SOLVENT EXTRACTION OF PALLADIUM FROM CHLORIDE SOLUTIONS BY ALKYLAMMONIUM DI(2-ETHYLHEXYL)DITHIOPHOSPHATES

ABSTRACT

The extraction of palladium (II) from chloride solutions (over a wide region of aqueous acidity) by di(2-ethylhexyl)dithiophosphates of tetraoctylammonium, tri-n-octylammonium and di-n-octylammonium in toluene at the constant chloride concentration has been studied. A synergistic effect was shown to be observed in these systems and it is explained by the formation of unusual complexes with mixed ligands. It has been established the palladium complexes, such as (R₃NH)[PdCl₂A], (R₃NH)[PdCl₂A] and (R₂NH₂)[PdCl₂A], involving both alkylammonium cation and dialkyldithiophosphate anion are extracted under conditions of the loaded organic phase using distribution methods depending on a composition of aqueous and organic phase. At the excess of R₃NHA or R₂NH·HA, PdA₂ is extracted into the organic phase. Table 8 reports the results obtained and indicates the domains of existence of the various species of palladium (II) extracted into the organic phase in the binary ex-tractant systems in comparison with the initial systems     

Synthesis of trimethylolpropane esters of tall oil fatty acids and properties of polyurethane coatings on their basis

Tall oil fatty acids (TOFA) were esterified with trimethylolpropane (TMP) without a catalyst at different molar ratios of TMP to TOFA. A molar ratio was defined, at which a polyol stable in long-term storage, with the maximum content of TMP monoesters, was synthesized. Fourier transform infrared spectroscopy and gas chromatography were used for the identification of the polyols’ chemical structure and composition. Based on the synthesized polyols, polyurethane coatings were prepared. The effect of the isocyanate index and concentration of traditional Sn-based and less toxic Bi-based catalysts on the gel time of the polyurethane composition, and the mechanical and thermal properties of the coatings was studied. It was found that the new coatings had high tensile strength and modulus of elasticity, comparable with the strength and modulus of the polyurethane based on diethanolamides of TOFA. The initial temperature of decomposition of these coatings was higher than that of the polyurethanes based on esters of TOFA and a number of uralkyds. The coatings based on TMP esters of TOFA were obtained without the use of solvents, and potentially, these esters can be used in spray-applied VOC-free polyurethane coatings’ formulation.     

Yellow–green organic light-emitting diode based on tris(2-methyl-8-quinolinolate) scandium

Efficient yellow–green electroluminescence emission at λ_max = 530 nm with CIE coordinates x = 0.3913, y = 0.4947 was obtained with organic light-emitting devices based on tris(2-methyl-8-quinolinolate) scandium (1). The device with the configuration of indium tin oxide/N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine/1/Yb exhibits current efficiency of 3.1 cd/A and power efficiency of 1.8 lm/W at a luminance of 100 cd/m². The DFT calculations demonstrate that structural changes of the scandium complex 1 influence the electroluminescence spectrum, the better agreement with experimental data being achieved when monodentate ligands are taken into consideration.     

Towards the integration of dark and photo fermentative waste treatment. 1. Hydrogen photoproduction by purple bacterium Rhodobacter capsulatus using potential products of starch fermentation

In this study, the H₂-photoproduction capacity of Rhodobacter capsulatus B10 was measured as a function of variations in the nature and concentration of volatile fatty acids (VFAs) and other products of dark fermentation. When an equimolar mixture of VFAs was provided, C4 substrates (butyrate and isobutyrate) were not consumed until the C2–C3 substrates (acetate, propionate, and lactate) became unavailable, but in order for the cells to produce H₂ at high rates they could not be exposed to severe growth substrate depletion. Among other possible fermentation products, the highest inhibition was observed by the addition of butanol (50% inhibition at 50 mM). The influence of high concentrations of VFAs, phosphate (used to stabilize the pH during dark fermentation) and some heavy metals (known inhibitors of methanogenesis) was also shown. Based on the results, the conditions of fermentation can be manipulated to avoid the inhibition of subsequent H₂ photoproduction by photosynthetic bacteria.     

Reversible Hydriding of LaNi5 − xAlx ― Pd Composites in the Presence of Carbon Monoxide

Carbon monoxide is one of the most dangerous impurities in gas mixtures involved in the hydriding of intermetallic compounds, and up to the present time the concentration limit 0.03 vol.% CO has not been surmounted. The objective of the present work was to investigate the possibility of reversibly hydriding LaNi_{5 − x} Al _x ― Pd composites in gas mixtures containing up to 5 vol.% CO. The experimental specimens were mixtures of palladium black and LaNi₅, LaNi_4.7Al_0.3, LaNi_4.5Al_0.5, LaNi_4.2Al_0.8, and LaNi₄Al powders cold pressed at 300 MPa. The intermetallics were preliminarily dispersed by hydriding and mechanical grinding. The concentration of palladium black in the powder mixtures was varied from 0 to 1.5 mass%. It was shown that it is possible to reversibly hydride LaNi_{5 − x} Al _x ― Pd composites in mixtures of hydrogen and carbon monoxide containing up to 5 vol.% CO at the temperatures 423 and 473 K. It was established that alloying LaNi₅ with aluminum in amounts which raised the stoichiometric concentration above 0.5 stabilized the absorption properties of LaNi_{5 − x} Al _x ― Pd in the presence of CO. The composition LaNi₄Al was optimal. Palladium additions to LaNi_{5 − x} Al _x ― Pd composites also increased the stability of hydrogen absorption by the intermetallic. It is noted that the effect of palladium was more positive than that of aluminum.

     

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.     

Quantitative estimates of gas maldistribution and methods for their localization in absorption columns

In the present work, we carry out evaluation of gas flow maldistribution in different types of gas distributing devices (GDD) and packings by using experimental data for the output velocity profiles for both the absorption pilot column and industrial column. Two GDD construction types—with circular and with local tube gas feed, together with their modifications—are investigated. Two pilot columns—with random packing RSRM 1.5″ and with structured ceramic Honey-comb packing, and one industrial contact economizer with Honey-comb and inclined rings—have been studied. Six types of quantitative estimations of GDD and packings maldistribution are determined by the help of MATHCAD. Then, their sensitivity toward several factors, such as the type of GDD and packing, the initial gas flow velocity, the number and dimension of measuring cells on the column cross-section, the measurement error, and so on, is investigated. It is found that only two of the quantitative maldistribution estimations take into account the formation of maldistribution clusters, which deteriorates the uniform gas distribution. A novel method for quantitative determination of these clusters and also for identification of the zones at column cross-section, in which they appeared, has been developed. It is established that the measurement error and the dimension of measuring cell deeply influence the number, the area, and spatial distribution of these zones on the cross-section, as well as the values of maldistribution estimates.     

Oligonucleotide Insecticides for Green Agriculture: Regulatory Role of Contact DNA in Plant–Insect Interactions

Insects vastly outnumber us in terms of species and total biomass, and are among the most efficient and voracious consumers of plants on the planet. As a result, to preserve crops, one of the primary tasks in agriculture has always been the need to control and reduce the number of insect pests. The current use of chemical insecticides leads to the accumulation of xenobiotics in ecosystems and a decreased number of species in those ecosystems, including insects. Sustainable development of human society is impossible without useful insects, so the control of insect pests must be effective and selective at the same time. In this article, we show for the first time a natural way to regulate the number of insect pests based on the use of extracellular double-stranded DNA secreted by the plant Pittosporum tobira. Using a principle similar to one found in nature, we show that the topical application of artificially synthesized short antisense oligonucleotide insecticides (olinscides, DNA insecticides) is an effective and selective way to control the insect Coccus hesperidum. Using contact oligonucleotide insecticide Coccus-11 at a concentration of 100 ng/μL on C. hesperidum larvae resulted in a mortality of 95.59 ± 1.63% within 12 days. Green oligonucleotide insecticides, created by nature and later discovered by humans, demonstrate a new method to control insect pests that is beneficial and safe for macromolecular insect pest management.