Gas-phase reactivity of silver and copper coordinated monosaccharide cations studied by electrospray ionization and tandem mass spectrometry

The analytical distinction of the most common isomeric underivatized hexoses was investigated by means of mass spectrometry experiments. Electrospray ionization and tandem mass spectrometry were used in the analysis of silver and copper-coordinated monosaccharides (D-glucose, D-galactose, D-fructose, O-methyl-alpha-D-glucose and O-methyl-beta-D-glucose). The results show that cationization by Ag(+) allows the differentiation of the three first monosaccharides while the complexes formed by association of Cu(+) with these three monosacharides display a similar reactivity that prevents stereoisomer distinction. Unlike copper, silver adduct-ions of both alpha and beta anomeric O-methyl-D-glucoses exhibit specific decomposition patterns (i.e. a loss of methanol for the alpha-anomer and a loss of silver hydride for the beta-anomer), which allow an easy characterization. A theoretical survey of selected complexes, based on the use of DFT calculations were carried out on both anomers in order to rationalize the experimental findings.     

Electrochemical Synthesis of Trifluoromethane Sulfinic Acid Salt From CF3Br and SO2

The electroreduction of a mixture of SO₂ and CF₃Br in DMF, in an undivided cell with a soluble anode (Mg or Zn) lead to salt of trifluoromethane sulfinic acid in high yield.     

Noncommutative symmetric functions with matrix parameters

We define new families of noncommutative symmetric functions and quasi-symmetric functions depending on two matrices of parameters, and more generally on parameters associated with paths in a binary tree. Appropriate specializations of both matrices then give back the two-vector families of Hivert, Lascoux, and Thibon and the noncommutative Macdonald functions of Bergeron and Zabrocki.     

Nonparametric inference under competing risks and selection-biased sampling

The aim of this paper is to carry out statistical inference in a competing risks setup when only selection-biased observation of the data of interest is available. We introduce estimators of the cumulative incidence functions and study their joint large sample behavior.     

Convenient access to C-2 or C-5 substituted 4-azaindole derivatives

Functionalization at C-2 and C-5 of N-benzenesulfonyl-4-azaindole 1 was performed by lithiation reactions and original palladium-catalyzed chemistry. It led to very useful new substituted 4-azaindole derivatives in fair to high yields.     

The new ternary pnictides Er12Ni30P21 and Er13Ni25As19: Crystal structures and magnetic properties

The new ternary pnictides Er₁₂Ni₃₀P₂₁ and Er₁₃Ni₂₅As₁₉ have been synthesized from the elements. They crystallize with hexagonal structures determined from single-crystal X-ray data for Er₁₂Ni₃₀P₂₁ (space group P6₃/m, a=1.63900(3) nm, c=0.37573(1) nm, Z=1, R_F=0.062 for 1574 F-values and 74 variable parameters), and for Er₁₃Ni₂₅As₁₉ (Tm₁₃Ni₂₅As₁₉-type structure, space group P6?, a=1.6208(1) nm, c=0.38847(2) nm, Z=1, R_F=0.026 for 1549 F-values and 116 variable parameters). These compounds belong to a large family of hexagonal structures with a metal-metalloid ratio of 2:1. HRTEM investigations were conducted to probe for local ordering of the disordered structure at the nanoscale. The magnetic properties of the phosphide Er₁₂Ni₃₀P₂₁ have been studied in the temperature of range 2<T<300 K and with applied fields up to 5 T. The magnetic susceptibility follows the Curie-Weiss law from 4 to 300 K. The measured value of μ_eff=9.59 μ_B corresponds to the theoretical value of Er³⁺.     

Amorphous structure and electronic properties of the Ge1Sb2Te4 phase change material

Ge1Sb2Te4 is one of the most commonly used phase change materials, due to the large optical and electrical contrast between a metastable crystalline phase and the amorphous phase. We use ab initio molecular dynamics to generate an amorphous Ge1Sb2Te4 structure. By analysing the distance distributions, we show that the structure can be analysed in terms of 21% of tetrahedrally coordinated Ge atoms and 79% of 3-fold Ge atoms. These are involved in distorted octahedral shells with bond length correlations that are similar to the a-GeTe structure as a consequence of a Peierls-distortion. The electronic properties are shown to be in reasonable agreement with the experiment with an electronic gap of 0.45 eV with. The optical conductivity curve is also in agreement with the experiment, with a maximal conductivity at an energy of ～3 eV.     

In situ chemical fabrication of polyaniline/multi-walled carbon nanotubes composites as supports of Pt for methanol electrooxidation

Science China Chemistry - In this study, platinum (Pt)-polyaniline(PANI)/MWNTs catalysts were synthesized by two sequential reactions. First, core-shell structural PANI/MWNTs composites were...     

Spectroscopic Properties and Laser Induced Fluorescence Determination of Some Endocrine Disrupting Compounds

This work presents spectroscopic properties of some Endocrine Disrupting Compounds (EDCs), frequently found in food and in natural water. Studied molecules belong to the groups of phenolic and phthalate EDCs. In a first part, we have examined their absorption and fluorescence properties. Fluorescence emission wavelengths are about 300 nm for phenolic compounds and 360 nm for phtalate compounds; main excitation wavelengths being comprised between 210 nm and 230 nm. Fluorescence lifetimes measured are short (about 4 ns) and the fluorescence quantum yield has been determined. In a second part, to avoid the time consuming solvent extraction step, an analytical application to evaluate the performance of a direct analysis by laser induced fluorescence spectroscopy of ECDs traces in tap water and in raw water is presented. Good detection limits have been obtained, i.e.: 0.35 μg.L⁻¹ of chlorophenol in tap water, which are always lower than the reported Predictive Non Efficient Concentration (PNEC).