Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Abstract View references (60)Here we show the long term performance at high temperatures of a multi-tube module containing 8 membranes in 4 parallel lines with a total of 545 cm 2 area. The membranes were prepared via thin film dip coating of cobalt oxide silica (CoO xSi) sol-gel on tubular alumina supports. A preliminary study found that the sol-gel containing 20 mol% cobalt oxide formed the best microporous structure with the highest surface area and pore volume. All resulting membranes delivered permeances of ∼1 × 10 -7 mol m -2 s -1 Pa -1 at 500 °C, indicating a high repeatability for the membrane fabrication process. The permselectivities of helium (He) and hydrogen (H 2) over carbon dioxide (CO 2) and nitrogen (N 2) increased from 10-20 at 100 °C to values close to 1000 at 500 °C. Additionally, the apparent energies of activation (E act) for the smaller kinetic diameter gases He and H 2 at 12.2 and 19.5 kJ mol -1 were high and contrary to the negative values for larger gases N 2 and CO 2 at -1.8 and -7.4 kJ mol -1. These remarkable results were attributed to the molecular sieving mechanism of the microporous silica which was enhanced by the embedding of cobalt oxide into the matrix, delivering structural control with an average pore size of 3 Å. The E act for H 2 permeance was higher than that of He, indicating that the cobalt oxide played an important role in H 2 transport. Two membrane lines performed exceptionally well for binary gas mixture processing with H 2 purity reaching values close to 100% in the permeate stream for argon (Ar) concentrations of up to 80% in the retentate stream. A major finding here is that the binary gas selectivity was independent of temperature, contrary to the permselectivity observed for single gas permeance. Further, the H 2 flow rate was greatly affected by the concentration of Ar in the mixture, while the temperature dependency played only a marginal role. In particular, competitive adsorption in the percolative pathways containing pore constrictions or bottlenecks of the anisotropic CoO xSi matrix allowed Ar to impede H 2 diffusion. Finally, the CoO xSi membranes proved thermally stable and robust for 2000 h of testing for various thermal cycles up to 500 °C. © The Royal Society of Chemistry 2012.
Energy & Environmental Science

hal-01683199
https://hal.univ-antilles.fr/hal-01683199
DOI : 10.1039/c2ee03247c

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Although leishmaniasis has been studied for over a century, the fight against cutaneous, mucocutaneous and visceral forms of the disease remains a hot topic. This review refers to the parasitic cell wall and more particularly to the constitutive glycoconjugates. The structures of the main glycolipids and glycoproteins, which are species-dependent, are described. The focus is on the disturbance of the lipid membrane by existing drugs and possible new ones, in order to develop future therapeutic agents
ISSN: 1477-0520

hal-01174899
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01174899
DOI : 10.1039/c5ob00563a
PUBMED : 26130402

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Low-level water measurements of geological materials are fundamental in understanding the volatile inventories of the Earth from the mantle to crustal reservoirs. Here we describe the development of microanalytical techniques using the new SHRIMP SI ion microprobe to measure the abundances of OH− (as a proxy for water) in volcanic glass and nominally anhydrous minerals (NAMs). Samples were first analysed at the Carnegie Institute of Washington (CIW) on their Cameca ims-6f with calibrations based on previous FTIR and manometry analyses. SHRIMP SI is a large geometry ion microprobe and is currently mainly used for O and S isotope analyses. The analytical protocol used here incorporates multiple collection of 16O− and 16O1H− allowing rapid measurements. A single calibration line incorporating all glasses and NAMs for the SHRIMP SI allows calibration of 16O1H−/16O− to H2O over a wide range in concentration (50 to 15 000 ppm H2O). This calibration line has around a 10% uncertainty, which appears to be limited only by sample heterogeneity. The current background for SHRIMP analysis is between 20–40 ppm but this is expected to improve with improved pumping on the source chamber. A current limitation to water analysis of NAM samples, by any technique, is having a range of standard materials to enable OH− calibration to absolute H2O concentrations. Data are presented for 7 NAM samples (2 olivines, 2 orthopyroxenes and 3 clinopyroxenes) that appear to be promising as potential standards for international laboratory H2O measurements. These NAM samples have been analysed and characterised here by SHRIMP SI, FTIR, EMP and the Cameca ims-6f ion microprobe at CIW. Four of these samples have previously been measured by manometry to determine absolute H2O concentrations.
ISSN: 0267-9477

hal-01243514
https://hal.archives-ouvertes.fr/hal-01243514
DOI : 10.1039/c5ja00047e

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 Royal Society of Chemistry
Résumé : International audience
Owing to the electron donor-acceptor properties of GO, the active sites (≡Fe2+) of Fe3O4 are not oxidised (≡Fe3+) in the heterogeneous Fenton-like reaction. GO plays a sacrificial role via the oxidation of (C=C) carbon domains, and transferring electrons to Fe3O4. Therefore, GO-Fe3O4 confers superior catalytic efficiency, recyclability and longevity, otherwise not available in Fe3O4. © The Royal Society of Chemistry 2015.
ISSN: 1359-7345

hal-01683211
https://hal.univ-antilles.fr/hal-01683211
DOI : 10.1039/c5cc02292d

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Chemical mediation regulates behavioral interactions between species and thus affects population structure,community organization and ecosystem function. Among marine taxa that have developed chemicalmediation strategies, gastropods belong to a diverse group of molluscs found worldwide, including specieswith a coiled, reduced or absent shell. Most gastropods use natural products to mediate a wide range ofbehaviors such as defense, prey location or interactions with con- and hetero-geners. Their chemicallydefended diet, such as cyanobacteria, algae, sponges, bryozoans and tunicates, provides them witha considerable opportunity either as shelter from predators, or as a means to enhance their own chemicaldefense. In addition to improving their defenses, molluscs also use prey secondary metabolites in complexchemical communication including settlement induction, prey detection and feeding preferences. Theassimilation of prey secondary metabolites further provides the opportunity for interactions withconspecifics via diet-derived chemical cues or signals. This review intends to provide an overview on thesequestration, detoxification, and biotransformation of diet-derived natural products, as well as the role ofthese compounds as chemical mediators in gastropod-prey interactions.
ISSN: 0265-0568

hal-01563402
https://hal-univ-perp.archives-ouvertes.fr/hal-01563402
DOI : 10.1039/c6np00097e

Éditeur(s) : HAL CCSD The Royal Society of Chemistry
Résumé : International audience
This review is devoted to the description of synthetic strategies for glycodendrimers synthesis. Dendrimers can be classified into three categories: carbohydrate-coated, carbohydrate-centered and carbohydrate-based dendrimer. In this paper we will focus on the third one, in which the core unit is originated from a monosaccharide. Compare to classical Pamam, Boltorn cores, carbohydrate units add much more three dimension information, coded in the chirality in almost each carbon. Various coupling chemistry have been developed and are presented here: glycosylation, amide bound formation, and click chemistry (thiol-ene reaction, epoxide - thiol reaction).
Carbohydrate Chemistry: Volume 40

ISBN : 978-1-84973-965-8
hal-01362709
https://hal.archives-ouvertes.fr/hal-01362709
DOI : 10.1039/9781849739986-00257

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A versatile sol-gel route has been developed for the preparation of hierarchical porous silica membrane material with highly dispersed platinum nanoparticles (Pt-NPs). The outstanding feature of the "one pot" synthesis developed in this work lies in the successful preparation of a stable complex suspension made of silica sol, multi-scale porogens and Pt nanoparticles. The multi-scale porogens were based on non-ionic triblock copolymers and aqueous latex suspension to create mesopores and macropores, respectively, with finely tuned pore size and organization. For further functionalization of the membranes, Pt nanoparticles of about 4 nm in diameter were prepared by irradiating with microwaves (MW) the Pt precursors added in the starting suspension. This original path is suggested to enable a pre-organization of Pt nanoparticles in the ordered mesoporous structure. The suspensions were then deposited as thin films on either dense or macroporous supports, and further thermally treated at 450°C to remove the porogen units. Hierarchical porous layers composed of micropores (<2 nm), ordered mesopores (∼4 nm) and macropores (∼70 nm) with or without Pt were prepared and characterized. The resulting membranes are foreseen to exhibit great potential as multifunctional membranes for gas separation coupled with catalytic reaction. © The Royal Society of Chemistry 2008.
ISSN: 0959-9428

hal-01680586
https://hal.univ-antilles.fr/hal-01680586
DOI : 10.1039/b807029f

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
ISSN: 2046-2069

hal-01116129
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01116129
DOI : 10.1039/C3RA47255H

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A series of graphene oxide (GO) and zinc partially substituted magnetite GO-Fe1-xZnxOy (0 ≤ x ≤ 0.285) catalysts were synthesised through a precipitation-oxidation method. The rate constants for the degradation of acid orange seven (AO7) proceeded at a significant faster rate under UV-irradiation (up to 670%) than the conventional heterogeneous Fenton-like reaction. The resultant catalysts were mesoporous, so there was no mass transfer limitation for AO7 to access active sites in the catalysts. Further, maximum increases of rate constant up to 220% occurred as the zinc molar concentration increased from x = 0 to x = 0.159. GO enhanced to incorporation of zinc into the combined metal oxide, whilst zinc limited crystal growth, thus forming smaller crystallite sizes. These features proved to be essential for the improved catalytic activity of the resultant catalysts. The optimised zinc molar value at x = 0.159 delivered the best catalytic activity. © The Royal Society of Chemistry 2016.
ISSN: 2046-2069

hal-01683215
https://hal.univ-antilles.fr/hal-01683215
DOI : 10.1039/c6ra04068c

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
ISSN: 1359-7345

hal-01636961
https://hal.archives-ouvertes.fr/hal-01636961
DOI : 10.1039/c6cc07942c

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : Fluorescence is a remarkable property of many natural products in addition to their medicinal and biological values. Herein, we provide a review on these peculiar secondarymetabolites to stimulate prospecting of them as original fluorescent tracers, endowed with unique photophysical properties and with applications in most fields of biology. The compounds are spectrally categorized (i.e. fluorescing from violet to the near infra-red) and further structurally classified within each category. Natural products selected for their high impact in modern fluorescence-based biological studies are highlighted throughout the article. Finally, we discuss aspects of chemical ecology where fluorescent natural products might have key evolutionary roles and thus open new research directions in the field.
ISSN: 0265-0568

hal-01604139
https://hal.archives-ouvertes.fr/hal-01604139
DOI : 10.1039/c6np00111d
PRODINRA : 391732
PUBMED : 28125109

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
LA-ICP-MS analysis of the chemical composition of biogenic carbonate has many applications in the environmental sciences but the characteristics of the material produced by the ablation process are largely unknown. To fill this gap, we have undertaken a study of the chemical and physical nature of particles produced by laser ablation of biogenic carbonates. SEM imaging suggests that laser ablation produces two distinct particle populations, one consisting of microsize particles and the other of nanosize particles. A 213 nm laser gives rise to a higher proportion of microsize particles than a 193 nm laser, probably because the 213 nm laser couples less completely with carbonate material. The microsize particles appear to form by photomechanical fracturing along lines of cleavage or weakness, rather than by hydrodynamic sputtering (as is generally observed for silicates). Chemical analysis of the carbonate particles suggests that little chemical fractionation of biogenic carbonates occurs during the ablation process or during transport to the plasma. This is supported by the constancy of the fractionation factor ([X/Ca](measured)/[X/Ca] true) during the course of an ablation of a carbonate standard. In contrast, changes in the fractionation factor during the first few seconds of ablation of the NIST 612 are observed for some elements. This difference in fractionation is likely to result from the different formation mechanisms of the microsize particles.
ISSN: 0267-9477

hal-00411933
https://hal.archives-ouvertes.fr/hal-00411933
DOI : 10.1039/b706727e

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
ISSN: 2050-750X

hal-01650964
https://hal.archives-ouvertes.fr/hal-01650964
DOI : 10.1039/c5tb00420A