Revisiting tetranitrophenolsulfonephthalein

Among the vast series of phenolsulfonephthalein dyes, the nitro derivatives and especially 3,3′,5,5′‐tetranitrophenolsulfonephthalein (nitrophenol crimson) remain practically unexplored, whereas the halogen and alkyl derivatives have been studied comprehensively. This striking difference is probably due to the enormous influence of the four NO₂ groups on the properties of the dye. As a result, the protolytic behaviour is unlike even that of tetrabromo phenolsulfonephthalein, and the recognised scheme of acid–base and tautomeric equilibrium of the sulfonephthaleins is unable to explain it. The molecular form H₂R was isolated as a sultonic tautomer, and an X‐ray crystal structure analysis was carried out. Our studies of the UV‐vis absorption spectra in water, methanol, dimethyl sulfoxide, acetonitrile, acetone, and dichloromethane, as well as in aqueous micellar solutions of surfactants, allowed us to evaluate the true molar absorptivity of the dianion R^2?, and to elucidate the enormous tendency to form yellow trianionic carbinol ROH^3?, even in the presence of traces of H₂O. Nuclear magnetic resonance and electrospray data confirm the proposed scheme of ionisation and tautomerism of nitrophenol crimson.     

The ecological peculiarities of the testate amoebae population in the Middle Ob flood plain

The biodiversity and distribution of testate amoebae in the Middle Ob flood plain soils have been studied. The biodiversity of Testacea in the soils consists of 83 species and varieties from 12 families. The population of Testacea in flood plain habitats is rich in water forms, especially in the flood plain part of the catena, because of annual floods. The study showed that the density of Testacea in the forest plots is approximately 10 times higher than in the meadow ones. The species diversity of Testacea in the meadows of the flood plain includes 40 species and varieties. It was found that there is an enrichment of the fauna of Testacea in the flood plain meadows with water forms and a decrease in the population of Testacea in the soil according to the depth. The decrease in the diversity and number down the soil profile is related to the decrease in the amount of the oxygen available and general induration of soil. On the whole, the population composition of Testacea in the soils of the pine forest consists of typical representatives of humus substrates with low values of pH, small stock of humus and mineral nutrition. The soils of mature pine forests are rich in Testacea; they have a similar complex of morphological types, mainly because of the moss cover and forest litter thickness.     

One‐Step Synthesis of Chiral Azamacrocycles via Palladium‐Catalyzed Enantioselective Amination of 1,5‐Dichloroanthraquinone and 1,5‐Dichloroanthracene

Asymmetric amination of 1,5‐dichloroanthraquinone and 1,5‐dichloroanthracene with di‐ and trioxadiamines catalyzed by palladium complexes with various chiral phosphine ligands gave chiral macrocycles with ee values of up to 60%. The dependence of the chemical yields and enantiomeric excess on the nature of the starting compounds and the phosphine ligands employed was demonstrated. An unexpected spontaneous resolution upon crystallization of the macrocycle comprising anthraquinone and dioxadiamine moieties was observed while in the case of the macrocycle with a trioxadiamine linker racemic monocrystals were obtained. Crystallization of the enantiomerically enriched mixtures afforded chiral macrocycles with 88–99% ee.     

Paenibacillus polymyxa purified bacteriocin to control Campylobacter jejuni in chickens

Campylobacter spp. cause numerous foodborne diseases. Poultry is thought to be a significant source of this zoonosis. Although many interventions designed to control this agent have been researched, none have succeeded. We evaluated a bacteriocin-based treatment to reduce Campylobacter jejuni colonization in poultry. A previously described purified bacteriocin (class IIa; molecular mass, 3,864 Da), secreted by Paenibacillus polymyxa NRRL-B-30509, was microencapsulated in polyvinylpyrrolidone, and 0.25 g of the purified bacteriocin was incorporated into 1 kg of chicken feed. One-day-old chickens were orally challenged and colonized with one of four isolates of C. jejuni, then reared in isolation facilities. Birds were provided ad libitum access to standard broiler starter feed and water for 7 days until 3 days before sampling, when only the treated groups of birds were provided the bacteriocin-emended feed described. In each of the eight (four by two replicates) trials, significant reductions in colonization by C. jejuni were observed (P < or = 0.05). As an example of this highly consistent data, in the first trial, 10 untreated 10-day-old chickens were colonized at a mean log 7.2 + 0.3 CFU/g of feces, whereas none of the 10 bacteriocin-treated 10-day-old chickens were colonized with detectable numbers of C. jejuni. Bacteriocin treatment dramatically reduced both intestinal levels and frequency of chicken colonization by C. jejuni. Feeding bacteriocins before poultry slaughter appears to provide control of C. jejuni to effectively reduce human exposure. This advance is directed toward on-farm control of pathogens, as opposed to the currently used chemical disinfection of contaminated carcasses.     

The effect of red pigment on the amyloidization of yeast proteins

The intensity of amyloid-bound thioflavine T fluorescence was studied in crude lysates of yeast strains carrying mutations in the ADE1 or ADE2 genes and accumulating the red pigment (a result of polymerization of aminoimidazoleribotide), and in white isogenic strains--either adenine prototrophs or carrying mutations at the first stages of purine biosynthesis. We found that the red pigment leads to a drop of amyloid content. This result, along with the data on separation of protein polymers of white and red strains in PAGE, suggests that the red pigment inhibits amyloid fibril formation. The differences in transmission of the thioflavine T fluorescence pattern by cytoduction and in blot-hybridization of pellet proteins of red and white [PSI(+) ] strains with Sup35p antibodies confirmed this conclusion. Purified red pigment treatment also led to a decrease of fluorescence intensity of thioflavine T bound to insulin fibrils and to yeast pellet protein aggregates from [PSI(+) ] strains. This suggests red pigment interaction with amyloid fibrils. Comparison of pellet proteins from red and white isogenic strains separated by 2D-electrophoresis followed by MALDI analysis has allowed us to identify 48 pigment-dependent proteins. These proteins mostly belong to functional classes of chaperones and proteins involved in glucose metabolism, closely corresponding to prion-dependent proteins that we characterized previously. Also present were some proteins involved in stress response and proteolysis. We suppose that the red pigment acts by blocking certain sites on amyloid fibrils that, in some cases, can lead in vivo to interfere with their contacts with chaperones and the generation of prion seeds.     

Tobacco-specific nitrosamines in new tobacco products.

New tobacco products, designed to attract consumers who are concerned about the health effects of tobacco, have been appearing on the market. Objective evaluation of these products requires, as a first step, data on their potentially toxic constituents. Tobacco-specific nitrosamines (TSNAs) are an important class of carcinogens in tobacco products, but virtually no data were available on their levels in these products. In the present study, we analyzed several new products-Ariva, Stonewall, Exalt, Revel, Smokey Mountain, and Quest-for TSNAs and compared their TSNA levels with those in nicotine replacement products and conventional smokeless tobacco and cigarette brands. TSNAs were not detected in Smokey Mountain, which is a tobacco-free snuff product. The lowest levels among the new products containing tobacco were in Ariva and Stonewall (0.26-0.28 microg/g wet weight of product). The highest levels in the new products were found in Exalt (3.3 microg/g tobacco), whereas Revel and Quest had intermediate amounts. Only trace amounts were found in nicotine replacement products, and conventional brands had levels consistent with those reported in the literature. These results demonstrate that TSNA levels in new tobacco products range from relatively low to comparable with those found in some conventional brands.     

Antioxidant activity screening of extracts from Sideritis species (Labiatae) grown in Bulgaria

Plant samples from several species and populations of the genus Sideritis (Labiatae) grown in Bulgaria (S scardica, S syriaca and S montana) were extracted with different solvents. Their antioxidant activities were determined by the β‐carotene bleaching test (BCBT), 2,2′‐diphenyl‐1‐picrylhydrazyl (DPPH^?) radical scavenging method and static headspace gas chromatography (HS‐GC) and compared with the antioxidant activity of two reference compounds of different polarity, viz butylated hydroxytoluene (BHT) and rosmarinic acid. The pure reference compounds were applied in a ten‐times lower concentration than the plant extracts. The highest antioxidant activity in the BCBT, close to that of BHT, was observed for the more apolar extracts. The inhibitory effect on β‐carotene bleaching of the polar extracts and rosmarinic acid was much lower than that of BHT. The inhibition of hexanal formation in bulk safflower oil by most of S syriaca and S scardica extracts was as effective as BHT but less so than rosmarinic acid. S montana extracts showed weak antioxidant or even pro‐oxidant properties. Extracts from butanol and from ethyl acetate and the total methanol extracts from all Sideritis plants studied showed a strong radical scavenging activity against DPPH^?, close to that of rosmarinic acid. S montana extracts were, as a whole, slightly weaker radical inhibitors than the extracts from the other two species. The antioxidant activity of Sideritis extracts was attributed to the presence of flavonoid and phenylpropanoid glycosides. Copyright © 2003 Society of Chemical Industry     

A possibilistic approach to risk aversion

In this paper a possibilistic model of risk aversion based on the lower and upper possibilistic expected values of a fuzzy number is studied. Three notions of possibilistic risk premium are defined for which calculation formulae in terms of Arrow–Pratt index and a possibilistic variance are established. A possibilistic version of Pratt theorem is proved.     

Orientated crystallization in drawn thermoplastic polyimide modified by carbon nanofibers

The solid state crystallization in drawn thermoplastic polyimide films is studied as a function of draw ratio (DR) under the effect of vapor grown carbon fiber nanoinclusions. The nucleating effect of the nanoinclusions coupled with the orientation effect of drawing generates a unique orientated layered lamellar structure, characteristic of smectic‐like mesophase. The degree of draw induced orientated crystallization increases with the content of nanoinclusions and with the DR, and is reflected in the mechanical behavior of the film. Generally, the Young's modulus and the yield point of the drawn crystalline films in the drawing direction are significantly higher compared with the noncrystalline counterparts. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Kinetics and mechanism of low-temperature ozone decomposition by Co-ions adsorbed on silica

Kinetics and mechanism of low-temperature ozone ((5–50) × 10⁻³ mol/m³ in the gas–air mixture) decomposition by Co-catalysts supported on silica have been studied. Co-ions adsorbed on silica react with surface oxygen species, thus resulting in an active catalyst. Low concentrations of Co-ions form a monolayer on the surface. Their specific catalytic activity remained constant, but sharply decreased at higher concentrations due to a formation of polynuclear Co-complexes. Ozone decomposition may occur either as a stoichiometric or catalytic process, depending on the ozone and catalyst concentrations. The turnover number increases with ozone concentration reaching a saturation point. It also increases with Co-concentration in the beginning, but drops at a concentration >1 × 10⁻⁴ mol/g. The mechanism of the reaction is discussed.