Preconcentration of transition metal ions from ethanol solution onN-acyl-N′-benzoylthiourea — Modified silica gel

Silica gel was chemically modified with anN-acyl-N-benzoylthiourea group. This material behaved as a selective means of preconcentrating Cu(II), Zn(II) and Cd(II) from ethanol by the column technique. Ethanolic solutions having 6 mol of the metal ions were percolated through the column and retentions of 100% were achieved for all metals. Zinc and copper were eluted quantitatively from the column bed with 5mL of ethanolic O.1molL^–1 (for Zn) and 0.9 mol L^–1 (for Cu) citric acid. Cadmium was recovered totally with 60 mL of ethanolic 2.0 mol L^–1 citric acid. The modified silica was shown to be chemically stable after various adsorption-elution cycles (at least twenty).     

Dielectric properties of Bauhinia monandra and concanavalin A lectin monolayers, part I

The dielectric properties of the galactose-binding lectins Bauhinia monandra (BmoLL) and Concanavalin A (Con A) were assessed by surface potential measurements of their spread monolayers on an aqueous subphase containing a monovalent electrolyte. For both lectins the curves of surface potential versus mean molecular area (DeltaV-A) and the independently recorded isotherms of surface pressure versus mean molecular area (Pi-A) were shown to be pH-dependent. As the subphase pH changed from 2 to 9, a noticeable trend to higher surface pressures accompanied the compression of the monolayers. Conversely, the surface potentials values of both monolayers decreased with increasing pH. For Con A, with the single exception of the pH 9 case, lowering the pH yielded DeltaV values higher than those for BmoLL. The contribution of the electric double layer (Psi0) to the overall DeltaV values at a given Pi (15 mN/m) was calculated using a modified Davies equation and assuming that at this surface pressure the monolayers of both studied lectins were stable. While at all studied pHs the Psi0 values for Con A exceeded those calculated for BmoLL, for both lectins they were insensitive to pH changes. This provided evidence that the reorientation of lectin molecules, during compression predominantly contributed to the alteration of the overall DeltaV values. The calculated Psi0 values made possible the evaluation of the dipole moments for BmoLL and Con A, and it has been estimated that the decrease in the pH of the subphase from 9 to 2 produced a 1.6-fold (twofold) increase in the value of for BmoLL (Con A). The differences in dielectric properties between the two film-forming lectins have been attributed to the differences in their structures. Indeed, the circular dichroism (CD) spectrum of Con A showed the predominance of beta-plated sheet structures while that of BmoLL was typically rich in alpha-helix structures.     

In situ and simultaneous nanostructural and spectroscopic studies of ZnO nanoparticle and Zn-HDS formations from hydrolysis of ethanolic zinc acetate solutions induced by water

The simultaneous formation of nanometer sized zinc oxide (ZnO), and acetate zinc hydroxide double salt (Zn-HDS) is described. These phases, obtained using the sol-gel synthesis route based on zinc acetate salt in alcoholic media, were identified by direct characterization of the reaction products in solution using complementary techniques: nephelometry, in situ Small-Angle X-ray Scattering (SAXS), UV-Vis spectroscopy and Extended X-ray Absorption Fine Structures (EXAFS). In particular, the hydrolytic pathway of ethanolic zinc acetate precursor solutions promoted by addition of water with the molar ratio N=[H₂O]/[Zn²⁺] = 0.05 was investigated in this paper. The aim was to understand the formation mechanism of ZnO colloidal suspension and to reveal the factors responsible for the formation of Zn-HDS in the final precipitates. The growth mechanism of ZnO nanoparticles is based on primary particle (radius ≈ 1.5 nm) rotation inside the primary aggregate (radius <3.5 nm) giving rise to an epitaxial attachment of particles and then subsequent coalescence. The growth of second ZnO aggregates is not associated with the Otswald ripening, and could be associated with changes in equilibrium between solute species induced by the superficial etching of Zn-HDS particles at the advanced stage of kinetic.     

Pore size distribution of unsupported SnO2 membranes prepared by sol-gel process

Unsupported SnO₂ membranes were prepared by sol-gel process and characterized by N₂ adsorption-desorption isotherms and X-ray diffraction. Results show that the texture of dried samples does not change appreciably with the concentration of electrolyte. All of the pore size range used in ultrafiltration process was screened using sintering temperature between 300 and 700°C.     

Cp2TiCl-promoted isomerization of trisubstituted epoxides to exo-methylene allylic alcohols on carvone derivatives

The ring-opening reaction of trisubstituted epoxides promoted by Cp2TiCl led to exo-methylene allylic alcohols as major compounds when 0.5 M solutions of the epoxides were added to 0.1 M solutions of the reagent at room temperature in THF. In most cases, the allylic alcohols were contaminated with saturated alcohols. Normal and reverse addition modes led to the alternate product being favored. The different stereochemical outcome of cis- and trans-epoxy acetates is rationalized in terms of mechanistically biased elimination processes.     

Determination of total arsenic by batch hydride generation atomic absorption spectrometry in injectable drugs containing high levels of Sb(V) as N-methylglucamine antimonate

A procedure for the determination of arsenic by batch hydride generation atomic absorption spectrometry (HG AAS) in commercial samples of injectable drugs, containing high concentrations of Sb(V), is described. The procedure is based on the complexing effect for Sb of citric, oxalic and acetic acids as reaction media. Aqua regia was used for sample digestion prior to As determination by HG AAS. The following experimental conditions for the determination of total As, as As(V), were evaluated: the acid medium and its concentration, sodium tetrahydroborate concentration, purge time, and influence of the different oxidation states of As. The effect of the delay time after mixing of sample and acid solution was also studied. Optimized conditions were: 10% (m/v) citric acid, 1.5% (m/v) sodium tetrahydroborate solution and 30 s for purge time. A delay time of 1 h was required after the digested sample had been mixed with citric acid, before As determination could be carried out. No interference on As(III) and As(V) signals was observed in the presence of up to 1 mg Sb(V). The tolerance limits for Ni(II), Cu(II) and Pb(II) were 1 mg, 100 μg and 100 μg, respectively. Recovery tests for As(III) and As(V) resulted in values between 97 and 101%. Characteristic mass and detection limit (3σ), using the recommended conditions, were 0.52 and 0.8 ng, respectively, for total As.     

Temperature-dependent energy transfer in cadmium telluride quantum dot solids

Efficiently luminescing colloidal CdTe quantum dots (QDs) were used for the preparation of monodispersed and mixed size QD solids. Luminescence spectra and decay times of the QD emission were measured as a function of temperature to study energy transfer (ET) processes in the QD solids. In the luminescence decay curves of the emission of the largest QDs (acceptors), a rise time of the luminescence signal is observed due to energy transfer from smaller QDs. Both the rise time (a measure for the energy transfer rate) and the luminescence decay time lengthen upon cooling. This is explained by the decreased dipole strength of the excitonic emission of the QDs in the solid due to the presence of a singlet and a lower lying triplet level. Studies of energy transfer in heteronuclear QD solids reveal that single-step ET dominates.     

Nevirapine quantification in human plasma by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry. Application to bioequivalence study

A rapid, sensitive and specific method to quantify nevirapine in human plasma using dibenzepine as the internal standard (IS) was developed and validated. The method employed a liquid-liquid extraction. The analyte and the IS were chromatographed on a C(18) analytical column, (150 x 4.6 mm i.d. 4 microm) and analyzed by tandem mass spectrometry in the multiple reaction monitoring mode. The method had a chromatographic run time of 5.0 min and a linear calibration curve over the range 10-5000 ng ml(-1) (r(2) > 0.9970). The between-run precision, based on the relative standard deviation for replicate quality controls was 1.3% (30 ng ml(-1)), 2.8% (300 ng ml(-1)) and 3.6% (3000 ng ml(-1)). The between-run accuracy was 4.0, 7.0 and 6.2% for the above-mentioned concentrations, respectively. This method was employed in a bioequivalence study of two nevirapine tablet formulations (Nevirapina from Far-Manguinhos, Brazil, as a test formulation, and Viramune from Boehringer Ingelheim do Brasil Química e Farmacêutica, as a reference formulation) in 25 healthy volunteers of both sexes who received a single 200 mg dose of each formulation. The study was conducted using an open, randomized, two-period crossover design with a 3 week washout interval. The 90% confidence interval (CI) of the individual ratio geometric mean for Nevirapina/Viramune was 96.4-104.5% for AUC((0-last)), 91.4-105.1% for AUC((0-infinity)) and 95.3-111.6% for C(max) (AUC = area under the curve; C(max) = peak plasma concentration). Since both 90% CI for AUC((0-last)) and AUC((0-infinity)) and C(max) were included in the 80-125% interval proposed by the US Food and Drug Administration, Nevirapina was considered bioequivalent to Viramune according to both the rate and extent of absorption.     

Constrained optimization with stochastic feasibility regions applied to vehicle path planning

In real-time trajectory planning for unmanned vehicles, on-board sensors, radars and other instruments are used to collect information on possible obstacles to be avoided and pathways to be followed. Since, in practice, observations of the sensors have measurement errors, the stochasticity of the data has to be incorporated into the models. In this paper, we consider using a genetic algorithm for the constrained optimization problem of finding the trajectory with minimum length between two locations, avoiding the obstacles on the way. To incorporate the variability of the sensor readings, we propose a modified genetic algorithm, addressing the stochasticity of the feasible regions. In this way, the probability that a possible solution in the search space, say x, is feasible can be derived from the random observations of obstacles and pathways, creating a real-time data learning algorithm. By building a confidence region from the observed data such that its border intersects with the solution point x, the level of the confidence region defines the probability that x is feasible. We propose using a smooth penalty function based on the Gaussian distribution, facilitating the borders of the feasible regions to be reached by the algorithm.