Minor and trace sterols in marine invertebrates. 34 Isolation and structure elucidation of 24-methyl-5α-cholesta-7,9(11), 24(28)-trien-3β-ol,the first naturally occurring Δ7, 9(11) unsaturated marine sterol

The lipid fraction of a Black Sea sponge, $\text{Haliclona flavescens}$, was investigated for its sterol composition. Twenty-three sterols were identified, including the hitherto unknown 24-methyl-5α-cholesta-7, 9(11), 24(28)-trien-3β-ol ($\text{3}$). Identification and structure elucidation were based upon 360 MHz ¹H-NMR and MS analyses.     

Prevalence of newly generated naive regulatory T cells (Treg) is critical for Treg suppressive function and determines Treg dysfunction in multiple sclerosis

The suppressive function of regulatory T cells (T(reg)) is impaired in multiple sclerosis (MS) patients. The mechanism underlying the T(reg) functional defect is unknown. T(reg) mature in the thymus and the majority of cells circulating in the periphery rapidly adopt a memory phenotype. Because our own previous findings suggest that the thymic output of T cells is impaired in MS, we hypothesized that an altered T(reg) generation may contribute to the suppressive deficiency. We therefore determined the role of T(reg) that enter the circulation as recent thymic emigrants (RTE) and, unlike their CD45RO(+) memory counterparts, express CD31 as typical surface marker. We show that the numbers of CD31(+)-coexpressing CD4(+)CD25(+)CD45RA(+)CD45RO(-)FOXP3(+) T(reg) (RTE-T(reg)) within peripheral blood decline with age and are significantly reduced in MS patients. The reduced de novo generation of RTE-T(reg) is compensated by higher proportions of memory T(reg), resulting in a stable cell count of the total T(reg) population. Depletion of CD31(+) cells from T(reg) diminishes the suppressive capacity of donor but not patient T(reg) and neutralizes the difference in inhibitory potencies between the two groups. Overall, there was a clear correlation between T(reg)-mediated suppression and the prevalence of RTE-T(reg), indicating that CD31-expressing naive T(reg) contribute to the functional properties of the entire T(reg) population. Furthermore, patient-derived T(reg), but not healthy T(reg), exhibit a contracted TCR Vbeta repertoire. These observations suggest that a shift in the homeostatic composition of T(reg) subsets related to a reduced thymic-dependent de novo generation of RTE-T(reg) with a compensatory expansion of memory T(reg) may contribute to the T(reg) defect associated with MS.     

Cinnamoyl- and hydroxycinnamoyl amides of glaucine and their antioxidative and antiviral activities

The aporphine alkaloid glaucine has been converted into 3-aminomethylglaucine and its free amino group has been linked to cinnamic, ferulic, sinapic, o-, and p-coumaric acids. The antioxidative potential of the synthesized amides was studied against DPPH(*) test. All of the tested compounds demonstrated higher radical scavenging activity than glaucine and 3-aminomethylglaucine, and lower antioxidative effect than the free hydroxycinnamic acids. The newly synthesized compounds were tested in vitro for antiviral activity against viruses belonging to different taxonomic groups.     

Some aspects of the initiation of callus and suspension cultures of Valeriana officinalis var. Diliana

New developments in the aspect of plant tissue cultivation of an important pharmaceutical species are discussed. There are some pathways of production cell cultures of Valeriana officinalis on agar and liquid media. The aim is to obtain suspension cultures able to produce biological active substances of the group of valepotreates as well as some new substances eventually. We gave a morphological characteristic of the different aggregated and differentiated suspension cultures.     

The pollutants in rime and fog water and in air at Milesovka Observatory (Czech Republic)

Samples of rime/fog water and dust in the air were collected in order to compare concentrations of pollutants. Particular attention was paid to particles of heavy metals (Al, As, Cu, Fe, Pb, Ti and Zn). The concentrations of pollutants from the air are different in rime water and fog water. Both (fog) water and ice crystals fixed Ti, Cu, As and Pb ions minimally (less than 1%). Rime captured 11.6% Al, 9.3% Zn, 4.4% Fe and 91.2% Mn from the air. Fog water absorbed 9.8% Al, 9.0% Fe, 55.6% Mn, and 48.7% Zn from the air. Fog water absorbed Zn much better (48.7%) than rime (9.3%). Rime absorbed Mn better (91.2%) than fog water (55.6%).     

Complexation of ferric oxide particles with pectins of ordered and random distribution of charged units

Complexation between ferric oxide particles and pectins with degree of methylation 50% but having ordered or random arrangement of free carboxyl groups is investigated by electric light scattering and electrophoresis. The influence of charge distribution in pectin chain on the electrical properties of oppositely charged oxide particles and stability of their suspensions is examined as a function of pectin concentration. Although the difference in charge density of pectin samples is ~5%, we found small but measurable difference in the behavior of both oxide/pectin complexes. This is attributed to condensation of counterions near the chains of pectin with ordered distribution of charges, leading to a decrease in the effective charge density and to a corresponding decrease in the contour length of the adsorbing pectin chains. Two parameters are sensitive to the conformation of the adsorbed chains in suspensions, stabilized by pectin adsorption (at particle charge reversal). The electro-optical effect is higher for the complex with less charged pectin, which is explained with larger amount of chains, adsorbed in more coiled conformation than the chains of pectin with random distribution of free carboxyl groups. The addition of small amounts of CaCl(2) has no significant influence on the thickness of the layer from the less charged pectin, in agreement with a more compact conformation of the chains in this adsorbed layer. In contrast, the thickness of the layer from pectin with random distribution of charged groups decreases with increasing concentration of CaCl(2), indicating a more loose structure of this layer.     

Effect of pectin charge density on formation of multilayer films with chitosan

The effect of pectin charge density on the formation of multilayer films with chitosan (PEC/CHI) is studied by means of electro-optics. Pectins of low (21%) and high (71%) degrees of esterification, which are inversely proportional to the pectin charge density, are used to form films on colloidal beta-FeOOH particles at pH 4.0 when the CHI is fully ionized. We find that, after deposition of the first 3-4 layers, the film thickness increases linearly with the number of adsorbed layers. However, the increase in the film thickness is larger when the film is terminated with CHI. Irregular increase of the film thickness is more marked for the PEC with higher density of charge. Oscillation in the electrical polarizability of the film-coated particles with the number of deposited layers is also registered in the PEC/CHI films. The charge balance of the multilayers, calculated from electrical polarizability of the film-coated particles, is positive, with larger excess of positive charge within the film constructed from CHI and less charged PEC. This is attributed to the ability of CHI to diffuse into the film at each deposition step. Despite the CHI diffusion, the film thickness increases linearly due to the dissolution of unstable PEC/CHI complexes from the film surface.     

The beginning of the Upper Paleolithic in the Iranian Zagros. A taphonomic approach and techno-economic comparison of Early Baradostian assemblages from Warwasi and Yafteh (Iran)

Southwest Asia is a key region in current debates surrounding the appearance of the first cultures attributed to anatomically modern humans, particularly the Aurignacian and preceding cultural units of the Iranian Zagros, Levant, and the Balkans (Baradostian, Ahmarien, Kozarnikien, etc.). The Zagros mountain range encompasses an immense territory that remains understudied with regard to the Upper Paleolithic as well as the first bladelet industries traditionally presumed to be the work of anatomically modern humans. Concerning the emergence of the Aurignacian, the sites of Warwasi rockshelter and Yafteh cave in the central Zagros are considered to show evidence of in situ evolution of the Upper Paleolithic from the local Mousterian. This hypothesis is tested by way of a taphonomic, techno-typological and economic approach applied to the Upper Paleolithic levels of Warwasi (spits LL–AA) and Yafteh (the series from the lower part of the sequence). A comparison of the techno-economic features of both assemblages demonstrates a conceptual bond with contemporaneous techno-complexes from Levant and Europe (Ahmarian, Protoaurignacian, etc.). The techno-typological Middle Paleolithic character of the Warwasi lithic assemblage permits a discussion of a possible in situ dependence/continuum from the Mousterian or perhaps particular activities linked to the type of the occupation of the site. However, bladelet technology cannot be considered as rooted in the Zagros Mousterian. Consequently the origin of the Aurignacian sensu stricto has to be reconsidered.     

Synthesis of cinnamoyl and hydroxycinnamoyl amino acid conjugates and evaluation of their antioxidant activity.

Fifteen amides of cinnamic, ferulic and sinapic acids with natural and unnatural C-protected amino acids have been synthesized. The amides (E)-N-(feruloyl)-L-tyrosine methyl ester (10), (E)-N-(feruloyl)-L-phenylalanine t-butyl ester (11), (E)-N-(sinapoyl)-L-tyrosine methyl ester (13) and (E)-N-(sinapoyl)-L-phenylalanine t-butyl ester (15) with a free carboxyl group of amino acids have been found in nature. The rest of the compounds are unknown. The hydroxycinnamoyl amino acid conjugates have been studied for their antioxidant activity (AOA) in bulk phase lipid autoxidation. The highest AOA has been found for the compounds 11 and 15, which contain the same phenylalanine moiety.