Chemical Changes of Wood Treated with Caffeine.

Earlier studies have revealed that wood treated with caffeine was effectively protected against decay fungi and molds. However, there is a need to establish how the caffeine molecule behaves after wood impregnation and how it can protect wood. The objective of the research was to characterize the interaction between caffeine and Scots pine (Pinus sylvestris L.) wood as well as to assess the stability of the alkaloid molecule in lignocellulosic material. For this purpose, an elementary analyzer was used to assess the nitrogen concentration in the treated wood. The results showed that caffeine is easily removed from the wood structure through large amounts of water. The changes occurring in the wood structure after impregnation were evaluated with regard to the results obtained by Fourier transform infrared (FTIR) spectroscopy of two model mixtures with caffeine and cellulose or lignin for the purpose of conducting a comparison with the spectrum of impregnated and non-impregnated samples. The observed changes in FTIR spectra involve the intensity of the C=O(6) caffeine carbonyl group and signals from guaiacyl units. It might indicate favorable interactions between caffeine and lignin. Additionally, molecular simulation of the caffeine's interaction with the guaiacyl ß-O-4 lignin model compound characteristic for the lignin structure using computational studies was performed. Consequently, all analyses confirmed that caffeine may interact with the methylene group derived from the aromatic rings of the guaiacyl group of lignin. In summary, scanning electron microscope (SEM) observations suggest that caffeine was accumulated in the lignin-rich areas of the primary walls.

Effect of the Solvent on Propolis Phenolic Profile and its Antifungal, Antioxidant, and In Vitro Cytoprotective Activity in Human Erythrocytes Under Oxidative Stress.

Propolis is a natural bee product with various beneficial biological effects. The health-promoting properties of propolis depend on its chemical composition, particularly the presence of phenolic compounds. The aim of this study was to evaluate the relationship between extraction solvent (acetone 100%, ethanol 70% and 96%) and the antifungal, antioxidant, and cytoprotective activity of the extracts obtained from propolis. Concentrations of flavonoids and phenolic acids in the propolis extracts were determined using ultrahigh-performance liquid chromatography. The antioxidant potential of different extracts was assessed on the basis of 2,2-diphenyl-1-picrylhydrazyl (DPPH·) free-radical-scavenging activity, Fe3+-reducing power, and ferrous ion (Fe2+)-chelating activity assays. The ability of the extracts to protect human red blood cell membranes against free-radical-induced damage and their antifungal activity was also determined. The results showed that the concentration of flavonoids in the propolis extracts was dependent on the solvent used in the extraction process and pinocembrin, chrysin, galangin, and coumaric acid were the most abundant phenols. All extracts exhibited high antioxidant potential and significantly protected human erythrocytes against oxidative damage. On the other hand, the antifungal activity of the propolis extracts depended on the solvent used in extraction and the fungal strains tested. It needs to be stressed that, to the best of our knowledge, there is no study relating the effect of solvent used for extraction of Polish propolis to its phenolic profile, and its antifungal, antioxidant, and cytoprotective activity.

Antifungal, anticancer, and docking studies of colchiceine complexes with monovalent metal cation salts.

Complexes of colchiceine with monovalent cation perchlorates and iodides have been obtained and characterized by spectroscopic methods. DFT and spectroscopic studies reveal that the dihedral angle ω1-1a-12-12a , crucial for colchicine biological mechanism of action, that is, binding to tubulins depends on the diameter of the complexed metal cation. Biological tests indicated no antifungal properties of colchicine (it was active only toward A.pullulans), in contrast to its derivative-(colchiceine). Complexation of colchiceine with metal cations improved significantly the antifungal potency, even below MIC <1 µg/ml. The colchiceine complexes were more potent than colchiceine, and some of them were even more potent than the fungicidal standard IPBC. The highest potency of colchiceine complexes was noted against A. pullulans (MIC = 0.5 µg/ml). In contrast to the findings concerning antifungal potency, the anticancer studies showed complexes of colchicine more active (~IC50  = 2 nM) than those of colchiceine (~IC50  = 6 µM). MDA-MB-231 breast cancer cell lines and human lung fibroblasts CCD39Lu were also tested.

7-Deacetyl-10-alkylthiocolchicine derivatives - new compounds with potent anticancer and fungicidal activity.

A series of new semi-synthetic 7-deacetyl-10-alkylthiocolchicne derivatives with ethyl, n-propyl, i-propyl and n-butyl substituents were synthesised and characterised by spectroscopic methods, elemental analysis, DFT calculations and molecular docking simulations. All the synthesized compounds have been tested for fungicidal and anticancer activities against SKOV-3, LoVo, MCF-7, MDA-MB-231 and the lung-derived fibroblast CCD39Lu. All the new colchicine derivatives exhibit significantly higher cytotoxicity towards the SKOV-3 tumour cell line than the natural product - colchicine. The most effective cytotoxic agents were 7-deacetyl-10-n-buthylthiocolchicine and 7-deacetyl-10-i-propylthiocolchicine. Among all the compounds tested, 7-deacetyl-10-n-buthylthiocolchicine exhibited the highest fungicidal activity. Molecular modeling indicated that several mutations found in the ß-tubulin unit of the tested fungal strains are crucial for antifungal activity and selectivity of 7-deacetyl-10-n-buthylthiocolchicine. The obtained results may be useful for the development of selective colchicine derivatives as effective fungicidal and/or anticancer drugs.