Chronocoulometric study of the electrochemistry of Prussian blue

During the electrochemical oxidation of Prussian blue (PB) to Prussian yellow (PY), an electrocatalytic oxygen production proceeds at the electrode when aqueous electrolyte solutions are used. The formed oxygen is scavenged by the PY, probably by absorption, and it is consumed during the electrochemical reduction of PY to PB by a heterogeneous chemical reaction of PB with oxygen to PY and hydrogen peroxide. Because of this catalytic regeneration of PY, it is impossible to determine the amount of low-spin iron by chronocoulometry using a potential program in which PB is first oxidized to PY and then the charge is measured to reduce PY to PB. The latter charge is biased by the electrocatalytic PY regeneration.     

Cytogenetic effects of tritium incorporated into DNA of human lymphocytes

The number of chromosomal and chromatid breaks, deletions, as well as fragments, have been followed in correlation to the physical dose as assessed by the specific radioactivity of DNA. Human lymphocytes from adult donors were incubated for 44 hours in media supplemented with tritiated thymidine. An uneven distribution of labelling in the cell population has been found and about 50% of the population of cells remained unlabelled. The dose-response curve was flat reflecting loss of damaged cells and/or repair of damage. The dose-response curve showed that at the experimental conditions used the dose of 100 mGy absorbed from incorporated tritium caused about 0.1 deletions per. cell. Doubling the number of deletions to about 0.2 per cell required approximately a five times higher absorbed dose.     

Molecular dynamics simulations of a nucleoside analogue of 1,4-dihydro-4-oxoquinoline-3-carboxylic acid synthesized as a potential antiviral agent: Conformational studies in vacuum and in water

Conformational analysis of nucleosides may have direct applications to the structure–activity relationship (SAR) studies and in the design of new drug candidates. Although conformational analysis may be accessed in many different ways, in this work it was performed using molecular dynamics (MD) simulation in order to study the dynamic behavior of a nucleoside derivative of 1,4-dihydro-4-oxoquinoline-3-carboxylic acid, synthesized by our group as a potential antiviral agent. The MD simulation was carried out during 10 ns in vacuum and in a box of water at two different temperatures (i.e., 300 and 600 K) using the AMBER force field. The in vacuum MD simulation results are in agreement with the crystallographic structure and with the DFT calculations of the nucleoside, revealing the anti conformer as the more stable one. The simulation in water, however, shows that both conformers may exist at 300 K, the temperature of the in vivo and in vitro assays, revealing that both the syn and anti conformers should be considered in a MD simulation study of the inhibitor–enzyme complex. Simulations are also in agreement with the NOE experiment, which shows that the anti conformer is the preferential one in DMSO-d6 solution at 298 K.     

New aspects of the electroadsorption of ethyl xanthate on copper electrodes

The interaction of the ethyl xanthate (EX) anion with a copper electrode in a borate buffer solution, pH 9.2, has been investigated by cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), electrochemical impedance spectroscopy (EIS), and measurements of contact angle (CA) under controlled potential. The results obtained allow establishing that, in the potential range from -0.80 and -0.60 V, two parallel reactions were characterized. These reactions were the ethyl xanthate electroadsorption and the hydrogen evolution reaction (HER). This last reaction has not been described by previous authors. Besides, the EIS measurements show that the mechanism of the HER on copper electrodes is not affected by the presence of a ethyl xanthate species. The EQCM study shows that in the electrodesorption process the departure of each ethyl xanthate species from the copper electrode is accompanied with the simultaneous entry of four to five water molecules. This fact is in accordance with the number of copper atoms involved in the adsorption of one ethyl xanthate species.     

Hexaruthenium carbonyl cluster complexes with basal edge-bridged square pyramidal metallic skeleton: efficient synthesis of 2-imidopyridine derivatives and determination of their reactive sites in carbonyl substitution reactions

The reactions of [Ru(3)(CO)(12)] with half equivalent of 2-amino-6-methylpyridine (H(2)ampy) or 2-aminopyridine (H(2)apy) in refluxing xylene give the hexanuclear products [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-L)(mu-CO)(2)(CO)(14)] (L = ampy, 1; apy, 2). These reactions represent the first high-yield syntheses of hexanuclear complexes with a basal edge-bridged square pyramidal metallic skeleton. Five metal atoms of these complexes are bridged by the N-donor ligand in such a way that the edge-bridging metal atom is attached to the pyridine nitrogen, while the basal atoms of the square pyramid are capped by an imido fragment that arises from the activation of both N-H bonds of the NH(2) group. The reactive sites of these complexes in CO substitution reactions have been determined by studying the reactivity of 1 with triphenylphosphine. Two kinetically controlled monosubstitutions take place on the edge-bridging metal atom in positions cis to the pyridine nitrogen, leading to a mixture of two isomers of formula [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(13)(PPh(3))] (3 and 4). On heating at 80 degrees C, these monosubstituted isomers are transformed, via a dissociative pathway, into the product of thermodynamic control (5), which has the PPh(3) ligand on the apical Ru atom. The di- and trisubstituted derivatives [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(PPh(3))(2)] (6) and [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(11)(PPh(3))(3)] (7) are stepwise formed from 3-5 and PPh(3). Compound 6 has the PPh(3) ligands on the edge-bridging and apical Ru atoms, and compound 7 has an additional PPh(3) ligand on an unbridged basal Ru atom. The compound [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(mu-dppm)] (8), in which a basal and the apical Ru atoms are spanned by the dppm ligand, has been isolated from the reaction of 1 with bis(diphenylphosphino)methane.     

Simultaneous determination of propacetamol and paracetamol by derivative spectrophotometry

The present paper describes a procedure that phenols in air were preconcentrated in a membrane cell and their content was determined by adsorptive polarography. First, the phenols in air samples were preconcentrated in a membrane cell using 2.0 M NaOH solution, then in a pH 1.3 buffer solution p-bromophenylamine forms a diazoate with NaNO(2), and into the mixture the collected phenols were added to form azo-compound in a pH 13 buffer solution. The azo-compound can be adsorbed at the mercury electrode and yields a sensitive oscillopolarographic wave. Over the range 2.0x10(-8)-2.0x10(-5) M, the peak currents are linearly proportional to the concentration of phenols. The detection limit is 5.0x10(-9) M.     

Binary mixtures based on polycaprolactone and cellulose derivatives

Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste. Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the environmentally friendly transformation of biocomposites.     

Hydride generation atomic fluorescence spectrometric determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter using multivariate optimization

A highly sensitive and simple method, based on hydride generation and atomic fluorescence detection, has been developed for the determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter samples. Atmospheric particulates matter was collected on glass fiber filters using a medium volume sampler (PM1 particulate matter). Two-level factorial designs have been used to optimise the hydride generation atomic fluorescence spectrometry (HG-AFS) procedure. The effects of several parameters affecting the hydride generation efficiency (hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations and flow rates) have been evaluated using a Plackett-Burman experimental design. In addition, parameters affecting the hydride measurement (delay, analysis and memory times) have been also investigated. The significant parameters obtained (sodium tetrahydroborate concentration, sodium tetrahydroborate flow rate and analysis time for As; hydrochloric acid concentration and sodium tetrahydroborate flow rate for Se(IV); and sodium tetrahydroborate concentration and sodium tetrahydroborate flow rate for Te(IV)) have been optimized by using 2ⁿ + star central composite design. Hydrochloric acid concentration and sodium tetrahydroborate flow rate were the significant parameters obtained for Sb and Bi determination, respectively. Using a univariate approach these parameters were optimized. The accuracy of methods have been verified by using several certified reference materials: SRM 1648 (urban particulate matter) and SRM 1649a (urban dust). Detection limits in the range of 6 × 10⁻³ to 0.2 ng m⁻³ have been achieved. The developed methods were applied to several atmospheric particulate matter samples corresponding to A Coruña city (NW Spain).     

Reactivity of benzoyl chlorides in nonionic microemulsions: potential application as indicators of system properties

The solvolysis reactivity of benzoyl chlorides entails a high sensitivity on medium properties. A systematic study of the reaction of a series of these substrates, varying the electron-withdrawing character of the substituent, has been performed in nonionic microemulsions. The kinetic effects due to variation of microemulsion compositions can be assigned to modifications in system properties, to be precise, to modifications in interface properties. Microemulsion properties that are obtained from kinetic analysis of solvolysis show a good agreement with the characterization of the microemulsion that was made via 1H NMR and solvatochromic fluorescence probes. Benzoyl chlorides with electron-donating groups react through a dissociative mechanism, whereas electron-withdrawing groups favor an associative mechanism. A comparative analysis of reactivity between the different substrates at the interface shows a variation in the contributions of both reaction pathways, associative and dissociative, to the whole reaction mechanism. The confined media shift the point where the mechanism changes from an associative to a dissociative pathway, far away from the turning point in water. Furthermore, the change in mechanism can be modulated by modification of the microemulsion composition.