Factors affecting interaction of radiocobalt with river sediments

The paper aims at the analysis of principal factors affecting interaction of radiocobalt with freshwater solids, important for migration of radiocobalt in surface streams. Uptake and release of radiocobalt by sediment from a small river have been studied as a function of pH and composition of aqueous phase, the cobalt concentration and contact time, using laboratory model experiments. A factor of primary importance is the contact time due to slow and two-step kinetics of radiocobalt uptake, which also strongly depends on the concentration of sediment in suspension. pH exerts the most significant effect on the interaction in the pH region of 5–7.5, where the uptake increases with pH. Ionic strength of water phase (I) and concentration of cobalt in water (c) affect the interaction only at rather high values of I or c and their variation can be neglected in the modelling of radiocobalt transport in streams under ordinary conditions. Desorption by river water of radiocobalt pre-adsorbed on the sediment passes through a maximum with desorption time, decreases with increasing adsorption time and increases upon drying of the sediment prior to desorption. Results obtained are compared with literature data and conclusions are drawn concerning the mechanism of radiocobalt uptake by the sediment.     

Sublimation Properties of α,ω-Diamines Revisited from First-Principles Calculations

Sublimation enthalpies of alkane-α,ω-diamines exhibit an odd-even pattern within their homologous series. First-principles calculations coupled with the quasi-harmonic approximation for crystals and with the conformation mixing model for the ideal gas are used to explain this phenomenon from the theoretical point of view. Crystals of the odd and even alkane-α,ω-diamines distinctly differ in their packing motifs. However, first-principles calculations indicate that it is a delicate interplay of the cohesive forces, phonons, molecular vibrations and conformational equilibrium which governs the odd-even pattern of the sublimation enthalpies within the homologous series. High molecular flexibility of the alkane-α,ω-diamines predetermines higher sensitivity of the computational model to the quality of the optimized geometries and relative conformational energies. Performance of high-throughput computational methods, such as the density functional tight binding (DFTB, GFN2-xTB) and the explicitly correlated dispersion-corrected Møller - Plesset perturbative method (MP2C-F12), are benchmarked against the consistent state-of-the-art calculations of conformational energies and interaction energies, respectively.     

Core-valence correlation potentials based on density functional theory. Applications to valence-electron-only calculations on Na and K diatomics

The core-valence correlation potential has been derived for Na and K employing atomic calculations which make use of the density functional formula worked out by Lee, Yang and Parr based on Colle-Salvetti approach. The numerical potential is fitted with a small number of Gaussians leading to a very simple expression for an one-electron corevalence correlation operator? _cv . The core-valence correlation corrections can be computed by applying? _cv on a quite general class of wavefunctions. Applications of the? _cv operator within the framework of valence-electron-only calculations using effective Hamiltonians are presented for Na and K atoms, for Na₂, K₂, NaK and their cations. Almost all the corrections calculated for the physical properties due to the core-valence correlation lead to results which are in good agreement with those obtained from much more sophisticated treatments and experimental data.     

Enantioseparations of non-benzenoid and oligo-Tröger’s bases by HPLC on Whelk O1 column

The separation of enantiomers of several ‘bis- and tris-Tröger’s bases’ by HPLC on commercially available chiral stationary phase Whelk O1 is described for the first time. The observed structure–enantioselectivity relationships are in agreement with the previously established molecular recognition model. For all ‘bis- and tris-Tröger’s bases’ studied, satisfactory to excellent enantioselectivities were observed.     

Synthesis,structure and properties of eight novel molybdenum(VI) complexes of the types: [MoO2LD] and [{MoO2L}2D] (L = thiosemicarbazonato ligand,D = N-donor molecule)

Eight new molybdenum(VI) complexes with 4-(diethylamino)salicylaldehyde and 2-hydroxy-3-methoxybenzaldehyde thiosemicarbazones have been prepared. They were characterized as mononuclear [MoO₂LD] or dinuclear [{MoO₂L}₂D] complexes. In all the compounds the MoO₂²⁺ core is coordinated by a tridentate ONS thiosemicarbazonato ligand and by the N-donor molecule (imidazole, pyridine or γ-picoline). All the complexes were characterized by chemical analysis, IR spectroscopy and thermogravimetry. Three of the mononuclear complexes, dioxo[(2-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato)(pyridine)]molybdenum(VI), dioxo[(2-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato)(γ-picoline)]molybdenum(VI) and dioxo[(2-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato)(imidazole)]molybdenum(VI) were also characterized by single-crystal X-ray structural analysis. A spectrophotometric method for the determination of molybdenum based on extraction of ion-pairs formed by the cationic surfactant and the [MoO(SCN)₄]⁻ anion is described.     

Sorption of cesium from water solutions on potassium nickel hexacyanoferrate-modified <Emphasis Type="Italic">Agaricus bisporus</Emphasis> mushroom biomass

In order to gain biosorbent that would have the ability to bind cesium ions from water solution effectively, potassium nickel hexacyanoferrate(II) (KNiFC) was incorporated into the mushroom biomass of Agaricus bisporus. Cesium sorption by KNIFC-modified A. bisporus biosorbent was observed in batch system, using radiotracer technique using ¹³⁷Cs radioisotope. Kinetic study showed that the cesium sorption was quite rapid and sorption equilibrium was attained within 1 h. Sorption kinetics of cesium was well described by pseudo-second order kinetics. Sorption equilibrium was the best described by Freundlich isotherm and the distribution coefficient was at interval 7,662–159 cm³ g⁻¹. Cesium sorption depended on initial pH of solution. Cesium sorption was very low at pH₀ 1.0–3.0. At initial pH 11.0, maximum sorption of cesium was found. Negative effect of monovalent (K⁺, Na⁺, NH₄ ⁺) and divalent (Ca²⁺, Mg²⁺) cations on cesium sorption was observed. Desorption experiments showed that 0.1 M potassium chloride is the most suitable desorption agent but the complete desorption of cesium ions from KNiFC-modifed biosorbent was not achieved.     

Thermal properties and the structure of amorphous Sb2Se3 thin film

The amorphous Sb₂Se₃ film with a thickness ~0.9 µm was prepared by thermal evaporation and its composition was confirmed using an energy-dispersive X-ray analysis. The amorphous state was checked by an X-ray diffraction analysis. The optical gap E _g ^opt was determined to be 1.32 eV. The glass transition temperature could not be found by either a differential scanning calorimetry or a thermomechanical analysis. The film was crystallized and characterized using the quasi-isothermal method. The temperature dependence of the isobaric heat capacity was raised monotonously and no drop over the course of the crystallization was observed. The temperature-modulated thermomechanical analysis determined a temperature T = 133 °C which can be assumed to be the temperature of the structural reorganization beginning. Raman spectra of amorphous Sb₂Se₃ revealed that the vibrations of both the amorphous and crystalline phase are close to one other. Raman scattering revealed that both the short and the medium-range order of amorphous and crystalline phases are similar.     

Extraction of europium and americium into nitrobenzene by using synergistic mixture of hydrogen dicarbollylcobaltate and tetraisopropyl methylene diphosphonate

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of tetraisopropyl methylene diphosphonate [T(iPr)MDP, L] has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, HL₂ ⁺, ML₂ ³⁺, ML₃ ³⁺ and ML₄ ³⁺ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes EuL _n ³⁺ and AmL _n ³⁺, where n = 2, 3, 4 and L is T(iPr)MDP, in water-saturated nitrobenzene are comparable.     

Synthesis,characterization and antimicrobial activity of pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with 2,6-diacetylpyridine bis(trimethylammoniumacetohydrazone)

Pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with condensation product of 2,6-diacetylpyridine and trimethylammoniumacetohydrazide (Girard’s T reagent) were synthesized and characterized by elemental analyses, IR and UV–vis spectra, molar conductivity, and magnetic susceptibility. Crystal structures of the Co(II) and Ni(II) complexes were also determined. Antimicrobial activities of the ligand and metal complexes were examined.