Practical synthetic routes to solvates of U(OTf)3: X-ray crystal structure of [U(OTf)3(MeCN)3]n, a unique U(III) coordination polymer

The reaction of UH3 or U metal with triflic acid results in the formation of a mixture of species including U(OTf)4 and leads to the reproducible isolation of the mononuclear U(IV) hydroxo complex [U(OTf)3(OH)(py)4] (1) and the U(IV) dinuclear mu-oxo-complex [{U(OTf)2(py)3}2{mu-O}{mu-OTf}2] (2). The X-ray crystal structures of these complexes have been determined. Analytically pure complex 1 can be prepared in a 17-27% yield providing a good precursor for the synthesis and study of the reactivity of the hydroxo complexes with different coordination environments. Two practical synthetic methods for the preparation of Lewis base adducts of U(OTf)3 are described. Analytically pure [U(OTf)3(py)4] (4) was easily and reproducibly prepared (50-60% yield) by protonolysis of the amide U{N(SiMe3)2}3 with pyridinium triflate in pyridine. Salt metathesis of UI3(thf)4 with potassium triflate in acetonitrile resulted in the complete substitution of the iodide counterions by triflate producing the acetonitrile solvate [U(OTf)3(MeCN)3]n (3). The solid-state structure of 3 shows the formation of a unique U(III) coordination polymer in which the metal ions are connected by three triflates acting as bidentate bridging ligands to form a 1D chain.     

Identification of phytoestrogens in bovine milk using liquid chromatography/electrospray tandem mass spectrometry

In an international context of promoting scientific research on food safety, the interest in molecules having potential hormonal disrupting effects is growing. While industrial endocrine disruptors (phthalates, alkylphenols, PCBs, etc.) have been studied for several years, natural compounds like phytoestrogens remain less investigated. Accordingly, a research project was initiated with its main objectives to develop efficient analytical methods for a wide range of phytoestrogens in various food matrices, and to evaluate their occurrence in food products. Electrospray ionization with tandem mass spectrometric (MS/MS) analysis of isoflavones (genistein, daidzein, equol, formononetin, biochanin A), lignans (enterolactone, enterodiol), and coumestans (coumestrol) was investigated. This study revealed the formation of a large number of fragment ions in both positive and negative modes, corresponding to specific cleavages of the hydroxyl, carbonyl, and/or methoxy groups, and to Retro-Diels-Alder reactions. An LC/ESI-MS/MS method was developed consistent with the 2002/657/EC European decision criteria. An extraction and clean-up method was developed for milk samples. The identification limit for the proposed method appears to be under 1 ng/mL. The developed methodology was applied to various milk samples, and the occurrence of isoflavones (particularly equol) was demonstrated in the concentration range 1-30 ng/mL. The efficiency of the proposed analytical method permitted evaluation of a new and promising approach to a global risk assessment of natural estrogenic active substances including phytoestrogens and their metabolites.     

Direct measurement of the end-to-end distance of individual polyfluorene polymer chains.

Wide-field imaging of individual multichromophoric molecules and successive photobleaching were used to determine, accurately, the relative position of the chromophores in such systems. First, a polyphenylene dendrimer with well-defined geometry was used to establish the accuracy in localization that can be obtained by this methodology. For a signal-to-noise ratio of 20, interchromophoric distances could be measured with 4 nm accuracy. Next, the method was used to determine the end-to-end distribution of an end-capped polyfluorene polymer. From comparison between the experimental and simulated distributions, information on the conformation of the polymer could be deduced. It was found that the polymer has a nonlinear conformation. A conjugation length of six monomer units gave the best fit of the experimental data to the proposed model.     

Isotope ratio monitoring of small molecules and macromolecules by liquid chromatography coupled to isotope ratio mass spectrometry

In the field of isotope ratio mass spectrometry, the introduction of an interface allowing the connection of liquid chromatography (LC) and isotope ratio mass spectrometry (IRMS) has opened a range of new perspectives. The LC interface is based on a chemical oxidation, producing CO2 from organic molecules. While first results were obtained from the analysis of low molecular weight compounds, the application of compound-specific isotope analysis by irm-LC/MS to other molecules, in particular biomolecules, is presented here. The influence of the LC flow rate on the CO2 signal and on the observed delta13C values is demonstrated. The limits of quantification for angiotensin III and for leucine were 100 and 38 pmol, respectively, with a standard deviation of the delta13C values better than 0.4 per thousand. Also, accuracy and precision of delta13C values for elemental analyser-IRMS and flow injection analysis-IRMS (FIA-LC/MS) were compared. For compounds with molecular weights ranging from 131 to 66,390 Da, precision was better than 0.3 per thousand, and accuracy varied from 0.1 to 0.7 per thousand. In a second part of the work, a two-dimensional (2D)-LC method for the separation of 15 underivatised amino acids is demonstrated; the precision of delta13C values for several amino acids by irm-LC/MS was better than 0.3 per thousand at natural abundance. For labelled mixtures, the coefficient of variation was between 1% at 0.07 atom % excess (APE) for threonine and alanine, and around 10% at 0.03 APE for valine and phenylalanine. The application of irm-LC/MS to the determination of the isotopic enrichment of 13C-threonine in an extract of rat colon mucosa demonstrated a precision of 0.5 per thousand, or 0.001 atom %.     

Cyanine-based near infra-red organic photoredox catalysis

Direct metal-free near infra-red photoredox catalysis is applied to organic oxidation, photosensitization and reduction, involving cyanines as photocatalysts. This photocatalyst is competitive with conventional reactions catalyzed under visible light. Kinetic and quenching experiments are also reported. Interestingly, these systems are compatible with water media, opening perspective for various applications.

Direct metal-free near infra-red photoredox catalysis is applied to oxidation, reduction and photosensitization, involving cyanines as photocatalysts. Mechanistic insights through kinetic and quenching experiments are also reported.     

Preparation of large macrocyclic peptides using the oxime resin

We exploited a peptide cyclization-cleavage reaction on oxime resin (PCOR) to obtain in one key step large macrocyclic peptides. Herein, we report on the different parameters affecting the cyclization-oligomerization reaction, whether to favor cyclic monomer or cyclic oligomers formation.     

Multi-residue liquid chromatography/tandem mass spectrometric analysis of beta-agonists in urine using molecular imprinted polymers

Ion suppression, a matrix effect that affects quantitative mass spectrometry, is one of the main problems encountered in liquid chromatography/tandem mass spectrometry. Two different clean-up steps for the multi-residue analysis of beta-agonists in urine were evaluated with respect to minimisation of ion suppression, namely, a mixed-phase solid phase extraction (SPE) column, i.e., clean screen Dau (CSD), and a molecular imprinted polymer (MIP) SPE column. Ion suppression experiments revealed that CSD sample clean-up can lead to false negative results for some beta-agonists, and that clean-up using MIP columns is more selective for beta-agonists than the use of CSD columns.     

Multi-gas sensing based on photoacoustic spectroscopy using tunable laser diodes

Multi-hydrogenated compounds detection based on photoacoustic (PA) spectroscopy is reported. Three near-infrared semiconductor lasers are used with a resonant PA cell operated in its first longitudinal mode to monitor methane, water vapour and hydrogen chloride in the parts per million range. The design of our cell results from simulations performed in order to optimise its performances. Influence of the buffer gas on the PA signal has also been analysed, both theoretically and experimentally. A reduction of the PA signal of almost one order of magnitude has been observed between N(2) and He, which demonstrates the importance of the buffer gas in PA spectroscopy. Finally, detection limits of 0.5 ppm of CH(4) and 3 ppm of HCl has been achieved experimentally in nitrogen and an H(2)O sensitivity of 0.2 ppm has been estimated.     

Pyrrolothienopyrazines: étude chimique de la pyrrolo[1,2-a]-thiéno[3,2-e]pyrazine

The reactivity of pyrrolol[1,2-a]thienol[3,2-e]pyrazine towards quaternisation, bromination, nitration, sulfonation, Friedel Crafts, Vilsmeier Haack and Reissert's reactions is studied. Assisgnment of structures to the products is based on ir, nmr and mass spectral studies or on unequivocal syntheses.     

Quality specifications for evaluation and comparison of performance among external quality assessment schemes in occupational and environmental laboratory medicine

Quality specifications (QS) are proposed for lead in blood and for aluminium, copper, selenium and zinc in serum as part of the aim to set standards of performance for laboratories so that results can be demonstrated to be fit for the purpose to which they are applied. The QS were established taking account of the analytical state-of-the-art, physiological variations in the concentrations of the analyte and the clinical purpose for which the assay is to be used. A procedure was devised that uses these QS to give equivalence of assessment among external quality assessment schemes (EQAS), thus avoiding conflicting information which has been demonstrated in the past. Advantages of this procedure are: to provide direct comparison of performance of laboratories taking part in different schemes, to provide equivalence of assessment of laboratory performance necessary to establish mutual recognition agreements, and to demonstrate the fitness for purpose of results from participants.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia