Efficiency of wollastonite and ammonium polyphosphate combinations on flame retardancy of polystyrene

The thermal and fire properties of polystyrene (PS) flame retarded by a system composed of ammonium polyphosphate (APP) and wollastonite (W) were investigated by thermogravimetric analysis, pyrolysis‐combustion flow calorimeter, pyrolysis gas chromatography mass spectrometry, cone calorimetry and epiradiator. The combustion residues were observed by scanning electron microscopy/energy dispersive X‐ray spectroscopy and analyzed by X‐ray diffraction. The combination of both additives enables increasing the thermal stability of PS while increasing simultaneously the high temperature residue. The peak of HRR was also significantly reduced while time to ignition varied depending on the composition. It was shown that the degradation pathway of PS was affected by the presence of the additives implying a reduction of the effective heat of combustion. In the condensed phase, APP decomposition promotes char formation and favors the reactivity between phosphorus and silicate. A layer composed of char, W and a mixture of calcium and silicon phosphate is formed at the sample surface during combustion. This layer is cohesive enough to limit the release of combustible gases to the gas phase. Moreover, the thermally stable protective layer reaches high temperature enabling the re‐irradiation of a part of the incident heat flux. The flame retardancy of PS is thus enhanced. Copyright © 2012 John Wiley & Sons, Ltd.     

Vacuum Ultraviolet Action Spectroscopy of Polysaccharides

We studied the optical properties of gas-phase polysaccharides (maltose, maltotetraose, and maltohexaose) ions by action spectroscopy using the coupling between a quadrupole ion trap and a vacuum ultraviolet (VUV) beamline at the SOLEIL synchrotron radiation facility (France) in the 7 to 18 eV range. The spectra provide unique benchmarks for evaluation of theoretical data on electronic transitions of model carbohydrates in the VUV range. The effects of the nature of the charge held by polysaccharide ions on the relaxation processes were also explored. Finally the effect of isomerization of polysaccharides (with melezitose and raffinose) on their photofragmentation with VUV photons is presented.

The Charging of Micellar Nanoparticles in Electrospray Ionization

Charging of nanoparticles through electrospray has scarcely been explored. Spherical nanometer‐sized amphiphilic block copolymer nanoparticles with diameters ranging from ～65 to ～150 nm were electrosprayed and analysed by charge detection spectrometry. Herein, we explore the charging of these micellar nano‐objects by conducting a thorough study in different solvents, including pure water, and upon the addition of “supercharging” agents. The charge (z) of micellar nanoparticles electrosprayed from water solution is compared to the Rayleigh’s limiting charge (z_R) of a charged water droplet of the same dimensions. An average ratio (z/z_R) of 0.6–0.65 is observed for the micellar macro‐ions, supporting the charge residue mechanism, where the number of charges available to the micellar macro‐ion is limited by the number of charges on the nanodroplet, which is a function of the surface tension of the solvent. Also we show the possibility of increasing the charging of micellar nanoparticles in the negative mode by adding organic bases (in particular piperidine) to water/methanol solutions.     

Effects of partial anion substitution on the thermoelectric properties of silver(I) chalcogenide halides in the system Ag5Q2X with Q=Te, Se and S and X=Br and Cl

A selection of mixed conducting silver chalcogenide halides of the general formula Ag₅Q₂X with Q=sulfur, selenium and tellurium and X=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag₅Te₂Cl showed a defined d¹⁰-d¹⁰ interaction in the disordered cation substructure at elevated temperatures where Ag₅Te₂Cl is present in its high temperature α-phase. A significant drop of the thermal diffusivity has been observed during the β−α phase transition reducing the values from 0.12 close to 0.08 mm² s⁻¹. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values.Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag₅Q₂X were determined around the silver-order/disorder β−α phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the β−α phase transition. Thermal conductivities are low reaching values around 0.2-0.3 W m⁻¹ K⁻¹ at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag₅Q₂X phases.     

Photo-SRM: laser-induced dissociation improves detection selectivity of Selected Reaction Monitoring mode

Selected Reaction Monitoring (SRM) carried out on triple‐quadrupole mass spectrometers coupled to liquid chromatography has been a reference method to develop quantitative analysis of small molecules in biological or environmental matrices for years and is currently emerging as a promising tool in clinical proteomic. However, sensitive assays in complex matrices are often hampered by the presence of co‐eluted compounds that share redundant transitions with the target species. On‐the‐fly better selection of the precursor ion by high‐field asymmetric waveform ion mobility spectrometry (FAIMS) or increased quadrupole resolution is one way to escape from interferences. In the present work we document the potential interest of substituting classical gas‐collision activation mode by laser‐induced dissociation in the visible wavelength range to improve the specificity of the fragmentation step. Optimization of the laser beam pathway across the different quadrupoles to ensure high photo‐dissociation yield in Q2 without detectable fragmentation in Q1 was assessed with sucrose tagged with a push‐pull chromophore. Next, the proof of concept that photo‐SRM ensures more specific detection than does conventional collision‐induced dissociation (CID)‐based SRM was carried out with oxytocin peptide. Oxytocin was derivatized by the thiol‐reactive QSY® 7 C₅‐maleimide quencher on cysteine residues to shift its absorption property into the visible range. Photo‐SRM chromatograms of tagged oxytocin spiked in whole human plasma digest showed better detection specificity and sensitivity than CID, that resulted in extended calibration curve linearity. We anticipate that photo‐SRM might significantly improve the limit of quantification of classical SRM‐based assays targeting cysteine‐containing peptides. Copyright © 2011 John Wiley & Sons, Ltd.     

Phosphorus Modified Cardanol: A Greener Route to Reduce VolaTile Organic Compounds and Impart Flame Retardant Properties to Alkyd Resin Coatings

Novel phosphorylated cardanol molecules based on phosphonate (PO₃CR) and phosphate (PO₄CR) functions were synthetized. Those molecules have two main actions which are described in this article: the reduction in volatile organic compounds (VOC) and the development of flame retardant (FR) properties conferred on alkyd resins used as coatings for wood specimen. Phosphorylated cardanol compounds have been successfully grafted by covalent bonds to alkyd resins thanks to an auto-oxidative reaction. The impact of the introduction of PO₃CR and PO₄CR on the film properties such as drying time and flexibility has been studied and the thermal and flame retardant properties through differential scanning calorimeter, thermogravimetric analysis and pyrolysis-combustion flow calorimeter. These studies underscored an increase in the thermal stability and FR properties of the alkyd resins. In the cone calorimeter test, the lowest pHRR was obtained with 3 wt% P of phosphate-cardanol and exhibited a value of 170 KW.m⁻², which represented a decrease of almost 46% compared to the PO_xCR-free alkyd resins. Moreover, a difference in the mode of action between phosphonate and phosphate compounds has been highlighted. The most effective coating which combined excellent FR properties and good coating properties has been obtained with 2 wt% P of phosphate-cardanol. Indeed, the film properties were closed to the PO_xCR-free alkyd resin and the pHRR decreased by 41% compared to the reference alkyd resin.     

Circularly Polarized Luminescence from Cyclic (Alkyl)(Amino) Carbene Derived Propellers

Organic circularly polarized luminescence (CPL)-active molecular emitters featuring dynamic propeller-like luminophores were prepared in one step from cyclic(alkyl)(amino) carbenes (CAACs). These molecules exhibit through-space arene-arene π-delocalization and rapid intramolecular inter-system crossing (ISC) in line with their helical character.