Rapid high-performance liquid chromatographic determination with fluorescence detection of furosemide in human body fluids and its confirmation by gas chromatography-mass spectrometry

Furosemide (FD: Lasix) is a loop diuretic which strongly increases both urine flow and electrolyte urinary excretion. Healthy volunteers were administered 40 mg orally (dissolved in water) and concentrations of FD were determined in serum and urine for up to 6 h for eight subjects, who absorbed water at a rate of 400 ml/h. Quantification was performed by HPLC with fluorescence detection (excitation at 233 nm, emission at 389 nm) with a limit of detection of 5 ng/ml for a 300-microliters sample. The elution of FD was completed within 4 min using a gradient of acetonitrile concentration rising from 30 to 50% in 0.08 M phosphoric acid. The delay to the peak serum concentration ranged from 60 to 120 min. FD was still easily measurable in the sera from all subjects 6 h after administration. In urine, the excretion rates reached their maximum between 1 and 3 h. The total amount of FD excreted in the urine averaged 11.2 mg (range 7.6-14.0 mg), with a mean urine volume of 3024 ml (range 2620-3596 ml). Moreover, the urine density was lower than 1.010 (recommended as an upper limit in doping analysis to screen diuretics) only for 2 h. An additional volunteer was administered 40 mg of FD and his urine was collected over a longer period. FD was still detectable 48 h after intake. Gas chromatography-mass spectrometry with different types of ionization was used to confirm the occurrence of FD after permethylation of the extract. Negative-ion chemical ionization, with ammonia as reactant gas, was found to be the most sensitive method of detection.     

Impact of dissolution on the uncertainty of spent fuel analysis

One of the objectives of the French Alternative Energies and Atomic Energy Commission in the Marcoule Centre is to accurately quantify the composition of nuclear spent fuel, i.e. to determine the concentration of each isotope with suitable measurement uncertainty. These analysis results are essential for the validation of calculation codes used for the simulation of fuel behaviour in nuclear reactors and for nuclear matter accountancy. The different experimental steps are first the reception of a piece of spent fuel rod at the laboratory of dissolution studies, and then dissolution in a hot cell of a sample of the spent fuel rod received. Several steps are necessary to obtain a complete dissolution. Taking into account these process steps, and not only those of analysis for the evaluation of measurement uncertainties, is new, and is described in this paper. The uncertainty estimation incorporating the process has been developed following the approach proposed by the Guide to the Expression of Uncertainty in Measurement (GUM). The mathematical model of measurement was established by examining the dissolution process step by step. The law of propagation of uncertainty was applied to this model. A point by point examination of each step of the process permitted the identification of all sources of uncertainties considered in this propagation for each input variable. The measurement process presented involves the process and the analysis. The contents of this document show the importance of taking the process into account in order to give a more reliable uncertainty assessment to the result of a concentration or isotope ratio of two isotopes in spent fuel.     

Formation of a Single-Crystal Aluminum-Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure-Directing Agents

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al³⁺ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.     

Photochemische Umwandlungen. XXXVIII [1]. Synthese und Eigenschaften Methoxycarbonyl-substituierter «Quadricyclanone»

The three methoxycarbonyl-substituted quadricyclanones 7a , 7b and 7c have been synthesized in good to excellent yields. Some of their physical (UV., NMR.) and chemical properties (e.g. condensation and pyrolysis reactions) are discussed.     

Space-filling bearings in three dimensions

We present the first space-filling bearing in three dimensions. It is shown that a packing which contains only loops of an even number of spheres can be constructed in a self-similar way and that it can act as a three-dimensional bearing in which spheres can rotate without slip and with negligible torsion friction.     

The Laguerre polyhedral decomposition: application to protein folds

An extension of the Voronoi tessellation, the Laguerre polyhedral decomposition, is introduced and applied to the analysis of the packing geometry of amino-acids in folded proteins. This method considers an ensemble of points with different weights and therefore it is well suited for a geometrical analysis of a set of objects with a wide size distribution. With this method it is shown that the true volumes occupied by the amino-acids inside a protein is better described than with the standard Voronoi procedure. This method allows defining unambiguously (without cut-off distance) the neighborhood for each amino-acid in a given protein and contact matrices can be established which contain all topological informations on the internal structure. Finally, a statistical analysis of the geometrical characteristics of the polyhedra attached to each amino-acid is done over a collection of 35 proteins. Received 20 November 2002 / Received in final form 26 March 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: sadoc@lps.u-psud.fr     

Entanglements in glass

Ground state and elementary excitations (tunnelling modes) in glass are obtained from an analysis of its symmetry, a local gauge invariance. The configuration of glass is represented as a discrete fiber bundle. The base space is a continuous random network, standard model of the structure of covalent glasses. The connection is determined naturally by the elasticity of the network. The bundle is non-trivial, the elastic connection is entangled in one of two ways. Sources of non-triviality are closed loops, threading through odd rings in the network. To restore gauge invariance, tunnelling must occur between the two possible configurations about an odd loop. Entanglement and elementary excitations are labelled by permutations of the covalent bonds incident on an atom.Work supported by the Herbette Foundation.     

Photochemische Umwandlungen,XXXVII [1]. Synthese von Methylen-tetracyclo[3.2.0.02,7.04,6]heptan-Derivaten

Several isopropylidene-, benzylidene- and benzhydrylidene-norbornadiene derivatives ( 11 , 16 ) have been synthesized. The [2π+2π] cycloadditions leading to the tetracyclic isomers 12 and 17 resp. upon direct photoexcitation proceed practically quantitatively in the case of the trienes 11 , much less specifically, however, with 16 . Sensitization by acetone or fluorenone allows the isolation of the quadricyclanes 17 in 20–90% yields.