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International audience; A novel fluorescent aryl-extended phenoxycalix[4]pyrrole ditopic sensor with enhanced cation recognition properties was efficiently synthesized via click chemistry and characterized through both molecular fluorescence and nuclear magnetic resonance spectroscopy. Results demonstrate the selectivity of this fluorescent sensor for fluoride when taking into account its interaction with anions, while its cation binding properties showed selectivity for iron, and its sensing properties for several cations in dimethylsulfoxide. This work introduces a new ditopic receptor able to complex major environmentally relevant species and depicts the importance of click chemistry in the introduction of new tetra-chromophoric calix[4]pyrrole binding platforms with specific photophysical properties.

International audience; A HPLC double reaction monitoring MS/MS method was developed for the determination of a wide range (>20) of sulphonamide residues in several edible animal (sheep, pork, beef, chicken and dromedary) tissues. Sample preparation was based on the simultaneous extraction into acetonitrile solution followed by a clean-up using primary secondary amine beads. Quantification was carried out using matrix-matched calibration curves. The limit of detection (LOD) and limit of quantification (LOQ) ranged from 0.5 to 14.5 μg kg-1 and from 1.8 to 48.4 μg kg-1, respectively. The decision limit (CCα) and decision capability (CCβ) obtained were below 100 μg kg-1 for sulphonamides and below 5 μg kg-1 for dapsone. The method was validated in terms of recoveries and inter- and intra-day precision by reference analyses of meat samples using LC-Orbitrap MS and by the analysis of a reference material. The method was applied to the analysis of several animal tissue samples collected in Lebanon. The highest values were observed for sulfamethazine and sulfadimethoxine at 70.2 and 62.5 μg kg-1 in sheep tissues.

International audience; The degradation of imazalil was achieved in three different advanced oxidation processes, namely UV/TiO2, UV/K2S2O8 and UV/TiO2/K2S2O8. The most relevant findings showed that for the UV/TiO2 system, the best efficiency was obtained at alkaline pH for which the rate of degradation is governed by imazalil adsorption onto TiO2, while for the UV/TiO2/K2S2O8 system, the best efficiency was obtained at acidic pH for which the rate of degradation is governed by persulfate adsorption onto TiO2 surface. In this last case, sulfate adsorption can reduce e−/h+ recombination while sulfate radicals are generated. Concerning the UV/K2S2O8 system, it was shown that pH does not play an important role in the degradation and persulfate concentration is the main factor governing the rate of degradation. Experiments with tert-butanol were achieved at different pH and the results showed that at pH = 6.5 and with a ratio [K2S2O8]/[imazalil] = 100, hydroxyl radicals were responsible for 67.6% of the degradation in the UV/TiO2 system, 3.1% in the UV/K2S2O8 system, meaning that the degradation should be mainly attributed to sulfate radicals and 33.2% in the UV/TiO2/K2S2O8 system meaning that both OHradical dot and SO4radical dot− were involved in the degradation. Coming to the comparison of photoproducts by using LC/MS/MS (pH = 6.5), the conclusion is that hydroxylated products were more produced in the UV/TiO2 system while a mechanism involving a charge transfer would be responsible of the degradation with persulfate systems. TOC analysis shows that total mineralization was reached faster in systems containing persulfate.

International audience; The photocatalytic degradation of imazalil, a probably carcinogen fungicide, was carried out in an aqueous suspension of titanium dioxide under UV irradiation. The influence of alcohols as hydroxyl scavengers (isopropanol, methanol) on the degradation was studied and different concentrations were used. We conclude that the degradation of imazalil occurs mainly by OHradical dot attack, since 80% of the degradation was inhibited in the presence of isopropanol [isopropanol] = 1000 [imazalil]. Using HPLC/DAD and LC-MS/MS analysis, nine intermediates were identified giving monohydroxylated, dihydroxylated and mostly a hole attack for other products. Their kinetic evolution profiles were plotted and compared to those with isopropanol. The quantity of photoproducts formed by OHradical dot radicals was decreased in the presence of isopropanol. After that a tentative pathway mechanism was proposed including mainly hydroxyl radical attack with the participation of holes in the degradation. Ion chromatography showed that nitrogen groups in imidazole were converted to both NH4+ and NO3−. In addition, TOC was examined in details and total mineralization was reached.

International audience; Eutrophication and harmful algal blooms have become a worldwide environmental problem. Understanding the mechanisms and processes that control algal blooms is of great concern. The phytoplankton community of Karaoun Reservoir, the largest water body in Lebanon, is poorly studied, as in many freshwater bodies around the Mediterranean Sea. Sampling campaigns were conducted semi-monthly between May 2012 and August 2013 to assess the dynamics of its phytoplankton community in response to changes in physical-chemical and hydrological conditions. Karaoun Reservoir is a monomictic waterbody and strongly stratifies between May and August. Changes in its phytoplankton community were found to be a result of the interplay between water temperature, stratification, irradiance, nutrient availability and water level. Thermal stratification established in spring reduced the growth of diatoms and resulted in their replacement by green algae species when nutrient availability was high and water temperatures lower than 22 °C. At water temperature higher than 25 °C and low nutrient concentrations in summer, blooms of the cyanobacterium Microcystis aeruginosa occurred. Despite different growth conditions in other lakes and reservoir, cyanobacterium Aphanizomenon ovalisporum dominated at temperatures lower than 23 °C in weakly stratified conditions in early autumn and dinoflagellate Ceratium hirundinella dominated in mixed conditions, at low light intensity and a water temperature of 19 °C in late autumn. We believe that the information presented in this paper will increase the knowledge about phytoplankton dynamics in the Mediterranean region and contribute to a safer usage of reservoir waters.

International audience; RATIONALE:Boscalid is a carboximide fungicide mainly used for vineyard protection as well as for tomato, apple, blueberry and various ornamental cultivations. The structural elucidation of by-products arising from the UV-visible photodegradation of boscalid has been investigated by gas chromatography/multi-stage mass spectrometry (GC/MS(n) ) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) couplings. The potential toxicities of transformation products were estimated by in silico calculations.METHODS:Aqueous solutions of boscalid were irradiated up to 150 min in a self-made reactor equipped with a mercury lamp. Analyses were carried out using a gas chromatograph coupled with an ion trap mass spectrometer operated in both electron ionization (EI) and chemical ionization (CI) modes and a liquid chromatograph coupled with a quadrupole time-of-flight (Q-TOF) mass spectrometer operated in electrospray ionization (ESI) mode. Multiple-stage collision-induced dissociation (CID) experiments were performed to establish dissociation pathways of ions. The QSAR (Quantitative Structure-Activity Relationship) T.E.S.T. program allowed the estimation of the toxicities of the by-products.RESULTS: Eight photoproducts were investigated. Chemical structures were proposed not only on the interpretation of multi-stage CID experiments, but also on kinetics data. These structures led us to suggest photodegradation pathways. Three photoproducts were finally detected in Lebanon in a real sample of grape leaves for which routine analysis had led to the detection of boscalid at 4 mg kg(-1).CONCLUSIONS: With one exception, the structures proposed for the photoproducts on the basis of mass spectra interpretation have not been reported in previous studies. In silico toxicity predictions showed that two photoproducts are potentially more toxic than the parent compound considering oral rat LD50 while five photoproducts may induce mutagenic toxicity. With the exception of one compound, all photoproducts may potentially induce developmental toxicity.

International audience; A new high performance liquid chromatography-high resolution mass spectrometry (HPLC-HRMS) method was developed for a simultaneous multi-residue analysis of 22 sulfonamides (SAs) and their metabolites in edible animal (pig, beef, sheep and chicken) tissues. Sample preparation was optimized on the basis of the "QuEChERS" protocol. The analytes were identified using their LC retention times and accurate mass; the identification was further confirmed by multi-stage high mass accuracy (

International audience; Chrysosporum ovalisporum is a cylindrospermopsin toxin producing cyanobacterium that was reported in several lakes and reservoirs. Its growth dynamics and toxin distribution in field remain largely undocumented. Chrysosporum ovalisporum was reported in 2009 in Karaoun Reservoir, Lebanon. We investigated the factors controlling the occurrence of this cyanobacterium and vertical distribution of cylindrospermopsin in Karaoun Reservoir. We conducted bi-weekly sampling campaigns between May 2012 and August 2013. Results showed that Chrysosporum ovalisporum is an ecologically plastic species that was observed in all seasons. Unlike the high temperatures, above 26 °C, which is associated with blooms of Chrysosporum ovalisporum in Lakes Kinneret (Israel), Lisimachia and Trichonis (Greece) and Arcos Reservoir (Spain), Chrysosporum ovalisporum in Karaoun Reservoir bloomed in October 2012 at a water temperature of 22 °C during weak stratification. Cylindrospermopsin was detected in almost all water samples even when Chrysosporum ovalisporum was not detected. Chrysosporum ovalisporum biovolumes and cylindrospermopsin concentrations were not correlated (n = 31, r2= −0.05). Cylindrospermopsin reached a maximum concentration of 1.7 μg L−1. The vertical profiles of toxin concentrations suggested its possible degradation or sedimentation resulting in its disappearance from the water column. The field growth conditions of Chrysosporum ovalisporum in this study revealed that it can bloom at the subsurface water temperature of 22 °C increasing the risk of its development and expansion in lakes located in temperate climate regions. © 2014 by the authors; licensee MDPI, Basel, Switzerland.

International audience; The intercalation of L-DOPA into the interlayer space of saponite, a 2:1 phyllosilicate, and the nature of host−guest interactions are investigated by a combined experimental and theoretical approach. L-DOPA zwitterions are accommodated vertically in the interlayer region as a bilayer of partially interdigitated species. The hydration state of the nanocomposite as well as the interaction geometry of L-DOPA molecules in the clay interlayer, are determined by periodic DFT calculations and found to be in agreement with experimentally obtained data. New insights into the transport properties for biomolecules in saponite are discussed.

International audience; Concentrations of 20 minor, trace, and ultratrace elements relevant to human health (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Si, Sn, V, and Zn) were determined in three varieties of Lebanese bread (white and brown double loaf bread, Saj bread) sampled at five geographical regions (Grand Beirut, South of Lebanon, North of Lebanon, Mount of Lebanon, and Beka'a) during the wet and dry seasons. The analyses were carried out by double-focusing sector-field inductively coupled plasma-mass spectrometry (DF-SF-ICP-MS). The data were discussed in terms of nutritional elements supplied by type of bread, the risk of contamination by toxic elements (As, Cd, Pb) owing to the manufacturing process, and variations related to geographic distribution and seasonal sampling.

International audience; Concentrations of 20 minor, trace and ultratrace elements relevant to human health (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Si, Sn, V) were determined in four different varieties of the most consumed cheese in Lebanon (Halloumi, Double Crème, Baladi, Labneh) sampled at five different provinces (Grand Beirut, South of Lebanon, North of Lebanon, Mount of Lebanon and Beka'a) during the wet and dry seasons. The analyses were carried out by double focussing sector field inductively coupled plasma-mass spectrometry (ICP-MS) in order to avoid errors due to polyatomic interferences. Levels of toxic elements (As, Cd, Pb) were generally below the WHO permissible levels in dairy products. Concentrations of most elements were considerably affected by the type of cheese, the geographical site and the season of sampling.

Water pollution presents a very critical problem facing industrial and developping countries. The environmental monitoring of the contaminants seems necessary to understand their sources and impacts. Among a wide variety of organic pollutants present in water, polycyclic aromatic hydrocarbons (PAHs) and pesticides are of particular importance as widespread, persistent, and toxic contaminants. They are usually present at trace levels in the acquatic surfaces; therefore their detection and control require selective and sensitive analytical procedures. The Solid-Phase Extraction (SPE) followed by the Gas-Chromatography coupled to Mass Spectrometry (GC-MS) are the most commonly used techniques for their analysis in water. Thesis objectives are focused on the development of new analytical methods for the extraction and analysis of these two families of pollutants present in water. To overcone the contraints of the traditional SPE, a new approach was developed consisting on the introduction of the centrifugation in several steps of the procedure. The new method showed practical environmental and economical advantages in terms of sample preparation time, simplicity, reduction in solvent use, and cost and is particularly suitable for routine applications requiring a high sample throughput. A programmed temeperature vaporizing (PTV) injection method was also optimized and validated in order to improve the detection limits for the GC-MS analysis of PAHs. The evaluation of the quality of different water systems in Lebanon including rainwater, groundwater, drinking water and surface water was accomplished in this study., La pollution des eaux est particulièrement problématique pour les pays industrialisés et les pays en développement. Des suivis environnementaux se sont alors avérés nécessaires afin de progresser dans la compréhension des origines et des conséquences de la présence de ces polluants. Parmi les polluants organiques les plus dangereux, les Hydrocarbures Aromatiques Polycycliques (HAP) et les pesticides qui peuvent se retrouver à l'état de traces dans les milieux aquatiques. Leur analyse nécessite des méthodes analytiques à la fois spécifiques et sensibles. L'Extraction sur Phase Solide (SPE) suivi d'une analyse par la Chromatographie Gazeuse couplée à la Spectrométrie de Masse (GC-MS) est la méthode la plus couramment employée. Les travaux de thèse s'inscrivent ainsi dans l'optique générale visant à développer des nouvelles méthodes analytiques pour l'extraction et l'analyse de ces deux familles de polluants organiques présents dans l'eau. Afin de pallier les contraintes classiques de la SPE, une nouvelle approche a été développée qui consiste à introduire la technique de centrifugation dans certaines étapes de la procédure SPE. La nouvelle méthode élaborée a permis de réduire considérablement le temps de préparation et d'économiser l'utilisation et le rejet des solvants organiques, en réduisant presque 10 fois les volumes nécessaires à l'obtention des rendements de récupération satisfaisants. Une méthode d'analyse par injection à température programmable (PTV) a été optimisée afin d'améliorer les seuils de détection des HAP. Cette étude a permis également d'avoir les informations sur la qualité des eaux de pluie, eaux souterraines et eaux de surface au Liban quant au niveau de leur contamination pour les HAP et les pesticides.

International audience; In the present study, HPLC/ESI-MS and stopped-flow HPLC/1H NMR methods were developed and applied to separate and characterize the byproducts arising from TiO2-catalyzed photodegradation of the herbicide iodosulfuron methyl ester (IOME) in aqueous solution under UV irradiation. Prior to identification, irradiated solutions of IOME (200 and 1000 mg·L-1) were concentrated by solid-phase extraction using two cartridges: Isolute C18 and Isolute ENV+. Analytical separation was achieved on a C18 reversed-phase column with ACN/H2O (HPLC/MS) or ACN/D2O (HPLC/NMR) as mobile phase and a linear gradient with a chromatographic run time of 35 min. The combination of UV and MS data allowed the structural elucidation of more than 20 degradation products, whereas 1 H NMR data permitted an unequivocal confirmation of the identities of major products and the differentiation of several positional isomers, in particular, the hydroxylation isomers. The obtained results permitted us to propose a possible degradation scheme and to put in evidence the presence of privileged sites for the attack of OH radicals. This work shows, for the first time, the application of combined HPLC with UV, MS, and NMR detection for complete structural elucidation of photocatalytic degradation products, and it will be of particular value in studies on the elimination of pollutants in aqueous solutions by photocatalysis.