Oxydation humide des polluants organiques par l'oxygène moléculaire activée par le couple H²O²/Fe²+: Optimisation des paramètres opératoires

L'oxydation humide par l'oxygène moléculaire (procédé WAO) activée par le couple (H202/Fe2+) a été mise en oeuvre pour l'oxydation de la pollution organique aqueuse à travers deux composés modèles: l'acide succinique, normalement oxydable, et l'acide acétique, réputé réfractaire. L'influence des différents facteurs a été étudiée par la planification d'expériences. Après leur recensement, une étape préliminaire de criblage a été menée à bien en utilisant une matrice de Plackett et Burman. Seuls les paramètres les plus influents ont été gardés pour l'étape ultérieure d'établissement de modèles prévisionnels à partir d'une matrice composite centrée orthogonale. Les modèles établis ont été validés et ont permis de déterminer les conditions optimales de fonctionnement. L'effet de la température fait apparaître un optimum, à environ 200 °C, au-delà duquel la décomposition du peroxyde devient trop rapide. L'effet de la quantité de peroxyde d'hydrogène introduit est déterminant et l'ajout de moins de 20 % de la quantité stoechiomé- trique permet d'obtenir à 200 °C, avec environ 10 ppm de sels de fer, une efficacité de traitement d'environ 70% pour un composé normalement oxydable. Dans des conditions analogues, le procédé conventionnel sans promoteur conduit à une efficacité inférieure à 5 %.Wet air oxidation (WAO) is a liquid phase oxidation process using molecular oxygen at high temperature (250-300°C) and high pressure (50-150 bar). It can help treating toxic organic aqueous wastes from chemical industries with efficiencies up to 98% after 1 hour. The process can also help treating sludges from domestic sewage treatment facilities. It is usually very cost effective because of the very high operating pressure.This paper deals with the promoted wet air oxidation of acetic acid, rnodel compound for refractory wastes, and succinic acid, model for readily oxidized wastes. The study was conducted in order to determine the promoting effect when adding small dosages of hydrogen peroxide (with iron salts) during oxidation by molecular oxygen. It was previously shown that the initiating step is very temperature dependent (Reaction I) and limits the overall oxidation process The addition of small amounts of H2O2/Fe2+ (Fenton's reagent) can promote the forrnation of very reactive OH• radicals able to develop R• radicals (Reaction IV), even at a low temperature. Then, the oxidation (Reactions VI and VII) continues using molecular oxygen, but the peroxide should be added continuously during a batch test in order to maintain the initiating step.An optimal design methodology was used in order to assess the dependency of the oxidation effrciency on the various parameters and mainly on the promotors. At frrst, a Plackett and Burman design of experiments (PE1) was used to screen the most important variables among those likely to have an effect. The design of experiments, the conditions of the runs and the results (tables 1 to 3) allowed the determination of a new experimental domain and the selection of the four most important variables for the further design of experiments. At the same time, the effect of an addition of phenol (able to reduce iron to the ferrous species, more efficient) was considered. For succinic acid oxidation, a central composite optimal design (PE2) was used (tables 4 and 5). The results allowed us to establish a predictive model (Relationship lX, table 6 and figure 2) and typical results are presented in figures 3 and 4. Approximately 50% oxidation efficiencies could be obtained at 200°C; without peroxide addition, only 5% efficiency is obtained under similar conditions. Moreover, it was observed that the optimum temperature is around 205°C and that phenol is not compatible with peroxide as a promotor. A third optimal design (PE3) was used to predict the efficiency of the method for the treatrnent of acetic acid, a model for a refractory waste. It is composed only of a fractional factorial design (table 7 and 8) and the bias corresponds to the main quadratic effect of temperature (Relationship XIII and table 10). The optimum temperâture is also 205°C and greater than 20% oxidation efficiencies are obtained; at such a temperature, acetic acid cannot be oxidized with the conventional process.The results obtained for the two model compounds validate this oxidation technique. The addition of about 10 ppm of ferrous iron and of less than 20% of the stoichiometric amount in hydrogen peroxide can turn a high pressure WAO process into a medium pressure one

Magnetic and thermal properties of 4f-3d ladder-type molecular compounds

We report on the low-temperature magnetic susceptibilities and specific heats of the isostructural spin-ladder molecular complexes L$_{2}$[M(opba)]_{3\cdot xDMSO$\cdot y$H$_{2}$O, hereafter abbreviated with L$_{2}$M$_{3}$ (where L = La, Gd, Tb, Dy, Ho and M = Cu, Zn). The results show that the Cu containing complexes (with the exception of La$_{2}$Cu$_{3}$) undergo long range magnetic order at temperatures below 2 K, and that for Gd$_{2}$Cu$_{3}$ this ordering is ferromagnetic, whereas for Tb$_{2}$Cu$_{3}$ and Dy$_{2}$Cu$_{3}$ it is probably antiferromagnetic. The susceptibilities and specific heats of Tb$_{2}$Cu$_{3}$ and Dy$_{2}$Cu$_{3}$ above $T_{C}$ have been explained by means of a model taking into account nearest as well as next-nearest neighbor magnetic interactions. We show that the intraladder L--Cu interaction is the predominant one and that it is ferromagnetic for L = Gd, Tb and Dy. For the cases of Tb, Dy and Ho containing complexes, strong crystal field effects on the magnetic and thermal properties have to be taken into account. The magnetic coupling between the (ferromagnetic) ladders is found to be very weak and is probably of dipolar origin.Comment: 13 pages, 15 figures, submitted to Phys. Rev.

Impaired exercise training-induced muscle fiber hypertrophy and Akt/mTOR pathway activation in hypoxemic patients with COPD

Exercise training (ExTr) is largely used to improve functional capacity of chronic obstructive pulmonary disease (COPD) patients. However, ExTr partially restores muscle function in COPD patients, suggesting that confounding factors may limit the efficiency of ExTr. In the present study, we hypothesized that skeletal muscle adaptations triggered by ExTr could be compromised in hypoxemic COPD patients. Vastus lateralis muscle biopsies were obtained from normoxemic (n = 15; resting arterial PO2 = 68.5 +/- 1.5 mm Hg) and hypoxemic (n = 8; resting arterial PO2 = 57.0 +/- 1.0 mm Hg) COPD patients before and after a 2 month-ExTr program. ExTr induced a significant increase in exercise capacity both in normoxemic and hypoxemic COPD patients. However, ExTr increased citrate synthase and lactate dehydrogenase enzyme activities only in skeletal muscle of normoxemic patients. Similarly, muscle fiber cross-sectional area and capillary-to-fiber ratio were only increased in normoxemic patients. Expression of atrogenes (MuRF1, MAFbx/Atrogin-1) and autophagy-related genes (Beclin, LC3, Bnip, Gabarapl) remained unchanged in both groups. The phosphorylation level of Akt (Ser473), GSK-3beta (Ser9) and p70S6k (Thr389), which was non-significantly increased in normoxemic patients in response to ExTr, was significantly decreased in hypoxemic patients. We further showed on C2C12 myotubes that hypoxia completely prevented IGF-1-induced phosphorylation of Akt, GSK-3beta and p70S6K. Together, our observations suggest a role for hypoxemia in the adaptive response of skeletal muscle of COPD patients to ExTr

Time Correlation Functions of Three Classical Heisenberg Spins on an Isosceles Triangle and on a Chain: Strong Effects of Broken Symmetry

At arbitrary temperature $T$, we solve for the dynamics of single molecule magnets composed of three classical Heisenberg spins either on a chain with two equal exchange constants $J_1$, or on an isosceles triangle with a third, different exchange constant $J_2$. As T\rightrarrow\infty, the Fourier transforms and long-time asymptotic behaviors of the two-spin time correlation functions are evaluated exactly. The lack of translational symmetry on a chain or an isosceles triangle yields time correlation functions that differ strikingly from those on an equilateral trinagle with $J_1=J_2$. At low $T$, the Fourier transforms of the two autocorrelation functions with $J_1\ne J_2$ show one and four modes, respectively. For a semi-infinite $J_2/J_1$ range, one mode is a central peak. At the origin of this range, this mode has a novel scaling form.Comment: 9 pages, 14 figures, accepted for publication in Phys. Rev.

Elemental nitrogen partitioning in dense interstellar clouds

Many chemical models of dense interstellar clouds predict that the majority of gas-phase elemental nitrogen should be present as N2, with an abundance approximately five orders of magnitude less than that of hydrogen. As a homonuclear diatomic molecule, N2 is difficult to detect spectroscopically through infrared or millimetre-wavelength transitions so its abundance is often inferred indirectly through its reaction product N2H+. Two main formation mechanisms each involving two radical-radical reactions are the source of N2 in such environments. Here we report measurements of the low temperature rate constants for one of these processes, the N + CN reaction down to 56 K. The effect of the measured rate constants for this reaction and those recently determined for two other reactions implicated in N2 formation are tested using a gas-grain model employing a critically evaluated chemical network. We show that the amount of interstellar nitrogen present as N2 depends on the competition between its gas-phase formation and the depletion of atomic nitrogen onto grains. As the reactions controlling N2 formation are inefficient, we argue that N2 does not represent the main reservoir species for interstellar nitrogen. Instead, elevated abundances of more labile forms of nitrogen such as NH3 should be present on interstellar ices, promoting the eventual formation of nitrogen-bearing organic molecules.Comment: Accepted for publication in the Proceedings of the National Academy of Sciences of the United States of America - published online since June 11, 201

Proteasomal degradation of the histone acetyl transferase p300 contributes to beta-cell injury in a diabetes environment

In type 2 diabetes, amyloid oligomers, chronic hyperglycemia, lipotoxicity, and pro-inflammatory cytokines are detrimental to beta-cells, causing apoptosis and impaired insulin secretion. The histone acetyl transferase p300, involved in remodeling of chromatin structure by epigenetic mechanisms, is a key ubiquitous activator of the transcriptional machinery. In this study, we report that loss of p300 acetyl transferase activity and expression leads to beta-cell apoptosis, and most importantly, that stress situations known to be associated with diabetes alter p300 levels and functional integrity. We found that proteasomal degradation is the mechanism subserving p300 loss in beta-cells exposed to hyperglycemia or pro-inflammatory cytokines. We also report that melatonin, a hormone produced in the pineal gland and known to play key roles in beta-cell health, preserves p300 levels altered by these toxic conditions. Collectively, these data imply an important role for p300 in the pathophysiology of diabetes

Abundances in intermediate-mass AGB stars undergoing third dredge-up and hot-bottom burning

High dispersion near-infrared spectra have been taken of seven highly-evolved, variable, intermediate-mass (4-6 Msun) AGB stars in the LMC and SMC in order to look for C, N and O variations that are expected to arise from third dredge-up and hot-bottom burning. The pulsation of the objects has been modelled, yielding stellar masses, and spectral synthesis calculations have been performed in order to derive abundances from the observed spectra. For two stars, abundances of C, N, O, Na, Al, Ti, Sc and Fe were derived and compared with the abundances predicted by detailed AGB models. Both stars show very large N enhancements and C deficiencies. These results provide the first observational confirmation of the long-predicted production of primary nitrogen by the combination of third dredge-up and hot-bottom burning in intermediate-mass AGB stars. It was not possible to derive abundances for the remaining five stars: three were too cool to model, while another two had strong shocks in their atmospheres which caused strong emission to fill the line cores and made abundance determination impossible. The latter occurrence allows us to predict the pulsation phase interval during which observations should be made if successful abundance analysis is to be possible.Comment: Accepted for publication in MNRA

Persistence of Gamma-H2AX Foci in Irradiated Bronchial Cells Correlates with Susceptibility to Radiation Associated Lung Cancer in Mice

The risk of developing radiation-induced lung cancer differs between different strains of mice, but the underlying cause of the strain differences is unknown. Strains of mice also differ in their ability to efficiently repair DNA double strand breaks resulting from radiation exposure. We phenotyped mouse strains from the CcS/Dem recombinant congenic strain set for their efficacy in repairing DNA double strand breaks during protracted radiation exposures. We monitored persistent gamma-H2AX radiation induced foci (RIF) 24 hours after exposure to chronic gamma-rays as a surrogate marker for repair deficiency in bronchial epithelial cells for 17 of the CcS/Dem strains and the BALB/cHeN founder strain. We observed a very strong correlation R2 = 79.18%, P < 0.001) between the level of persistent RIF and radiogenic lung cancer percent incidence measured in the same strains. Interestingly, spontaneous levels of foci in non-irradiated strains also showed good correlation with lung cancer incidence (R2=32.74%, P =0.013). These results suggest that genetic differences in DNA repair capacity largely account for differing susceptibilities to radiation-induced lung cancer among CcS/Dem mouse strains and that high levels of spontaneous DNA damage is also a relatively good marker of cancer predisposition. In a smaller pilot study, we found that the repair capacity measured in peripheral blood leucocytes also correlated well with radiogenic lung cancer susceptibility, raising the possibility that such phenotyping assay could be used to detect radiogenic lung cancer susceptibility in humans

Analysis of transcripts differentially expressed between fruited and deflowered ‘Gala’ adult trees: a contribution to biennial bearing understanding in apple

Background The transition from vegetative to floral state in shoot apical meristems (SAM) is a key event in plant development and is of crucial importance for reproductive success. In perennial plants, this event is recurrent during tree life and subject to both within-tree and between-years heterogeneity. In the present study, our goal was to identify candidate processes involved in the repression or induction of flowering in apical buds of adult apple trees. Results Genes differentially expressed (GDE) were examined between trees artificially set in either ‘ON’ or ‘OFF’ situation, and in which floral induction (FI) was shown to be inhibited or induced in most buds, respectively, using qRT-PCR and microarray analysis. From the period of FI through to flower differentiation, GDE belonged to four main biological processes (i) response to stimuli, including response to oxidative stress; (ii) cellular processes, (iii) cell wall biogenesis, and (iv) metabolic processes including carbohydrate biosynthesis and lipid metabolic process. Several key regulator genes, especially TEMPRANILLO (TEM), FLORAL TRANSITION AT MERISTEM (FTM1) and SQUAMOSA PROMOTER BINDING PROTEIN-LIKE (SPL) were found differentially expressed. Moreover, homologs of SPL and Leucine-Rich Repeat proteins were present under QTL zones previously detected for biennial bearing. Conclusions This data set suggests that apical buds of ‘ON’ and ‘OFF’ trees were in different physiological states, resulting from different metabolic, hormonal and redox status which are likely to contribute to FI control in adult apple trees. Investigations on carbohydrate and hormonal fluxes from sources to SAM and on cell detoxification process are expected to further contribute to the identification of the underlying physiological mechanisms of FI in adult apple trees

High-field magnetization study of the S = 1/2 antiferromagnetic Heisenberg chain [PM Cu(NO3_3)2_2(H2_2O)2_2]n_n with a field-induced gap

We present a high-field magnetization study of the $S$ = 1/2 antiferromagnetic Heisenberg chain [PM Cu(NO$_3$)$_2$(H$_2$O)$_2$]$_n$. For this material, as result of the Dzyaloshinskii-Moriya interaction and a staggered $g$ tensor, the ground state is characterized by an anisotropic field-induced spin excitation gap and a staggered magnetization. Our data reveal the qualitatively different behavior in the directions of maximum and zero spin excitation gap. The data are analyzed via exact diagonalization of a linear spin chain with up to 20 sites and on basis of the Bethe ansatz equations, respectively. For both directions we find very good agreement between experimental data and theoretical calculations. We extract the magnetic coupling strength $J/k_B$ along the chain direction to 36.3(5) K and determine the field dependence of the staggered magnetization component $m_s$.Comment: 5 pages, 2 figures (minor changes to manuscript and figures