Quantification of fexofenadine in human plasma by liquid chromatography coupled to electrospray tandem mass spectrometry using mosapride as internal standard

A rapid high-performance liquid chromatography/positive ion electrospray tandem mass spectrometry method was developed and validated for the quantification of fexofenadine in human plasma using mosapride as internal standard. Following solid-phase extraction, the analytes were separated using an isocratic mobile phase on a reverse-phase column and analyzed by MS/MS in the multiple reaction monitoring mode using the respective [M+H]+ ions, m/z 502/466 for fexofenadine and m/z 422/198 for the IS. The method exhibited a linear dynamic range of 1-500 ng/mL for fexofenadine in human plasma. The lower limit of quantification was 1 ng/mL with a relative standard deviation of less than 5% for fexofenadine. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. The total chromatographic run time of 2 min for each sample made it possible to analyze more than 400 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies.     

Excess enthalpies for mixtures of cyclohexanone with isomeric propanols and butanols at 298.15 K

Excess enthalpies (H ^E ) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K have been measured over the entire composition range. All mixed endothermically with the maximum values ofH ^E occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic ketone + an alcohol are made on the basis of these results.     

PHOTOREDUCTION OF SOME NITROBIPHENYL ETHER HERBICIDES TO NITRO RADICAL ANIONS BY β-CAROTENE AND RELATED COMPOUNDS

Abstract —The nitrobiphenyl ether herbicides; 4-nitrobiphenyl ether, bifenox, nitrofen, acifluorfen, acifluorfen-methyl, acifluorfen-ethyl, and oxyfluorfen were reduced to their corresponding nitro radical anions by visible light in the presence of β-carotene, lycopene, retinol, retinal, retinoic acid and retinyl acetate in anaerobic solutions at high pH. It was more difficult to obtain spectra of bifenox, nitrofen and oxyfluorfen than acifluorfen derivatives, probably due to their poor solubilities. In neutral solutions the steady-state concentration of the nitro radical anions was low due to their faster rate of dispropor-tionation and the poor solubility of β-carotene. In the presence of retinal, the nitro radical anion of acifluorfen was produced at pH 7.4. Compounds containing conjugated double bonds such as crotonaldehyde and 2.4-hexadienal also reduced acifluorfen and its derivatives to their respective nitro radical anions in the presence of light. Ubiquinone-50 which does not contain conjugated double bonds in the side chain did not reduce acifluorfen under similar conditions.     

Laser-driven proton acceleration and applications: Recent results

The acceleration of high-energy ion beams following the interaction of short (t < 1 ps) and intense (Iλ² > 10¹⁸ W cm^-2 μm²) laser pulses with solid targets is a field of research currently attracting high interest in the scientific community, due to some of the unique properties of these ion sources, promising routes toward the optimization of their energy content, and a number of possible, innovative applications in the scientific, technological and medical areas. Work on the characterization and development of these sources has progressed enormously over the past few years, thanks to the contribution of many groups worldwide. This paper will report some recent results, obtained in experiments carried out at the RAL and LULI laboratories, in which we investigated the ion acceleration mechanism, developed a technique to control the ion beam divergence and energy spectrum, and applied a proton radiography technique to investigate electric and magnetic field production following laser-matter interaction.     

Simultaneous quantification of atorvastatin and active metabolites in human plasma by liquid chromatography-tandem mass spectrometry using rosuvastatin as internal standard

A simple, sensitive, selective and rapid liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the quantification of atorvastatin and its active metabolites ortho-hydroxyatorvastatin and para-hydroxyatorvastatin in human plasma using rosuvastatin as internal standard (IS). Following simple liquid-liquid extraction, the analytes were separated using an isocratic mobile phase on a reversed-phase C18 column and analyzed by MS in the multiple reaction monitoring mode using the respective [M+H]+ ions, m/z 559/440 for atorvastatin, m/z 575/466 for ortho-hydroxyatorvastatin, m/z 575/440 for para-hydroxyatorvastatin and m/z 482/258 for the IS. The assay exhibited a linear dynamic range of 0.1-20 ng/mL for atorvastatin and its two metabolites in human plasma. The lower limit of quantification was 100 pg/mL with a relative standard deviation of less than 8%. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. The average absolute recoveries of atorvastatin, ortho-hydroxyatorvastatin, para-hydroxyatorvastatin and the IS from spiked plasma samples were 54.2 +/- 3.2, 50.1 +/- 3.8, 65.2 +/- 3.6 and 71.7 +/- 2.7%, respectively. A run time of 2.5 min for each sample made it possible to analyze more than 300 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies.     

Boiling induced nanoparticle coating and its effect on pool boiling heat transfer on a vertical cylindrical surface using CuO nanofluids

Experiments were performed to study boiling induced nanoparticle coating and its influence on pool boiling heat transfer using low concentrations of CuO- nanofluid in distilled water at atmospheric pressure. To investigate the effect of the nanoparticle coated surface on pool boiling performance, two different concentrations of CuO nanofluids (0.1 and 0.5?g/l) were chosen and tests were conducted on a clean heater surface in nanofluid and nanoparticle coated surface in pure water. For the bare heater tested in CuO nanofluid, CHF was enhanced by 35.83 and 41.68?% respectively at 0.1 and 0.5?g/l concentration of nanofluid. For the nanoparticle coated heater surface obtained by boiling induced coating using 0.1 and 0.5?g/l concentration of nanofluid and tested in pure water, CHF was enhanced by 29.38 and 37.53?% respectively. Based on the experimental investigations it can be concluded that nanoparticle coating can also be a potential substitute for enhancing the heat transfer in pure water. Transient behaviour of nanofluid was studied by keeping heat flux constant at 1,000 and 1,500?kW/m² for 90?min in 0.5?g/l concentration. The boiling curve shifted to the right indicating degradation in boiling heat transfer due to prolonged exposure of heater surface to nanofluid. Experimental outcome indicated that pool boiling performance of nanofluid could be a strong function of time and applied heat flux. The longer the duration of exposure of the heater surface, the higher will be the degradation in heat transfer.     

Synthesis of 5-fluoro- and 5-hydroxymethanoprolines via lithiation of N-BOC-methanopyrrolidines. Constrained Cγ-exo and Cγ-endo Flp and Hyp conformer mimics

Proline derivatives with a C(γ)-exo pucker typically display a high amide bond trans/cis (K(T/C)) ratio. This pucker enhances n→π* overlap of the amide oxygen and ester carbonyl carbon, which favors a trans amide bond. If there were no difference in n→π* interaction between the ring puckers, then the correlation between ring pucker and K(T/C) might be broken. To explore this possibility, proline conformations were constrained using a methylene bridge. We synthesized discrete gauche and anti 5-fluoro- and 5-hydroxy-N-acetylmethanoproline methyl esters from 3-syn and 3-anti fluoro- and hydroxymethanopyrrolidines using directed α-metalation to introduce the α-ester group. NBO calculations reveal minimal n→π* orbital interactions, so contributions from other forces might be of greater importance in determining K(T/C) for the methanoprolines. Consistent with this hypothesis, greater trans amide preferences were found in CDCl(3) for anti isomers en-MetFlp and en-MetHyp (72-78% trans) than for the syn stereoisomers ex-MetFlp and ex-MetHyp (54-67% trans). These, and other, K(T/C) results that we report here indicate how substituents on proline analogues can affect amide preferences by pathways other than ring puckering and n→π* overlap and suggest that caution should be exercised in assigning enhanced pyrrolidine C(γ)-exo ring puckering based solely on enhanced trans amide preference.     

A ligand-free and base-free copper catalyzed reaction: arylation of ammonia and primary amines as their acetate salts

A ligand-free, base-free copper catalyzed arylation of ammonia and primary amines as their corresponding acetate salts are established. The Carboxylate group is believed to be catalyzing the arylation of ammonia. This reaction is specific for primary amines.     

Exchange interactions in some low-dimensional metal dithiolene complexes

Low-dimensional systems are formed by planar metal dithiolene complexes which stack as columnar structures in the solid state. Stronger interactions among units within a chain leads to highly anisotropic magnetic properties. The magnetic effects are a manifestation of exchange interaction,J and can be studied through detailedepr techniques in conjunction with magnetic susceptibility and x-ray crystal structure. A brief review of such studies carried out mostly in our laboratory is presented along with the relevant background materials.     

Symmetry breaking in quantum chaotic systems

We show, using semiclassical methods, that as a symmetry is broken, the transition between universality classes for the spectral correlations of quantum chaotic systems is governed by the same parametrization as in the theory of random matrices. The theory is quantitatively verified for the kicked rotor quantum map. We also provide an explicit substantiation of the random matrix hypothesis, namely that in the symmetry-adapted basis the symmetry-violating operator is random.