Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A full equilibrium treatment of molecular aggregation is presented for prototypes of 1D and 3D aggregates, with and without nucleation. By skipping complex kinetic parameters like aggregate size-dependent diffusion, the equilibrium treatment allows to predict directly time-independent quantities such as critical concentrations. The relationships between the macroscopic equilibrium constants for the different paths are first established by statistical corrections and so as to comply with the detailed balance constraints imposed by nucleation, and the composition of the mixture resulting from homogeneous aggregation is then analyzed using the polylogarithm function. Several critical concentrations are distinguished: the residual monomer concentation in equilibrium (RMC) and the critical nucleation concentration (CNC), that is the threshold concentration of total subunits necessary for initiating aggregation. When increasing the concentration of total subunits, the RMC converges more strongly to its asymptotic value, the equilibrium constant of depolymerization, for 3D aggregates and in case of nucleation. The CNC moderately depends on the number of subunits in the nucleus, but sharply increases with the difference between the equilibrium constants of polymerization and nucleation. As the RMC and CNC can be numerically but not analytically determined, ansatz equations connecting them to thermodynamic parameters are proposed
PCCP : Physical chemistry chemical physics

Droits : info:eu-repo/semantics/OpenAccess
hal-01565995
https://hal.archives-ouvertes.fr/hal-01565995
https://hal.archives-ouvertes.fr/hal-01565995/document
https://hal.archives-ouvertes.fr/hal-01565995/file/Aggregates_in_equilibrium.pdf
DOI : 10.1039/c6cp08369b

Éditeur(s) : HAL CCSD
Résumé : International audience
The corrosion rates in the presence of some indole derivates, namely, 9H-pyrido[3,4-b]indole (norharmane) and 1-methyl-9H-pyrido[3,4-b]indole (harmane), as inhibitors of C38 steel corrosion inhibitor in 1 M HCl solution, were measured by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques, in the range of temperatures from 25 to 55∘C. Results obtained revealed that the organic compounds investigated have inhibiting properties for all temperatures. The inhibition was assumed to occur via adsorption of the indole molecules on the metal surface. Adsorption of indole derivates was found to follow the Langmuir isotherm. The apparent activation energies, enthalpies, and entropies of the dissolution process and the free energies and enthalpies for the adsorption process were determined by potentiodynamic polarization and electrochemical impedance. The fundamental thermodynamic functions were used to collect important information about indole inhibitory behaviour.
international Journal of Corrosion

hal-01683120
https://hal.univ-antilles.fr/hal-01683120
DOI : 10.1155/2013/139798

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
During the treatment process of drinking water, disinfectants (chlorine, ozone, chlorine dioxide) react on water containing organic matter and bromide to produce disinfection by-products at trace levels. Among them, five of the nine existing halo-acetic acids (HAAs) are commonly found in drinking water (monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), monobromoacetic acid (MBAA), dibromoacetic acid (DBAA), and Trichloroacetic acid (TCAA)), including four classified in the 2B IARC group of potential carcinogens (BCAA, DBAA, DCAA, TCAA). With respect to drinking water quality, guidelines are proposed by WHO (2006) and water quality standards are imposed in many countries such as less than 100 μg/L for the sum of the five HAAs by US EPA (1998) and Canadian Health Department (2008). For this purpose, two analytical methods are commonly used, GC/MS with derivatization and LC/MS, UV or conductivity. A new method, based on two-dimensional ion chromatography (IC 2D) with suppressed conductivity is proposed. This method presents the main advantage of offering a quick implementation compared to GC or LC methods: direct injection, slight maintenance, lower cost of investment, by leading to good performances (specificity and sensitivity). The use of two different selectivity columns, and the fractionation on the first dimension canceling interferences, improves the specificity. The sensitivity is enabled by interfacing a preconcentration column between the two different internal diameter columns. The analytical conditions are optimized for the analysis of nine HAAs. The performances of the method are evaluated. The optimized method applied to natural water samples demonstrates its ability to quantify HAAs at trace levels in drinking water.
Microchemical Journal

hal-00877151
https://hal-univ-rennes1.archives-ouvertes.fr/hal-00877151
https://hal-univ-rennes1.archives-ouvertes.fr/hal-00877151/document
DOI : 10.1016/j.microc.2013.07.012

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
The impact of stratospheric ozone on the tropospheric general circulation of theSouthern Hemisphere (SH) is examined with a set of chemistry‐climate models participatingin the Stratospheric Processes and their Role in Climate (SPARC)/Chemistry‐ClimateModel Validation project phase 2 (CCMVal‐2). Model integrations of both the past andfuture climates reveal the crucial role of stratospheric ozone in driving SH circulationchange: stronger ozone depletion in late spring generally leads to greater polewarddisplacement and intensification of the tropospheric midlatitude jet, and greater expansion ofthe SH Hadley cell in the summer. These circulation changes are systematic as polewarddisplacement of the jet is typically accompanied by intensification of the jet and expansion ofthe Hadley cell. Overall results are compared with coupled models participating in theIntergovernmental Panel on Climate Change Fourth Assessment Report (IPCC AR4), andpossible mechanisms are discussed. While the tropospheric circulation response appearsquasi‐linearly related to stratospheric ozone changes, the quantitative response to a givenforcing varies considerably from one model to another. This scatter partly results fromdifferences in model climatology. It is shown that poleward intensification of the westerly jetis generally stronger in models whose climatological jet is biased toward lower latitudes.This result is discussed in the context of quasi‐geostrophic zonal mean dynamics.
ISSN: 2169-897X

hal-00337060
https://hal.archives-ouvertes.fr/hal-00337060
https://hal.archives-ouvertes.fr/hal-00337060/document
https://hal.archives-ouvertes.fr/hal-00337060/file/Bock_et_al-2008-Journalsur Geophysical_Research__Solid_Earth_%281978-2012%29.pdf
DOI : 10.1029/2008JD010327

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A shallow field experimental site for CO2 injection was established at Maguelone (Languedoc, France), in order to test in an integrated manner a suite of surface and downhole hydrogeophysical monitoring methods. The objective is to improve monitoring of gas transport in the shallow subsurface and to determine the sensitivity of CO2 monitoring systems for leakage detection. The site offers a natural laboratory to study the processes associated with CO2 injection in a clastic and clay-rich context saturated with saline fluids. Prior to CO2 injection, three nitrogen (N2) injections were undertaken in 2012 to measure the site response to neutral gas injection. In 2013, a volume of 111 m3 (mass of 220 kg) of CO2 was injected during 3.5 h at 15 m depth. During each experiment, the gas plumes were successfully detected from pressure monitoring, time-lapse induction logging and downhole resistivity monitoring with dipole–dipole array. Increases in resistivity are attributed to free gas propagation (either N2 or CO2) whereas decreases in resistivity correlate with CO2 dissolution in the pore fluid. Chemical analyses confirm this hypothesis with a decrease in pH and an increase in the concentration of dissolved species in the latter case.
ISSN: 1750-5836

hal-01355943
https://hal.archives-ouvertes.fr/hal-01355943
DOI : 10.1016/j.ijggc.2015.12.005

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Sapat peridotite in Kohistan (NW Pakistan) is a 12x1 km sized body of meta-harzburgites, dunites, pyroxenites and meta-gabbros in the hanging wall of the Indus Suture Zone. Field relations, micro-textures, bulk and mineral chemistry document melt-rock reactions producing dunites at the expense of meta-harzburgites, and a consecutive olivine-clinopyroxenite formation from the same melt type. The association of mesa-gabbros, dunites, and pyroxenites is interpreted as a crust-mantle transition zone produced by the percolation of highly depleted primitive arc melt. The meta-harzburgites represent large portions of refractoty mantle that have suffered melt extraction and metasomatism prior to their interaction with the dunite-forming primitive arc melt and the establishment of the crust-mantle transition zone. Uncommon vein assemblages in the dunites that include Cr-clinochlore, calcite and olivine document a late percolation of slab-related, volatile-rich fluids. Taking into account the highly refractory composition of the Sapat mantle, its structural position, the evidence for interaction with highly depleted arc melts and the sub-solidus interaction with volatile-rich arc fluids, the Sapat ultramafic rocks are interpreted as being derived from the frontal Kohistan arc, representing a crust-mantle transition formed by arc magmatism.
ISSN: 0024-4937

hal-00424515
https://hal.archives-ouvertes.fr/hal-00424515
DOI : 10.1016/j.lithos.2008.07.004

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
A novel spiro-indolofuranone fused to a thiazine skeleton, orbicularisine (1), was isolated from gills of the mollusk Codakia orbicularis. The isolation and structure elucidation using spectroscopic evidence including mass and NMR spectroscopy are described. The final structure of 1 was supported by key HMBC correlation.
ISSN: 0163-3864

hal-01547430
http://hal.upmc.fr/hal-01547430
http://hal.upmc.fr/hal-01547430/document
http://hal.upmc.fr/hal-01547430/file/Goudou_2017_Orbicularisine.pdf
DOI : 10.1021/acs.jnatprod.7b00149

Éditeur(s) : HAL CCSD
Résumé : International audience
Abstract View references (38)This work presents a facile, scalable method for the fabrication of graphene oxide-iron oxide (GO-Fe3O4) nanocomposites produced by co-precipitation of iron ions onto the GO surfaces in basic aqueous media. FTIR and XRD characterisation suggests that Fe3O4 was chemically anchored to the GO sheets, possibly via the carboxyl and hydroxyl groups. Small GO loadings of 0.5 and 1 wt% were not sufficient to alter the Fe3O4 structures. However, increasing the GO loading to 5 and 10 wt% resulted in significant loss in pore volume, thus suggesting the lamellar GO sheets decorated with Fe3O4 were assembling into GO-Fe3O4 nanocomposite stacks. It was found that the GO-Fe3O4 nanocomposites had an enhanced catalytic activity in the heterogeneous Fenton-like oxidation of Acid Orange 7 (AO7) compared to pure GO flat sheets and Fe3O4 nanoparticles. Interestingly, the GO-Fe3O4 nanocomposite with 5 wt% loading ratio exhibited the best catalytic activity with 76% degradation of AO7 dye observed within 90 min of reaction. This was attributed to the synergistic effect of GO by enriching the adsorbed AO7 molecules onto the nanocomposite to be further oxidised in the vicinities of active sites. This finding suggests the promising employment of GO-Fe3O4 nanocomposites in removing organic dyes from polluted water by heterogeneous Fenton-like reaction. © 2014 by American Scientific Publishers.
SCIENCE OF ADVANCED MATERIALS

hal-01683207
https://hal.univ-antilles.fr/hal-01683207
DOI : 10.1166/sam.2014.1812

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
ISSN: 0927-7757

hal-00360369
https://hal.archives-ouvertes.fr/hal-00360369
DOI : 10.1016/j.colsurfa.2008.07.054

Éditeur(s) : HAL CCSD
Résumé : Structure elucidation of unknown compounds has been the task of natural products chemists for a long time and their approach seems to be the most efficient when it comes to identification. Very recently, Kokkotou et al. proposed a work-flow based on an integrative approach for new metabolite identification. This approach, including prediction of 2D NMR HSQC spectra, demonstrated the necessity for implementation of new algorithms leading to the prediction of 2D NMR spectra. Herein we present a method based on both quantum mechanics (QM) and Hierarchical Organisation of Spherical Environments (HOSE) of the prediction 2D NMR spectra.
https://hal.archives-ouvertes.fr/hal-01416667

hal-01416667
https://hal.archives-ouvertes.fr/hal-01416667
https://hal.archives-ouvertes.fr/hal-01416667/document
https://hal.archives-ouvertes.fr/hal-01416667/file/MRC_v1.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Extractives that provide natural resistance to Bagassa guianensis Aubl. heartwood were examined. Soil-bed tests showed that the B. guianensis heartwood resistance was significantly reduced after ethyl acetate extraction, whereas methanol and especially water extractions improved the resistance. The ethyl acetate extract was submitted to a bioguided fractionation, and fractions were tested against one wood-destroying fungal strain (Pycnoporus sanguineus) and two human pathogenic fungal strains (Candida glabrata (yeast) and Trichophyton rubrum (filamentous dermatophyte)). Fraction F7, which exhibited the strongest antifungal activity, was subsequently fractionated by high performance liquid chromatography (HPLC). Six previously described compounds were isolated. Although the two moracins, 6-O-methyl-moracin N (3) and moracin N (4) were the most active against fungal strains with MIC values between 4 and 16 μg ml−1, the isolated compounds showed less or equivalent antifungal activity than the initial fraction. Possible synergism between compounds 3 and 4 and other secondary metabolites have been hypothesized. Our study demonstrated that this extract as a whole might be used as a wood preservation or antimycotic product.
International Biodeterioration and Biodegradation

hal-00694532
https://hal.archives-ouvertes.fr/hal-00694532
DOI : 10.1016/j.ibiod.2011.10.016

Éditeur(s) : HAL CCSD
Résumé : International audience
International Conference NOCMAT 2007
Maceio-Alagoas, Brazil

hal-00807968
https://hal.univ-antilles.fr/hal-00807968

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The current design studies on sodium-cooled fast reactors (SFRs) are breaking with the past since they are guided by a new set of design criteria arising from the objectives of Generation IV reactors. The new safety requirements lead to designing reactors with breakeven breeding cores because in terms of reactivity control, they minimize the need to limit the consequences of an inadvertent control rod withdrawal event. Furthermore, as the reactivity control needs are low, a breakeven core enables the use of absorbing materials with reduced efficiency (natural boron, hafnium, etc.), which may be less costly than enriched boron. However, control rods designed with low absorbing materials may present the disadvantage of a nonnegligible loss of efficiency due to their consumption under irradn. This paper presents a methodol. to accurately calc. and to analyze the impact of this consumption on reactivity control.
ISSN: 0302-2927

hal-01088526
https://hal.archives-ouvertes.fr/hal-01088526
DOI : 10.13182/NSE13-59

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
The HIWATE (Health Impacts of long-term exposure to disinfection byproducts in drinking WATEr) project was a systematic analysis that combined the epidemiology on adverse pregnancy outcomes and other health effects with long-term exposure to low levels of drinking water disinfection byproducts (DBPs) in the European Union. The present study focused on the relationship of the occurrence and concentration of DBPs with in vitro mammalian cell toxicity. Eleven drinking water samples were collected from five European countries. Each sampling location corresponded with an epidemiological study for the HIWATE program. Over 90 DBPs were identified; the range in the number of DBPs and their levels reflected the diverse collection sites, different disinfection processes, and the different characteristics of the source waters. For each sampling site, chronic mammalian cell cytotoxicity correlated highly with the numbers of DBPs identified and the levels of DBP chemical classes. Although there was a clear difference in the genotoxic responses among the drinking waters, these data did not correlate as well with the chemical analyses. Thus, the agents responsible for the genomic DNA damage observed in the HIWATE samples may be due to unresolved associations of combinations of identified DBPs, unknown emerging DBPs that were not identified, or other toxic water contaminants. This study represents the first to integrate quantitative in vitro toxicological data with analytical chemistry and human epidemiologic outcomes for drinking water DBPs.
ISSN: 0013-936X

hal-00875923
https://hal.archives-ouvertes.fr/hal-00875923
DOI : 10.1021/es3024226
PUBMED : 22958121

Éditeur(s) : HAL CCSD
Résumé : The aim of this work was to search for new bioactive compounds, displaying either antiplasmodial or antifungal activity. Two strategies were developed here: the evaluation of traditional remedies identified as antimalarial through ethnopharmacological study, and the search for antifungal essential oils, the criterium being here a bioinspired approach. Our work led to the discovery that the antimalarial activity of Quassia amara L. (Simaroubaceae) fresh young leaves was due to the presence of a known quassinoid, simalikalactone D. In the case of Psidium acutangulum DC. (Myrtaceae), a flavonol glycosides mixture explained the activity observed for the decoction. The search for antifungal essential oils from the Amazonian flora lead to the identification of several interesting species, thus validating our bioinspired strategy. The essential oil of Otacanthus azureus (Linden) Ronse was among the most active ones, either alone or in combination with azole drugs. Eventually, a metabolomic study of the GC/MS composition of these oils allowed us to develop a statistical tool which could help to select interesting antifungal products. This work thus demonstrate the major interest of the two strategies - ethnopharmacology and bioinspiration - for the search of new bioactive compounds.
L'objectif du travail effectué était la recherche de nouvelles substances actives d'origine végétale, présentant soit une activité antiplasmodiale soit une activité antifongique. Cette étude a été menée suivant deux stratégies différentes: l'étude de remèdes traditionnels antipaludiques identifiés suite à des enquêtes ethnopharmacologiques, et la mise en évidence des propriétés antifongiques d'huiles essentielles grâce à une stratégie bioinspirée. La première partie du travail a permis de mettre en évidence le rôle d'un quassinoïde connu, la simalikalactone D, dans l'activité antipaludique d'une tisane de jeunes feuilles fraîches de Quassia amara L. (Simaroubaceae). Dans le cas de la décoction de rameaux de Psidium acutangulum DC. (Myrtaceae), c'est cette fois un mélange de flavonoïdes glycosylés qui est responsable de l'activité du remède. Dans le cadre de la recherche de nouvelles substances antifongiques, le criblage effectué a permis d'identifier de nombreuses huiles essentielles présentant des activités intéressantes, validant ainsi la démarche bioinspirée retenue dans ce cas. L'huile essentielle d'Otacanthus azureus (Linden) Ronse a en particulier démontré une activité remarquable, à la fois seule et en combinaison avec des antifongiques azolés. Enfin, l'étude métabolomique de la composition des huiles essentielles a permis de mettre au point un outil pouvant orienter la sélection des huiles en fonction des données obtenues en GC/MS dans l'optique de la recherche de nouvelles substances antifongiques. Ce travail démontre donc la validité des stratégies retenues - ethnopharmacologie et bioinspiration - dans la recherche de nouvelles substances bioactives.
https://tel.archives-ouvertes.fr/tel-00718910

tel-00718910
https://tel.archives-ouvertes.fr/tel-00718910
https://tel.archives-ouvertes.fr/tel-00718910/document
https://tel.archives-ouvertes.fr/tel-00718910/file/TheseEH2011_SUBST_BIOACTIVES.pdf

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : The distribution of water and ions in nanoporous membranes, in particular close to their surfaces with external reservoirs, is investigated by means of molecular dynamics (MD) simulations using classical polarizable force fields. A sodium iodide (NaI) aqueous solution is considered in uncharged weakly hydrophilic (WH) and highly hydrophilic (HH) nanoporous materials modeled by a single truncated nanopore in contact with two reservoirs. In the inner part of the nanopore, the spatial distribution of water and ions is obtained by coupling semi-infinitesimal longitudinal and semi-infinitesimal radial descriptions. In the HH material, in contrast with the WH material, species are no longer uniformly distributed in the inner nanopore and water molecules are distributed in a nearly frozen axially periodic corona-like structure which leads to the formation of ionic tunnels. In the reservoirs, water molecules and ions attracted by the membrane surface create a necking of the confined solution which acts as a barrier at the entrance of the nanopore. In the WH nanopore subsurface, close to the surface of the membrane, the species distribution is analogous to the interface distribution between an aqueous electrolyte solution and air. In the HH nanopore subsurface, this distribution is modulated by the water corona-like structure. These results provide useful information for predicting properties of nanoporous membranes, in particular the drastic reduction of diffusion coefficients in HH materials, and give a guide to designing synthetic membranes for applications in nanofiltration, etc.
ISSN: 1932-7447

hal-00682155
https://hal.archives-ouvertes.fr/hal-00682155
DOI : 10.1021/jp2078924

Éditeur(s) : HAL CCSD Nature Publishing Group
Résumé : International audience
Abstract The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications.
ISSN: 2045-2322

hal-01683204
https://hal.univ-antilles.fr/hal-01683204
DOI : 10.1038/srep02449

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This work shows the preparation and separation performance assessment of carbon membranes derived from phenolic resin by a vacuum-assisted method and carbonisation in an inert atmosphere. The vacuum time played an important role in tailoring the structure of the membranes. For instance, pore volumes and surface areas increased from 0.81 and 834 to 2.2 cm3g−1and 1910 m2g−1, respectively, as the vacuum time exposure increased from 0 to 1200 s. The significant structural changes correlated very well with water permeation, as fluxes increased by 91% as the vacuum time increased from 0 to 1200 s reaching up to 169 L m−2h−1at 5 bar. Molecular weight cut-off tests showed no rejection for the smaller glucose and sucrose molecules, though this increased to ~ 80% and full rejection for 36 kDa and 400 kDa polyvinyl pyrrolidine. Interestingly, FTIR spectra showed that the peaks of C–H stretching vibration (2800–3200 cm−1) and C–O stretching (1030 cm−1) became more pronounced as a function of increasing vacuum time, strongly suggesting that the use of vacuum further assisted in the polycondensation of phenolic oligomers. Based on these outcomes, a cluster to cluster model is proposed, whereby vacuum application promoted crosslinking reactions of the phenolic resin, creating microporous regions within the clusters, and mesoporous regions between the clusters. © 2016 Elsevier B.V
ISSN: 0376-7388

hal-01683220
https://hal.univ-antilles.fr/hal-01683220
DOI : 10.1016/j.memsci.2016.11.002

Éditeur(s) : HAL CCSD
Résumé : 00000
International audience
Australian Journal of Chemistry - an International Journal for Chemical Science publishes research papers from all fields of chemical science.
Australian Journal of Chemistry

hal-01483154
https://hal.archives-ouvertes.fr/hal-01483154
DOI : 10.1071/CH16455

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The implication of oxidative stress as primary mechanism inducing doxorubicin (DOX) cardiotoxicity is still questionable as many in vitro studies implied supra-clinical drug doses or unreliable methodologies for reactive oxygen species (ROS) detection. The aim of this study was to clarify whether oxidative stress is involved in compliance with the conditions of clinical use of DOX, and using reliable tools for ROS detection. We examined the cytotoxic mechanisms of 2 μM DOX 1 day after the beginning of the treatment in differentiated H9c2 rat embryonic cardiac cells. Cells were exposed for 2 or 24 h with DOX to mimic a single chronic dosage or to favor accumulation, respectively. We found that apoptosis was prevalent in cells exposed for a short period with DOX: cells showed typical hallmarks as loss of anchorage ability, mitochondrial hyperpolarization followed by the collapse of mitochondrial activity, and nuclear condensation. Increasing the exposure period favored a shift to necrosis as the cells preferentially exhibited early DNA impairment and nuclear swelling. In either case, measuring the fluorescence lifetime of 1-pyrenebutyric acid or the intensities of dihydroethidium or amplex red showed a consistent pattern in ROS production which was a slight increased level far from representative of an oxidative stress. Moreover, pre-treatment with dexrazoxane provided a cytoprotective effect although it failed to detoxify ROS. Our data support that oxidative stress is unlikely to be the primary mechanism of DOX cardiac toxicity in vitro.
ISSN: 0300-8177

hal-01285736
https://hal-univ-perp.archives-ouvertes.fr/hal-01285736
DOI : 10.1007/s11010-016-2653-x