Transport of Carbamazepine,Ciprofloxacin and Sulfamethoxazole in Activated Carbon: Solubility and Relationships between Structure and Diffusional Parameters

The transport of carbamazepine, ciprofloxacin and sulfamethoxazole in the different pores of activated carbon in an aqueous solution is a dynamic process that is entirely dependent on the intrinsic parameters of these molecules and of the adsorbent. The macroscopic processes that take place are analyzed by interfacial diffusion and reaction models. Modeling of the experimental kinetic curves obtained following batch treatment of each solute at 2 µg/L in tap water showed (i) that the transport and sorption rates were controlled by external diffusion and intraparticle diffusion and (ii) that the effective diffusion coefficient for each solute, with the surface and pore diffusion coefficients, were linked by a linear relationship. A statistical analysis of the experimental data established correlations between the diffusional parameters and some geometrical parameters of these three molecules. Given the major discontinuities observed in the adsorption kinetics, the modeling of the experimental data required the use of traditional kinetic models, as well as a new kinetic model composed of the pseudo first or second order model and a sigmoidal expression. The predictions of this model were excellent. The solubility of each molecule below 60 °C was formulated by an empirical expression.     

Identification and quantification of diethylene glycol contamination in glycerine raw material

Fourier-transform infrared spectroscopy (FTIR) was successfully used for quantitative determination of diethylene glycol in glycerin raw material. In addition to the pure samples of both diethylene glycol and glycerin, nine binary mixtures of the two components with mixing ratios ranging from (70 to 98)%wt were created and studied as a training set. Glycerine showed, thereby, characteristic infrared bands at 1110, 992, 974, and 922?cm^?1 while those of diethylene glycol appear at 1085, 887, and 881?cm^?1. The quantitative determination of diethylene glycol in binary mixtures with glycerin was achieved upon using the absorbance difference between the 992?cm^?1 and the 881?cm^?1 as well as between 1110 and 1085?cm^?1 bands. With an average %error of 0.60 and 1.74, respectively and a limit of detection down to 0.85%, the created calibration curves from the training set were applied successfully to determine the composition of another eight binary mixtures of the two materials representing a validation set. The method was also applied to aqueous solutions of diethylene glycol and glycerin that contains (25 and 50)%wt water. Once more, training and validation sets of mixtures with different diethylene glycol and glycerin ratios at the two water percentages were prepared and measured. Again, successful determination of diethylene glycol in these aqueous solutions was achieved with an average %error of 0.92 and 0.47, respectively.     

Microwave irradiation and COMU: a potent combination for solid-phase peptide synthesis

Here we demonstrate the compatibility of Oxyma-based uronium-type coupling reagent COMU with microwave-assisted peptide synthesizers. Consistent with previous reports, COMU displayed higher efficiency than benzotriazole classical immonium salts HATU and HBTU in the demanding synthesis of the Aib derivative of Leu-Enkephalin pentapeptide and did not yield Oxyma-based byproducts. Thus, the combination of microwave irradiation and COMU resulted in a similar performance in considerably shorter time to that achieved by manual synthesis.     

Pulsed KrF excimer laser induced degradation of cellulose based insulating paper

We report on the accelerated ageing of cellulose based insulating paper by means of pulsed UV laser irradiation (λ = 248 nm) under various experimental conditions including paper composition, background gas (He, N₂ and air) and moisture content of the paper. The temperature reached by the paper samples during their laser irradiation was monitored by means of real-time IR imaging. It is shown that the equilibrium temperature (T _eq) reached by the paper increases from ~30 to ~270 °C when the laser energy density was raised from 15 to 550 mJ cm⁻². The laser irradiated samples were systematically characterized by means of scanning electron microscopy (SEM) observations and degree of polymerization (DP_v) measurements. Interestingly, it is found that, for a given moisture content, the degradation level of the cellulose is mainly triggered by the T _eq value reached during the laser irradiation. Moreover, their moisture content was found to influence significantly the number of laser produced bond scissions (it doubles when the moisture content is increased from 0.5 to 6%); the paper degradation is apparently not affected by the presence of oxygen as the background gas. These results suggest that the laser induced cellulose degradation occurs through a direct photolysis (i.e. direct breakage of C–C, C–O and C–H bonds), leading to radicals formation, which, in turn, are believed to induce the acid hydrolysis degradation mechanism, the latter being moisture dependent. The activation energy (E _a) of each gaseous species collected after the laser degradation was estimated. Their E _a values were found to be in good agreement with the one associated to the laser depolymerisation of cellulose (i.e. ~56 kJ mol⁻¹), suggesting thereby a direct correlation between the cellulose degradation and the formation of the detected gaseous species. Finally, the pulsed laser irradiation can be seen as an attractive tool to identify primarily generated molecules, on a very short time scale, that can be used as relevant chemical markers for the monitoring of the ageing of transformers materials with cellulose.     

Molecular-dynamics study of photodissociation of water in crystalline and amorphous ices

We present the results of classical dynamics calculations performed to study the photodissociation of water in crystalline and amorphous ice surfaces at a surface temperature of 10 K. A modified form of a recently developed potential model for the photodissociation of a water molecule in ice [S. Andersson et al., Chem. Phys. Lett. 408, 415 (2005)] is used. Dissociation in the top six monolayers is considered. Desorption of H(2)O has a low probability (less than 0.5% yield per absorbed photon) for both types of ice. The final outcome strongly depends on the original position of the photodissociated molecule. For molecules in the first bilayer of crystalline ice and the corresponding layers in amorphous ice, desorption of H atoms dominates. In the second bilayer H atom desorption, trapping of the H and OH fragments in the ice, and recombination of H and OH are of roughly equal importance. Deeper into the ice H atom desorption becomes less important and trapping and recombination dominate. Motion of the photofragments is somewhat more restricted in amorphous ice. The distribution of distances traveled by H atoms in the ice peaks at 6-7 Angstroms with a tail going to about 60 Angstroms for both types of ice. The mobility of OH radicals is low within the ice with most probable distances traveled of 2 and 1 Angstrom for crystalline and amorphous ices, respectively. OH is, however, quite mobile on top of the surface, where it has been found to travel more than 80 Angstroms. Simulated absorption spectra of crystalline ice, amorphous ice, and liquid water are found to be in very good agreement with the experiments. The outcomes of photodissociation in crystalline and amorphous ices are overall similar, but with some intriguing differences in detail. The probability of H atoms desorbing is 40% higher from amorphous than from crystalline ice and the kinetic-energy distribution of the H atoms is on average 30% hotter for amorphous ice. In contrast, the probability of desorption of OH radicals from crystalline ice is much higher than that from amorphous ice.     

A novel spectrophotometric method for batch and flow injection determination of sulfite in beverages

A novel spectrophotometric assay method for batch and flow injection determination of sulfite in beverages is described. The method involves a reaction with diaquacobyrinic acid heptamethyl ester (diaquacobester, DACbs) in acetate buffer of pH 3 to form a highly stable sulfite cobester complex (SO₃Cbs). In the absence of sulfite, the reagent displays three absorption maxima at 349, 409 and 525 nm. Addition of sulfite is associated with the development of a new absorption band at 313 nm, an increase in the intensity of the band at 425 nm and a decrease in the absorbance of the bands at 349 and 525 nm. Variations of the absorptions at 313, 349, 425 and 525 nm are linearly proportional to sulfite concentrations over the range of 0.05–25 μg ml⁻¹with a detection limit of 0.01–0.2 μg ml⁻¹. Negligible interferences are caused by most common ions. Validation of the method according to the quality assurance standards shows suitability for quality control assessment of sulfite in complex matrices without prior treatment. The method has the advantages of high selectivity, good sensitivity, fast reaction, high stability of the reagent and reaction product and absorbance measurements at four different wavelengths in the same run. The method is successfully applied to determine the sulfite contents of some beverages. The results compare fairly well with data obtained using the standard method.     

Absolute nodal coordinate formulation of large-deformation piezoelectric laminated plates

The Absolute Nodal Coordinate Formulation (ANCF) has been initiated in 1996 by Shabana (Computational Continuum Mechanics, 3rd edn., Cambridge: Cambridge University Press, 2008). It introduces large displacements of planar and spatial finite elements relative to the global reference frame without using any local frame. A sub-family of beam, plate and cable finite elements with large deformations are proposed and employed the 3D theory of continuum mechanics. In the ANCF, the nodal coordinates consist of absolute position coordinates and gradients that can be used to define a unique rotation and deformation fields within the element. In contrast to other large deformation formulations, the equations of motion contain constant mass matrices as well as zero centrifugal and Coriolis inertia forces. The only nonlinear term is a vector of elastic forces. This investigation concerns a way to generate new finite element in the ANCF for laminated composite plates. This formulation utilizes the assumption that the bonds between the laminae are thin and shear is non-deformable. Consequently, the Equivalent Single Layer, ESL model, is implemented. In the ESL models, the laminate is assumed to deform as a single layer, assuming a smooth variation of the displacement field across the thickness. In this paper, the coupled electromechanical effect of Piezoelectric Laminated Plate is imposed within the ANCF thin plate element, in such a way as to achieve the continuity of the gradients at the nodal points, and obtain a formulation that automatically satisfies the principle of work and energy. Convergence and accuracy of the finite-element ANCF Piezoelectric Laminated Plate is demonstrated in geometrically nonlinear static and dynamic test problems, as well as in linear analysis of natural frequencies. The computer implementation and several numerical examples are presented in order to demonstrate the use of the formulation developed in this paper. A comparison with the commercial finite element package COMSOL MULTIPHYSICS () is carried out with an excellent agreement.     

The density of superconductivity in domains with corners

We compute the \(L^2\)-norm of any minimizer of the Ginzburg–Landau functional in a planar domain with a finite number of corners. Our computations are valid for a uniform applied magnetic field, large Ginzburg–Landau parameter and in the regime where superconductivity is confined near the corners of the domain.