PVC-based Cu (II)-Schiff base complex membrane coated graphite electrode for the determination of the triiodide ion

A triiodide-selective electrode based on copper (II)-Schiff base complex as a membrane carrier is proposed. The electrode was prepared by incorporating the carrier into a plasticized polyvinylchloride (PVC) membrane and was directly coated on the surface of a graphite electrode. The obtained electrode showed a near Nernstian slope of 57.0 ± 0.4 mV/decade to I ₃ ⁻ ions over an activity range of 1.0 × 10⁻⁵−1.0 × 10⁻¹ M with a limit of detection of 4.8 × 10⁻⁶ M. The response time of the electrode was fast (5 s) and the electrode could be used for about 2 months without considerable divergence in response. The potentiometric selectivity coefficients were evaluated and displayed anti-Hofmeister behavior. The electrode was used as an indicator electrode in the potentiometric titration of the triiodide ion and in the determination of ascorbic acid in vitamin C tablets. The text was submitted by the authors in English.     

Thick rhodium electrodeposition on copper backing as the target for production of palladium-103

The Rh target preparation for production of ¹⁰³Pd was investigated by using a thick electrodeposition of rhodium metal on a copper backing. The electrodeposition experiments were performed in acidic sulfate media using RhCl₃·3H₂O, Rh₂(SO₄)₃ (recovered from hydrochloric acid solution) and also in the commercially available Rhodex plating baths. For high current beam irradiation of a Rh target, the qualities of the deposit of the three baths were compared in terms of thermal shock, crack-free and morphology criteria. The quality of the plating obtained from a sulfate bath [Rh₂(SO₄)₃] was comparable with the one obtained from commercially available Rhodex bath. The optimum conditions of the electrodepositions were as follows: 4.8 g rhodium [as Rh₂(SO₄)₃], pH 2, DC current density of ca 8.5 mA·cm^–2, 1% sulfamic acid (w/v) and temperature 40–60 °C.The authors would like to thank their colleagues at the VUB-Cyclotron department for help and assistance in preparation of the electrodeposition equipment and taking the SEM photomicrographs and also K. Aardaneh (NRCAM) for his assistance.     

The Role of Bi3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid

Metal oxo clusters and metal oxides assemble and precipitate from water in processes that depend on pH, temperature, and concentration. Other parameters that influence the structure, composition, and nuclearity of “molecular” and bulk metal oxides are poorly understood, and have thus not been exploited. Herein, we show that Bi³⁺ drives the formation of aqueous Fe³⁺ clusters, usurping the role of pH. We isolated and structurally characterized a Bi/Fe cluster, Fe₃BiO₂(CCl₃COO)₈(THF)(H₂O)₂, and demonstrated its conversion into an iron Keggin ion capped by six Bi³⁺ irons ( Bi₆Fe₁₃ ). The reaction pathway was documented by X‐ray scattering and mass spectrometry. Opposing the expected trend, increased cluster nuclearity required a pH decrease instead of a pH increase. We attribute this anomalous behavior of Bi/Fe(aq) solutions to Bi³⁺, which drives hydrolysis and condensation. Likewise, Bi³⁺ stabilizes metal oxo clusters and metal oxides in strongly acidic conditions, which is important in applications such as water oxidation for energy storage.     

A dispersive liquid–liquid microextraction based on a task-specific ionic liquid for enrichment of trace quantity of cadmium in water and food samples

In this work, a hydrophilic task-specific ionic liquid (TSIL) of 1-chloroethyl-3-methylimidazolium chloride functionalized with 8-hydroxyquinoline was used in a dispersive liquid–liquid microextraction method followed by flame atomic absorption spectrometry for the enrichment and determination of trace amounts of cadmium (Cd²⁺) ions. The simultaneous chelation and extraction of Cd²⁺ ions was carried out by the TSIL. Fine droplets of the water-immiscible TSIL containing target analyte were generated in situ by addition of an anion exchanger potassium hexafluorophosphate (KPF₆) salt to the sample tube. After phase separation by centrifugation for 4 min, the sedimented TSIL was diluted with acidified ethanol for measurement of Cd²⁺ content. Some significant parameters influence the preconcentration of Cd²⁺ ions such as sample pH, TSIL volume, amount of KPF₆, non-ionic surfactant and salt concentration were investigated. Under the optimal conditions, calibration curve was linear in the range of 5–250 µg L^?1 Cd²⁺ with correlation coefficient of 0.9975 and a detection limit of 0.55 µg L^?1. The relative standard deviation for six replicate measurements of 50 µg L^?1 Cd²⁺ was 1.5%. The method was successfully applied for the extraction and determination of Cd²⁺ ions in water and food samples.     

Spectroscopic (Ft-Ir,Nmr, Uv-Vis,Fluorescence) and Dft Studies (Molecular Structure,Ir and Nmr Spectral Assignments,Nbo and Fukui Function) of Schiff Bases Derived from 2-Chloro-3-Quinolinecarboxaldehyde

Two Schiff bases are newly prepared by the condensation of 2-chloro-3-quinolinecarboxaldehyde with ethylenediamine and 1,4-butanediamine. The Schiff bases are characterized by the elemental analysis, IR, ¹H and ¹³CNMR, UV-Vis, and fluorescence spectroscopies. Structural parameters together with the theoretical assignment of their vibrational frequencies and NMR chemical shifts are determined using density functional theory (DFT) approaches. There is good consistency between the DFT-calculated results and the experimental data, confirming the validity of the optimized geometries for the investigated Schiff bases. Optimized geometries of two Schiff bases are not planar, however, the substitutions are essentially in the same plane with the pyridine rings. Shapes of the frontier orbitals are determined using the natural bond orbital (NBO) analysis. Due to a high energy gap between the frontier orbitals, both Schiff bases are stable. Based on the Fukui function analysis, two Cl atoms and two azomethine nitrogen atoms are four suitable donor atoms for coordination to metal ions. Effects of the temperature and pH on the UV-Vis absorbance and fluorescence intensity of the Schiff bases are studied in a DMSO solution.     

Crack-free,thick rhodium deposition on copper substrate using Rhodex solution

Summary Rhodium electrodeposition on a copper substrate was investigated for ¹⁰³Pd production. The electrodeposition was carried out by the commercially available Rhodex plating baths. The optimum conditions of the electrodeposition for complete depletion of Rh were: 6.2 g/l rhodium, DC current density of 12.83 mA ^. cm^-2 and 60 °C temperature.     

Vapor–liquid equilibria of binary tri-potassium citrate + water and ternary polypropylene oxide 400 + tri-potassium citrate + water systems from isopiestic measurements over a range of temperatures

Water activity measurements have been carried out on the aqueous solutions of both tri-potassium citrate (K₃Cit) and polypropylene oxide (PPO) 400 + K₃Cit over a range of temperatures at atmospheric pressure. The data obtained is used to calculate the vapor pressure as a function of temperature and concentration. The effect of temperature on the constant water activity lines of aqueous PPO + K₃Cit systems has been studied and it was found that, at higher temperatures the higher concentration of polymer is in equilibrium with a certain concentration of the salt. Also it was found that the vapor pressure depression for an aqueous PPO + K₃Cit system is more than the sum of those for the corresponding binary solutions. The experimental water activities have been correlated successfully with the segment-based local composition Wilson model. The agreement between the correlation and the experimental data is good.     

Thermodynamic Properties of Aqueous Glucose–Urea–Salt Systems

In this work, the thermodynamic behavior of aqueous solutions containing the solutes NaCl, glucose, and/or urea is investigated. These substances are vital components for living bodies and further they are main components of blood serum. Osmotic coefficients were determined by cryoscopic measurements in single-solute and multi-solute aqueous solutions containing salts (NaCl, KCl, CaCl₂), glucose, and/or urea. The results show that NaCl determines the osmotic coefficients in the urea/glucose/NaCl/water system. Investigation of the effect of different salts on osmotic coefficients revealed ion-specific effects. At physiologically important solute concentrations in typical blood serum solutions, the osmotic coefficients were found to be in the range of 0.90–0.93. In a second step, the state of water in different glucose/salt/water and urea/salt/water systems was investigated. Depending on the kind of salt, the chemical potential of water in urea/salt/water is either higher or lower than in glucose/salt/water systems at equal nonelectrolyte concentrations. This result was found to be independent of the salt molality. Finally, the investigated systems were modeled with the Pitzer model and the ePC-SAFT equation of state, which allowed predicting of the properties of these multi-solute aqueous solutions.     

Comparative study of honeycomb optimization using Kriging and radial basis function

Structural optimization for crashworthiness criteria is of particular significance especially at early stage of design. The comparative study of Kriging and radial basis function network (RBFN) was performed in order to improve the crashworthiness effects of honeycomb. Improving the crashworthiness characteristic of honeycomb was achieved using LS-OPT® and domain reduction strategy. This optimization is performed on the basis of validated numerical simulation to establish the approximated model to illustrate the relationship between the responses and design variables. The results showed that Kriging meta-model is excelled in accuracy, robustness and efficiency compared to radial basis function (RBF) and crashworthiness characteristic of honeycomb is improved by 4%.