Inner sphere oxidation of N,N′-ethylenebis(isonitrosoacetyleacetoneimine)copper(II) by N-bromosuccinimide in aqueous weakly acidic solutions

The kinetics of oxidation of N,N′-ethylenebis(isonitrosoacetyleacetoneimine)copper(II) complex, Cu^IIL, by N-bromosuccinimide (SBr) in weakly aqueous acidic solutions was studied under pseudo-first-order conditions. Plots of ln(A _∞  ? A _t ) versus time where A _t and A _∞ are absorbance values of the Cu(III) product at time t and infinity, respectively, showed marked deviations from linearity. The curves showed an acceleration of reaction rate consistent with an autocatalytic behavior. In the presence of Hg(II) ions, plots of ln(A _∞  ? A _t ) versus time are linear up to >85 % of reaction. The value of the observed rate constant, k _obs, increases with decreasing pH. At constant reaction conditions, the dependence of the observed rate constants, k _obs, is described by Eq. (1). 1 $$ k_{\text{obs}} = k_{\text{o}} + k_{1} \left[ {{\text{H}}^{ + } } \right] $$ The dependence of both k _o and k ₁ on [SBr] is not linear. The mechanism of the title reaction is consistent with an inner sphere mechanism in which a pre-equilibrium step precedes the electron transfer step. The overall rate law is represented by Eq. (2) where [Cu^IIL]_t and K ₁ represent the total copper(II) complex concentration and the pre-equilibrium formation constant, respectively. 2 $$ d\left[ {{\text{Cu}}^{\text{III}} {\text{L}}^{ + } } \right]/dt = \left\{ {\left( {k_{\text{o}} + k_{1} \left[ {{\text{H}}^{ + } } \right]} \right)\left[ {\text{SBr}} \right]\left[ {{\text{Cu}}^{\text{II}} {\text{L}}} \right]_{t} } \right\}/\left( {1 + K_{1} \left[ {\text{SBr}} \right]} \right) $$ .     

Effective atomic numbers for CoCuNi alloys using transmission experiments

Effective atomic numbers for CuCoNi alloys against changing Ni contents were measured in the X-ray energy range from 15.746 to 40.930 keV. The gamma rays emitted a ²⁴¹Am point source have been send on absorbers to be used transmission arrangement. The X-rays were counted by a Si(Li) detector with a resolution of 160 eV at 5.9 keV. The compositions of the Ni films were determined to be 0.03, 0.47, 0.62, 1.23, 1.22 and 1.6 by a scanning electron microscopy in CuCoNi alloys prepared against changing Ni contents. CoCuNi alloy films were prepared with an electrodeposition technique. Also, the total effective atomic numbers of each alloy were estimated using mixture rule. The measured values were compared with estimated values for alloys.     

Peripheral and non-peripheral-designed multifunctional phthalocyanines; synthesis, electrochemistry, spectroelectrochemistry and metal ion binding studies

A novel type of ionophore ligands, 3′-(2,3-dihydroxypropylthio)-phthalonitrile and 4′(2,3-dihydroxypropylthio)-phthalonitrile, and their α- and β-tetrasubstituted metallo phthalocyanines, (MPc), (M = Zn^II, Co^II, Mn^IIICl, Fe^IIIAc, Cu^II) have been prepared and fully characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR, and MS (ESI and Maldi-TOF). The complexes are soluble in both polar and non-polar solvents, such as MeOH and EtOH, THF, CHCl₃ and CH₂Cl₂. The spectroscopic properties of the complexes are affected strongly by the electron-donating sulfanyl units on the periphery of the phthalocyanines. The cation binding properties of the complexes, for example using Ag^I and Pd^II, were evaluated by UV-Vis spectroscopy and the results show the formation of polynuclear phthalocyanine complexes. Functional donors on the periphery of the zinc and copper complexes coordinate to Ag^I and Pd^II to give ca. a 2:1 metal-phthalocyanine complex binding ratio for the concentration of 2.5 × 10⁻⁵ M (Pc) and 1.0 × 10⁻³ M (Metal ions). Voltammetric and in-situ spectroelectrochemical studies were performed to characterize the redox behavior of the complexes. An in-situ electrocolorimetric method was applied to investigate the colors of the electro-generated anionic and cationic forms of the complexes.     

Humidity sensing properties of ZnO-based fibers by electrospinning

Zinc oxide (ZnO) based fibers with a diameter of 80-100 nm were prepared by electrospinning. Polyvinyl alcohol (PVA) and zinc acetate dihydrate were dissolved in water and the polymer/salt solution was electrospun at 2.5 kV cm⁻¹. The resulting electrospun fibers were subjected to calcination at 500 °C for 2 h to obtain ZnO-based fibers. Humidity sensing properties of the fiber mats were investigated by quartz crystal microbalance (QCM) method and electrical measurements. The adsorption kinetics under constant relative humidity (RH) between 10% and 90% were explained using Langmuir adsorption model. Results of the measurements showed that ZnO-based fibers were found to be promising candidate for humidity sensing applications at room temperature.     

Evaluation of some pollutant levels in environmental samples collected from the area of the new campus of Taif University

The levels of radioactivity and heavy metals in soil, plant and groundwater samples collected from the area of the new campus of Taif University, Saudi Arabia, and its neighbouring areas have been determined. High-resolution gamma-ray spectroscopy was used for radioactivity measurements, and inductively coupled plasma atomic emission spectroscopy was used to determine the concentration of heavy metals. The means of ²²⁶Ra, ²²⁸Ra and ⁴⁰K concentrations in water samples collected from four wells were found to be 0.13±0.03, 0.05±0.03 and 1.3±0.5 Bq l^?1, respectively. The means of ²³⁸U, ²²⁶Ra, ²²⁸Ra (²³²Th for soil samples) and ⁴⁰K concentrations in wild plant and soil samples were found to be 3.7±4.1, 8.8±11.6, 3.8±2.9 and 1025±685, and 8.6±3.4, 12.8±3.4, 16.6±7.1 and 618±82 Bq kg^?1 dry weight (DW), respectively. The ¹³⁷Cs of artificial origin was also detected in soil samples with a mean concentration of 3.8±2.2 Bq kg^?1 DW. Evaluating the results, it can be concluded that the concentrations of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K in soil samples fall within the world average. Furthermore, 19 trace and major elements in groundwater samples and 22 elements in soil and plant samples were determined. The sampling locations of soil can be classified into three groups (relatively high, medium and low polluted) according to their calculated metal pollution index using the contents of trace and major elements. A cluster analysis of the contents of radioactivity and trace element contents in soil samples shows the presence of two main distinct clusters of sampling locations.     

Study of radon in ground water and physicochemical parameters in Khartoum state

This study was conducted primarily to measure and map radon activity concentration in wells within water supply network of Khartoum State. Ground water samples were collected before and after autumn and analysed using low level γ-spectrometry equipped with HPGe-detector. Radon activity concentration was found in the range of 1.58–345.10 Bq/L with an average value of 59.20 ± 6.60 Bq/L. Upon comparing the radon concentration values obtained with EPA it was found they were far below the maximum contaminant level of EPA with the exception five samples. Physicochemical water parameters were measured and no correlation was noted between radon concentration and these parameters. The overall annual effective dose for adults due to radon ingestion is less than WHO recommended reference dose level for most except 14 samples.     

Determination of 226Ra, 232Th and 40K in teeth by use of gamma spectroscopy

This study entails the measurement of the specific activity of natural radionuclides (²²⁶Ra, ⁴⁰K and ²³²Th) in 18 tooth samples obtained from the clinic of the Universiti Sains Malaysia (USM), Penang, by using an HPGe detector. The specific activity of ²²⁶Ra, ⁴⁰K and ²³²Th was measured to estimate the hazard index of the radionuclides, radium equivalent activities (Ra_eq), external, internal hazard indices (H_ex, H_in), and absorbed dose (D_out, D_in). The maximum values of concentration of ²²⁶Ra, ²³²Th and ⁴⁰K in the tooth samples were found to be 60.82, 60.29 and 594.22?Bq kg^?1, respectively. Maximum values of Ra_eq, H_ex, H_in, D_out and D_in were found to be 192.78?Bq kg^?1, 0.520, 0.685, 89.29 and 169.81?nGy h^–1, Iγ and Iα as 0.702 and 0.304, respectively. The results were lower than the average world value (UNSCEAR). In addition, a strong correlation was found between the concentrations of ²²⁶Ra and Ra_eq, between energy and net area, as well as between radionuclides (²²⁶Ra, ⁴⁰K and ²³²Th) in tooth samples and age of volunteers. This study showed that the concentrations and hazard indices of tooth samples are below the recommended safe levels; therefore, the study area is considered safe in terms of radiological health hazards.     

The mass attenuation coefficients in some vanadium and nickel compounds

The mass attenuation coefficients for V₂O₃, VO₂, VF₃, NH₄VO₃, VF₄, NiF₂, NiCl₂, NiCl₂H₂O, NiF₂4H₂O, NiCl₂6H₂O, Ni(ClO₄)₂6H₂O were measured in the X-ray energy range from 15.746 to using a Si(Li) detector. The measured values are compared with the theoretical ones calculated using WinXcom.