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.     

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.     

Asymptotic analysis of differential-delay equations and nonuniqueness of periodic solutions

We study the differential-delay equation x′(t) = ?αf(x(t–1)), where α is a positive parameter and f is an odd function which decays like x^?r at infinity. In particular, we consider the case r ? 2, and prove the existence of periodic solutions with special symmetries which are different from previously known periodic solutions of minimal period 4. For r = 2 we prove sharp asymptotic estimates for the minimal periods of these solutions. Our results disprove a conjecture of R. D. Nussbaum.     

Development and validation of a sensitive UHPLC‐MS/MS method for the simultaneous analysis of tramadol,dextromethorphan chlorpheniramine and their major metabolites in human plasma in forensic context: application to pharmacokinetics

The prerequisites for forensic confirmatory analysis by LC/MS/MS with respect to European Union guidelines are chromatographic separation, a minimum number of two MS/MS transitions to obtain the required identification points and predefined thresholds for the variability of the relative intensities of the MS/MS transitions (MRM transitions) in samples and reference standards. In the present study, a fast, sensitive and robust method to quantify tramadol, chlorpheniramine, dextromethorphan and their major metabolites, O‐desmethyltramadol, dsmethyl‐chlorpheniramine and dextrophan, respectively, in human plasma using ibuprofen as internal standard (IS) is described. The analytes and the IS were extracted from plasma by a liquid–liquid extraction method using ethyl acetate–diethyl‐ether (1:1). Extracted samples were analyzed by ultra‐high‐performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (UHPLC‐ESI‐MS/MS). Chromatographic separation was performed by pumping the mobile phase containing acetonitrile, water and formic acid (89.2:11.7:0.1) for 2.0 min at a flow rate of 0.25 μL/min into a Hypersil‐Gold C₁₈ column, 20 × 2.0 mm (1.9 µm) from Thermoscientific, New York, USA. The calibration curve was linear for the six analytes. The intraday precision (RSD) and accuracy (RE) of the method were 3–9.8 and ?1.7–4.5%, respectively. The analytical procedure herein described was used to assess the pharmacokinetics of the analytes in 24 healthy volunteers after a single oral dose containing 50 mg of tramadol hydrochloride, 3 mg chlorpheniramine maleate and 15 mg of dextromethorphan hydrobromide. Copyright © 2014 John Wiley & Sons, Ltd.