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International audience; Thin-film composite of chitosan/nickel phthalocyanine (NiPc) was electrochemically deposited on the fingers of interdigitated gold electrodes, applying chronoamperometric polymerization technique. The presence of crystallized NiPc in the chitosan was confirmed by EDX and FTIR analysis. Acetone, ethanol, and methanol gas-sensing properties of the films prepared at optimum conditions were studied at atmospheric temperature, through differential measurements at an optimized frequency of 10 kHz, using a lock-in amplifier. The conductometric sensor presents the highest sensitivity of 60.2 μS.cm−1(v/v) for methanol and 700 ppm as the limit of detection. For validation, the methanol content of a commercial rubbing alcohol was determined.

A conductometric transducer is proposed for the first time for the detection of ethanol vapor. This ethanol microsensor is prepared by encapsulation of alcohol dehydrogenase (ADH) in chitosan. Interdigitated electrodes fabricated by silicon technology were used. The electrodeposition of chitosan allows the addressing of the chitosan film on the microconductometric devices and to encapsulate ADH and nicotinamide adenine dinucleotide (NAD+), which was monitored by FTIR. The analytical performance of the ethanol microsensor was determined in gaseous methanol, ethanol, and acetone samples, collected from the headspace above aqueous solutions of known concentration. The response time (tRec) of the sensor varies from 7 to 21 s from lower concentrations to higher concentrations. The detection limit is 0.12v/v % in the gas phase, corresponding to 0.22 M in the liquid phase. The relative standard deviation for the same sensor is from 12% for lower concentrations to 2% for higher concentrations. The ethanol sensor presents 2.6 times lower sensitivity for methanol and 28.3 times lower sensitivity for acetone. A detection of ethanol in the headspace of a red wine sample lead to an alcohol content in good agreement with the value given by the producer.

Urban air pollution is partly due to exhaust emissions from road transport. Vehicle emissions have been regulated for more than 30 years in many countries around the world. Each motor type is equipped with a specific emission control system. In gasoline vehicles, a three-way catalytic converter (TWC) is implemented to remove at the same time hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). However, TWCs are only efficient above 200 °C and at a stoichiometric air-to-fuel ratio in the exhaust. However, deviations from stoichiometry occur during fast accelerations and decelerations. This study reports the analysis of unregulated VOCs commercial mini-TWC fed by model gasoline gas mixtures. A synthetic gas bench was used to control the model exhaust containing two model hydrocarbons (propene and propane) to identify the conditions at which VOCs are created under non-optimal conditions. Most of the pollutants such as N2O and VOCs were emitted between 220 and 500 °C with a peak at around 280 °C, temperature which corresponds to the tipping point of the TWC activity. The combination of different mass spectrometric analysis (online and offline) allowed to identify many different VOCs: carbonated (acetone, acetaldehyde, acroleine), nitrile (acetonitrile, propanenitrile, acrylonitrile, cyanopropene) and aromatic (benzene, toluene) compounds. Growth mechanisms from propene and to a lesser extend propane are responsible for the formation of these higher aromatic compounds that could lead to the formation of secondary organic aerosol in a near-field area.

International audience; A novel and ideal immunosensor platform with customized tailored chemistry is suggested by combining the characteristics of nanofibers (NFs) and dendrimers. Polystyrene (PS) NFs were doped with polyamidoamine (PAMAM) dendritic polymer and utilized for covalent immobilization of FITC-labeled anti-human TNF-alpha antibodies by activation of the amine groups of dendrimer on the surface of NFs using a glutaraldehyde (GA) coupling agent. SEM, ATR-FTIR, contact angle, EDX, XPS, TGA, and fluorescence microscopy were performed. The findings demonstrated that (1) PS-PAMAM NFs were produced with significantly smaller diameters (295 +/- 94 nm), more uniform morphology, and more hydrophilic (44 +/- 5.5 degrees) with dendrimer amine groups on the surface that can provide a better path for antibodies to be immobilized compared to pure PS NFs, (2) the PAMAM was distributed evenly throughout the NFs, (3) GA was uniformly applied to the surface of NFs via covalent bonding, (4) the PAMAM played a critical role in substantially increasing antibody immobilization at the surface of each NFs without causing agglomeration. According to the findings, the P5-PAMAM electrospun mat is suitable for immobilizing biomolecules and may be utilized as a support to boost immunosensor sensitivity.

International audience; Low methoxyl pectin is known to gel with divalent cations (e.g. Ca2+, Zn2+). In this study, a new way of pectin gelation in the presence of an active pharmaceutical ingredient, chlorhexidine (CX), was highlighted. Thus chlorhexidine interactions with pectin were investigated and compared with the well-known pectin/Ca2+ binding model. Gelation mechanisms were studied by several physico-chemical methods such as zeta potential, viscosity, size measurements and binding isotherm was determined by Proton Nuclear Magnetic Resonance Spectroscopy (H-1 NMR). The binding process exhibited similar first two steps for both divalent ions: a stoichiometric monocomplexation of the polymer followed by a dimerization step. However, stronger interactions were observed between pectin and chlorhexidine. Moreover, the dimerization step occurred under stoichiometric conditions with chlorhexidine whereas non-stoichiometric conditions were involved with calcium ions. In the case of chlorhexidine, an additional intermolecular binding occurred in a third step.

International audience; In order to analyze light hydrocarbons mixtures with silica monolithic columns, a conventional gas chromatograph was modified to work with carrier gas pressure as high as 60bar. To understand hydrodynamic flow and retention with short columns (less than 30cm), special attention was required due to the temperature difference between the oven area and the FID detector which contain a significant length of the column. Efficiency and selectivity using various carrier gases (helium, nitrogen and carbon dioxide) at different inlet pressure for different oven temperature were studied. Carrier gas nature was a very significant parameter: on one side, linked to adsorption mechanism for gases like nitrogen and carbon dioxide onto the stationary phase modifying retention and selectivity, on the other side in relation to the minimum theoretical plate height which was as low as 15μm (66 000 platem(-1)) using carbon dioxide as carrier gas. The chromatographic system was then used to separate methane, ethane, ethylene, acetylene, propane, cyclopropane, and butane in less than 30s.

In this work, an enzymatic sensor, based on a bionanocomposite film consisting of a polyelectrolyte complex (PEC) (Chitosan/kappa-carrageenan) doped with gold nanoparticles (AuNPs) encapsulating glucose oxidase (GOD) deposited on a gold electrode (Au) for glucose sensing, is described. Using the electrocatalytic synergy of AuNPs and GOD as a model of enzyme, the variation of the current (&micro, A) as a function of the log of the glucose concentration (log [glucose]), shows three times higher sensitivity for the modified electrode (283.9) compared to that of the PEC/GOD modified electrode (93.7), with a detection limit of about 5 &micro, M and a linearity range between 10 &micro, M and 7 mM. The response of the PEC/AuNPs/GOD based biosensor also presents good reproducibility, stability, and negligible interfering effects from ascorbic acid, uric acid, urea, and creatinine. The applicability of the PEC/AuNPs/GOD based biosensor was tested in glucose-spiked saliva samples and acceptable recovery rates were obtained.

The physicochemical and kinetic properties of resols prepared with different catalysts (NaOH, LiOH and Ba(OH)2) and variable formaldehyde/phenol ratios (2.5 £ R £ 3.5) were followed to determine their effects on the mechanisms and reaction products at a fixed pH and temperature. Kinetic monitoring and quantification of residual monomers were carried out by liquid chromatography coupled with mass spectrometry (LC/UV/MS), by 13C nuclear magnetic resonance (NMR) and by chemical assay for formaldehyde. Oligomer formation (n ≥ 2) was determined by LC/UV/MS, size exclusion chromatography (SEC) and 13C NMR. It was found that minor compounds form during syntheses (phenol methanol hemiacetals, hemiacetals of phenol and of oligomers…) and that the ratio R affects primarily the kinetics of formation of monomers and oligomers, in contrast to the catalysts that modify reaction mechanisms. The understanding of the structure of the resols was an important step for the determination of the final properties of the material.

International audience; New biosourced alternated poly(ether)Ester-Amides PeEA were prepared by polycondensation in solution or in bulk of unprecedented aminoalcohols based on 1,4:3,6-dianhydrohexitols (DAH) with aromatic and aliphatic diacyl chlorides (sebacoyl, terephtaloyl and isophtaloyl). Optimization of the polymerization in solution has been investigated using MALDI ToF MS and NMR spectroscopy to ascertain the structures and end chain nature of the resulting polymers. The influence of the DAH stereochemistry and the polymerization mode on the structures and thermal properties was demonstrated by MALDI ToF and complementary analytical techniques (DSC and SEC). Isomannide based polymers revealed amorphous but showed higher Tg (around 80 °C for sebacoyl and 180 °C for isophtaloyl) whereas the isosorbide based polymers were semi crystalline. Best properties were obtained in bulk using isomannide based aminoalcohol and sebacoyl chloride (Tg of 82 °C and Mw of 32 kDa, PDI = 1.41).

The physicochemical characterization of the structures of the oligomers (n < 4) in resols has been carried out by fragmenting monomers in LC/UV/MS and LC/UV/MS/MS. Fragmentation mechanisms are related to the numbers and positions of substituents on the aromatic ring and to the types of oligomer junctions. It was more difficult to determine the structures of phenol hemiacetals and dimer hemiacetals because of the large number of position isomers. The resols were prepared with differing molar ratios R = Formaldehyde/Phenol and catalysts. They were cross-linked using two industrially recommended heat cycles. The progression of resin cross-linking was determined by solid state 13C NMR (CP/MAS). The residual percentage of monomers and oligomers at n < 4 was determined in leachates (water and methanol) and characterized by LC/UV/MS. The results for cross-linking advancement were correlated with the various synthesis parameters (ratio R, type of catalyst and heat cycle).