Heat capacities of concentrated multicomponent aqueous electrolyte solutions at various temperatures

The specific heat capacities of the aqueous multicomponent system NaCl +KCl+MgCl₂+CaCl₂ with ionic strength between 8.3 and 9.6 (resembling Dead Sea waters) were measured between 15°C and 45°C. The obtained data were fitted to an empirical equation as a function of concentration and temperature. The thermodynamic functions of the studied multicomponent system were found to be strongly influenced by changes in MgCl₂ concentrations. The application of Young's rule to such concentrated systems was checked at 25°C. The calculated (by Young's rule) specific heat capacitiesC _p and apparent molar heat capacities C_p, of these multicomponent electrolyte solutions were in reasonable agreement with the measured values (–0.008 J-g^–1-K^–1 and –2.6 J-mol^–1-K^–1, respectively).     

Si-E (E = N, O, F) bonding in a hexacoordinated silicon complex: new facts from experimental and theoretical charge density studies

The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment.     

Density functional calculation of the electronic circular dichroism spectra of the transition metal complexes [M(phen)3]2+ (M = Fe, Ru, Os)

The circular dichroism spectra of the tris-bidentate metal complexes Lambda-[M(phen)3]2+, with M = Fe, Ru, Os and phen = 1,10-tris-phenanthroline, are investigated computationally, employing time-dependent density functional theory. Good agreement with experimental spectra is obtained for Ru and Os. The Lambda-[Os(phen)3]2+ spectrum is analyzed in detail. It is shown how relativistic effects red shift CD bands where the Os 5d-orbital participates to a large extent in the excitations. Further, the participation of the metal in the ligand pi --> pi exciton CD is determined to be of the order of 10%. Though solvent effects can have a noticeable effect on individual transitions and rotatory strengths, they are demonstrated to have only a very small overall effect on the resulting simulated CD spectra. For Lambda-[Fe(phen)3]2+, the results are shown to be rather sensitive to the choice of the applied hybrid and nonhybrid density functionals, and the optimized geometries based thereupon. In particular, the sign pattern of the lower-energy part (up to 33 x 10(3) cm(-1)) of the Lambda-[Fe(phen)3]2+ CD spectrum is difficult to reproduce. Some combinations of functionals and geometries yield good agreement with experiment, but no "best" approach can be devised based on the available results. Possible sources of errors in the spectrum of Lambda-[Fe(phen)3]2+ due to deficiencies in the functionals and the exchange-correlation kernels are investigated.     

Isolation of selenium organic species from antarctic krill after enzymatic hydrolysis

Total selenium content and its distribution in the soluble and insoluble protein-bound fractions obtained after aqueous extraction of antarctic krill samples were determined. About 26% of the total selenium (2.4 g g^–1 dry weight) was found in the supernatant; the rest was in the pellet. Isolation of low molecular selenium-containing fractions was also performed by enzymatic digestion of the protein, followed by size-exclusion chromatography in conjunction with atomic absorption spectrometry. From the applied various proteinases (pronase E, subtilisin Carlsberg, trypsin, chymotrypsin, proteinase and proteinase N from Bacillus subtilis and Novo 0.6 MPX enzyme), the treatment with pronase E led to best recovery of selenium. About 96% of the total Se was found in the hydrolysate, mainly in low molecular weight fractions. Eighty percent of the Se species were in fractions with molecular weights in the range of amino acids and short peptides. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC-ICP-MS) allowed the identification of selenomethionine and the assumption that selenocystine or its derivatives were the main species in these fractions.     

Recovery of 177Lu from Irradiated HfO2 Targets for Nuclear Medicine Purposes

A new method of production of one of the most widely used isotopes in nuclear medicine, ¹⁷⁷Lu, with high chemical purity was developed; this method includes irradiation of the HfO₂ target with bremsstrahlung photons. The irradiated target was dissolved in HF and then diluted and placed onto a column filled with LN resin. Quantitative sorption of ¹⁷⁷Lu could be observed during this process. The column later was rinsed with the mixture of 0.1 M HF and 1 M HNO₃ and then 2 M HNO₃ to remove impurities. Quantitative desorption of ¹⁷⁷Lu was achieved by using 6 M HNO₃. The developed method of ¹⁷⁷Lu production ensures high purification of this isotope from macroquantities of hafnium and zirconium and radioactive impurities of carrier-free yttrium. The content of ^177mLu in ¹⁷⁷Lu in photonuclear production was determined. Due to high chemical and radionuclide purity, ¹⁷⁷Lu obtained by the developed method can be used in nuclear medicine.     

Influence of Multiple Binding Sites on the Supramolecular Assembly of N-[(3-pyridinylamino) Thioxomethyl] Carbamates

In this study, we investigated how the presence of multiple intermolecular interaction sites influences the heteromeric supramolecular assembly of N-[(3-pyridinylamino) thioxomethyl] carbamates with fluoroiodobenzenes. Three targets—R-N-[(3-pyridinylamino) thioxomethyl] carbamate (R = methyl, ethyl, and isobutyl)—were selected and crystallized, resulting in three parent structures, five co-crystals, and one co-crystal solvate. Three hydrogen-bonded parent crystal structures were stabilized by N-H···N hydrogen bonding and assembled into layers that stacked on top of one another. Molecular electrostatic potential surfaces were employed to rank binding sites (Npyr > C=S > C=O) in order to predict the dominant interactions. The N-H⋯H hydrogen bond was replaced by I⋯Npyr in 3/6 cases, I⋯C=S in 4/6 cases, and I⋯O=C in 1 case. Interestingly, the I⋯C=S halogen bond coexisted twice with I⋯Npyr and I⋯O=C. Overall, the MEPs were fairly reliable for predicting co-crystallization outcomes; however, it is crucial to also consider factors such as molecular flexibility. Finally, halogen-bond donors are capable of competing for acceptor sites, even in the presence of strong hydrogen-bond donors.     

Grain Boundary Grooving as an Indicator of Grain Boundary Phase Transformations

The atomic force microscopy (AFM) was used to study the grain boundary (GB) groove profiles far away from the melting temperature T _m. It is shown that AFM allows one to measure the temperature dependence of the GB energy in a rather broad temperature interval (from 0.85 T _m to T _m). The GB energy and GB segregation of Bi were measured at 1123 K in the interval of the Bi bulk concentration x ^v _Bi from 5 to 140 ppm Bi. The transition from monolayer to multilayer adsorption is observed for the 19a GB at 1123 K and x ^v _Bi = 60 at. ppm Bi. At the same point (1123 K and x ^v _Bi = 60 at. ppm Bi) a discontinuity of the first derivative of the GB energy is observed. These features were explained using the model of GB prewetting phase transformation developed previously.     

Chiffres non nuls dans le développement en base entière des nombres algébriques irrationnels

We give an effective lower bound for the number of non-zero digits among the first N digits of the expansion of an irrational algebraic number in an integer base.