Determination of Arsenic by Electrothermal Atomic Absorption Spectrometry Using Arsine Preconcentration on Palladium-Containing Adsorbents

A procedure was developed for the preconcentration of arsine on palladium-containing adsorbents followed by the determination of arsenic by electrothermal atomic absorption spectrometry. Aqueous suspensions of the adsorbent were placed in a graphite furnace at the determination step. The selection of the adsorbent was substantiated; adsorption properties of palladium-containing adsorbents were studied to validate their modifying properties. The absolute and concentration limits of detection for arsenic were 28 pg and 12 ng/L, respectively (sample volume of 100 mL).     

Mössbauer study of (Bi,Pb)-2223 superconductors irradiated with 86Kr ions

⁵⁷Fe Mössbauer spectroscopy was used to study the effects of heavy ion irradiation on (Bi_0.93Pb_0.17)Sr_1.9Ca_2.05(Cu_1.02Fe_0.01)₃O_y superconductors. The Mössbauer spectra of the irradiated superconductor showed significant changes in the subspectra belonging to different Cu microenvironments into which Fe ions were substituted. The relative occurrence of Fe occupying the square pyramidal fivefold oxygen coordinated Cu sites decreased while Fe^{3 +} substituting the square planar fourfold oxygen coordinated Cu sites increased upon bombardment by 246 MeV ⁸⁶Kr⁸⁺ ions. This observation was interpreted on the basis of partial replacement of the apical oxygen atoms in the square pyramids surrounding one of the Cu sites. Such oxygen vacancies create additional square planar coordination sites for Cu. These results also support the covalent character of Cu-O bonds in the superconducting layer as well as the ionic character of bond of apical oxygen to Cu.     

Mechanism of formation of organic carbonates from aliphatic alcohols and carbon dioxide under mild conditions promoted by carbodiimides. DFT calculation and experimental study

Dicyclohexylcarbodiimide (CyN=C=NCy, DCC) promotes the facile formation of organic carbonates from aliphatic alcohols and carbon dioxide at temperatures as low as 310 K and moderate pressure of CO2 (from 0.1 MPa) with an acceptable rate. The conversion yield of DCC is quantitative, and the reaction has a very high selectivity toward carbonates at 330 K; increasing the temperature increases the conversion rate, but lowers the selectivity. A detailed study has allowed us to isolate or identify the intermediates formed in the reaction of an alcohol with DCC in the presence or absence of carbon dioxide. The first step is the addition of alcohol to the cumulene (a known reaction) with formation of an O-alkyl isourea [RHNC(OR')=NR] that may interact with a second alcohol molecule via H-bond (a reaction never described thus far). Such an adduct can be detected by NMR. In alcohol, in absence of CO2, it converts into a carbamate and a secondary amine, while in the presence of CO2, the dialkyl carbonate, (RO)2CO, is formed together with urea [CyHN-CO-NHCy]. The reaction has been tested with various aliphatic alcohols such as methanol, ethanol, and allyl alcohol. It results in being a convenient route to the synthesis of diallyl carbonate, in particular. O-Methyl-N,N'-dicyclohexyl isourea also reacts with phenol in the presence of CO2 to directly afford for the very first time a mixed aliphatic-aromatic carbonate, (MeO)(PhO)CO. A DFT study has allowed us to estimate the energy of each intermediate and the relevant kinetic barriers in the described reactions, providing reasonable mechanistic details. Calculated data match very well the experimental results. The driving force of the reaction is the conversion of carbodiimide into the relevant urea, which is some 35 kcal/mol downhill with respect to the parent compound. The best operative conditions have been defined for achieving a quantitative yield of carbonate from carbodiimide. The role of temperature, pressure, and catalysts (Lewis acids and bases) has been established. As the urea can be reconverted into DCC, the reaction described in this article may further be developed for application to the synthesis of organic carbonates under selective and mild conditions.     

Microcalorimetry, energetics and binding studies of DNA-dimethyltin dichloride complexes

The interaction of dimethyltin dichloride (Me₂SnCl₂) with calf thymus DNA was studied at 27 °C, pH 7.6 using various techniques including isothermal titration calorimetry (ITC) and UV-Vis, fluorescence and IR spectrophotometries. The binding isotherm and enthalpy curve for Me₂SnCl₂-DNA interaction was a biphasic transition process. This was determined by the analysis of the binding data with the Hill equation. The first phase of the enthalpy curve (exothermic process) was consistent with the first set of binding site, the second phase (endothermic process, less exothermicity) was consistent with second set of binding site from the cited interactions. Our results showed that the first set of binding sites is occupied by one mole of ligand bound per near 1 base pair of DNA. The DNA-ethidium bromide (EB) complex, in the presence of Me₂SnCl₂, caused the quenching of the fluorescence emission. The Scatchard plots illustrated a non-intercalating manner for such quenching. The DNA-EB complex results indicated that the binding of Me₂SnCl₂ is with the phosphate groups of DNA at low ligand concentrations (<9 mM). This was confirmed with the IR spectrophotometric spectra. However, the binding at higher ligand concentrations (>9 mM) was with the base groups of DNA. Therefore, these results suggest that the Me₂SnCl₂ binding to DNA at low concentrations occurs through an outside interaction by an exothermic process. However, the partial unfolding of the DNA caused at higher concentrations of Me₂SnCl₂ is through an endothermic process involving interactions with the base groups.     

Metal organic chemical vapour deposition (MOCVD) of bone mineral like carbonated hydroxyapatite coatings

For the first time, the MOCVD technique has been used to deposit carbonated hydroxyapatite onto Ti6AL4V substrates using volatile monomeric (liquid) complexes [Ca(beta-diketonate)(2)(L)] and P(OEt)(3).     

A novel formal total synthesis of cephalotaxine

A formal total synthesis of cephalotaxine (CET), the parent structure of antileukemia Cephalotaxus alkaloids, was achieved through a novel synthesis of the pentacyclic amino enone 4 by a rapid annulation of readily available beta-(3,4-methylenedioxy)phenethylamine (2), delta-valerolactone, and bromoacetone.     

Effect of some additives on the reactions in fly ASH-Ca(OH)2 system

Differential thermal analysis and thermogravimetry were used to evaluate the effect of some additives, such as CaSO₄, CaCl₂ and silica fume amorphous silica from ferrosilicon synthesis on the mechanism and kinetics of reactions occurring in fly ash-Ca(OH)₂ system. The accelerating role of these additives was demonstrated from the data relating to Ca(OH)₂ consumption in hydrated pastes, determined by TG measurements. This revised version was published online in July 2006 with corrections to the Cover Date.     

Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction

Prolonged storage ( approximately 2 years) or gentle heating (50-80 degrees C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novel solid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT), and requires a much higher temperature (>130 degrees C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT). X-ray structural analysis of the above dihalothiophenes reveals short Hal.Hal distances between adjacent molecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the melt but is significantly slower and leads to poorly conductive material. Detailed studies of the reaction were performed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it is exothermic by 14 kcal/mol and requires activation energy of approximately 26 kcal/mol (for DBEDOT). The temperature dependence of the conductivity of SSP-PEDOT (sigma(rt) = 20-80 S/cm) reveals a slight thermal activation. It can be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOT with conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces.     

Thermal characterisation of alumina supported chromium and platinum–chromium catalysts

This study presented results on reduction of alumina supported chromium and platinum–chromium catalysts using temperature programmed reduction method (TPR). It has been shown that catalysts after earlier oxidation step but without calcinations one undergo reduction in lower temperature in comparison to calcined only catalysts. Moreover, addition platinum to Cr/Al₂O₃ catalysts also caused decrease of reduction temperature. It has been observed that over the examined catalysts oxidation CO to CO₂ and reduction CO to CH₄ occurs. However, on Pt–Cr catalysts both reactions proceed at lower temperature compare to Cr catalysts.     

Determination of cadmium in urine by platform ET-AAS independent of matrix composition

Summary The optimization of the heating conditions, absorbance profiles, the influence of different matrix composition and the effect of delivering different volumes of urine samples were examined in order to evaluate the use of simple aqueous standards for the determination of cadmium in urine samples, using atomic absorption spectrometry with electrothermal atomization and the L'vov platform. Three reference materials were analysed for cadmium by the proposed method. The results indicate that a direct and accurate determination of urine cadmium is possible by using simple aqueous calibration standards, independently of the composition of the urine matrix.