Thermodynamics of solvent extraction of thorium by solutions of HHTA and mixtures of HHTA and TBP

The changes in free energy, enthalpy and entropy for the extraction of thorium by solutions of thenoyltrifluoroacetone (HTTA) and mixtures of solutions of HTTA and tri-n-butylphosphate (TBP), in three diluents, viz. cyclohexane, benzene and chloroform, were determined using the solvent extraction data obtained at different temperatures. From these data the thermodynamic parameters associated with the formation of Th(TTA)₄ · TBP in the respective organic diluents were evaluated. Trends in the enthalpy changes were attributed to different degrees of association of the diluents with themselves and with the solutes present in them.     

Liquid chromatography tandem mass spectrometry method for the quantification of clonidine with LLOQ of 10 pg/mL in human plasma

A sensitive high-performance liquid chromatography-positive ion electrospray tandem mass spectrometry method was developed and validated for the quantification of clonidine in human plasma. Following liquid-liquid 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 230 to 44 for clonidine and m/z 254 to 44 for the internal standard. The assay exhibited a linear dynamic range of 10-2000 pg/mL for clonidine in human plasma. The lower limit of quantification was 10 pg/mL with a relative standard deviation of less than 6.8%. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. A run time of 2.5 min for each sample made it possible to analyze more than 250 human plasma samples per day. The validated method was successfully used to analyze human plasma samples for application in pharmacokinetic studies. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Total synthesis of the originally proposed and revised structures of palmerolide A and isomers thereof

Palmerolide A is a recently disclosed marine natural product possessing striking biological properties, including potent and selective activity against the melanoma cancer cell line UACC-62. The total syntheses of five palmerolide A stereoisomers, including the originally proposed (1) and the revised [ent-(19-epi-20-epi-1)] structures, have been accomplished. The highly convergent and flexible strategy developed for these syntheses involved the construction of key building blocks 2, 19-epi-2, 20-epi-2, ent-2, 3, ent-3, 4, and ent-4, and their assembly and elaboration to the target compounds. For the union of the building blocks, the Stille coupling reaction, Yamaguchi esterification, Horner-Wadsworth-Emmons olefination, and ring-closing metathesis reaction were employed, the latter being crucial for the stereoselective formation of the macrocycle of the palmerolide structure. The Horner-Wadsworth-Emmons olefination and the Yamaguchi lactonization were also investigated and found successful as a means to construct the palmerolide macrocycle. The syntheses were completed by attachment of the enamide moiety through a copper-catalyzed coupling process.     

Quantification of tenatoprazole in rat plasma by HPLC: validation and its application to pharmacokinetic studies

A simple, reliable HPLC method with UV detection (295 nm) in rat plasma was developed and validated for quantification of tenatoprazole, a novel proton pump inhibitor, which is in clinical trials. Following a single-step liquid-liquid extraction, the analyte and internal standard were separated using an isocratic mobile phase on a reverse phase C(18) column. The lower limit of quantitation was 20 ng/mL, with a relative standard deviation of less than 10%. A linear dynamic range of 20-6000 ng/mL was established. This HPLC method was validated with between-batch and within-batch precision of 2.9-6.3 and 1.4-5.8%, respectively. The between-batch and within-batch accuracy was 95.1-104.1 and 92.4-101.0%, respectively. This validated method is simple and repeatable enough to be used in pharmacokinetic studies.     

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.