Insights into the simultaneous chronopotentiometric stripping measurement of indium(III), thallium(I) and zinc(II) in acidic medium at the in situ prepared antimony film carbon paste electrode

The simultaneous measurement of microgram per liter concentration levels of indium(III), thallium(I) and zinc(II) at the antimony film carbon paste electrode (SbF-CPE) is demonstrated. The antimony film was deposited in situ on a carbon paste substrate electrode and employed in chronopotentiometric stripping mode in deoxygenated solutions of 0.01 M hydrochloric acid (pH 2). The chronopotentiometric stripping performance of the SbF-CPE was studied and compared with constant current chronopotentiometric stripping and anodic stripping voltammetric operation. In comparison with its bismuth and mercury counterparts, the SbF-CPE exhibited advantageous electroanalytical performance; namely, at the bismuth film electrode, the measurement of zinc(II) was practically impossible due to hydrogen evolution, whereas the mercury film electrode exhibited a poorly developed signal for thallium(I). The SbF-CPE revealed favorable calculated LoDs (3σ) of 1.4 μg L⁻¹ for thallium(I) and 2.4 μg L⁻¹ for indium(III) along with good linear response in the examined concentration range from 10 to 100 μg L⁻¹ with correlations coefficients (R²) of 0.992 for thallium(I) and 0.994 for indium(III) associated with a 120 s deposition time. The chronopotentiometric stripping performance of the SbF-CPE was characterized also by satisfactory reproducibility of 1.62% for indium(III), 3.96% for thallium(I) and 2.11% for zinc(II) (c = 40 μg L⁻¹, n = 11).     

Cationic peptides that increase the thermal stabilities of 2'-O-MeRNA/RNA duplexes but do not affect DNA/DNA melting

Several different cationic nonapeptides have been synthesized and investigated with respect to how they can influence the thermal melting of 2′‐O‐methylRNA/RNA and DNA/DNA duplexes. Each peptide has a C‐terminal L ‐phenylalanine unit and is otherwise uniformly composed of a sequence of a specific basic D ‐amino acid that in most cases will be largely charged at neutral pH. These N‐terminal octamer stretches are composed variously of the amino acids D ‐lysine, D ‐diaminobutyric acid (D ‐Dab), D ‐diaminopropionic acid (D ‐Dap), or D ‐histidine. None of the peptides substantially affected the thermal melting of DNA/DNA duplexes, which was in sharp contrast with their effects on 2′‐O‐methylRNA/RNA duplexes. In particular, the peptides based on diaminopropionic and diaminobutyric acid units had strong positive effects on the melting temperatures of the 2′‐O‐methylRNA duplexes (up to 16 °C higher with 1 equivalent of peptide) at pH 7, whereas at pH 6 the effect was even more drastic (ΔT_m up to +25 °C). The shorter R groups of the Dap and Dab groups appear to have a better length than lysine for enhancement of the thermal melting of the 2′‐O‐methylRNA/RNA duplex, an effect that is more pronounced at lower pH but substantial even at pH 7, although the Dap derivative is not likely to be fully protonated. The dramatic difference between the influence, or lack thereof, on the 2′‐O‐methylRNA/RNA and the DNA/DNA thermal meltings suggest that, although electrostatic interactions probably play a role, there is another major and structurally dependent component influencing the properties of the duplexes. This is also seen in the observation that the oligo‐Dap and oligo‐Dab peptides give greater melting point enhancements than both the lysine peptide (with a longer side chain) and a β‐linked Dap peptide with a shorter side chain and a longer backbone.     

A New Look at Agenda‐Setting Effects—Comparing the Predictive Power of Overall Political News Consumption and Specific News Media Consumption Across Different Media Channels and Media Types

The purpose of this study was to compare the predictive power of overall political news consumption and media‐specific news consumption, on perceived issue salience across different media channels and media types in the context of the 2006 Swedish parliamentary election. Findings suggest that overall consumption of political news is significantly more important than consumption of specific media outlets in predicting changes in issue salience. Although the study demonstrates that the Swedish news media collectively can exert considerable agenda‐setting influence over their audiences, it could, however, not find any consistent evidence of differences related to media channels or media types. The reasons for and implications of the results are discussed.     

Optimisation of puffing naked barley

The expansion of volume (the puffing index) of naked barley was investigated at various operating conditions of the puffing process. The purpose was to optimise the manufacture of expanded grains of the naked barley cultivars that have exceptional nutritional value for humans. The influence of the following parameters on the puffing index was investigated: the mass and the moisture content of the charge of the puffing barrel, pressure and temperature during the puffing process, the cultivar of barley, pre-processing of the grain (grinding and polishing), adding water into the barrel and the sensory quality of the product.

A regression equation was established for the calculation of the puffing index as a function of the operating parameters. The puffing index is influenced especially by the operating temperature and pressure. There was no influence found of mass of the charge, the cultivar of barley, the degree of grinding of barley, washing of the grains and adding water on the puffing index. The puffing index is not the sole indicator of the quality of the expanded product. It is necessary to take into account the sensory evaluation. A quality expanded naked barley was obtained at the operating temperature of 550 °C and pressure from 0.9 to 1.0 MPa with the moisture content of the charge around 16.5%.     

Evolution of physicochemical and electrocatalytic properties of NiCo2O4 (AB2O4) spinel oxide with the effect of Fe substitution at the A site leading to efficient anodic O2 evolution in an alkaline environment

Within the framework of this work, spinel-type ternary transition metal oxides of nickel, cobalt and iron with the composition Fe_xNi_1−xCo₂O₄ (0 ≤ x ≤ 1) were prepared and tested as promising electrocatalysts for the oxygen evolution reaction (OER) in alkaline water electrolysis. The hydroxide precipitation method was used for the synthesis. The morphology, structure and specific surface area of the prepared electrocatalysts were determined by means of scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, the Brunauer Emmet Teller method and X-ray photo electron spectroscopy. The electrochemical properties were tested by thin-film technique on a rotating disk electrode and in a single-cell laboratory water electrolyzer coupled with electrochemical impedance spectroscopy. The OER studies indicate that substitution of Ni by Fe increases the electrocatalytic activity of the resulting material significantly. The highest activity was achieved for x = 0.1. Whereas the current density obtained using a pure nickel anode in the water electrolysis test was 54 mA cm⁻² at a cell voltage of 1.85 V, in the case of the anode modified with NiCo₂O₄ catalyst the value was 87 mA cm⁻². Using ternary transition metal oxides in the water electrolysis test and under identical conditions, the catalyst with the highest activity displayed a current density of 115 mA cm⁻².     

The influence of electrolyte composition on electrochemical ferrate(VI) synthesis. Part III: anodic dissolution kinetics of a white cast iron anode rich in iron carbide

The anolyte composition and process temperature could improve the kinetics of iron anode dissolution and subsequent ferrate(VI) production significantly. This also holds for the anode composition. Following pure iron and silicon-rich steel (SRS), white cast iron (WCI) was the last representative of anode material tested that is typically used to produce ferrate(VI). Using anolytes 14 M NaOH, 14 M KOH, and mixtures thereof, the systems were studied by potentiodynamic methods, electrochemical impedance spectroscopy, and batch electrolysis experiments. Additionally, metallographic analysis of the material was performed. The dissolution kinetics increases with increasing temperature and also, at 60 °C, with increasing K⁺ content in the anolyte, but less progressively than in the case of SRS. Similar to SRS, WCI also easily dissolves into ferrate(VI) even at 20 °C in pure NaOH, thus indicating the inferior protective properties of oxo-hydroxide surface layers. In general, a maximum current efficiency of approx. 60 % was obtained at 60 °C in pure KOH solution. The authors conclude that, at 60 °C, the high efficiency of the synthesis is caused by the low protective properties of the oxo-hydroxide surface layer caused by the preferential dissolution of cementite and at the same time by the precipitation of the potassium salt of the product in the electrolyte immediately after its formation. This minimizes the effect of its decomposition.     

Laminated alumina/zirconia ceramic composites prepared by electrophoretic deposition

The electrophoretic deposition of alumina and zirconia powders from isopropanolic suspension in the presence of monochloroacetic acid was studied in the constant-current regime. The different levels of electric current during deposition from 250 μA to 48 mA were used. The green density of the deposit depends on the current density and then on the particle velocity during deposition, reaching values from 58% to 61% according to the electric current used. It was found that the lower the green density of the green deposit, the larger the pores. The low green density led to low final fired density and subsequently to the low Vickers hardness HV5 ranging from 2000 to 1650 depending on electric current used. Based on these findings microlaminates having various thickness ratios to achieve different residual stress levels were prepared consisting of alternating layers of alumina and zirconia.     

Topology optimization of structures with manufacturing and unilateral contact constraints by minimizing an adjustable compliance–volume product

In this paper the concept of extended optimality, or hyperoptimality, is adopted. By following this idea, a new compliance–volume product is suggested as objective. The volume appearing in the product is also raised to the power of a new design parameter which can be set to different values. In such manner design concepts with different volume fractions can be generated by using the approach of extended optimality. Both manufacturing constraints and unilateral contact constraints are included in the proposed method. The manufacturing constraints are implemented by adjusting the move limits such that the draw directions are satisfied. Both one draw direction as well as split draw constraints are considered. The contact conditions are modeled by the augmented Lagrangian approach such that the Jacobian in the Newton algorithm as well as in the adjoint equation becomes symmetric. The design parametrization is done by the SIMP model and Sigmund’s filter is utilized when the sensitivities are calculated. The proposed method is very robust and efficient. This is demonstrated by solving problems in both 2D and 3D. The numerical results are also compared to solutions obtained by performing compliance optimization with a constraint on the volume fraction.