Jadwiga Maj

13C-NMR study of 4-azasteroids in solution and solid state.

A group of biologically active 4-azasteroids was studied by 13C-NMR spectroscopy in solution and in the solid phase. A full assignment of signals in the spectra of samples in chloroform was performed for thirteen 4-azasteroids using two-dimensional techniques. Substituent and steric effects of a nitrogen atom, and their influence on chemical shifts of the neighboring carbon atoms are discussed. CP MAS spectra were obtained for five 4-azasteroids including finasteride. The spectra confirmed polymorphism of the latter compound. In addition to the polymorphic forms that are already known, a new molecular complex of finasteride with dioxane is reported.

Synthesis and Biological Activity of 22-Deoxo-23-oxa Analogues of Saponin OSW-1

Analogues of the potent cytotoxic saponin OSW-1 were prepared from the readily available steroidal 16β,17α,22-triol. The new 22-deoxo-23-oxa analogues of OSW-1 were screened against eight cancer cell lines and normal human fibroblasts. The analogues proved to be slightly less active than OSW-1 but also less toxic to normal cells. They induce concentration- and time-dependent apoptosis of mammalian cancer cells with caspase-3 activation.

GC-MS Analysis of β-Carotene Ethenolysis Products and their Synthesis as Potentially Active Vitamin A Analogues

ABSTRACT β-Carotene ethenolysis under promotion of well-defined ruthenium catalysts were examined as a novel method of synthesis of vitamin A derivatives. Efficient reaction was promoted by the second-generation Hoveyda catalyst. The products of ethenolysis in positions C15-C15′, C11-C12, and C9-C10 were detected, but cleavage of the C11-C12 double bond predominated. Even better regioselectivity at this position was observed for cross−metathesis between β-carotene and functionalized alkenes.

Comparison of Volatile Constituents of Acorus calamus and Asarum europaeum Obtained by Different Techniques

Abstract Different parts of Acorus calamus L. (Araceae) and Asarum europeaum L. (Aristolochiaceae) growing in Poland were subjected to headspace-SPME (HS-SPME) and the same plant material were hydrodistilled (HD) to obtain the profiles of their volatile constituents. In both cases, compounds of essential oils and headspace volatiles were identified and quantified by GC and GC/MS. The results showed that the similar compounds were detected in the vapor phases and in the oils derived from both plants. The 68 compounds in the oil and 40 in SPME headspace of A. calamus were identified representing 99.3% and 97.3% of the total components detected, respectively. The main constituents of the oil of A. calamus were acorenone (14.6%), shyobunone isomer (10.5%) and (Z)-asarone (10.4%). The acorenone integrated with (E)-asarone (50.1%), 6,11-oxidoacor-4-ene (9.0%), iso-caryophyllene (8.6%) were found as the main constituents in the SPME phase of A. calamus. The analysis of the oil and the SPME headspace of roots of A. europaeum led to detection of 34 and 34 compounds representing 86.9% and 80.5% of the total components detected, respectively. The main compounds of the oil were (E)-asarone, 59.1% and bornyl acetate, 7.5%. And the leading constituents of SPME phase of roots were (E)-asarone, 57.3% and bornyl acetate, 8.3%.

Decomposition of α-Tocopheryl Glycosides in Rat Tissues

ABSTRACT Background: The aim of our investigation was to estimate the stability of α-tocopheryl O-glycosides in relation to activity of exoglycosidases in selected rat tissues. Material and Methods: Acetylated glycosides were obtained in glucosidation of α-tocopherol using the Helferich method. The activity of exoglycosidases was determined by the Zwierz et al. method. Protein concentrations were determined by the biuret method. The concentration of released α-tocopherol was determined with the HPLC method. Results: The comparison of the amount of released α-tocopherol with the amount of released p-nitrophenol shows that glycoside bound in 2a–5a derivatives of α-tocopherol undergoes hydrolysis significantly harder than in appropriate 2b–5b p-nitrophenyl derivatives. Conclusion: The results indicate that tocopheryl O-glycosides are more resistant to enzymatic hydrolysis than appropriate p-nitrophenol O-glycosides 2a–5a. Among examined tocopheryl O-glycosides, galactoside 4 is the only compound that caused the significant increase in tocopherol concentration, as compared to its endogenic content.