Biosensitive element in the form of immobilized luminescent photobacteria for detecting ecotoxicants in aqueous flow-through systems.

We demonstrated the possibility of long-term and efficient application of a biosensitive element (BE) in the form of Photobacterium phosphoreum photobacteria immobilized in poly(vinyl alcohol) (PVA) cryogel for detecting various ecotoxicants (Zn(2) (+) , Cu(2) (+) , Hg(2) (+) , Pb(2) (+) , 2,4-dichlorophenoxyacetic acid, 2,6-dimethylphenol, pentachlorophenol, coumaphos, malathion, chlorpyrifos and methyl parathion) in flow-through media. The range of detectable concentrations of ecotoxicants was determined at 1 × 10(-8) to 1 × 10(-4) M for heavy metal ions and at 1 × 10(-8) to 1 × 10(-5) M for phenol derivatives and organophosphorus pesticides. Immobilized cells of photobacteria quantitatively reacted with these ecotoxicants; cell sensitivity exhibited no flow rate dependence in the range from 45 to 180 mL/h. At a constant concentration of ecotoxicant in the flow, the bioluminescence quenching profile of immobilized cells demonstrated an integral response. The BE could remain in a flow-through medium for at least 10 days while retaining 95% of luminescent activity in the absence of ecotoxicants. The BE tested in this work was demonstrated to have a long shelf life (> 60 weeks) at -80°C without changes in the baseline level of bioluminescence. Copyright © 2016 John Wiley & Sons, Ltd.

Genuine redox isomerism in a rare-earth-metal complex.

Redox isomerism is observed for a lanthanide complex for the first time. Upon lowering the temperature, an electron of [{(dpp-bian)Yb(µ-Cl)(dme)}(2)] (1) is transferred from the metal to the ligand (see picture), giving rise to marked shortening of Yb-N bonds and a hysteretic jump in the magnetic moment. The crystal packing is of a crucial importance, as two other crystal modifications of 1 do not undergo this effect.

Model Fuel Oxidation in the Presence of Molybdenum-Containing Catalysts Based on SBA-15 with Hydrophobic Properties.

We have studied for the first time the role of hydrophobicity of the mesoporous silicate SBA-15 on the activity and the service life of a catalyst in the peroxide oxidation of sulfur-containing compounds. Immobilization of the molybdate anion on the SBA-15 support via ionic bonding with triethylammonium groups allows us not only to decrease the reaction temperature to a relatively low value of 60 °C without a drop in the dibenzothiophene conversion degree but also to increase the service life of the catalyst to many times that of the known analogs. The support and catalyst structures were investigated by low-temperature nitrogen adsorption/desorption, Fourier-transform infrared spectroscopy, X-ray fluorescence analysis, and transmission electron microscopy. Immobilization of the molybdate anion on the SBA-15 support, modified with ammonium species, prevents the leaching of active sites. However, only alkyl-substituted ammonium species minimize DBT sulfone adsorption, which significantly increases the catalyst's service life. The synthesized catalyst Mo/Et3N-SBA-15 with hydrophobic properties is not sensitive to the initial sulfur content and hydrogen peroxide amount and retains its activity for at least six cycles of oxidation without regeneration. These catalysts can be efficiently used for clean fuel production.

One- and two-electron-transfer reactions of (dpp-Bian)Sm(dme)3.

The reduction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian) with an excess of samarium in 1,2-dimethoxyethane (dme) affords the Sm(II) complex (dpp-Bian)Sm(dme)(3) (1). The reaction of 1 with 0.5 mol equiv of 1,2-dibromostilbene proceeds with the formation of the dimeric Sm(III) complex [(dpp-Bian)SmBr(dme)](2) (2). Oxidation of both the metal and the dpp-Bian ligand takes place if 1 is reacted with equimolar amounts of 1,2-dibromostilbene or iodine, yielding the monomeric Sm(III) derivatives (dpp-Bian)SmBr(2)(dme) (3) and (dpp-Bian)SmI(2)(THF)(2) (4; THF = tetrahydrofuran), respectively. The reaction of 1 with 0.5 mol equiv of iodine followed by 0.5 mol equiv of tetramethylthiuram disulfide gives the Sm(III) complex (dpp-Bian)SmI[SC(S)NMe(2)](dme) (5). Compound 4 and tBuOK react with the formation of the iodine-bridged dimer [(dpp-Bian)SmI(OtBu)(THF)](2) (6). Complexes 1 and 2 have been characterized by (1)H NMR spectroscopy and complexes 2-6 by their molecular structures, which were determined by single-crystal X-ray diffraction.

Schwartz Value Clusters in Modern University Students.

People differ in their value hierarchies, i.e., in the importance they attach to basic personal values. A large number of studies were performed to establish similarities and differences between national, ethnic, or professional groups in terms of Schwartz's values structure. In addition to this sample-level approach, we found it useful to disclose a number of subgroups within those larger social groups, which are more homogeneous in themselves and reflect the individual-level types of personal values systems. The study was performed on university students (n = 1237) who were asked to fill in the SVS и PVQ Schwartz's questionnaires. The sample was then treated with the K-means cluster analysis, which resulted in the division of the initial sample into three subgroups or clusters according to their values hierarchy being measured separately at the (1) Normative Ideals scale and (2) the scale of Behavioral Priorities. These clusters were equally common among male and female students, but they were unequally found in young people coming from different ethnic groups and regions, demonstrating the role of socio-cultural environment in building up personal values. The results may extend our capabilities for the prediction of the social, economic, and political behavior of the younger generation.

Redox isomerism in the lanthanide complex [(dpp-Bian)Yb(DME)(mu-Br)]2 (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene).

Ytterbium reacts with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (1, dpp-Bian) in 1,2-dimethoxyethane (DME) to give complex (dpp-Bian)Yb(DME)(2) (2). Oxidation of 2 with an 0.5 mol equivalent of dibromostilbene affords dimeric compound [(dpp-Bian)Yb(DME)(mu-Br)](2) (3). Molecular structures of 2 and 3 were determined by single-crystal X-ray analysis. In complex 3 in a DME solution, a temperature-dependent reversible intramolecular electron transfer between the ligand and the metal takes place.