Neues zum chemischen Transport von CuO und Cu2O

New Results on the Chemical Transport of CuO and Cu₂O The preparation of CuO crystals by chemical transport reactions with HCl is already well known, a comparison with other transport agents based on the principal of thermodynamic equilibrium and also the rate of transport was missing up to now. We report about experiments with the transport agents HgCl₂, Cl₂, I₂, Nh₄Cl, or CuCl; the quantitative evaluation was made by means of the cooperative transport model on the basis of the free energy function. By this way it is possible to find favourable experimental conditions for the suitable transport agents at the outset. It turned out that HgCl₂ is an appropriate transport agent which can easily be weighed. Also I₂ is useful, whereas the effect fo transport with Cl₂ (1 atm/298 K), CuCl, or NH₄Cl is very small. We investigated the chemical transport of Cu₂o and the conditions for the change of its direction of transport.     

Conductivity studies on some alkali metal iodides in aqueous N,N-dimethylformamide solutions at 298.15K

Summary Conductance measurements for NaI, KI, RbI, and CsI in water/N,N-dimethylformamide mixtures over the whole composition range at 298.15K are reported. The data were analyzed employing theFuoss-Justice equation in terms of limiting molar conductances (_o),Walden products (_o), and association constants (K _A). The results indicate that the salts are weakly associated in the above solvent mixture. Variation in theWalden products with solvent composition are briefly discussed. The results were also compared with values reported previously for some alkali metal chlorides and bromides.

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Untersuchungen zur elektrischen Leitfähigkeit einiger Alkalimetalliodide in wäßrigen N,N-Dimethylformamidlösungen bei 298.15K

Zusammenfassung Die elektrische Leitfähigkeite von NaI, KI, RbI und CsI wurde in N,N-Dimethylformamid-Wasser-Mischungen verschiedener Zusammensetzung bei 298.15K gemessen. Die erhaltenen Daten wurden analysiert und bezüglich der Grenzäquivalenzleitfähigkeiten (_o), derWalden-Produkte (_o) und der Assoziationskonstanten (K _A) ausgewertet. Die Ergebnisse zeigen, daß diese Salze in den verwendeten Lösungsmittelgemischen nur schwach assoziiert sind. Die Änderungen derWalden-Produkte in Abhängigkeit der Lösungsmittelzusammensetzung werden kurz diskutiert. Abschließend werden die Resultate mit Ergebnissen früherer Messungen, in denen das Verhalten von Alkalimetallchloriden und Alkalimetallbromiden untersucht wurde, verglichen.

     

Cross-section calculations of proton induced (p,n) and (p,2n) reactions for production of diagnostic 67Ga, 81Rb, 111In, 123,124I, 123Cs and 123Xe radioisotopes

Investigation of pre-equilibrium (PEQ) and equilibrium (EQ) effects on proton induced reactions for production of radioisotopes are very important. Therefore, in this study, we have calculated the PEQ and EQ cross-sections for ⁶⁷Zn(p,n)⁶⁷Ga, ⁶⁸Zn(p,2n)⁶⁷Ga, ⁸²Kr(p,2n)⁸¹Rb, ¹¹¹Cd(p,n)¹¹¹In, ¹¹²Cd(p,2n)¹¹¹In, ¹²³Te(p,n)¹²³I, ¹²⁴Te(p,2n)¹²³I, ¹²⁴Te(p,n)¹²⁴I and ¹²⁴Xe(p,2n)¹²³Cs reactions for production diagnostic radioisotopes. Calculations have been performed by using the hybrid model, geometry dependent hybrid model and full exciton model of PEQ reaction mechanism with 1–40 MeV proton incident energy. We have also investigated the EQ effects on these reactions using the Weisskopf–Ewing model in the same energy range. The excitation functions including the PEQ and EQ effects on these reactions are evaluated by using the ALICE/ASH (2006) and the TALYS 1.4 (2011) codes. Our results have shown that using these codes is suitable for production diagnostic isotopes mentioned above. To obtain excitation functions for producing the diagnostic radioisotopes the PEQ mechanism has been found more dominant than that of the EQ. The results are discussed and compared with the available experimental data.     

Liquid chromatographic assessment of total and protein-bound homocysteine in human plasma

Homocysteine present in human blood plasma is derivatized with thiol selective ultraviolet labelling reagent, 2-chloro-1-methylpyridinium iodide, and separated from other plasma thiol derivatives by high-performance liquid chromatography (HPLC) with detection at 312 nm. The separation is carried out isocratically on LiChrospher RP-18 column using mobile phase consisting of pH 2.5 0.04 M trichloroacetic acid buffer and methanol in the ratio 9:1 (v/v) pumped at 0.5 ml min⁻¹ at 40°C. The homocysteine S-pyridinium derivative elutes at 6.5 min. To determine total and protein-bound homocysteine it is necessary to cleave disulphide bounds by the use of tri-n-butylphosphine in order to form free sulfhydryl group. The method provides quantitative information on total and protein-bound homocysteine based on assays with derivatization after reduction of whole plasma, and derivatization after reduction of acid precipitated proteins. The calibration graph is linear over the concentration range covering most experimental and clinical cases. The assay has a low pmol sensitivity and is reproducible; intra- and inter-day, relative standard deviation range from 1.79 to 5.09% and from 2.80 to 5.60%, respectively. The method is applied to the determination of total and protein-bound homocysteine in the plasma of healthy individuals.     

Determination by liquid chromatography of free and total cysteine in human urine in the form of its S-quinolinium derivative

A reversed-phase high-performance liquid chromatographic method for the determination of free and total cysteine in urine is described. The method involves reductive conversion of cysteine dimer and cysteine mixed disulphides to their reduced counterpart with the use of tri-n-butylphosphine, ultraviolet-labeling with 2-chloro-1-methylquinolinium tetrafluoroborate, and liquid chromatographic separation with isocratic conditions. In developing this method the following parameters were investigated and optimized: the time, pH and reagent excess in the derivatization step, and mobile phase buffer concentration, pH, organic modifier and column temperature in the separation step. The method provides quantitative information on free and total cysteine based on assays with derivatization before and after reduction with tri-n-butylphosphine. The calibration graph, obtained with the use of normal urine spiked with growing amounts of cystine, was linear over the concentration range covering most experimental and clinical cases. The assay has a low pmol detection and quantitation limits, low imprecision and high recovery. The method was validated for urine samples received from several donors. Cystine was chosen as a primary calibrator for these assays.     

Conductance studies of NaBPh4, NBu4I, NaI, NaCl, NaBr, NaClO4 and the limiting ionic conductance in water + propan-1-ol mixtures at 298.15 K

The electrical conductivities of NaBPh₄, NBu₄I, NaI, NaCl, NaBr and NaClO₄ have been studied in the mixtures of propan-1-ol with water. The obtained results were analysed using the Fuoss–Justice equation. The individual limiting ionic conductivities of Na⁺, NBu₄⁺, BPh₄⁻, I⁻, Cl⁻, Br⁻, ClO₄⁻ ions have been determined using the Fuoss–Hirsch assumption. The dependencies of the limiting molar conductances Λ_o and Walden products Λ_oη versus mixed solvent composition have been discussed.     

Tuning the hydrophobicity of mica surfaces by hyperthermal Ar ion irradiation

The hydrophobicity of surfaces has a strong influence on their interactions with biomolecules such as proteins. Therefore, for in vitro studies of bio-surface interactions model surfaces with tailored hydrophobicity are of utmost importance. Here, we present a method for tuning the hydrophobicity of atomically flat mica surfaces by hyperthermal Ar ion irradiation. Due to the sub-100 eV energies, only negligible roughening of the surface is observed at low ion fluences and also the chemical composition of the mica crystal remains almost undisturbed. However, the ion irradiation induces the preferential removal of the outermost layer of K(+) ions from the surface, leading to the exposure of the underlying aluminosilicate sheets which feature a large number of centers for C adsorption. The irradiated surface thus exhibits an enhanced chemical reactivity toward hydrocarbons, resulting in the adsorption of a thin hydrocarbon film from the environment. Aging these surfaces under ambient conditions leads to a continuous increase of their contact angle until a fully hydrophobic surface with a contact angle >80° is obtained after a period of about 3 months. This method thus enables the fabrication of ultrasmooth biological model surfaces with precisely tailored hydrophobicity.