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International audience; Cyclohexane oxidation chemistry was investigated using a near-atmospheric pressure JSR at 570 K and ϕ = 0.8. Numerous intermediates including hydroperoxides and highly oxygenated molecules were detected using synchrotron vacuum ultraviolet photoelectron photoion coincidence spectroscopy. Supported by high-level quantum calculations the analysis of photoelectron spectra allowed the firm identification of molecular species formed during the oxidation of cyclohexane. Besides, this work validates recently published gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry data. Unambiguous detection of characteristic hydroperoxides (e.g. γ-ketohydroperoxides) and their respective decomposition products provide support for the conventional O2-addition channels up to the third addition and their relative contribution to the cyclohexane oxidation.The results were also compared to the predictions of a recently proposed new detailed kinetic model of cyclohexane oxidation. Most of the predictions are in line with the current experimental findings highlighting the robustness of the kinetic model. However, the analysis of the recorded slow photoelectron spectra indicating the possible presence of C5 species in the kinetic model provides hints that substituted cyclopentyl radicals from cyclohexyl ring opening might play a minor role in cyclohexane oxidation. Potentially important missing reaction are discussed.

International audience; tert-Butyl hydroperoxide (tBuOOH) is a common intermediate in the oxidation of organic compounds that needs to be accurately quantified in complex gas mixtures for the development of chemical kinetic models of low temperature combustion. This work presents a combined theoretical and experimental investigation on the synchrotron-based VUV single photon ionization of gas-phase tBuOOH in the 9.0 - 11.0 eV energy range, including dissociative ionization processes. Computations consist of the determination of the structures, vibrational frequencies and the energetics of neutral and ionic tBuOOH. The Franck–Condon spectrum for the tBuOOH+ (X+) + e− ← tBuOOH (X) + hν transition is computed, where special treatment is undertaken because of the flexibility of tBuOOH, in particular regarding the OOH group. Through comparison of the experimental mass-selected threshold photoelectron spectra with explicitly correlated coupled cluster calculations and Franck–Condon simulations that account for the flexibility of the molecule, an estimation of the ionization energy is given. The appearance energy of the only fragment observed within the above-mentioned energy range, identified as the tert-butyl C4H9+, is also reported. Finally, the signal branching ratio between the parent and the fragment ions is provided as a function of photon energy, essential to quantify tBuOOH in gas-phase oxidation/combustion experiments via advanced mass spectrometry techniques.

Diethyl ether (DEE) has been proposed as a biofuel additive for compression-ignition engines, as an ignition improver for homogeneous charge compression ignition (HCCI) engines, and as a suitable component for dual-fuel mixtures in reactivity-controlled compression ignition (RCCI) engines. The combustion in these engines is significantly controlled by low-temperature (LT) chemistry. Fundamental studies of DEE LT oxidation chemistry and of its influence in fuel-mixture oxidation are thus highly important, especially at elevated pressures. Elevated pressure speciation data were measured for the LT oxidation of DEE, of its similarly-structured linear five-heavy-atom hydrocarbon fuel (n-pentane), and of a mixture of the two fuels in a jet-stirred reactor (JSR) in the temperature range of 400–1100 K and at various pressures up to 10 bar. The pressure influence on the LT oxidation chemistry of DEE was investigated by a comparison of the measured profiles of oxidation products. The results for DEE and n-pentane were then inspected with regard to fuel structure influences on the LT oxidation behavior. The new speciation data were used to test recent kinetic models for these fuels [Tran et al., Proc. Combust. Inst. 37 (2019) 511 and Bugler et al., Proc. Combust. Inst. 36 (2017) 441]. The models predict the major features of the LT chemistry of these fuels well and could thus subsequently assist in the data interpretation. Finally, the LT oxidation behavior of an equimolar mixture of the two fuels was explored. The interaction between the two fuels and the effects of the pressure on the fuel mixture oxidation were examined. In addition to reactions within the combined model for the two fuels, about 80 cross-reactions between primary reactive species generated from these two fuel molecules were added to explore their potential influences.

International audience; The oxidation of neopentane was studied in jet-stirred reactors at atmospheric pressure over a temperature range 500–850 K and ϕ = 0.5. The products were analyzed with chromatographic, mass spectrometric, and photoelectron spectroscopic setups complemented with theoretical calculations. This combination provides a comparison of photo-ionization mass spectrometry and gas chromatography for the quantification of mole fractions and highlights the relevant differences between them, while mass-tagged photoelectron spectroscopy sheds light onto the isomeric distribution. The new data and corresponding analyses are expected to provide valuable guidance for an extension of the kinetic model and the choice of experimental methods. The main first and second O2-addition products were observed in agreement with the literature (e.g., 3,3-dimethyloxetane, acetone, isobutene, and γ-ketohydroperoxide). The simulated mole fractions of the products using a literature kinetic model were compared to the experimental results. Even though the kinetic model has been validated previously, significant discrepancies between the measured and simulated mole fractions of 2-methylpropanal and methacrolein, two fuel-specific low-temperature oxidation products, were found. Furthermore, some experimentally observed species related to γ-ketohydroperoxide decomposition were not predicted indicating that the model is incomplete. The detection of 2-methylpropanal and formic acid highlighted the importance of the Korcek-type pathway.

International audience; Lignocellulosic biomass is the most abundant carbon source and it is a base of the whole biorefinery concept. Levoglucosan (1,6-anhydro-β-D-glucopyranose) (LG) is an anhydrous sugar formed as a major product during pyrolysis of cellulose. LG might be a promising chemical platform. It can be converted to different high added-value chemicals such as levoglucosenone, 5-hydroxymethylfurfural and styrene directly or through a glucose intermediate via chemical, catalytic and biochemical processes. In this critical review we focus not only on the pyrolytic methods for the synthesis of levoglucosan, but above all also on the recent scientific progress in the chemical and biochemical transformation of levoglucosan to highly valued compounds. The catalytic performances of the heterogeneous and enzymatic catalytic systems used for different reactions of LG conversion are reviewed. Specific properties of the active sites, roles of additives, and solvents and conditions are discussed in detail. We conclude on recommendations to further improve LG conversion to high added-value products.

International audience; The determination of the abundances of the CHx, C=O and aromatic groups in chondritic Insoluble Organic Matter (IOM) and coals by Infrared (IR) spectroscopy is a challenging issue due to insufficient knowledge on the absorption cross-sections and their sensitivity to the molecular environment. Here, we report a calibration approach based on a 13C synthetic model material whose composition was unambiguously determined by Direct-Pulse/Magic Angle Spinning Nuclear Magnetic Resonance (DP/MAS NMR). Ratios of the cross-sections of the CHx, C=O and aromatic groups have been determined, and the method has been applied to IOM samples extracted from four chondrites as Orgueil (CI), Murchison (CM), Tagish Lake (C2-ungrouped) and EET 92042 (CR), and to a series of coals. The estimate of the aliphatic to aromatic carbon ratio (nCHx/nAro) in IOM samples from Orgueil, Murchison and Tagish Lake chondrites is in good agreement with Single-Pulse/NMR estimates earlier published, and is lower by a factor of 1.3 in the case of the CR chondrite EET 92042 (but the error bars overlap). In contrast, the aliphatic to carbonyl ratio (nCHx/nC=O) is overestimated for the four chondrites. These discrepancies are likely due to the control of the absorption cross-section of the C=O and C=C bonds by the local molecular environment. Regarding coals, the use of published NMR analyses has brought to light that the integrated cross-section ratio ACHx/AAro varies with the vitrinite reflectance over an order of magnitude. Here as well, the local oxygen speciation plays a critical control in AAro, which decreases with increasing the vitrinite reflectance. We provide an analytical law that links ACHx/AAro and vitrinite reflectance, which will allow the determination of nCHx/nAro for any coal sample, provided its vitrinite reflectance is known.

International audience; Di-n-butyl ether (DBE, C8H18O) has been proposed as a promising biofuel for diesel engines, but details of its low-temperature (LT) oxidation chemistry are not well understood. This paper reports new speciation data obtained in the temperature range of 400–1100 K at ϕ=1 and nearly-atmospheric pressure, using a plug flow reactor combined with electron ionization molecular-beam mass spectrometry (MBMS) and two different jet-stirred reactors coupled with either online gas chromatography or tunable synchrotron vacuum ultraviolet photoionization-MBMS.The experimental results confirm that DBE is very reactive and exhibits two negative-temperature coefficient (NTC) zones around 500–550 K and 650–750 K. Speciation data with about 40 C0-C8 species are presented, including about 20 LT species not reported previously. Among those, fuel-specific C8H16O2 cyclic ethers were quantified. Also, butanoic acid, which is present in highest amounts among the detected LT intermediates, and C8H14O3 diones, were found to peak already near 500 K, suggesting their importance in the LT chemistry of DBE. Signals of several highly oxygenated peroxides (e.g., C8H14O5 and C8H16O6) were detected, indicating third O2 addition steps. Respective reaction pathways are suggested and discussed based on these experimental results.To better understand the LT chemistry of DBE, the present data were compared to two recent DBE models (Cai et al., 2014; Thion et al., 2017). Significant discrepancies between the experimental data and both models were found for important LT intermediates, of which many were not included in the respective mechanisms. The results reported in the present study thus provide new opportunities for refining DBE kinetic models.

International audience; Diethyl ether (DEE) has been recently suggested as a potential biofuel for compression-ignition engines that are known to be significantly controlled by low-temperature (LT) chemistry. However, the LT oxidation of DEE has not fully been understood in term of the formation of LT fuel-specific products. We have thus studied the oxidation of DEE by examining detailed profiles of its oxidation products under LT conditions (400-1100 K). To this end, we have used a dedicated experimental setup including a nearly-atmospheric jet-stirred reactor (JSR) coupled to online gas chromatography (GC). The experiments were complemented by measurements made with a JSR coupled to tunable synchrotron vacuum ultraviolet (SVUV) photoionization (PI) molecular-beam mass spectrometry (MBMS) for a cross-validation of the identification of important LT species. Experimental results indicate that DEE is very reactive; it starts to react around 425 K. DEE exhibits an unusual oxidation behavior with two negative temperature coefficient (NTC) zones in the JSR study. Because of this two-NTC observation, additional experiments were performed with a plug flow reactor (PFR) combined with electron ionization (EI)-MBMS, confirming this behavior in the two types of reactor. Moreover, about 20 oxidation species in C1-C4 range were detected with several intermediates containing 2-3 O-atoms. Acetic acid is found to peak at 525 K with a very large amount, suggesting that it is a key species in the early stage of DEE's LT oxidation. Possible DEE-consumption paths leading to acetic acid formation could play an important role in the oxidation mechanism of DEE. A new model is proposed based on the present experimental observations to include new primary LT reaction paths. The model reproduces the experimental phenomena quite well and enhances the understanding of the two-NTC-zone occurrence and of intermediates containing 2-3 O-atoms during the LT oxidation of DEE.

openaire: EC/H2020/101006744/EU//EHLCATHOL Small aromatic molecules with oxygen-containing functional groups (monoaromatic oxygenates) are common products of the catalytic depolymerization of lignin, which can be considered as a promising class of fuel additives. This mini-review article starts with an introduction of second generation (2G) of biofuel production from lignocellulose and the further conversion of lignin into fuel performance boosting blends. The discussion is divided into four parts. The first part gives a brief overview of the production of aromatic oxygenates from the catalytic conversion of lignin of different origin. The three following parts are focused on the aromatic oxygenates, for which combustion data can be found. The second part describes their chemical structure and physical properties. The third part is dominated by their global combustion performance, i.e., the commercial fuel parameters as lower heating value, octane and cetane numbers. A few studies on ignition delay times and laminar flame velocities are also described. The fourth part shortly reviews the kinetic studies presenting product quantifications, the proposed detailed kinetic models and the influence of the structure of the aromatic reactant on soot formation. To finish, a perspective on future research directions is given.

Understanding the chemistry behind the oxidation of ammonia/hydrogen mixtures is crucial for ensuring the flexible use of such mixtures in several applications, related to propulsion systems and power generation. In this work, the oxidation of ammonia/hydrogen blends was investigated through an experimental and kinetic-modeling study, where the low- and intermediate-temperature conditions were considered. An experimental campaign was performed in a flow reactor, at stoichiometric conditions and near-atmospheric pressure (126.7 kPa). The mole fraction of fuels, oxidizer and final products was measured. At the same time, a comprehensive kinetic model was set up, following a modular and hierarchical approach, and implementing the recently-available elementary rates. Such a model was used to interpret the experimental results, and to extend the analysis to literature data, covering several oxidation features. The reactivity boost provided by H2 addition was found to be approximately linear with its mole fraction in both flow- and jet-stirred-reactor conditions (except for the smallest H2 amounts in the flow reactor), in contrast with the more-than-linear increase in the laminar flame speed. The key role of HO2 in regulating fuel conversion and autoignition at low temperature was confirmed for binary mixtures, with H2NO being the bottleneck to the low-temperature oxidation of NH3-rich blends. On the other hand, the nitrogen fate was found to be mostly regulated by NHx + NO propagation and termination channels.

Flammable gas/solid hybrid mixture explosions are not well understood because of the interaction of the thermal transfer process, the combustion kinetics mechanisms and the interactions between turbulence and combustion. The main objective on this work is to study the explosion severity and flame burning velocities of carbon black nanoparticles/methane to better understand the influence of added nanopowders in gas explosions. Tests have been performed in a flame propagation tube and in the standard 20 L explosion sphere. The influence of carbon black particles on the explosions severity and in the front flame propagation has been appreciated by comparing the results obtained for pure gas mixtures. It appeared that the carbon black nanoparticles insertion increases around 10% the explosion severity for lean methane mixtures. Therefore, it seems that nanoparticles has an impact on the severity of the explosion even for quiescent systems, contrary to systems involving micro-sized powders that requires a dispersion at high turbulence levels. The increment on the maximum rate of pressure rise is higher for powders with lower elementary particle diameter, which is notably due to the fragmentation phenomena. A flame propagation numerical model associated to a gas/carbon black mixture has been developed to examine the influence of carbon blacks on the flame propagation. The results of the numerical model suggest that the radiative heat contribution promotes the flame acceleration. This result is consistent with the experimental increase on the explosion severity for some hybrid mixtures, Les explosions de mélanges de gaz inflammables/solides combustibles ne sont pas bien comprises en raison de la complexité des transferts thermiques, des mécanismes de cinétiques et des interactions entre la turbulence /combustion. L'objectif principal de ce travail est d'étudier la sévérité des explosions des nanoparticules de carbone noir/méthane afin de comprendre l'influence de l'insertion des nanoparticules sur les explosions de gaz. Des tests ont été effectués sur ces mélanges dans un tube de propagation de la flamme et dans une sphère d'explosion standard de 20 L. L'influence de la turbulence initiale et de la taille de particule élémentaire du noir de carbone a également été étudiée. Il semble que l'insertion de nanoparticules de noir de carbone augmente d'environ 10% la sévérité de l’explosion pour les mélanges pauvres en méthane. Par conséquent, il semble que les nanoparticules ont un impact sur la sévérité de l'explosion même pour les systèmes à basse turbulence, contrairement aux systèmes impliquant des poudres de taille micrométrique qui nécessitent une dispersion à des niveaux élevés de turbulence. L'augmentation de la vitesse maximale de montée en pression est plus élevée pour des poudres avec un petit diamètre de particule, notamment en raison des phénomènes de fragmentation. En outre, un modèle numérique de propagation de front de flamme associé à un mélange gaz/noir de carbone a été développé pour examiner l'influence du noir de carbone sur la propagation de la flamme. Les résultats du modèle numérique suggèrent que la contribution de la chaleur radiative favorise l'accélération de la flamme. Ces résultats sont en accord avec les résultats expérimentaux de sévérité de l'explosion pour certains mélanges hybrides

International audience; This study aims to characterize the sedimentation velocity and the rheology of suspensions of hematite particles suspended in strongly alkaline media at 100 and 110 degrees C, as done for an alternative electrochemical process in development for iron production by direct electrode reduction of hematite. Considering the medium used in the process, i.e. 12% (v/v) suspension of hematite particles in 50% sodium hydroxide aqueous, the sedimentation velocity of hematite particle at 110 degrees C is 0.010 mm/s, which is very slow because the average size of the solid particles is around 10 mu m and the significant collisions and inter-actions occuring between the particles in the concentrated suspension. Two geometries were used to characterize the theological behavior of the apparent viscosity of the suspension of 12% (v/v) (i.e. 33 wt%) at 100 degrees C: a conventional Couette geometry and a helical ribbon mixer. The suspension was found shear thinning in the range of shear rate studied. The rheological behavior of the suspension can be described by a power-law model. The apparent viscosity of the hematite suspension estimated at a shear rate between 0.5 and 10 s(-1) is between 100 and 20 mPa s for the two geometries. The apparent viscosity calculated from the terminal velocity of 10 mu m particles is of the same order of magnitude of the results obtained with the two rheometer configurations. The effect of the particle concentration on the sedimentation velocity and viscosity of the hematite suspensions was also studied.

Two halophytes, Atriplex halimus and Atriplex hortensis , were selected to be tested for phytodesalination of road runoff. A 60 d pot experiment was conducted and germination, survival, growth, and bioaccumulation of NaCl and trace metals by both species were monitored in conditions simulating those encountered in road runoff treatment systems. NaCl concentration was controlled in the hydration solution and ranged from 0 to 2 g/L. Germination and survival of young seedlings were not affected by salinity increase in the tested range. Growth was enhanced by NaCl in the hydration solution for A. halimus whereas water content (WC) was significantly and negatively correlated with NaCl concentration. No significant effect of NaCl concentration in the hydration solution was recorded on either growth or WC for A. hortensis . Both Atriplex species accumulated Na + and other cations. Results for Na/K molar ratio indicated that A. halimus was not affected as much as A. hortensis in its homeostasis and nutritional capacities. These results show that both Atriplex species are able to germinate, grow and accumulate sodium when watered with hydration solutions polluted with NaCl. They are therefore good candidates for phytodesalination of road runoff polluted by deicing salts, and should be tested at the pilot scale.

International audience; The activated sludge process (ASP) is the most commonly used process for wastewater treatment. Improving its performance is necessary from economic and environmental point of views. In this context, dynamic optimization is a powerful tool for assisting engineers in determining optimal operations and designs for ASPs. However, the real optimality of the solution strongly depends on the optimization problem statement, for which unfortunately, there is no standard or commonly accepted formulation. In a hopeful attempt to provide a guideline for future works on the topic, this paper reviews the literature devoted to optimal control and design of ASPs. The main issues to be addressed in order to get reliable solutions are discussed , among which: (1) Managing the inevitable mismatch between the model predictions and the real ASP operation. (2) Dealing with the unpredictable variations in the wastewater characteristics. (3) Accounting for the slowest dynamic processes occurring in ASPs. (4) Appropriately selecting the decision variables and the flowsheet structure in order to simplify the problem formulation from a mathematical perspective. (5) Conveniently choosing the cost functions expressions/correlations. (6) Successfully selecting the mathematical constraints in order to guarantee physically relevant operations.

International audience; In this work, a multi-objective dynamic optimization of the operating strategy of a small-size wastewater treatment plant is carried out. In-situ incineration of the excess sludge produced for electricity production is investigated in order to reduce the operating costs. The trade-offs between the treatment quality and the operating costs are characterized. Compared to the literature, emphasis is put on a more rigorous formulation of the problem and an accurate modeling of the underlying phenomena so as to get physically relevant solutions. Thus, from a mathematical perspective, the problem is formulated so that the solution is less sensitive to the - arbitrarily chosen-plant initial conditions. Modeling of physical phenomena e.g. the detrimental effect of the concentration of suspended solids in the mixed liquor, on oxygen transfer rate, has been included in the model. Several constraints are added to the problem so as to maintain the optimal solutions within the limits of validity of the mathematical model. The results provided a clear picture about the trade-offs between the treatment quality and the exploitation costs. Sludge incineration was shown to be of a high energetic profit, but it does not allow the plant to be electrically autonomous.

The large application potential of microbiomes has led to a great need for mixed culture methods. However, microbial interactions can compromise the maintenance of biodiversity during cultivation in a reactor. In particular, competition among species can lead to a strong disequilibrium in favor of the fittest microorganism. In this study, an invert emulsion system was designed by dispersing culture medium in a mixture of sunflower oil and the surfactant PGPR. Confocal laser scanning microscopy revealed that this system allowed to segregate microorganisms in independent droplets. Granulomorphometric analysis showed that the invert emulsion remains stable during at least 24 h, and that the introduction of bacteria did not have a significant impact on the structure of the invert emulsion. A two-strain antagonistic model demonstrated that this invert emulsion system allows the propagation of two strains without the exclusion of the less-fit bacterium. The monitoring of single-strain cultures of bacteria representative of a cheese microbiota revealed that all but Brevibacterium linens were able to grow. A consortium consisting of Lactococcus lactis subsp. lactis biovar diacetylactis, Streptococcus thermophilus, Leuconostoc mesenteroides, Staphylococcus xylosus, Lactiplantibacillus plantarum and Carnobacterium maltaromaticum was successfully cultivated without detectable biotic interactions. Metabarcoding analysis revealed that the system allowed a better maintenance of alpha diversity and produced a propagated bacterial consortium characterized by a structure closer to the initial state compared to non-emulsified medium. This culture system could be an important tool in the field of microbial community engineering.

International audience; The prediction of solvation quantities is an important issue in several fields of chemical and process engineering. In this regard, this work was conducted to increase the prediction power of the equation-of-state (EoS) approach by coupling the tc-PR (translated-consistent Peng-Robinson) EoS with COSMO-RS (Conductor-like Screening Model for Real Solvents) as gE model through an advanced mixing rule. Since the only input parameter of the COSMO-RS model is the charge density (σ) profile of each molecule, the resulting EoS (called tc-PR/COSMO-RS) does not require any binary interaction parameter contrary to other predictive cubic EoS, such as VTPR, PPR78, PSRK, and UMR-PRU. This feature allows the quantification of solvation data of a great number of systems from readily available pure-component properties (critical temperature and pressure, acentric factor and σ -profile). Satisfactory results were obtained for the prediction of solvation Gibbs energy data that were extracted from the extensive CompSol database (the average absolute deviation is 0.30 kcal/mol). The proposed model represents a very flexible alternative for the prediction of solvation data, since it can deal with a large variety of solutes in either a pure or mixed solvent, and for the entire phase diagram (including the supercritical region).

International audience; Anaerobic reactor is one of gas-liquid-solid three-phase bio-reactors and has attracted high attentions worldwide due to biogas, a renewable energy. As is well-known, hydrodynamic conditions play crucial roles in the performance of the three-phase reactors. But the knowledge about the hydrodynamic conditions around sludge (microbial aggregates) is limited. The hydrodynamic shear force exerted on sludge derives from the liquid flow and rising biogas bubbles nearby. The in situ investigation in a two-dimensional micro anaerobic reactor shows that 56.8-96.6% shear rate exerted on one piece of granular sludge (major axis of 2 mm and minor axis of 1.5 mm) in typical motions stems from the rising bubbles when biogas production rate is greater than 0.1 m(3) kgVSS(-1) d(-1), and the superficial liquid velocity of reactor was fixed at 6.48 mh(-1) in this study. Furthermore it linearly correlates with specific bubble population with R-2 of superior to 0.95. The specific bubble population plays more important roles in the shear rate on granules than the bubble diameter. Liquid flow is also important for the shear rate exerted on moving sludge in term of the relative velocity between sludge and liquid flow rather than the superficial liquid velocity. Thus the shear rate derived from liquid flow would be significantly lower than that part originated from bubbles. A high-speed digital camera and a particle image velocimetry (PIV) system were used to in situ quantify the bubbles and their behavior in reactor. This study could facilitate understanding and improving the hydrodynamic conditions in three-phase bio-reactors.

The oxidation of dimethylether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K, equivalence ratios of 0.25, 1 and 2, residence time of 2 s, pressure of 106.7 kPa (close to the atmospheric pressure) and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde which is one of the major product from DME oxidation as well as that of hydrogen peroxide which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bar on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine and flame data from literature. The kinetic analysis of the model enabled to highlight some specificities of the oxidation chemistry of DME: 1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H-atom abstraction) with oxygen yielding an olefin + HO2●; 2) the low-temperature reactivity is driven by the relative importance of the second addition to O2 (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting effect. 119

International audience; The purpose of this work is to analyze the efficiency of natural adsorbents (rice husk ash (RHA) versus corn husk ash (CHA)) for the dry purification of ethyl biodiesels obtained by transesterification via homogeneous catalysis of nonedible oils (Balagnites aegyptiaca, Azadirachta indica, and Jatropha curcas). The characterization of RHA and CHA was achieved by N2 adsorption/Brunauer–Emmett–Teller analysis and by scanning electron spectroscopy with microanalysis by energy dispersive X-ray spectroscopy. The quality of the three biodiesels, before and after dry treatment on adsorbent, was evaluated by various analytical methods (1H nuclear magnetic resonance, gas chromatography with a flame ionization detector, Karl Fischer titration, and inductively coupled plasma–atomic emission spectroscopy). Several operating conditions (presence of activated carbon in the ashes, temperature, contact time, and number of treatment cycles) were tested in order to define the best procedure. RHA combined with the selected procedure showed very satisfactory results for removal of impurities from the produced biodiesels (residual glycerides, free glycerin, water, catalyst, and metals introduced during the oil extraction) and thus may be an alternative to the conventional wet purification process (acidic water washing).

International audience; Ammonia has a potential as carbon-free and high-energy density compound for chemical storage of renewable energies and its synthesis from green H2 requires to be as energetically efficient as possible. In this work, a superstructure optimization methodology for process synthesis is proposed and applied to an ammonia production process. The approach covers three different scales: process, equipment, and molecules. Process scale refers to finding the optimal process structure, while the equipment scale is related to the best set of operating conditions, and the molecular scale studies two catalysts (Fe and Ru) with their respective kinetic rates. The optimization intends to minimize the Levelized Cost of Ammonia (LCOA) and maximize the energy efficiency. The best trade-off is found with the Ru catalyst, with an LCOA of 766 €/tNH3 and 57.2 % of energy efficiency. In comparison with reference cases, the LCOA decreases 0.6 % and the energy efficiency increases 1.5%. The main improvement is found in the pressure, 75 bar, reduced in 25 %. The production of 11.6 tNH3/day equals to 2.5 MW of stored power from 3 MW supplied as H2 to the process, with a total energy consumption of 10.67 kW h/kgNH3, including prior H2 and N2 production processes.

International audience; Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn 2+-doped Ag−In−Ga−Zn−S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag + , In 3+ , Ga 3+ , and Zn 2+ and of Mn(stearate) 2 in oleylamine. The influence of the Mn 2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn 2+), and robust photo-and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM −1 s −1 and r 2 = 0.57 mM −1 s −1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.

International audience; The present work studies the bubble formation in viscous liquids with the viscosity ranging from 5 to 400 mPa s by using a high-speed digital camera. The experiment was carried out in a flow-focusing device with square cross-section of 600 x 600 mu m. Results show that the viscous shear stress strongly influences the dynamics of bubble formation, including the shape and size of bubbles. The bubble size follows power-law relations with the gas flow rate, the flow rate and viscosity of the liquid phase respectively, indicating that bubbles formed in viscous fluids are controlled by a combination of squeezing mechanism and shearing mechanism. Therefore, the bubble size can be predicted by a power law function depending on the flow rate ratio of gas and liquid phases phi representing the squeezing mechanism and capillary number Ca representing the shearing mechanism. In addition, the dynamics of bubble formation in viscous liquids in a flow focusing device is also analyzed.

Food transition requires the replacement in human diet of animal-based proteins by alternative sources of proteins including plant-based proteins. This calls for a detailed knowledge of the functional properties of plant-based proteins, including their surface activity. In this framework, we provide here a comparative study of the interfacial properties of two plant proteins, extracted respectively from wheat and sunflower. We combine time- and concentration-dependent measurements of the surface tension and the surface rheology, as measured with a pendant-drop set-up, and of the surface excess concentration, as measured by ellipsometry, of plant protein interfacial films. We demonstrate a time-concentration superposition principle for the surface pressure and surface excess concentration, showing that the kinetics for the building of the interfacial films is essentially governed by the diffusion of the proteins from the bulk to the interface. We find that the rheological and structural properties of the interfacial protein films show markedly different behaviors for the two classes of protein, which is encoded in the structural features of the individual proteins: wheat proteins are more surface active than sunflower proteins, are keen to compress and re-arrange at an air-water interface, whereas sunflower proteins do not. This work provides qualitative and quantitative analysis of the comparative interfacial behavior of flexible and rigid plant proteins extracted respectively from wheat and sunflower, and demonstrates that a combination of several experimental techniques is necessary to obtain insightful information on the interfacial properties of any species.

International audience

International audience; The formation of gas bubbles in a liquid is of both academic and industrial interest, and sets the initial conditions for the hydrodynamics, heat and mass transfer as well as chemical reactions from a dispersed gaseous phase to the liquid phase in industrial processes. The literature on bubble formation from a single submerged orifice is large in both Newtonian and non-Newtonian fluids. Despite the numerous theoretical and experimental investigations, the mechanisms of bubble growth and detachment remain far from fully understood. The study of bubble formation at micro-scale and especially in the presence of a lateral liquid flow field is still very limited. This is the topic for consideration in the present paper. In particular, this study compares both qualitatively and quantitatively the formation of bubbles at micro- and macro-scales. A high-speed digital camera (up to 10,000 images s(-1)), a micro-Particle Image Velocimetry (mu-PIV) system and also a macro-PIV (PIV) were employed in this work, to measure the velocity flow field at micro- and macro-scales. At macro-scale, experiments were conducted in a square Altuglas column of 0.1 m filled with water or viscous Emkarox solutions using different orifice sizes and various gas flowrates. A rotating device above the orifice in the column was used to impose a shear flow on the forming bubble at the orifice. At micro-scale, different sizes of micro-reactors (600 and 1000 mu m) and different micro-devices were employed to compare the mechanism of bubble formation. A correlation based on dimensionless numbers was proposed to estimate the formed bubble volume at micro- and macro-scales in order to reveal the main factors governing the formation mechanisms.

International audience; The motion and interactions of three equal-interval parallel bubbles in non-Newtonian fluids were numerically simulated by volume of fluid method (VOF), in which the continuous surface tension model and the power-law model were adopted to represent surface tension and rheological properties of non-Newtonian fluids, respectively. The computational method was validated by the comparison of the processes of coalescence of two in-line bubbles and rising of two parallel bubbles between experiment and simulation. This method was then applied to study the effect of initial bubble diameter, initial horizontal bubble interval and rheological properties of non-Newtonian fluids on lateral coalescence and rising of three parallel bubbles. The dimensionless critical horizontal interval of bubble coalescence was obtained under different physical property conditions. The critical horizontal interval of bubble coalescence decreases with the increase of initial bubble diameter and flow index of non-Newtonian fluids. When the initial horizontal bubble interval is less than the critical horizontal interval of bubble coalescence, three bubbles will coalesce into a bigger bubble. The coalescing bubble could breakup into two identical daughter bubbles when the initial bubble diameter was increased or the flow index of non-Newtonian fluids was decreased. Three parallel bubbles rising in non-Newtonian fluids will experience repulsive interactions once the initial horizontal bubble interval is greater than the critical horizontal interval of bubble coalescence, the horizontal bubble interval increased gradually owing to the repulsive effect, while the vertical distance between bubbles varied dramatically for spherical bubble and ellipsoidal bubble due to the differences of their flow field structures.

International audience; Nanoparticles are widely suggested as targeted drug-delivery systems. In photodynamic therapy (PDT), the use of multifunctional nanoparticles as photoactivatable drug carriers is a promising approach for improving treatment efficiency and selectivity. However, the conventional cytotoxicity assays are not well adapted to characterize nanoparticles cytotoxic effects and to discriminate early and late cell responses. In this work, we evaluated a real-time label-free cell analysis system as a tool to investigate in vitro cyto- and photocyto-toxicity of nanoparticles-based photosensitizers compared with classical metabolic assays. To do so, we introduced a dynamic approach based on real-time cell impedance monitoring and a mathematical model-based analysis to characterize the measured dynamic cell response. Analysis of real-time cell responses requires indeed new modeling approaches able to describe suited use of dynamic models. In a first step, a multivariate analysis of variance associated with a canonical analysis of the obtained normalized cell index (NCI) values allowed us to identify different relevant time periods following nanoparticles exposure. After light irradiation, we evidenced discriminant profiles of cell index (CI) kinetics in a concentration- and light dose-dependent manner. In a second step, we proposed a full factorial design of experiments associated with a mixed effect kinetic model of the CI time responses. The estimated model parameters led to a new characterization of the dynamic cell responses such as the magnitude and the time constant of the transient phase in response to the photo-induced dynamic effects. These parameters allowed us to characterize totally the in vitro photodynamic response according to nanoparticle-grafted photosensitizer concentration and light dose. They also let us estimate the strength of the synergic photodynamic effect. This dynamic approach based on statistical modeling furnishes new insights for in vitro characterization of nanoparticles-mediated effects on cell proliferation with or without light irradiation.

High solid anaerobic digestion (HSAD) is a promising technology for the treatment of organic waste. Mixing process in HSAD is quite difficult with long mixing time, poor homogenization, significant short-circuiting and stagnant zones. However, the mass transfer in mixing process in HSAD has not been visualized due to the lack of a proper method. In this study, a novel approach for experimentally quantifying the mass transfer in HSAD’s mixing process was proposed in a mixing tank equipped with multistage impellers by means of the Laser Induced Fluorescence (LIF) technique. Flow field was investigated for better illustrating the mass transfer, thus Particle Image Velocimetry (PIV) and Computational Fluid Dynamics (CFD) technique were conducted for flow field measurement. The obtained results revealed that the feedstock tended to accumulate around the impeller in the HSAD system, especially near the 1st stage. The tracer diffused rapidly around the 1st impeller in t = 10 s, but the diffusion around the 2nd impeller was quite tough even after 4 h 08 min 23 s. And prolonging mixing time could not significantly improve the flow pattern along with the mixing. In this study, new insight was thrown into the visualization of the mass transfer in mixing process within a HSAD reactor. The visualization of mass transfer in the mixing process in HSAD could offer reference information to the study of the mixing process of HSAD even in full-scale.

International audience; Photodynamic therapy (PDT) is an emerging theranostic modality for various cancer as well as non-cancer diseases. Its efficiency is mainly based on a selective accumulation of PDT and imaging agents in tumor tissue. The vascular effect is widely accepted to play a major role in tumor eradication by PDT. To promote this vascular effect, we previously demonstrated the interest of using an active- targeting strategy targeting neuropilin-1 (NRP-1), mainly over-expressed by tumor angiogenic vessels. For an integrated vascular-targeted PDT with magnetic resonance imaging (MRI) of cancer, we developed multifunctional gadolinium-based nanoparticles consisting of a surface-localized tumor vasculature targeting NRP-1 peptide and polysiloxane nanoparticles with gadolinium chelated by DOTA derivatives on the surface and a chlorin as photosensitizer. The nanoparticles were surface-functionalized with hydrophilic DOTA chelates and also used as a scaffold for the targeting peptide grafting. In vitro investigations demonstrated the ability of multifunctional nanoparticles to preserve the photophysical properties of the encapsulated photosensitizer and to confer photosensitivity to MDA-MB-231 cancer cells related to photosensitizer concentration and light dose. Using binding test, we revealed the ability of peptide-functionalized nanoparticles to target NRP-1 recombinant protein. Importantly, after intravenous injection of the multifunctional nanoparticles in rats bearing intracranial U87 glioblastoma, a positive MRI contrast enhancement was specifically observed in tumor tissue. Real-time MRI analysis revealed the ability of the targeting peptide to confer specific intratumoral retention of the multifunctional nanoparticles.

International audience; The computation of solvation energies has many uses in several fields, such as design of separation processes, pharmacology and drug-design, and kinetic modeling. These applications require thermodynamic models capable of accurately predicting solvation energies, accounting for the temperature dependency of this property, and which are fast and robust. Within this framework, we compared two COSMO-based continuum solvation models (COSMO-RS and COSMO-SAC-dsp) with two versions of predictive cubic equations of state well-acknowledged for their efficiency (PSRK and UMR-PRU). For this purpose, a large experimental set of 65,000 datapoints extracted from the COMPSOL databank was considered. Comparisons between computed and experimental data were performed for Gibbs solvation energy and, for the first time in the literature, for both entropy and enthalpy of solvation simultaneously. For simpler binary mixtures, in which hydrogen bonding does not take place, all models were capable of providing accurate predictions, with average absolute deviations below 0.3 kcal/mol regarding the solvation Gibbs energy. For more complex associating mixtures, COSMO-RS showed the best correlation between experimental and calculated data, especially for aqueous systems; among EoS, it is observed that the PSRK model offers the best accuracy.

In the present work, L-glutamic acid production by Corynebacterium glutamicum fermentation on date juice extracts applying two fed-batch feeding modes, pulsed and continuous, were investigated. According to the obtained results, the continuous feeding fed-batch mode was found to be the most efficient process. Moreover the continuous feeding rate mode with a feeding medium containing date juice sugars enriched with ammonium sulfate was found even more favorable as it enhances the L-glutamic acid production by approximately 2.35 fold more than the batch culture and by about 1.17 fold more than the pulsed feeding. In this respect, comparing the traditional batch culture to the continuously fed culture with a medium containing date juice sugars with ammonium sulfate showed increases of 135.47% in L-glutamic acid production, 104% in productivity, 39.09% in biomass, and 47.69% in the yield respectively allowing us to reach a final L-glutamic acid concentration of about 138 g/L, the highest ever published.

International audience; The adsorption of a sunflower protein extract at two air− water and oil−water interfaces is investigated using tensiometry, dilational viscoelasticity, and ellipsometry. For both interfaces, a three step mechanism was evidenced thanks to master curve representations of the data taken at different aging times and protein concentrations. At short times, a diffusion limited adsorption of proteins at interfaces is demonstrated. First, a two-dimensional protein film is formed with a partition of the polypeptide chains in the two phases that depends strongly on the nature of the hydrophobic phase: most of the film is in the aqueous phase at the air−water interface, while it is mostly in the organic phase at the oil−water interface. Then a three-dimensional saturated monolayer of proteins is formed. At short times, adsorption mechanisms are analogous to those found with typical globular proteins, while strong divergences are observed at longer adsorption times. Following the saturation step, a thick layer expands in the aqueous phase and appears associated with the release of large objects in the bulk. The kinetic evolution of this second layer is compatible with a diffusion limited adsorption of the minor population of polymeric complexes with hydrodynamic radius R H ∼ 80 nm, evidenced in equilibrium with hexameric globulins (R H ∼ 6 nm) in solution. These complexes could result from the presence of residual polyphenols in the extract and raise the question of the role of these compounds in the interfacial properties of plant protein extracts.

Nickel hyperaccumulation in Blepharidium guatemalense Standl. (Rubiaceae) was found in the tropical forests of south-eastern Mexico. This study aimed to document the geographic extent of nickel hyperaccumulation in this species, to understand its process of hyperaccumulation and to explore nickel distribution within the tissues of this plant. To accomplish these objectives, a complete non-destructive elemental screening of herbarium specimens was performed with a hand-held X-ray fluorescence spectrometer. Besides, rhizosphere soils and plant tissues were collected in Mexico and analyzed for physical–chemical parameters. Finally, elemental distribution maps of nickel and other elements in plant tissues were obtained by X-ray fluorescence spectroscopy and microscopy. This study revealed that Blepharidium guatemalense is distributed throughout Chiapas, Tabasco and Campeche, reaching the maximum nickel concentration in leaves (4.3 wt%) followed by roots and seeds (2.0 wt%) and bark (1.8 wt%). Simultaneous hyperaccumulation of cobalt and nickel was found in 15% of the herbarium specimens. Blepharidium guatemalense has uncommon re-distribution mechanisms via phloem since this tissue is the highest nickel-enriched from all parts of the plant (from roots to leaves). A high total nickel (mean of 610 µg g−1) was found in rhizosphere soils even though no evidence of ophiolite emplacement in that area has been reported. Blepharidium guatemalense represents the first hypernickelophore (> 1 wt% Ni) to be reported as growing in soils that are neither ultramafic nor enriched by anthropogenic pollutants.

Cyclic and aromatic hydrocarbons are important components of usual commercial fuels, with C6-rings being among the most abundant cyclic structures. The combustion chemistry of C6-rings involves different levels of unsaturation, either as initial fuels (aromatics, naphtenes, …) or as intermediates formed during their combustion. In this work the ignition delays of cyclohexane, cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene are systematically studied using experiments and kinetic modeling. Shock tube experiments were performed at high-temperature (above 1200 K) and for mean pressures of 6 atm. A detailed chemical kinetic model was developed that includes the combustion chemistry of the four cyclo-C6 fuels. Electronic structure calculations were performed at the CCSD(T)/CBS//B2PLYP-D3 level of theory on the pericyclic reactions of the unsaturated fuels. Pressure-dependent rate coefficients were computed by solving the master equation, and included in the mechanism. The model was validated against the new ignition data and against data of the literature. It was able to reproduce the experimental ranking of reactivity: cyclohexene > 14-CHD > cyclohexane > benzene ≈13-CHD. Kinetic analyses were performed to explain this difference of reactivity. It is shown that pericyclic reactions play a major role in the initial decomposition of the unsaturated fuels.

International audience; A theoretical study of the thermal decomposition of β-1,4-xylan, a model polymer of hemicelluloses, is proposed for the first time. A mechanism based on unimolecular concerted reactions is elaborated in a comprehensive way. Elementary reactions, such as dehydrations, retro-aldol, retro Diels–Alder, retro-ene, glycosidic bond fissions, isomerizations, etc., are applied to β-1,4-xylan, as well as to the fragments formed. At each stage of the construction of the mechanism, the fragments previously retained are decomposed and the low energy paths are selected to define new fragments. Energy barriers are computed at the CBS-QB3 level of theory and rate coefficients of important reactions are calculated. It is shown that the main reaction pathways can be modelled by reactions involving two specific fragments, which react in closed sequences, similarly to chain-propagating reactions. The proposed reaction scheme allows to predict important species observed during the pyrolysis of xylan, such as aldehydes or CO. In addition, we show that dehydrations require high activation energy and cannot compete with the other reactions. Therefore, it seems difficult to explain, by means of unimolecular homogeneous gas phase reactions, the significant formation of specific species such as furfural as reported by several authors.

International audience; Urea is used in Selective Catalytic and Non Catalytic Reduction (SCR and SNCR) methods for NOx abatement in post-combustion processes. The decomposition of urea-water solution in exhaust systems leads to the formation of NH3, which is the NOx reducing agent. However, the decomposition of urea can also lead to the formation of unwanted pyrolysis by-products, particularly in region where the temperature and pressure conditions are not optimal or via wall-spray interactions. In this study, a gas phase kinetic model for urea pyrolysis is proposed to explain the growth of pyrolysis by-products of urea, and in particular, the route of formation of the major product: isocyanuric acid. Systematic theoretical calculations, using electronic structure calculations and transition state theory, were performed to explore all the possible unimolecular and bimolecular reactions of the initial species. Kinetic modeling was used to select the relevant reaction pathways at each growing step, and their rate constants were refined using CCSD(T)/CBS//B2PLYP-D3/cc-pvTZ calculations. Quantum calculations showed that the postulated growing schemes of the literature, based on the successive urea + HNCO ⇆ biuret, biuret + HNCO ⇆ triuret followed by the cyclization of triuret into isocyanuric acid are not energetically favored. It is observed that the most favored reaction route to isocyanuric acid involves carbamimidic acid, the urea tautomer, that first yields biuret in a reaction with HNCO and then is involved in the formation of triuret by reacting with a decomposition product of biuret. Isocyanuric acid is produced from the reaction between HNCO and the same decomposition product of biuret. This new mechanism of formation of isocyanuric acid is tested at different conditions to explore its most favored conditions of formation in the gas phase. Exploratory simulations of a pseudo condensed phase are also performed to qualitatively simulate condensed phase experiments and explain the observed pyrolysis yields.

International audience; The understanding of the thermal decomposition chemistry of chemical warfare nerve agents is largely limited by the scarcity of kinetic data. Because of the high toxicity of these molecules, experimental determination of their chemical properties is very difficult. In the present work, a comprehensive detailed kinetic model for the decomposition of sarin and some simulants, i.e. di-isopropyl methyl phosphonate (DIMP), diethyl methylphosphonate (DEMP), and triethyl phosphate (TEP) were developed, containing possible molecular and radical pathways. The importance of unimolecular pericyclic decomposition led to evaluate precisely the rate constants of these reactions with high level theoretical calculations. The QCISD(T)/cc-PV∞QZ//B2PLYPD3/6-311+G(2d,d,p) level of theory was selected after a benchmark. The contribution of hindered rotors was included with the 1D-HR-U approach. Tunneling was taken into account for H-atom transfer. Transition state theory was used to calculate high-pressure limit rate constants and pressure dependent rate constants were calculated using Master Equation modelling. The model was validated against experimental pyrolysis and oxidation experimental data available in literature. Flux analyses showed that whatever the conditions are, the first step of decomposition of the studied phosphorus compounds are pericyclic eliminations leading to successive decompositions, whereas bondbreaking or H-atom abstraction remain negligible, even at high temperature.

Preventing lipid oxidation, especially with the polyunsaturated fat-based products, is a major concern in sectors as agri-food and cosmetic. Even though the efficiency of synthetic antioxidants has been recognized, both consumers and manufacturers are looking for more innovative, healthy and quality products while rejecting synthetic additives due to their concern about safety, along with their environmental impact issues. In this context, plant biomass, which have shown to be rich in compounds, have raised interest for the isolation of novel naturally occurring antioxidants. Among their myriad of molecules, bioactive peptides, which are biologically active sequence of amino acid residues of proteins, seem to be of a great interest. Therefore, the number of identified amino acids sequences of bioactive peptides from plant biomass with potential antioxidant action is progressively increasing. Thus, this review provides a description of 129 works that have been made to produce bioactive peptides (hydrolysate, fraction and/or isolate peptide) from 55 plant biomass, along with the procedure to examine their antioxidant capacity (until 2019 included). The protein name, the process, and the method to concentrate or isolate antioxidant bioactive peptides, along with their identification and/or specificity were described. Considering the complex, dynamic and multifactorial physico-chemical mechanisms of the lipid oxidation, an appropriate in-vitro methodology should be better performed to efficiently probe the antioxidant potential of bioactive peptides. Therefore, the results were discussed, and perspective for antioxidant applications of bioactive peptides from plant biomass was argued., Graphical abstract Image 1, Highlights • Exhaustive description of 129 works made to produce bioactive peptides from 55 plant biomass. • Controlled proteolysis can be used as a sustainable strategy to produce peptides. • Presentation of the important points to consider when estimating the antioxidant capacity of peptides. • Methodology should be improved to better probe the antioxidant potential of peptides.

The effect of the lockdown imposed to limit the spread of SARS-CoV-2 in France between March 14 and May 11, 2020 on the wastewater characteristics of two large urban areas (with between 250,000 and 300,000 inhabitants) was studied. The number of outward and inward daily commuters was extracted from national census databases related to the population and their commuting habits. For urban area A, with the larger number of daily inward commuters (110,000, compared to 53,000 for B), lockdown was observed to have an effect on the monthly load averages of chemical oxygen demand, biochemical oxygen demand, total Kjeldahl nitrogen, total suspended solids and total phosphorus, all of which decreased (confidence level of 95%). This decrease, which varied between 20% and 40% and reached 45% for COD, can be related to the cessation of catering and activities such as hairdressing, which generate large amounts of graywater. The ammonium loads, due to the use of toilets before leaving for work and after returning from work, remained constant. In the case of urban area B, lockdown had no noticeable effect. More data would be necessary in the long term to analyze the effect of changes in the balance between ammonia and carbon sources on the operation of wastewater treatment plants.

1H-Phenalen-1-one is a very efficient and easy-to-synthesize photosensitizer. Many substitutions have been previously described, but most of them significantly reduce the singlet oxygen quantum yield. The chloromethyl derivative described elsewhere is a good starting point for the synthesis of many useful derivatives because of the methylene bridge that saves its unique photosensitizing properties. Eighteen new phenalenone derivatives have been synthesized, bearing amine, carboxylic acid, alcohol, azide, and other major functional groups in organic chemistry. These reactions were carried out in good-to-excellent yields, and most of these new compounds retained the singlet oxygen quantum yield of the parent molecule. These new derivatives are very promising precursors for a number of applications such as the development of photosensitive antimicrobial agents or materials.

The term “Industry 4.0″, which refers to a fourth industrial revolution, is a recent neologism. The rise of digital technology including, artificial intelligence, the Internet of things and networks, “smart” and responsive devices, etc … is more and more omnipresent. In solving the related challenges of Industry 4.0, it is necessary to improve the involvement and training of employers and employees. This is particularly true for their education in process safety. Two surveys were submitted to the relevant stakeholders. Their results showed absence of industry 4.0 topics in the current courses on process safety. On the other hand, a review of the master's degree programs available in Europe revealed the recent emergence of new highly specialized courses in some of the topics of industry 4.0. The definition of “Safety 4.0″ leads to recommend two potential global training pathways, with one corresponding to the requirements of Industry 4.0 & Safety 4.0 intersections, recommended within the framework of pedagogical taxonomy models.

The tension on the supply of surgical and FFP2 masks during the first wave of the COVID-19 pandemic leads to study the potential reuse of these masks. As washing is easily adaptable at home, this treatment solution was retained. In this work, thirty-six references of surgical masks and four FFP2 masks were tested without being worn or washed and after several washing cycles. The results highlighted a great heterogeneity of performances depending on the mask trademarks, both for surgical masks and FFP2. The quality of the meltblown and spunbond layers and the presence/absence of electrostatic charges at the fiber surface are put forward to explain the variability of results, both on differential pressures and filtration efficiencies. The differential pressure and the particle filtration efficiency of the washed masks were maintained up to 10 washing cycles and met the standard requirements. However, an immersion in water with a detergent induces an efficiency decrease for submicronic particles. This lower performance, constant after the first washing cycle, can be explained by the loss of electrostatic charges during the washing cycle. The modifications of surface properties after washing also lead to a loss of the hydrophobic behavior of type IIR surgical masks, which can therefore no more be considered as resistant to blood projections.

In this study we provide a multi-physical and multi-scale characterization of an organic Phase Change Material (PCM), i.e. hexadecane, for both itsliquid and solid phases and during the phase transition. Macroscopic thermal and physical properties provided are density and viscosity in the liquidphase and thermal conductivity and heat capacity in each phase. Further macroscopic measurements were done by differential scanning calorimetry (DSC), which was used to obtain a first estimation of temperatures at which the solid/liquid phase transition occurs. DSC results always show a well pronounced thermal hysteresis between melting (Tm) and solidification temperature (Ts). A similar hysteresis was also collected during rotational and oscillatory rheometry at the phase change, where Ts is found to depend on the applied cooling rate. Moreover, near Ts the forming solid structure is continuously affected by conditions imposed by the rheometer (i.e. applied shear rate or stress) and the breakage of crystals takes place even for the smallest imposed stress tested (0.001 Pa). Beside the bulk behavior, the local melting and solidification were studied at microscopic scale though Raman spectroscopy. The local melting temperature is very close to what found by DSC and by rheometry. On the other hand, crystallization onset is found at higher temperatures for long waiting times, thus considerably reducing the thermal hysteresis. Finally, we highlight a key influence of interfaces on the phase transition. Variations in boundary conditions (thermal and/or kinematical conditions) are found responsible for the way hexadecane’s solidification occurs. This strongly impacts the efficiency with which energy is generated and absorbed during the phase change and needs to be carefully taken into account when designing new thermal energy storage systems.

International audience; Preventing oxidation and microbial spoilage are both major concerns in food industries. In this context, this study aimed to valorize the total rapeseed meal proteins with controlled enzymatic proteolysis to generate potent mineral-chelating peptides from cruciferins while keeping intact the antimicrobial napins. Implementation of proteolysis of total rapeseed protein isolate with the Prolyve® enzyme highlighted an interesting selective hydrolysis of the cruciferins. Hence, the mechanism of this particular hydrolysis was investigated through a Design of Experiments method to obtain a model for the prediction of kinetics (cruciferin degradation and napin purity) according to the operating conditions applied. Then, multicriteria optimization was implemented to maximize the napin purity and yield while minimizing both enzymatic cost and reaction time. Antioxidant assays of the peptide fraction obtained under the optimal conditions proved the high metal-chelating activity preservation (EC50 = 247 ± 27 µg) for more than three times faster production. This fraction might counteract lipid oxidation or serve as preventing agents for micronutrient deficiencies, and the resulting purified napins may have applications in food safety against microbial contamination. These results can greatly help the development of rapeseed meal applications in food industries.

Despite conventional treatment combining complete macroscopic cytoreductive surgery (CRS) and systemic chemotherapy, residual microscopic peritoneal metastases (mPM) may persist as the cause of peritoneal recurrence in 60% of patients. Therefore, there is a real need to specifically target these mPM to definitively eradicate any traces of the disease and improve patient survival. Therapeutic targeting method, such as photodynamic therapy, would be a promising method for such a purpose. Folate receptor alpha (FRα), as it is specifically overexpressed by cancer cells from various origins, including ovarian cancer cells, is a good target to address photosensitizing molecules. The aim of this study was to determine FRα expression by residual mPM after complete macroscopic CRS in patients with advanced high-grade serous ovarian cancer (HGSOC). A prospective study conducted between 1 June 2018 and 10 July 2019 in a single referent center accredited by the European Society of Gynecological Oncology for advanced EOC surgical management. Consecutive patients presenting with advanced HGSOC and eligible for complete macroscopic CRS were included. Up to 13 peritoneal biopsies were taken from macroscopically healthy peritoneum at the end of CRS and examined for the presence of mPM. In case of detection of mPM, a systematic search for RFα expression by immunohistochemistry was performed. Twenty-six patients were included and 26.9% presented mPM. In the subgroup of patients with mPM, FRα expression was positive on diagnostic biopsy before neoadjuvant chemotherapy for 67% of patients, on macroscopic peritoneal metastases for 86% of patients, and on mPM for 75% of patients. In the subgroup of patients with no mPM, FRα expression was found on diagnostic biopsy before neoadjuvant chemotherapy in 29% of patients and on macroscopic peritoneal metastases in 78% of patients. FRα is well expressed by patients with or without mPM after complete macroscopic CRS in patients with advanced HGSOC. In addition to conventional cytoreductive surgery, the use of a therapeutic targeting method, such as photodynamic therapy, by addressing photosensitizing molecules that specifically target FRα may be studied.

International audience; Beta-nicotinamide adenine dinucleotide (NAD + /NADH) is an important enzymatic co-factor that can be efficiently regenerated using a rhodium-based catalyst as electron transfer mediator (i.e. [Cp*Rh(bpy)Cl] + , where Cp* = pentamethylcyclopentadienyl and bpy = 2,2-bipyridine). Here, the above mediated regeneration of NADH is implemented in a redox flow bioreactor hybridized with a gas diffusion electrode for hydrogen oxidation. The reactor was initially optimized with respect to rhodium complex and NAD + concentrations, humidification of the hydrogen gas, flow rates of both H 2 gas and electrolytic solution, and solution pH. The integration of an enzymatic reaction consuming the generated NADH was then investigated in a flow process, combining in series the electrochemical reactor to a biochemical cell with immobilized L-lactic dehydrogenase for the conversion of pyruvate to lactate. A high activity was achieved with a turnover number up to 370 h-1 for NADH regeneration. Coupled electrochemical regeneration to enzymatic reaction led to total turnover number values of 2000 and 6.3*10 6 for NADH electrochemical regeneration and bioconversion, respectively.

Context.The chemical building blocks of life contain a large proportion of nitrogen, an essential element. Titan, the largest moon of Saturn, with its dense atmosphere of molecular nitrogen and methane, offers an exceptional opportunity to explore how this element is incorporated into carbon chains through atmospheric chemistry in our Solar System. A brownish dense haze is consistently produced in the atmosphere and accumulates on the surface on the moon. This solid material is nitrogen-rich and may contain prebiotic molecules carrying nitrogen.Aims.To date, our knowledge of the processes leading to the incorporation of nitrogen into organic chains has been rather limited. In the present work, we investigate the formation of nitrogen-bearing ions in an experiment simulating Titan’s upper atmosphere, with strong implications for the incorporation of nitrogen into organic matter on Titan.Methods.By combining experiments and theoretical calculations, we show that the abundant N2+ion, produced at high altitude by extreme-ultraviolet solar radiation, is able to form nitrogen-rich organic species.Results.An unexpected and important formation of CH3N2+and CH2N2+diazo-ions is experimentally observed when exposing a gas mixture composed of molecular nitrogen and methane to extreme-ultraviolet radiation. Our theoretical calculations show that these diazo-ions are mainly produced by the reaction of N2+with CH3radicals. These small nitrogen-rich diazo-ions, with a N/C ratio of two, appear to be a missing link that could explain the high nitrogen content in Titan’s organic matter. More generally, this work highlights the importance of reactions between ions and radicals, which have rarely been studied thus far, opening up new perspectives in astrochemistry.

International audience; The phase behavior of the CO2 (1) + 2,3-dimethylbutane (2) binary mixture has been experimentally studied between 293 and 373 K. Saturation pressures, ranging from 14.0 to 112.2 bar, were visually measured using a high-pressure cell at carbon dioxide mole fractions between 0.20 and 0.93.78 experimental points have been measured: 67 bubble points and 11 dew points. Experimental results reveal that the vapor-liquid critical locus is a continuous curve between the two pure compounds, meaning that the studied binary system exhibits a type I or II phase behavior in the classification scheme of Van Konynenburg and Scott. The experimental data can be very satisfactorily represented by the Peng-Robinson equation of state with mixing rules that embed a temperature-dependent binary interaction parameter.

International audience; In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of Diesel fuel, n-heptane, ethylbenzene, n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1100 K and for a residence time of 2 s. Based on results previously obtained close to atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions were compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C7 diones was found significantly enhanced at 10 bar compared to lower pressures. The oxidation of ethyl-and n-butylbenzene was investigated at 10 bar for equivalence ratios of 0.5, 1 and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C8 fuels and of 19 products for the C10 one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.