl]acridin with Unstable Nitrile N-Oxides.

The investigation of cycloaddition reactions involving acridine-based dipolarophiles revealed distinct regioselectivity patterns influenced mainly by the electronic factor. Specifically, the reactions of methyl-(2E)-3-(acridin-4-yl)-prop-2-enoate and 4-[(1E)-2-phenylethenyl]acridine with unstable benzonitrile N-oxides were studied. For methyl-(2E)-3-(acridin-4-yl)-prop-2-enoate, the formation of two regioisomers favoured the 5-(acridin-4-yl)-4,5-dihydro-1,2-oxazole-4-carboxylates, with remarkable exclusivity in the case of 4-methoxybenzonitrile oxide. Conversely, 4-[(1E)-2-phenylethenyl]acridine displayed reversed regioselectivity, favouring products 4-[3-(substituted phenyl)-5-phenyl-4,5-dihydro-1,2-oxazol-4-yl]acridine. Subsequent hydrolysis of isolated methyl 5-(acridin-4-yl)-3-phenyl-4,5-dihydro-1,2-oxazole-4-carboxylates resulted in the production of carboxylic acids, with nearly complete conversion. During NMR measurements of carboxylic acids in CDCl3, decarboxylation was observed, indicating the formation of a new prochiral carbon centre C-4, further confirmed by a noticeable colour change. Overall, this investigation provides valuable insights into regioselectivity in cycloaddition reactions and subsequent transformations, suggesting potential applications across diverse scientific domains.

Medicinal mushrooms Ophiocordyceps sinensis and Cordyceps militaris.

The main component of Ophiocordyceps sinensis and Cordyceps militaris extracts are polysaccharides. These are natural biopolymers that represent a large class of biologically active components. These contribute to their pharmacological activity and effect on health. They contain monosaccharides that include rhamnose, ribose, arabinose, xylose, mannose, glucose, galactose, mannitol, fructose, and sorbose. The exopolysaccharide fraction has a large number of pharmacological effects, the two most important of which are immunomodulatory and antitumour. Among the contained polysaccharides is also mannoglucan, which shows weak cytotoxic activity against the SPC-I1) cancer cell line. More than ten nucleosides and their related compounds, including adenine, adenosine, inosine, cytidine, cytosine, guanine, uridine, thymidine, uracil, hypoxanthine, and guanosine, have been successively isolated from Ophiocordyceps sinensis. It contains many amino acids and polypeptides that are thought to affect the cardiovascular system. They also have a sedative and hypnotic effect, with tryptophan being the most effective component among them. Polysaccharides were extracted from four samples: sample 1 (grown on the substrate Oryza sativa indica, strain Ophiocordyceps sinensis), sample 2 (grown on the substrate Oryza sativa japonica, strain Ophiocordyceps sinensis), sample 3 (grown on the substrate Oryza sativa indica, strain Cordyceps militaris), sample 4 (grown on Oryza sativa japonica substrate, strain Cordyceps militaris). Through NMR spectroscopy and subsequent comparison with the literature, the majority of a chemical compound in deproteinized extracts 1 and 4 was found to be a hydrophilic polyglucan referred to as CBHP2).

Antioxidant Activity and Infrared Spectroscopy Analysis of Alcoholic Extracts Obtained from Paecilomyces hepiali (Ascomycetes).

This research studies the influence of substrate on the antioxidant activity of alcohol extracts of Paecilomyces hepiali. We used corn, rice, millet, and peas as substrates. Antioxidant activity was measured with the DPPH radical scavenging method. Concentrations of extracts (6.25, 3.12, 1.56, 0.78, and 0.39 mg/mL) were applied in all evaluations. Overall antioxidant activity was expressed as the concentration of substrate that decreased DPPH radical levels by 50% (IC50DPPH) for 7 methanol and 7 ethanol extracts. A comparison of IC50DPPH allowed us to conclude that the methanol extracts are more active in scavenging stable DPPH radicals than are the ethanol extracts. The substrate with antioxidant properties most suitable for cultivation of P. hepiali was rice supplemented with non-defatted soy flour. The extract most effective in scavenging stable radicals was the methanol extract of sample 4 (IC50DPPH = 2.33 mg/mL) cultivated on rice with nondefatted soy flour. The methanol extract of sample 7 cultivated on peas was less effective (IC50DPPH = 11.50 mg/mL). By crystallizing these extracts, we managed to obtain sufficient quantities of 6 samples in a solid state, for which infrared spectra were measured and confirmed the presence of amino acids in the extracts.

NMR and IR analysis of natural substances isolated from Cordyceps medicinal mushrooms.

There exist about 750 species of Cordyceps at present. A high price of natural Cordyceps and its lack in nature caused that the attention has been focused to its cultivation in laboratory conditions. The demand for this “fungus-parasite” is still quite high nowadays, as shown by the amount of commercial nutritional supplements. Phytochemical diversity has ensured that Cordyceps is used as an immunomodulatory and an antioxidant; it has anti-cancer, anti-inflammatory, anti-diabetic, antibacterial, anti-HIV effects. In the present study we focused on NMR and IR analyses of natural substances isolated from two species of Cordyceps: Cordyceps sinensis MFTCCB025/0216, MFTCCB026/0216 and Paecilomyces hepiali MFTCCB023/0216. Two types of rice substrates (Oryza sativa Indica and Oryza sativa Japonica) were used for cultivation. A total of five methanol extracts obtained by a reflux method of the ground mushroom were analysed. To determine the quality and quantity of the major chemical compounds, 1D and 2D NMR analysis has been used with 1H, 13C, COSY, NOESY, HSQC, HMBC and DEPT spectra. IR spectroscopy was chosen as a complementary analysis to determine functional groups. Linoleic acid, oleic acid and mannitol were identified as major compounds of the methanol extracts. Tyrosine, alanine, urea and the others biologically interesting substances were found as minor components.