Matrix-implanted laser desorption/ionization mass spectrometry

The implantation of low-velocity massive gold clusters is shown to be a method of choice for homogeneous incorporation of a metallic matrix into the near-surface region of a solid biopolymer for subsequent laser desorption/ionization (LDI) MS analysis. Matrix implanted (MI)LDI spectra from cluster-implanted pure test peptide or tissue exhibit molecular ion peaks similar to those observed by matrix-assisted LDI. Moreover, the ion emission is very reproducible from any spot on the surface of these test samples. MILDI promises to be a powerful technique for mass spectrometric analysis of native biological samples as demonstrated by the first results on rat brain tissues.     

The Dicalcium Phosphate Dihydrate Fixator and Stabilizer of Glutaraldehyde

The dicalcium phosphate dihydrate （A） reacts with glutaraldehyde （B） in aqueous solution with a yield of 95%. The resulting product （C） is chemically stable. The obtained purity is checked by UV-Visible and the structure is discussed on the basis of the Infrared absorption FTIR. The reaction mechanism is explained by the approach of the hydroxyl group （-OH） of one of the aldehyde functions （-CO） of 1.5 dipentanal with the enolic form, which stabilizes the product （C）. The reversible reaction is performed by mild oxidation of the compound （C） in aqueous medium at ambient temperature. The compound （A） is generated with high efficiency. The comparative spectral and thermography study confirms this result.     

In situ semi-quantitative analysis of polluted soils by laser-induced breakdown spectroscopy (LIBS)

Time-saving, low-cost analyses of soil contamination are required to ensure fast and efficient pollution removal and remedial operations. In this work, laser-induced breakdown spectroscopy (LIBS) has been successfully applied to in situ analyses of polluted soils, providing direct semi-quantitative information about the extent of pollution. A field campaign has been carried out in Brittany (France) on a site presenting high levels of heavy metal concentrations. Results on iron as a major component as well as on lead and copper as minor components are reported. Soil samples were dried and prepared as pressed pellets to minimize the effects of moisture and density on the results. LIBS analyses were performed with a Nd:YAG laser operating at 1064 nm, 60 mJ per 10 ns pulse, at a repetition rate of 10 Hz with a diameter of 500 μm on the sample surface. Good correlations were obtained between the LIBS signals and the values of concentrations deduced from inductively coupled plasma atomic emission spectroscopy (ICP-AES). This result proves that LIBS is an efficient method for optimizing sampling operations. Indeed, "LIBS maps" were established directly on-site, providing valuable assistance in optimizing the selection of the most relevant samples for future expensive and time-consuming laboratory analysis and avoiding useless analyses of very similar samples. Finally, it is emphasized that in situ LIBS is not described here as an alternative quantitative analytical method to the usual laboratory measurements but simply as an efficient time-saving tool to optimize sampling operations and to drastically reduce the number of soil samples to be analyzed, thus reducing costs. The detection limits of 200 ppm for lead and 80 ppm for copper reported here are compatible with the thresholds of toxicity; thus, this in situ LIBS campaign was fully validated for these two elements. Consequently, further experiments are planned to extend this study to other chemical elements and other matrices of soils.     

A reduced basis method for parametrized variational inequalities applied to contact mechanics

We investigate new developments of the reduced-basis method for parametrized optimization problems with nonlinear constraints. We propose a reduced-basis scheme in a saddle-point form combined with the Empirical Interpolation Method to deal with the nonlinear constraint. In this setting, a primal reduced-basis is needed for the primal solution and a dual one is needed for the Lagrange multipliers. We suggest to construct the latter using a cone-projected greedy algorithm that conserves the non-negativity of the dual basis vectors. The reduction strategy is applied to elastic frictionless contact problems including the possibility of using nonmatching meshes. The numerical examples confirm the efficiency of the reduction strategy.     

Effect of model ligands on iron redox speciation in natural waters using flow injection with luminol chemiluminescence detection

The effects of dissolved organic compounds on the determination of nanomolar concentrations of Fe(II) have been compared using two luminol-based flow injection chemiluminescence (FI-CL) methods. One used the direct injection of sample into the luminol reagent stream, and the other incorporated on-line solid-phase extraction of the analyte on an 8-hydroxyquinoline microcolumn. The CL signals from analyses of dissolved iron species (Fe(II) and Fe(III)) with model ligands and organic compounds were examined in high-purity water and seawater. The organic compounds included natural reducing agents (e.g., ascorbic acid), nitrogen sigma-donor/pi-acceptor compounds (e.g., 1,4-dipyridine, protoporphyrin IX), aromatic compounds (e.g., 1,4-dihydroxybenzene), synthetic iron chelators (e.g., EDTA), and natural iron binding compounds (e.g., desferrioxamine B, ferrichrome A). Fe(II) determinations for both luminol FI-CL methods were affected by submicromolar concentrations of redox-active compounds, strong iron binding ligands (i.e., log K(FeL) > 6), and compounds with electron-donating functional groups in both high-purity water and seawater. This was due to reactions between organic molecules and iron species before and during analysis, rather than chemiluminescence caused by the individual organic compounds. In addition, the effects of strong ligands and size speciation on Fe(II) recoveries from seawater following acidification (pH 2) and reduction (100 microM sodium sulfite) were investigated.