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International audience; Liquid chromatography is one of the most powerful separation techniques as illustrated by its leading role in analytical sciences through both academic and industrial communities. Its implementation in microsystems appears to be crucial in the development of µTAS. If electrophoretic techniques have been widely used in miniaturized devices, liquid chromatography has faced multiple challenges in the downsizing process. During the past five years significant breakthroughs have been achieved in this research area, in both conception and use of liquid chromatography on chip. This review emphasizes on the development of novel stationary phases and their implementation in microchannels. Recent instrumental advances are also presented, highlighting the various driving forces (pressure, electrical field) that have been selected and their respective ranges of applications.

International audience; In this paper, we develop a new strategy for designing organic molecules exhibiting at the same time a strong two-photon absorption and a good transparency in the visible region: the oligomeric strategy. At the present time, these two properties are hardly simultaneously fulfilled only by a few existing organic molecules. This approach does not involve any charge transfer and then contrasts with the donor−acceptor strategy. The one- and two-photon absorption properties of 9,9-dihexylfluorene oligomers are first presented and then analyzed thanks to a simple three-level excitonic coupling model. This model, which succeeds in reproducing the experimental data, is then used as a prospective tool, and a set of simple rules is extracted for improving the optical properties of this family of molecules.

This study describes the influence of different parameters on the production of original monodisperse and stable poly(hydroxy)urethane (PHU) nanoparticles with a size inferior to 100 nm by nanoprecipitation. DMSO and SDS were used as polymer solvent and surfactant respectively. Nanosuspensions were characterized by dynamic light scattering (DLS) and cryo-transmission electronic microscopy (cryo-TEM). A 23 full-factorial design was employed to study the main effects and interaction effects of three independent variables − polymer concentration in the organic phase (X1), water volume (X2) and surfactant concentration in the aqueous phase (X3) − on two responses – particle size (Y1) and size distribution (Y2). The results allowed to determine the experimental conditions favouring the smallest diameter or the narrowest size distribution. The critical micellar concentration value of SDS in various water-solvent mixtures helped to highlight the role of the surfactant in the PHU nanosuspension characteristics and stability. The results showed that the use of surfactant was mandatory for nanosuspension stabilization, but the presence of numerous surfactant micelles induced nanoparticle aggregation. Finally, the ageing study evidenced that nanosuspensions with the lowest size distribution were the most stable over time.

International audience

International audience; Biomimetic vesicles, mainly composed of self-assembled bilayers of phospholipids, have attracted great attention for applications in the biosensor field over a number of decades, as a means to amplify the signal through encapsulated signal probes. In this review paper the most important developments in biomimetic vesicles for electrochemical biosensing within the last 2 years are presented, with a focus on the format of bioassays, their inclusion in microfluidic chip devices and their use in mimicking cell membranes. Key issues and the remaining challenges for future commercialization are analyzed.

International audience; Polydiacetylene (PDA) inserted in films or in vesicles has received increasing attention due to its property to undergo a blue-to-red colorimetric transition along with a change from non-fluorescent to fluorescent upon application of various stimuli. In this review paper, the principle for the detection of various microorganisms (bacteria, directly detected or detected through the emitted toxins or through their DNA, and viruses) and of antibacterial and antiviral peptides based on these responsive PDA vesicles are detailed. The analytical performances obtained, when vesicles are in suspension or immobilized, are given and compared to those of the responsive vesicles mainly based on the vesicle encapsulation method. Many future challenges are then discussed

International audience

Investigations reported in this manuscript are focused on the development of an original approach for the detection of several toxic compounds, mainly aflatoxins and organophosphorus pesticides, using acetylcholinesterase (AChE)-based inhibitory electrochemical biosensors. In a first step, a new potentiometric biosensor using pH Sensitive Field-Effect Transistors (pH-FETs) as transducers was investigated for aflatoxin B1 (AFB1) determination and different elaboration and working parameters were optimized. The proposed biosensor was characterized by high operational stability and reproducibility of the signal during the work as well as during the storage. The biosensor was further evaluated for real samples analysis (wheat, sesame, walnuts and peas) and a mathematical simulation of the potentiometric biosensor response to aflatoxin B1 was proposed for the first time and validated. In a second step, a conductometric biosensor using interdigitated gold microelectrodes was developed. The sensitivity of the biosensor to aflatoxins and other classes of toxic substances, such as organophosphorus pesticides, heavy metals ions, glycoalkaloids, and surfactants, was determined. A new and original procedure, enabling the selective determination of multiclass toxins by applying successive reactivation solutions targeting either irreversible or reversible inhibitors, was finally proposed. Using this method, the electrochemical enzyme inhibitory biosensors could be applied to the analysis of aflatoxins and organophosphorus pesticides, as well as for the determination of total toxicity of the samples, Les travaux présentés dans ce manuscrit concernent le développement d‘une approche originale permettant la détermination de plusieurs composés (principalement aflatoxines et pesticides organophosphorés), à l‘aide de biocapteurs électrochimiques basés sur l‘inhibition de l‘acétylcholinestérase. Dans un premier temps, un nouveau biocapteur potentiométrique utilisant des transistors à effet de champ sensibles au pH (pH-FETs) comme transducteurs a été développé pour la détermination de l‘aflatoxine B1 (AFB1) et différent paramètres d‘élaboration et de fonctionnement du biocapteur ont été optimisés. Le biocapteur proposé est caractérisé par une stabilité opérationnelle élevée and bonne reproductibilité du signal en cours d‘utilisation et de stockage. Le biocapteur a ensuite été évalué pour l‘analyse d‘échantillons réels (blé, sésame, noix et pois) et une simulation mathématique de la réponse du biocapteur potentiométrique à l‘AFB1 a été proposée pour la première fois et validée. Dans un deuxième temps, un biocapteur conductimétrique utilisant des microélectrodes interdigitées en or a été développé. La sensibilité de ce biocapteur aux aflatoxines ainsi qu‘à d‘autres classes de substances toxiques, tels que les pesticides organophosphorés, les métaux lourds, les glycoalkaloïdes, et les surfactants, a été déterminée. Une nouvelle procédure originale, permettant la détermination sélective de toxines multiclasses par application successive de solutions de réactivation visant spécifiquement des inhibiteurs irréversibles ou réversibles, a été finalement proposée. En utilisant cette méthode, il a été montré que les biocapteurs enzymatiques pouvaient être appliqués à l‘analyse des aflatoxines et des pesticides organophosphorés, ainsi qu‘à la détermination de la toxicité globale des échantillons

Investigations reported in this manuscript are focused on the development of an original approach for the detection of several toxic compounds, mainly aflatoxins and organophosphorus pesticides, using acetylcholinesterase (AChE)-based inhibitory electrochemical biosensors. In a first step, a new potentiometric biosensor using pH Sensitive Field-Effect Transistors (pH-FETs) as transducers was investigated for aflatoxin B1 (AFB1) determination and different elaboration and working parameters were optimized. The proposed biosensor was characterized by high operational stability and reproducibility of the signal during the work as well as during the storage. The biosensor was further evaluated for real samples analysis (wheat, sesame, walnuts and peas) and a mathematical simulation of the potentiometric biosensor response to aflatoxin B1 was proposed for the first time and validated. In a second step, a conductometric biosensor using interdigitated gold microelectrodes was developed. The sensitivity of the biosensor to aflatoxins and other classes of toxic substances, such as organophosphorus pesticides, heavy metals ions, glycoalkaloids, and surfactants, was determined. A new and original procedure, enabling the selective determination of multiclass toxins by applying successive reactivation solutions targeting either irreversible or reversible inhibitors, was finally proposed. Using this method, the electrochemical enzyme inhibitory biosensors could be applied to the analysis of aflatoxins and organophosphorus pesticides, as well as for the determination of total toxicity of the samples; Les travaux présentés dans ce manuscrit concernent le développement d‘une approche originale permettant la détermination de plusieurs composés (principalement aflatoxines et pesticides organophosphorés), à l‘aide de biocapteurs électrochimiques basés sur l‘inhibition de l‘acétylcholinestérase. Dans un premier temps, un nouveau biocapteur potentiométrique utilisant des transistors à effet de champ sensibles au pH (pH-FETs) comme transducteurs a été développé pour la détermination de l‘aflatoxine B1 (AFB1) et différent paramètres d‘élaboration et de fonctionnement du biocapteur ont été optimisés. Le biocapteur proposé est caractérisé par une stabilité opérationnelle élevée and bonne reproductibilité du signal en cours d‘utilisation et de stockage. Le biocapteur a ensuite été évalué pour l‘analyse d‘échantillons réels (blé, sésame, noix et pois) et une simulation mathématique de la réponse du biocapteur potentiométrique à l‘AFB1 a été proposée pour la première fois et validée. Dans un deuxième temps, un biocapteur conductimétrique utilisant des microélectrodes interdigitées en or a été développé. La sensibilité de ce biocapteur aux aflatoxines ainsi qu‘à d‘autres classes de substances toxiques, tels que les pesticides organophosphorés, les métaux lourds, les glycoalkaloïdes, et les surfactants, a été déterminée. Une nouvelle procédure originale, permettant la détermination sélective de toxines multiclasses par application successive de solutions de réactivation visant spécifiquement des inhibiteurs irréversibles ou réversibles, a été finalement proposée. En utilisant cette méthode, il a été montré que les biocapteurs enzymatiques pouvaient être appliqués à l‘analyse des aflatoxines et des pesticides organophosphorés, ainsi qu‘à la détermination de la toxicité globale des échantillons

Pure diamond-like carbon (DLC) thin films and boron-doped DLC thin films have been deposited on silicon substrates using femtosecond pulsed laser. The amorphous carbon materials (DLC), have been deposited at room temperature by ablating graphite targets with an amplified Ti:sapphire laser of 800 nm wavelength and a pulse duration of 150 fs in high vacuum conditions. Doping with boron has been performed by ablating alternatively graphite and boron targets. In this study, the DLC films were used as working electrodes for the electrochemical detection of trace heavy metals namely, Cd 2+ , Pb 2+ , Ni 2+ and Hg 2+ , by using square wave anodic stripping voltammetry (SWASV) technique. Four metals were detected at −1.3 V deposition potential, and 90 s deposition time. The DLC films have been characterized by multiwavelength Raman spectrometry and high resolution scanning electron microscopy. The effect of the boron doping on the electrochemical behavior has been shown. The a-C:B 8%/Si 3 N 4 electrode gives the more sensitive detection. The four metals are detected simultaneously with a detection limit of 1 μg/L or 2 μg/L and a dynamic range from 1 or 2 to 25 μg/L for every metal, as presented in third table of this article. The different sensitivities obtained are 6.2, 20.0, 1.2 and 6.6 μA/ppb or μA μg −1 L for Cd 2+ , Pb 2+ , Ni 2+ and Hg 2+ , respectively.

International audience; We present a label-free biosensor capable to map local potential by photogenerating charge carriers in a field effect device. It consists in an amplitude-modulated laser beam scanning through an electrolyte/insulator/semiconductor structure at very low illumination around the equilibrium state of semiconductor. A proof of principle is demonstrated by depositing a self-assembled monolayer on the dielectric and by showing a clear photopotential change between naked and covered areas.

International audience; We demonstrate here the possibility of designing semiconducting thin films with controlled electrochemical properties. The thin films are composed of (i) an insulating binder and (ii) a semiconductor nanopowder which enables the fine tuning of the semiconducting properties of the layers. Thus, p-and n-type silicon particles (obtained from a top-down technique), or metal-oxide ZnO, SnO(2) and NiO nanoparticles (synthesized using a bottom-up protocol) are successfully integrated into spin-coated or screen-printed thin films and used as semiconducting materials. The flat band potential (Vfb) of the films is then easily tuned from DV to -1.138 V. (C) 2010 Elsevier B.V. All rights reserved.

International audience; The development of strategies based on mass spectrometry to help for deep structural analysis of acidic oligosaccharides remains topical. We thus examined the dissociation behavior of deprotonated ions of heparin-derived di- to tetra-saccharides under UV irradiation at 220 nm. Depending on the ionization state of the carboxylic groups, an oxidized species issued from electron photodetachment was observed in complement to photoinduced fragmentation of precursor ions. The influence of the charge location in the oligosaccharide dianions on the balance between photodissociation and electron photodetachment is examined and a way to direct the relaxation pathways, (i.e., dissociation versus electron detachment), is proposed using sodium adducts. The oxidized species was subjected to activated-electron photodetachment (activated-EPD) leading to complementary informative fragment ions to those issued from photodissociation. Directed photoinduced dissociation at 220 nm and activated-EPD should complement the more conventional CAD and IRMPD activation modes for deeper structural analysis of acidic oligosaccharides-derived anions.

We report a theoretical work on the electronic excitation spectrum of two heparins like disaccharides. Time dependent density functional theory (TD-DFT) calculated spectra for these sulfated and carboxylated disaccharides are presented. The orbitals involved in the observed electronic excitations are analyzed. ππ ∗ excitations involving the acidic functions lead to a strong optical absorption of these compounds between 270 and 220 nm, which is in agreement with experimental spectra reported previously [16] .

International audience; An all-inorganic protocol, entirely based on wet chemistry methods, has been studied to form nanosized Ag metallic particles in solution Liquid suspensions of anatase TiO(2) nanocrystallites have first been prepared through a sal-gel route Silver nanoparticles (NPs) have then been generated through the photocatalytic reduction of a silver salt, diluted in TiO(2) liquid suspensions, and exposed to UV light, which results in the formation of a mixed Ag-TiO(2) suspension. Mechanisms occurring in solutions during the metallization step and a post-metallization ageing period have been studied by UV/vis spectroscopy Chemico-structural and morphological properties of resulting silver NPs have been studied by transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. Ag-TiO(2) suspensions have then been impregnated on cotton-based textile samples and the antibacterial activity of so-functionalized textiles has been studied with respect to E colt and L. innocua bacteria It is shown that, while TiO(2) NPs attached to textile fibres have no antibacterial activity, functionalized textiles exhibit a strong antibacterial activity due to Ag NPs, and this activity can be reached for a large range of impregnated silver amounts. (C) 2010 Elsevier B.V. All rights reserved

The evolution of regulation on chemical substances (i.e. REACH regulation) calls for the progressive substitution of toxic chemicals in formulations when suitable alternatives have been identified. In this context, the method of Hansen solubility parameters was applied to identify an alternative solvent less toxic than methylene chloride used in a microencapsulation process. During the process based on a multiple emulsion (W/O/W) with solvent evaporation/extraction method, the solvent has to dissolve a polymer, poly(epsilon-caprolactone) (PCL), which forms a polymeric matrix encapsulating or entrapping a therapeutic protein as the solvent is extracted. Therefore the three partial solubility parameters of PCL have been determined by a group contribution method, swelling experiments and turbidimetric titration. The results obtained allowed us to find a solvent, anisole, able to solubilize PCL and to form a multiple emulsion with aqueous solutions. A feasibility test was conducted under standard operating conditions and allowed the production of PCL microspheres.

International audience

It is well known that mass transfer of a solid compound into a liquid phase is characterized by mutual properties of both sides. Solubilization capacity of the liquid phase is primary affected by its composition in inorganic species inducing salting in/out effect evaluated by Setschenow constant, generally defined at 298.15 K. On the other hand, the equilibrium process is highly influenced by polar compatibility issue. Therefore, the study of such transfer is essential in order to set the role of each party participating in the solid–liquid equilibrium. Thus, a comparison of transfer magnitude and feasibility of carbaryl from pure water, to seawater, and lab-made seawater was held. To do so, solubility of the compound was experimented at different temperature in multiple media. Solubility determination is based on the saturation of a specific heated fluid passing through a saturation cell. The solute transported is subsequently trapped in a specific extraction column. Back flashing method is then applied to dissolve the compound. After validation, aqueous solubility of carbaryl was studied as function of temperature ranging from (273.15 to 318.15 K) at atmospheric pressure. In addition, solubility was determined in pure, seawater, and corresponding lab-made water, thus solubility values ranged from 3.57E-06 to 3.49E-05 in pure water, from 3.04E-06 to 2.53E-05 in seawater and from 6.51E-06 to 3.61E-05 in lab-made water. As a result, thermophysical properties of transfer and usage of lab-made water on the mass transfer properties divergence was spotted. The Salting out phenomenon observed for carbaryl was interpreted by the internal pressure theory that suggests the reduction of internal cavities in the presence of salt, making solubilization process more difficult to achieve. Thus, showing an overall endogenic process with a positive Gibbs free energy of transfer that is highly affected by the magnitude of salting out effect and the temperature. The molar entropy of transfer increases versus temperature caused by the disorder of solvent molecules due to the dissolution process.

International audience; A novel synthetic approach toward redox-active calixarene-based receptors is described wherein ferrocene fragments have been introduced at the lower rim through anion-binding urea or amide connections. A thorough 1H NMR investigation on a series of calixarene-ferrocene receptors was performed in order to estimate their hydrogen bonding-driven self-association properties and improve our understanding of the correlation between molecular structures and redox properties.

International audience; A mono-functional silane reagent, 3-mercaptopropyltrimethoxysilane (MPS) was used to modify the surface of silicon wafers. The structure of the SAMs formed with the MPS was investigated by contact angle measurements, ellipsometry, AFM, and X-ray photoelectron spectroscopy (XPS). The deposition of a metallic gold layer via ultra-high vacuum (UHV) evaporation reveals good adhesion properties on Au/MPS/SiO2/Si structure. The “chemisorption” between the SAM and the gold evaporated layer is confirmed by adhesion tests and optimum curing treatment is found 1 h at 100 °C). This very simple methodology, avoiding the usage of Cr and other metals as undercoating layers and could be proposed further for (bio)sensors applications.

International audience; We report here the results of human olfactory receptor (OR) 17-40 stimulation with some odorants probed by means of the double-channel surface plasmon resonance platform NanoSPR-6. OR 17-40 tagged with N-terminal cmyc sequence was heterologously co-expressed with Gαolf protein in yeast, and receptor-carrying nanosomes were prepared from yeast membrane fraction. Then, receptors were specifically captured via anti-cmyc antibody attached to the gold-coated substrate in orientated or random way. Measurement of odorants effects were carried out in the presence of GTP-γ-S in differential mode in order to compensate bulk changes of refractive index. For the first time, biosensing efficiency of olfactory films was discussed in terms of their thickness and Gαolf accessibility to GTP-γ-S. Bell-shaped response profile with two maxima (near 1 nM and near 1 μM) was established for helional, which is documented as highly specific agonist of OR 17-40. Unrelated odorant heptanal used as control, did not evoke significant variations of differential signal.

The Siding Spring Southern Seyfert Spectroscopic Snapshot Survey (S7) is a targeted survey probing the narrow-line regions (NLRs) of a representative sample of \(\sim \) 140 nearby (z < 0. 02) Seyfert galaxies by means of optical integral field spectroscopy. The survey is based on a homogeneous data set observed using the Wide Field Spectrograph WiFeS. The data provide a 25 × 38 arcsec2 field-of-view around the galaxy centre at typically \(\sim \) 1.5 arcsec spatial resolution and cover a wavelength range between \(\sim \) 3,400–7,100 A at spectral resolutions of \(\sim \) 100 km s−1 and \(\sim \) 50 km s−1 in the blue and red parts, respectively. The survey is primarily designed to study gas excitation and star formation around AGN, with a special focus on the shape of the AGN ionising continuum, the interaction between radio jets and the NLR gas, and the nature of nuclear LINER emission. We provide an overview of the current status of S7-based results and present new results for NGC 6300.

In the last decade, silica monolithic capillaries have focused more and more attention on miniaturized separation techniques like capillary electrochromatography (CEC), nano-liquid chromatography (nano-LC) and chip electrochromatography owing to their unique chromatographic properties and their simplified preparation compared with packed columns. They are synthesized according to a sol-gel multi-step process that includes, after a gelation step at 40 degrees C leading to the formation of the macropores network and the silica skeleton, a post-gelation step (hydrothermal treatment at 120 degrees C in basic medium) that allows to tailor the mesopores and finally a calcination or a washing step to remove remaining polymers. In order to reduce the synthesis time, the number of synthesis steps and above all the temperature synthesis, to adapt the synthesis of such silica monoliths in polymeric microsystem devices, we extensively studied the influence of the hydrothermal treatment and its duration on textural (pore size distribution) and chromatographic properties (retention, efficiency) of in situ-synthesized capillary monoliths in nano-LC and CEC. This study was performed on pure silica and octyl chains grafted silica monoliths. Untreated monoliths show small pores (6 nm), whereas hydrothermally treated monoliths exhibit medium and large mesopores (8-17 nm). It was demonstrated that the hydrothermal treatment at 120 degrees C was not necessary for pure silica monolithic capillaries dedicated to normal phase liquid chromatography or hydrophilic interaction liquid chromatography (HILIC) and electrochromatography: the suppression of the hydrothermal treatment did not impair efficiencies in CEC and in nano-LC but contributed to increase in retention factors. Minimal plate heights of ca. 5 microm in CEC and 6 microm in nano-LC were obtained with or without hydrothermal treatment with bare silica. In the same way, the hydrothermal treatment was not necessary for grafted silica monoliths only dedicated to CEC. However, the results clearly indicate that the hydrothermal treatment becomes essential before grafting in order to preserve the efficiency of the monolithic silica capillaries dedicated to nano-LC: in this particular case, the suppression of the hydrothermal treatment leads approximately to a loss of a factor two in efficiency.

Proceedings Paper: Seminar on Analytical Chemistry and Ecotoxicology, 2006 Geneva, Switzerland; International audience; Size exclusion and anion-exchange chromatographies coupled with inductively coupled plasma-mass spectrometry (ICP-MS) were used for the speciation of selenium (Se) in a dietary supplement. A sequential extraction method resulted in 85% recovery of Se and 78% of the Se extracted could be identified. The results obtained show that selenomethionine and its oxide are the predominant compounds, while selenite and selenomethylcysteine are present at low concentrations. Methane seleninic acid, probably arising from the oxidation of selenomethylcysteine, accounted for 22% of total Se. High-molecular-weight compounds, probably proteins, were detected in sodium dodecyl sulfate (SDS) and driselase extracts by size exclusion chromatography.

International audience; A methyl-naphthyl functionalized cyclam (1,4,8,11-tetraazacyclotetradecane) (N-MNC) was deposited on gold electrodes and characterized by means of infrared spectroscopy in ATR mode, wettability, morphology and an electrochemical study. The proton conductivity of the N-MNC film was brought out, for the first time, by electrochemical impedance spectroscopy (EIS) and by cyclic voltammetry (CV); the anodic peaks located at 0.15 V and at 0.45-0.50 V, due to proton exchange, were shown to increase when electrolyte pH decreases. The chemical sensor based on an n-MNC functionalized gold electrode was studied in the presence of divalent (Cu2+, Ni2+, Zn2+) and trivalent (Fe3+) metallic ions. The influence of the metallic ion concentration on the ion-exchange resistance of the film and on the proton-exchange anodic peak was quantified. The highest sensitivity was obtained for Ni2+ and Fe3+, with a detection limit of 10(-8) M.

Silica monolithic capillaries (SMCs) were synthesized by a sol-gel process. First, a simplification of the synthesis was proposed by replacing the calcination and the drying steps which can have tremendous effects on chromatographic and physical properties, by a single water or methanol 2 h washing step. The efficiency of such a washing step was demonstrated and the comparison of the chromatographic and electrochromatographic properties between calcined and washed SMCs has shown that such a modification did not impair retention, efficiency, and stability of the monolith. This simplified procedure was carried out to synthesize SMCs with two different skeleton sizes. These capillaries were evaluated in electrochromatography and present high efficiencies (H = 5 microm) at least equal to the best ones reported in the literature. Furthermore, the influence of the skeleton size on the EOF of the second kind (EOF-2) was investigated with unmodified SMCs used under various experimental conditions including electrical field strength and buffer concentration. The ionic strength of the mobile phase and the applied electrical field that enable this EOF-2 were related to the size of the skeleton which was tuned by the synthesis conditions.

International audience; Some of advanced oxidation processes (AOP) are characterised by a special chemical feature: the ability to use the high reactivity of .OH radicals in driving oxidation processes. These radicals are suitable for achieving the complete abatement, even including the mineralization of less reactive pollutants. In this study, a photocatalytic process is used to degrade one herbicide of the imidazolinone family, Imazapyr. It was shown to be photodegraded rapidly and extensively in an aqueous solution. The decline of Imazapyr concentration in the solution followed a first-order kinetics. The apparent first order rate constant was found equal to 0.19 min-1 in distilled water at natural pH 3.8. The smaller activities found at acidic and basic pH were explained by considering the ionisation state of Imazapyr and the charge density of TiO2. The present work dealt with the influence of metal ions like Ni2+ and Cu2+ which are frequently present in agricultural wastewater on the photocatalytic efficiency of TiO2 in the elimination of Imazapyr. A detrimental effect of the presence of metallic species was observed only with samples containing amount of copper and nickel in the presence of TiO2. Several hypotheses were proposed to explain this phenomenon, passivation of TiO2 surface by adsorption of Cu2O and/or Cu°, formation of a complex or recombinaison of the e-/h+ pairs. At higher concentrations of metallic species like Cu2+ and Ni2+, a plateau was reached which could be explained by the photo-Fenton like reaction. In an attempt to understand the basic mechanisms of the degradation of Imazapyr in water by TiO2 photocatalysis, we discussed the primary degradation mechanism on the basis of the experimental results together with molecular orbital calculation of frontier electron density and partial charge.

This work investigates the efficiency of a chaotic micromixer using thermal lens spectrometry. The outlet of the mixing device was connected to a thermal lens detection head integrating the probe beam optical fibers and the sample capillary. The chaotic micromixer consisted of a Y-shaped poly(dimethylsiloxane) (PDMS) microchip in which ribbed herringbone microstructures were etched on the floor of the main channel. Due to the solvent composition dependence of the thermal lens response, the photothermal method was shown to be highly sensitive to nonhomogeneous mixing compared to fluorescence detection. The apparatus was applied to the determination of Fe2+ with 1,10-phenanthroline using flow injection analysis; a limit of detection of 11 μg L−1 of iron was obtained.

International audience; A novel impedimetric immunosensor for the detection of haemoglobin has been developed by mixed self-assembled monolayers on An. First, a mixed self-assembled monolayer (SAMs) consisting of 1,2 dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-(biotinyl) (biotinyl-PE) and 16-mercaptobexadecanoic acid (MHDA) on gold electrodes was studied. The conformational properties of the SAMs were characterised by cyclic voltammetry and impedance spectroscopy. After blocking non-specific binding sites in the mixed monolayer using non-specific IgG, neutravidin was used to bind to biotinyl sites present in the mixed monolayer. Finally, biotinylated anti-haemoglobin IgG was immobilised to the tethered neutravidin. The membrane resistance R-m, obtained from the assembly, decreased gradually after the addition of non-specific IgG, neutravidin and anti-haemoglobin to the monolayer. This decrease could be attributed to a rearrangement in the structure of the SAMs. The detection of antibody-antigen reaction demonstrates that the potentiometric immunosensor exhibited high sensitivity and a detection limit of 20 ng/ml (approximately 0.3 nM). (c) 2005 Elsevier B.V. All rights reserved.

The behaviour of imazapyr (2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid), a broad spectrum herbicide of the imidazolinone family, has been studied under UV radiation in the presence of metal salts. Complexation interactions between imazapyr and metal ions decreased imazapyr photolysis. A chemometric study compared the photodegradation of imazapyr in aqueous solutions in the presence of Na+, Ca2+ or Cu2+ and their concomitant anionic species (Cl−, NO3−) at various pesticide/metal ion molar ratios. The study showed the major role of metal ions in the degradation of imazapyr and its main photoproducts. The molecules were strongly stabilised on complexation with metal ions, leading to an increase in persistence of the pesticide. Copyright © 2006 Society of Chemical Industry

Proteomic microarrays show a wide range of applications for the investigation of DNA–protein, enzyme–substrate as well as protein–protein interactions. Among many challenges to build a viable “protein microarray”, the surface chemistry that will allow to immobilised various proteins to retain their biological activity is of paramount importance. Here we report a chemical functionalisation method allowing immobilisation of oligo-peptides onto silica surface (porous silica, glass, thermal silicon dioxide). Substrates were first derivatised with a monofunctional silane allowing the elaboration of dense and uniform monolayers in highly reproducible way. Prior to the oligo-peptides grafting, this organic layer was functionalised with an amino-polyethyleneglycol. The coupling step of oligo-peptides onto functionalised supports is achieved through activation of the C-terminal function of the oligo-peptides. Chemical surface modifications were followed by FTIR spectroscopy, AFM measurements and fluorescence scanning microscopy. A systematic study of the oligo-peptide grafting conditions (time, concentration, solvent) was carried out to optimise this step. The oligo-peptides grafting strategy implemented in this work ensure a covalent and oriented grafting of the oligo-peptides. This orientation is ensured through the use of fully protected peptide except the terminal primary amine. The immobilized peptides will be then deprotected before biological recognition. This strategy is crucial to retain the biological activity of thousands of oligo-probes assessed on a microarray.

International audience; Expressions for reversible differential pulse (DP) voltammograms at microdisk electrodes were established from experimental results as a function of pulse electrolysis parameters. Three expressions were computed numerically, depending on the electrode radius and varying the pulse interval, tau. They were compared to theoretical and numerical expressions established previously in literature reports for macrodisk and microcylinder electrodes. The other aim of this work was to determine the minimum value of the pulse interval for which DP voltammograms observed at microdisk electrodes are not distorted. It appeared that no distortion is observed even at very short values of tau, meaning that microdisk electrodes are a good alternative to macroelectrodes in order to reduce time analysis in DPV DP measurements were carried out at platinum electrodes for two reversible reactions: hexacyanoferrate (II) and iodide oxidation reaction

International audience; To make ultrathin films for the fabrication of artificial olfactory systems, odorant biosensors, we have investigated mixed Langmuir and Langmuir-Blodgett films of odorant-binding protein/amphiphile. Under optimized experimental conditions (phosphate buffer solution, pH 7.5, OBP-1F concentration of 4 mg L-1, target pressure 35 mN m(-1)), the mixed monolayer at the air/water interface is very stable and has been efficiently transferred onto gold supports, which were previously functionalized by self-assembled monolayers (SAMs) with 1-octadecanethiol (ODT). Atomic force microscopy and electrochemical impedance spectroscopy were used to characterize mixed Langmuir-Blodgett (LB) films before and after contact with a specific odorant molecule, isoamyl acetate. AFM phase images show a higher contrast after contact with the odorant molecule due to the new structure of the OBP-1F/ODA LB film. Non-Faradaic electrochemical spectroscopy (EIS) is used to quantify the effect of the odorant based on the electrical properties of the OBP-1F/ODA LB film, as its resistance strongly decreases from 1.18 M Omega (before contact) to 25 k Omega (after contact).

International audience

International audience; In this work we describe a new urea biosensor, based on the immobilization of bacteria, Proteus mirabilis on gold electrode. To improve the stability of the bio-system, additional materials were used such as functionalized Fe 3 O 4 nanoparticles (NPs), cationic (PAH), anionic (PSS) polyelectrolytes, Bovine Serum Albumin (BSA) and glutaralde-hyde as a cross-linking agent. The electrochemical performances of the developed bacteria biosensor was evaluated using the electrochemical impedance spectroscopy (EIS) and cyclic voltammetry measurements. The adhesion of the bacteria cell on gold electrode was evaluated using contact angle measurements. The morphology of bacteria and its interaction with Fe 3 O 4 nanoparticles were evaluated with the atomic force microscopy (AFM). As a result, a sensitive, stable and reproducible urea biosensor was developed.

Intermolecular interactions between protein and its partners represent highly attractive targets for the elaboration of therapeutic compounds abble to interfere in biological processes. A novel approach in drug design called Fragment-Based Drug Design (FBDD) consists of designing bioactive molecules like inhibitors, from the 3D structure of the complex formed between a protein and a fragment molecule (MW < 300g/mol). Here we suggest using the chemical shift, to study these protein-ligand structures. We will particularly focus on the measurement of Chemical Shift Perturbations (CSP) induced by the fragment-binding on protein’s nuclei. We will evidence the potency of this NMR tool through simulation of CSP induced by fragment interaction on protein target and the comparison with experimental CSP. Two protein targets will be used and the comparison between experimental and simulated data will evidence on one hand, the structural rearrangement of the protein Bcl-xL upon fragment-binding. On the other hand, we will demonstrate that this quantitative use of CSP is unable to determinate fragment orientations inside the protein PRDX5 binding site. We will compare the performances of the method for different kinds of protein and proposing answers to better understand the behaviour of CSP toward their different electronic contributions, Les interactions intermoléculaires entre une protéine et ses différents partenaires représentent des cibles de plus en plus prisées pour l'élaboration de composés thérapeutiques capables d'intervenir dans des processus biologiques. La méthode FBDD (Fragment-Based Drug Design) permet de concevoir des molécules bioactives tels que des inhibiteurs, à partir de la structure tridimensionnelle du complexe formé entre la protéine et une molécule fragment. Dans le cadre de ce projet de thèse nous proposons d'utiliser le déplacement chimique pour l'étude des structures 3D de ces complexes protéine-ligand. Nous nous focaliserons sur la mesure des perturbations de déplacement chimique CSP (Chemical Shift Perturbations) des atomes d'une protéine cible, induites par la liaison d'un fragment. Nous démontrerons la puissance de cet outil RMN à travers la simulation des CSP induits par l'interaction d'un fragment sur une protéine cible et leur comparaison aux CSP expérimentaux. L'analyse sera réalisée sur deux protéines cibles et la comparaison des données expérimentales et simulées permettra dans un premier temps de mettre en évidence un réarrangement structural de la protéine Bcl-xL lors de son interaction avec un fragment. Puis, dans un second temps, nous montrerons que cette analyse quantitative des CSP peut permettre de déterminer l'orientation des fragments dans le site d'interaction de la protéine PRDX5. Nous comparerons alors les performances de la méthode pour différents types de protons proposant ainsi de nouvelles pistes pour la compréhension du comportement des CSP vis-à-vis de leurs contributions électroniques

Nowadays, electrochemical biosensors are rapid, reliable, cost-effective and label-free tools for in field monitoring of environmental pollutants, for assessing the food safety criterion and for detection of the territory military residues. We developed biological receptors based affinity biosensors for electrochemical detection of estradiol in environment samples and odorant molecules in pork meat adulteration. The sensitive, selective, rapid, simple, repetitive, stable and effective biosensors were produced. In addition, another strategy entrapment based on integrated nano-material was used to produce a biomimetic sensor for explosives detection, which has shown good valuable in environmental protection and homeland security. In the end, certain significant prospective are discussed, De nos jours, les biocapteurs électrochimiques constituent des outils rapides, fiables, rentables et sans marquage pour la détection sur site des polluants environnementaux et l’évaluation des critères de sécurité alimentaire et pour la détection des résidus militaires sur le terrain. Nous avons développé des biocapteurs d’affinité basés sur des récepteurs biologiques pour la détection électrochimique de l'estradiol dans des échantillons environnementaux et de molécules odorantes dans l'adultération de viande de porc. Des biocapteurs sensibles, sélectifs, rapides, simples reproductible, stables et efficaces ont été élaborés. En outre, une autre stratégie basée sur des nanomatériaux intégrés a été employée pour élaborer un capteur biomimétique pour la détection d’explosifs, qui a montré de bonnes qualités dans la protection de l'environnement. A la fin du manuscrit, certaines perspectives sont discutées

International audience; Thermal lens spectrometry has been used for the determination of iron in calf serum. The method is based on dissociation of Fe3+ from proteins, reduction of Fe3+ to Fe2+ and formation of a coloured complex between Fe2+ and bathophenanthroline. Contrary to the spectrophotometric method, it is shown that thermal lens spectrometry is less sensitive to scattering caused by the presence of small particles remaining in the test solution after the deproteinization step. The background signal is very small and the response is only slightly dependent on the amount of scattering particles. The method is reliable, sensitive and reproducible. The limit of detection for iron is 4 ppb and the relative standard deviation is around 2%. It is expected that the volume of serum sample necessary for an analysis can be reduced to less than 100 mul.

The LIBS (Laser Induced Breakdown Spectroscopy) technique is an elemental analysis technique based on the use of the optical emission spectrum from a sample of laser ablation. Today, LIBS has not emerged as a technique of choice for the majority of applications, as is the case for inductive coupled plasma techniques. One of the main reasons for this is the difficulty in providing accurate quantitative measurements. So there is now a need to better understand and characterize plasmas and phenomena from laser-Matter interaction on all types of materials to improve the performance of this analytical technique. This laser/material interaction is specific to the type of material analyzed, so it is essential to study these effects on a wide range of materials. Two types of samples have been used to study LIBS plasmas: materials containing rare earths and plastics. Work on rare earths were used to select the analytical lines free of spectral interference from other elements of this family and sensitive enough to carry out a quantitative analysis. This study highlighted the fact that the matrix effects due to the amount of rare earth and nature of the sample are important. These matrix effects are unique to each element and matrix, so they are to be considered in all LIBS analysis of a sample containing several rare earths. If the accumulation of a large number of rare earths (i.e 12) has a significant effect on the signal of the analytes, the effect of a limited number (i.e. 2 to 4) could be compensated by use on an internal standard. In the context of the LIBS analysis of plastic materials, a detailed study of the signal using different plasma conditions was performed. The quantitative analysis was focused on several elements, including bromine and chlorine which are difficult to excite. Through the use of a controlled atmosphere of helium, the detection of halogens used as flame retardants in plastics was significantly improved. An important matrix effect was observed at 266 nm in comparison with the results obtained at 532 nm. However, these differences at 266 nm allowed the discrimination of four families of polymers studied. In the presence of helium, significant differences were obtained for the C2 / He and CN / He ratios. This criteria was found to be relevant for the discrimination between the different types of plastics studied, La LIBS (Laser Induced Breakdown Spectroscopy) est une technique d'analyse élémentaire basée sur l'exploitation du spectre d'émission optique issu de l'ablation laser d'un échantillon. Aujourd'hui, la LIBS ne s'est pas encore imposée comme une technique de choix pour la majorité des applications comme c'est le cas pour les techniques de plasma à couplage inductif. L'une des principales raisons à cela est la difficulté à fournir des mesures quantitatives justes. Il existe donc aujourd'hui une nécessité de mieux comprendre et caractériser les plasmas et les phénomènes issus de l'interaction laser-Matière sur tout type de matériaux pour améliorer les performances de cette technique analytique. Cette interaction laser/matière étant, de plus, spécifique au type de matériau analysé, il est indispensable d'étudier ces effets sur une vaste gamme de matériaux. Deux types d'échantillons ont donc été utilisés pour étudier les plasmas LIBS: des matériaux contenant des terres rares et des matériaux plastiques. Les travaux réalisés sur les terres rares ont permis de sélectionner des raies d'analyse « disponibles », c'est-À-Dire sans interférences spectrales provenant des autres éléments de cette famille et suffisamment sensibles pour réaliser une analyse quantitative. Cette étude a mis en avant le fait que les effets de matrice dus à la quantité de terres rares et à la nature de l'échantillon sont importants. Ces effets de matrice sont propres à chaque élément et à chaque matrice, ils sont donc à prendre en considération pour toute analyse LIBS d'un échantillon contenant plusieurs terres rares. Si l'accumulation d'un grand nombre de terres rares a un effet significatif sur le signal d'un de ces analytes, leurs présences en nombre et quantité limitée (2 à 4) donnent un effet compensable par étalonnage interne. Dans le cadre de l'analyse LIBS des matériaux plastiques, une étude détaillée du signal en utilisant différentes conditions de plasma a été réalisée. L'analyse quantitative s'est portée sur plusieurs éléments dont certains difficiles à exciter comme le brome et le chlore. Grâce à l'utilisation d'une atmosphère contrôlée d'hélium, la détection des halogènes employés comme retardateurs de flamme dans les plastiques, a été possible. Un important effet de matrice a été observé à 266 nm en comparaison avec les résultats obtenus à 532 nm. Cependant, ces différences marquées à 266 nm ont permis la discrimination des quatre familles de polymères étudiées. En présence d'hélium, des différences significatives ont été obtenues pour les rapports C2/He et CN/He. En les traçant l'un en fonction de l'autre, il est ainsi possible de discriminer les différents types de plastiques étudiés

Over the past 10 years, indoor air quality has become a real Health and Safety concern, especialty in the workplace, which has led to the legislation proposal of concentrations guidelines for pollutants such as Volatiles Organic Compounds (VOC). To comply with the Safety requirements, The Claude Bernard University Lyon 1 has institutionalized and developed an Environment, Health and Safety Unit (HSE Unit), to provide the analyses for the Health and Safety team (SHS). This specialist unit has developed a supervision methodology to control the indoor air quality in all the buildings of the university, including all the 80 research and training laboratories. In order to carry out the assessment, the SHS team defined 45 compounds classified as priority, according to their threshold limit values (TLV-TWA or TLV-STEL) to the workers. To this list of 45 VOC another list containing 48 VOC is added. Evaluation of the trapping capacity of each sorbent, for a mix containing 93 VOC has been studied. Moreover, separation and identification methods were developed and optimized allowing to reach a quantification limit lower than professional limit value exposure. Using these methods and the results of the trapping comparisons, different applications were implemented, such as sampling campaigns in different laboratories; Aujourd'hui, la gestion du risque en milieu profesionnel ainsi que l'évaluation de l'exposition aux polluants, tels que les Composés Organiques Volatils (COV) présents dans l'air deviennent une nécessité tant la qualité de l'air des lieux de travail peut être à l'origine de problèmes de santé ou de maladies professionnelles reconnues. Dans le but de répondre à ces exigences de sécurité, l'Université Claude Bernard Lyon 1 a institutionnalisé et développé une Cellule Analyse Hygiène Sécurité et Environnement en lien direct avec le service SHS préexistant. Cette cellule est chargée de la mise en place d'une méthodologie de surveillance de la qualité de l'air intérieur de l'ensemble des locaux de l'université (14 sites, environ 80 laboratoires) en accord avec le code du travail et de l'environnement. Afin de pouvoir assurer l'ensemble des analyses inhérentes aux lieux de travail, le SHS a défini 45 composés comme prioritaires ajoutés à la liste du SHS et portent à 93 le nombre de COV identifiés et quantifiés. La méthode de séparation et d'identification mise en place permet d'atteindre des limites de quantification largement inférieures aux VLCT et VLEP 8 heures fixées par la législation. Des campagnes de prélèvement ont pu ainsi être organisées en collaboration avec le SHS et être lancées au sein de l'université

International audience

The inertness’ value of plastics that are on contact with foodstuffs is governed by the European rule N°10/2011. In Lebanon, the lack of the Rules and Regulations of plastics’ usage led for a non-controlled packing in production as in storage, which will cause a sanitary risk to the consumer and to the population. The purpose of this research was to appreciate the migration’s phenomena of contaminants from the PET to the water. For this, there was an analysis of potential migrants such as VOC and SV to verify their tenor’s conformity relative to the MCL in international regulations. The aldehydes’ dosage in the water was performed by the derivation with the 2,4-DNPH, followed by a concentration on a C18 cartridge, then separation and quantification was done by HPLC-UV. The SV compounds’ analysis was realized by SPME-GC-FID method on a PDMS / DVB fiber. The BTEX and the styrene’s analysis was done by HS-trap-GC-FID method. These methods were validated in accordance with standard NF T 90-210 with a LQ less than the MCL. The volatile compounds in the bottled water and in the PET were analyzed by HS-trap-GC-MS method. The presence of FA, AA, DEP and BTEX in the bottled water with the PET was confirmed. It was highlighted that temperature and sun exposition influence the aldehydes’ migration. The acetaldehyde’s concentration after incubation at 40ºC wasn’t negligible and can modify the water’s organoleptic properties. The PET’s analyze reveals the presence of hydrocarbons, aldehydes, alcohols and ketones, L'évaluation de l'inertie des matières plastiques au contact de denrées alimentaires est régie par le règlement européen N°10/2011. Au Liban, l'absence de législations relatives à l'usage des matières en plastiques a conduit à des emballages non contrôlés au niveau de la production et du stockage, ce qui peut induire un risque sanitaire pour le consommateur. L'objectif de ce travail a été d'apprécier les phénomènes de migration des contaminants du PET vers l'eau. Pour cela, l'analyse de certains migrants potentiels a été initiée tels que des COV et des SV afin de vérifier la conformité de leur teneur par rapport aux LMA dans les règlementations internationales. Le dosage des aldéhydes dans l'eau a été effectué par dérivation avec la 2,4-DNPH, suivie d'une étape de préconcentration sur une cartouche en C18, puis séparation et quantification par HPLC-UV. L'analyse des composés SV a été réalisée par SPME-GC-FID sur une fibre en PDMS/DVB. L'analyse des BTEX et du styrène a été réalisée par HS-Trap-GC-FID. Ces méthodes ont été validées conformément à la norme NF T 90-210 avec des LQ inférieures aux LMA. L'analyse des COV dans l'eau embouteillée et dans le PET a été réalisée par HSTrap- GC-MS. La présence de FA, d'AA, de DEP et des BTEX dans l'eau embouteillée en PET a été confirmée. Il a été mis en évidence que la température et l'exposition solaire influencent la migration des aldéhydes. Les concentrations d'AA trouvées après incubation à 40ºC ne sont pas négligeables et peuvent modifier les propriétés organoleptiques de l'eau. L'analyse du PET montre la présence des hydrocarbures, des aldéhydes, des alcools, et des cétones

Anion exchange phenomena inside various functional coatings have been investigated by means of impedance measurements. Emphasis is given to the selectivity of anions that would allow the application to ion-selective electrodes based on electrolyte/insulator/semiconductor devices. The selectivity of anion exchange with respect to anion type follows the empirical Hofmeister sorting series. But other parameters are also operating such as the chemical nature of the anionic sites and the possible anion-dependent swelling of the electrode's coating by the solvent., Les phénomènes d'échange anionique dans divers revêtements fonctionnels ont été étudiés au moyen de mesures d'impédance. L'accent est mis sur la sélectivité des anions qui permettrait l'application d'électrodes sélectives d'ions basées sur les dispositifs : électrolyte / isolant / semi-conducteur. La sélectivité de l'échange d'anions par rapport au type d'anions suit la série empirique de Hofmeister. Mais d'autres paramètres sont également présents tels que la nature chimique des sites anioniques et le gonflement possible du revêtement d'électrode par le solvant qui dépend de la nature de l'anion. Mots clés : échange anionique, sélectivité ionique, mesures d'impédance 1. Introduction The elaboration of ion-sensitive sensors requires a suit

National audience

This paper presents a first observational investigation of the faint Of?cp star NGC 1624-2, yielding important new constraints on its spectral and physical characteristics, rotation, magnetic field strength, X-ray emission and magnetospheric properties. Modeling the spectrum and spectral energy distribution, we conclude that NGC 1624-2 is a main sequence star of mass M {\simeq} 30 M{\odot}, and infer an effective temperature of 35 {\pm} 2 kK and log g = 4.0 {\pm} 0.2. Based on an extensive time series of optical spectral observations we report significant variability of a large number of spectral lines, and infer a unique period of 157.99 {\pm} 0.94 d which we interpret as the rotational period of the star. We report the detection of a very strong - 5.35 {\pm} 0.5 kG - longitudinal magnetic field , coupled with probable Zeeman splitting of Stokes I profiles of metal lines confirming a surface field modulus of 14 {\pm} 1 kG, consistent with a surface dipole of polar strength >~ 20 kG. This is the largest magnetic field ever detected in an O-type star, and the first report of Zeeman splitting of Stokes I profiles in such an object. We also report the detection of reversed Stokes V profiles associated with weak, high-excitation emission lines of O iii, which we propose may form in the close magnetosphere of the star. We analyze archival Chandra ACIS-I X-ray data, inferring a very hard spectrum with an X-ray efficiency log Lx/Lbol = -6.4, a factor of 4 larger than the canonical value for O-type stars and comparable to that of the young magnetic O-type star {\theta}1 Ori C and other Of?p stars. Finally, we examine the probable magnetospheric properties of the star, reporting in particular very strong magnetic confinement of the stellar wind, with {\eta}* {\simeq} 1.5 {\times} 10^4, and a very large Alfven radius, RAlf = 11.4 R*., Comment: 17 pages, MNRAS accepted and in press

Core shell Ag@SiO2 -Streptavidin- Cy3 nanoparticles were prepared. Ag@SiO2 nanoparticles were synthesized via a sol–gel method. Then, Streptavidin- Cy3 was covalently bonded to the Ag@SiO2 surface. These core-shell nanoparticles were characterized by steady-state fluorescence spectroscopy and fluorescence scanning. In presence of the silver core, a 2.5-time enhancement of Cy3 fluorescence intensity was obtained. This result shows that these nanoparticles can be potentially helpful in surface analysis based on biochip.

International audience

Taking in account the increasing needs and demands in environmental and consumer protection, CTCis always seeking improvement in analytical methods and development of new ones dealing with leather,fabrics and aqueous samples. In this thesis, several new methods were developed to be able to handleanalytical requests dealing with leather and textile materials being parts of shoes, clothes and other leathergoods.A GC/MS method using chemical ionization was developed to detect short polychlorinated alkanes down to aconcentration of 0.6 μg/L in aqueous sample and 2 mg/kg in leather samples. Alkylphenols and theirethoxylates were similarly determined by GC/MS down to 0.05 μg/L.Flame retardants are another large class of chemicals becoming suspicious. Polybromodiphenylethers weredetermined in aqueous samples and leathers. The respective GC/MS highest limits of quantification (LOQ)were0.05 µg/l and 80 μg/kg. Other members of this class are hexabromocyclododecane andorganophosphates. Both were determined by LC/MS-MS with LOQ of about 6 mg/kg.Carcinogenic polyaromatic hydrocarbons were also determined in leather samples using GC/MS-MS down to250 μg/kg.The last improved GC/MS analytical method was handling sewage sludge seeking multi residues of organicpolluants down to the 0.1 µg/l level or below. The analytical performances developed or improved allowedfor an efficient and useful control of the various sample received from the CTC customers and followinginternational quality rules; Dans le cadre de la protection de l’environnement et du consommateur, CTC effectue des tests enchimie analytique sur de nombreux paramètres en matrices aqueuses, cuir et textile. Les nouvelles substancesmises sur le marché ainsi que les réglementations évoluant sans cesse, le développement de nouvellesméthodes d’analyses est donc nécessaire.Plusieurs méthodes analytiques ont ainsi été développées. Pour l’analyse des rejets d’effluents industriels desinstallations classées et pour l’analyse d’innocuité de produits utilisant le cuir ou le textile (chaussures,maroquinerie, prêt-à-porter…).Les chloroalcanes ont été dosés en chromatographie gazeuse (GC) associée à la spectrométrie de masse (MS)utilisant l’ionisation chimique, à la fois en matrices aqueuses (limite de quantification, LQ, à 0,6 μg/l) et sur lescuirs (LQ à 2 mg/kg).Une analyse des alkylphénols et alkylphénols ethoxylates a été développée pour les matrices aqueuses parGC/MS (LQ à 0,05 μg/l).Plusieurs familles de retardateurs de flammes ont ensuite été étudiées. Les polybromodiphénylethers peuventêtre dosés dans les eaux (LQ

Photodissociation lifetimes and fragment channels of gas-phase, protonated YAn (n = 1,2) peptides and their dimers were measured with 266 nm photons. The protonated monomers were found to have a fast dissociation channel with an exponential lifetime of ∼200 ns while the protonated dimers show an additional slow dissociation component with a lifetime of ∼2 μs. Laser power dependencemeasurements enabled us to ascribe the fast channel in the monomer and the slow channel in the dimer to a one-photon process, whereas the fast dimer channel is from a two-photon process. The slow (1 photon) dissociation channel in the dimer was found to result in cleavage of the H-bonds after energy transfer through these H-bonds. In general, the dissociation of these protonated peptidesis non-prompt and the decay time was found to increase with the size of the peptides. Quantum RRKM calculations of the microcanonical rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system,estimated separately on the basis of the equipartition theorem. It demonstrates encouraging results in predicting fragmentation lifetimes of protonated peptides. Finally, we present the first experimental evidence for a photo-induced conversion of tyrosine-containing peptides into monocyclic aromatic hydrocarbon along with a formamide molecule both found in space. © 2012 American Institute of Physics. [doi:10.1063/1.3671943]