Éditeur(s) : HAL CCSD Humana Press
Résumé : International audience
The sodium-proton exchanger 1 (NHE-1) is a membrane transporter that exchanges Na(+) for H(+) ion across the membrane of eukaryotic cells. It is cooperatively activated by intracellular protons, and this allosteric regulation is modulated by the biophysical properties of the plasma membrane and related lipid environment. Consequently, NHE-1 is a mechanosensitive transporter that responds to osmotic pressure, and changes in membrane composition. The purpose of this study was to develop the relationship between membrane surface tension, and the allosteric balance of a mechanosensitive transporter such as NHE-1. In eukaryotes, the asymmetric composition of membrane leaflets results in a difference in surface tensions that is involved in the creation of a reservoir of intracellular vesicles and membrane buds contributing to buffer mechanical constraints. Therefore, we took this phenomenon into account in this study and developed a set of relations between the mean surface tension, membrane asymmetry, fluid phase endocytosis and the allosteric equilibrium constant of the transporter. We then used the experimental data published on the effects of osmotic pressure and membrane modification on the NHE-1 allosteric constant to fit these equations. We show here that NHE-1 mechanosensitivity is more based on its high sensitivity towards the asymmetry between the bilayer leaflets compared to mean global membrane tension. This compliance to membrane asymmetry is physiologically relevant as with their slower transport rates than ion channels, transporters cannot respond as high pressure-high conductance fast-gating emergency valves.
ISSN: 1085-9195

inserm-00871709
http://www.hal.inserm.fr/inserm-00871709
http://www.hal.inserm.fr/inserm-00871709/document
http://www.hal.inserm.fr/inserm-00871709/file/art_3A10.1007_2Fs12013-012-9340-7.pdf
DOI : 10.1007/s12013-012-9340-7

Éditeur(s) : HAL CCSD Springer Verlag (Germany)
Résumé : International audience
A hybrid linear ion-trap Fourier-transform ion cyclotron resonance mass spectrometer was used for top-down characterization of the abundant human salivary Cystatins, including S, S1, S2, SA, SN, C, and D, using collisionally activated dissociation (CAD) after chromatographic purification of the native, disulfide intact proteins from saliva. Post-translational modifications and protein sequence polymorphisms arising from single nucleotide polymorphisms (SNPs) were assigned from precursor and product ion masses at a tolerance of 10 ppm allowing confident identification of individual intact mass tags. Cystatins S, S1, S2, SA and SN were cleaved of a N-terminal 20 amino-acid signal peptide, and Cystatin C a 26-residue peptide, to yield a generally conserved N-terminus. In contrast, Cystatin D isoforms with 24 and 28 amino-acid residue N-terminal truncations were found such that their N-termini were not conserved. Cystatin S1 was phosphorylated at Ser3, while S2 was phosphorylated at Ser1 and Ser3 of the mature protein, in agreement with previous work. Both Cystatin D isoforms carried the polymorphism C46R (SNP: rs1799841). The 14328 Da isoform of Cystatin SN previously assigned with polymorphism P31L due to a SNP (rs2070856) was found only in whole saliva. Parotid secretions contained no detectable Cystatins while whole saliva largely mirrored the contents of submandibular/sublingual (SMSL) secretions. Top-down high-resolution mass spectrometry is a powerful tool for the identification and characterization of potential protein biomarkers in saliva.
ISSN: 1044-0305

hal-00677483
https://hal.archives-ouvertes.fr/hal-00677483
DOI : 10.1016/j.jasms.2010.01.025

Éditeur(s) : HAL CCSD Elsevier
Résumé : Remerciements :- Dr. Jacques Delabie- Andrea Yockey-Dejean- Geoff Brown- Jean-Pierre Andrieu
Background: Most ant venoms consist predominantly of small linear peptides, although some contain disulfide linked peptides as minor components. However, in striking contrast to other ant species, some Anochetus venoms are composed primarily of disulfide-rich peptides. In this study, we investigated the venom of the ant Anochetus emarginatus with the aim of exploring these novel disulfide-rich peptides.Methods: The venom peptidome was initially investigated using a combination of reversed-phase HPLC and mass spectrometry, then the amino acid sequences of the major peptides were determined using a combination of Edman degradation and de novo MS/MS sequencing. We focused on one of these peptides, U-1-PONTX-Ae1a (Ae1a), because of its novel sequence, which we predicted would form a novel 3D fold. Ae1a was chemically synthesized using Fmoc chemistry and its 3D structure was elucidated using NMR spectroscopy. The peptide was then tested for insecticidal activity and its effect on a range of human ion channels.Results: Seven peptides named poneritoxins (PONTXs) were isolated and sequenced. The three-dimensional structure of synthetic Ae1a revealed a novel, compact scaffold in which a C-terminal beta-hairpin is connected to the N-terminal region via two disulfide bonds. Synthetic Ae1a reversibly paralyzed blowflies and inhibited human L-type voltage-gated calcium channels (Ca(v)1).Conclusions: Poneritoxins from Anochetus emarginatus venom are a novel class of toxins that are structurally unique among animal venoms.General significance: This study demonstrates that Anochetus ant venoms are a rich source of novel ion channel modulating peptides, some of which might be useful leads for the development of biopesticides.
ISSN: 0304-4165

hal-01511987
https://hal.archives-ouvertes.fr/hal-01511987
https://hal.archives-ouvertes.fr/hal-01511987/document
https://hal.archives-ouvertes.fr/hal-01511987/file/2016_Touchard_Biochimica_Biophysica_%7B4B3BE6A3-AE83-4C6E-B678-BBFB5CC84AF7%7D.pdf
DOI : 10.1016/j.bbagen.2016.07.027

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Predicting the impact of underground engineering on the environment requires the knowledge of natural media at different scales. In particular, understanding basic phenomena controlling the properties of rocks in the presence of complex fluids necessitates a detailed atomic description of the solid/fluid/solid contacts, the subject of Part I of the present study. First, building the solid interspace between two different crystals in a non-periodic situation is achieved using the ab initio and molecular mechanics code GenMol (TM). A description of the fluid confined within the interspace is then derived from the original genetic iterative multi-species (GIMS) algorithm implemented in the same code. This approach consists of equilibrating chemical potentials, cycle after cycle and species after species, between the confined fluid and the free natural fluid. An elementary iteration for a species k consists of different steps incrementing the number N-k of particles k, with other numbers N-k remaining constant. At each step, an optimum fluid composition is obtained by a genetic process distributing the fluid particles on a grid by stochastic shots, followed in fine by a refining process. The effectiveness of the GIMS approach is demonstrated in the case study of a fluid confined between two (0 0 1) kaolinite faces, with apertures h varying between 4 and 10 A. connected to a 9-species external solution [H2O, Cl-, Na+ CO2(aq), NaCl(aq), Ca2+, Mg2+, HCO3-, H3O+] where concentrations are ranging from 55 to 10(-4) mol/L. The results show a drastic variation in the solute/solvent and cations/ions ratios in the confined fluid when aperture h is lowered to less than 1 nm. These results obtained with a very rapid convergence of the iterative algorithm combined with a very competitive genetic optimizer are validated with high precision on a free solution. This description of contacts between crystals is original and unattainable by standard crystal interface approaches. It opens the way to understanding and/or predicting phenomena between crystals in a complex natural environment, such as adhesion or repulsion investigated in the Part II of this study.
ISSN: 0022-0248

hal-00544569
https://hal.archives-ouvertes.fr/hal-00544569
DOI : 10.1016/j.jcrysgro.2010.08.009

Éditeur(s) : HAL CCSD American Physical Society
Résumé : International audience
Absolute M-shell x-ray production cross sections have been measured and calculated for Au and Bi for electron incident energies from close to the ionization threshold up to 38 keV. The experimental cross sections were deduced from M alpha x-ray intensities emitted from ultrathin Au and Bi samples deposited on self-supporting C films. The measurements were performed on an electron microprobe using several wavelength-dispersive spectrometers. The x-ray production cross sections were also evaluated theoretically using ionization cross sections calculated from the plane-wave and the distorted-wave Born approximations. Experimental results are compared with the calculated cross sections and also with the results of two analytical formulas widely used in many applications. Good agreement is found between the measured cross sections and the predictions from the distorted-wave Born approximation, which indicates that this approximation is suited for the calculation of M-shell ionization cross sections of heavy elements.
ISSN: 1050-2947

hal-00411432
https://hal.archives-ouvertes.fr/hal-00411432
DOI : 10.1103/PhysRevA.78.022704

Éditeur(s) : Elsevier Science Bv
Résumé : The rollback of a segmented slab of oceanic lithosphere is typically accompanied by vertical lithospheric tear fault(s) along the lateral slab edge(s) and by strike slip movement in the upper plate, defined as a STEP fault (Subduction Tear Edge Propagator). The Neogene evolution of the Central Mediterranean is dominated by the interaction between the slow Africa–Eurasia convergence and the SE-ward rollback of the Ionian slab, that leads to the back-arc opening of the Tyrrhenian Sea. Here, we present post-stack time migrated and pre-stack depth migrated Archimede (1997) multichannel seismic lines, that were acquired offshore eastern Sicily, at the foot of the Malta escarpment. First, we identify the recent deformation along the lateral ramp of the Calabrian accretionary wedge. Towards the east, the Calabrian wedge is formed by the accretion of the post-evaporitic sediments, above a decollement at the base of the Messinian evaporites. At the latitude of Syracuse, 50 km east of the Malta escarpment, a major N150°E trending crustal scale and vertical fault slices through the entire accretionary wedge. This fault cuts by several kilometers, through the pre-evaporitic Messinian sediments and into the basement. The vertical offset along this vertical fault decreases from north to south, and the fault is no longer observed on the seismic lines, 50 km SE of the Alfeo seamount. A previously published Moho depth isocontour map, offshore Sicily and the recent GPS data, combined with the presence of strike slip movements NE onshore Sicily, allow us to identify this 200 km long crustal-scale fault as the surface expression of a STEP fault. The presence of syntectonic Pleistocene sediments on top this crustal-scale fault suggests a recent lithospheric vertical movement of the STEP fault, in response to the rollback of the Ionian slab and to the SE-ward advance of the Calabria-Peloritan block
Tectonophysics (0040-1951) (Elsevier Science Bv), 2013-08 , Vol. 602 , P. 141-152

Droits : 2013 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/00118/22878/21386.pdf
DOI:10.1016/j.tecto.2012.12.026
http://archimer.ifremer.fr/doc/00118/22878/

Éditeur(s) : HAL CCSD IWA Publishing
Résumé : International audience
UV spectrophotometry is largely used for water and wastewater quality monitoring. The measurement/estimation of specific and aggregate parameters such as nitrate and dissolved organic carbon (DOC) is possible with UV spectra exploitation, from 2 to multi wavelengths calibration. However, if nitrate determination from UV absorbance is known, major optical interferences linked to the presence of suspended solids, colloids or dissolved organic matter limit the relevance of UV measurement for DOC assessment. A new method based on UV spectrophotometric measurement of raw samples (without filtration) coupling a dual pathlength for spectra acquisition and the second derivative exploitation of the signal is proposed in this work. The determination of nitrate concentration is carried out from the second derivative of the absorbance at 226 nm corresponding at the inflexion point of nitrate signal decrease. A short optical pathlength can be used considering the strong absorption of nitrate ion around 210 nm. For DOC concentration determination the second derivative absorbance at 295 nm is proposed after nitrate correction. Organic matter absorbing slightly in the 270-330 nm window, a long optical pathlength must be selected in order to increase the sensitivity. The method was tested on several hundred of samples from small rivers of two agricultural watersheds located in Brittany, France, taken during dry and wet periods. The comparison between the proposed method and the standardised procedures for nitrate and DOC measurement gave a good adjustment for both parameters for ranges of 2-100 mg/L NO3 and 1 30 mg/L DOC. (C) 2016 Elsevier Ltd. All rights reserved.
ISSN: 0043-1354

hal-01460742
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01460742
DOI : 10.1016/j.watres.2016.11.010
PUBMED : 27838025

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The kinetics of hydrogenation of dry iron-bearing olivine single crystals was determined by performing hydration experiments under hydrothermal conditions at high pressure. The experiments were performed in a multi-anvil press at 3 GPa, for a temperature range between 900 and 1200 °C and for various durations. The oxygen fugacity was buffered along Ni-NiO joint. Polarized Fourier transform infrared spectroscopy and recent empirical calibration were used to quantify the hydroxyl distributions in the samples along crystallographic axes after the experiments. The chemical diffusion coefficients are similar (barely slower) than in olivine hydrated at lower pressure (0.2 and 0.3 GPa) for the same diffusion mechanism. Under the given experimental conditions, the anisotropy of diffusion is the same as for proton-vacancy mechanism, with diffusion along the [0 0 1] axis faster than along the [1 0 0]. However, the anisotropy at 3 GPa is weaker compared to measurements at lower pressures and the analysis of concentration profiles using 3D models shows that an isotropic solution could also be relevant. Fits of the diffusion data to an Arrhenius law yield activation energies for the slightly faster [0 0 1] axis of the crystallographic axes around 198 ± 5 kJ mol−1, a value only slightly lower than the results from previous experimental studies for natural iron-bearing olivine hydrogenated at lower confining pressure. At 3 GPa, hydrogenation can be well approximated by a single mechanism controlled by coupled diffusion of protons and octahedral vacancies (di- and tri-valent ions). The diffusion rates are fast enough to alter hydrogen concentration within olivine in xenoliths ascending from the mantle or experiencing hydrogen-rich metasomatism events, but too slow to permit complete homogenization of hydrogen in olivine-rich rocks at kilometer scale in less than one My.
ISSN: 0031-9201

hal-01412663
https://hal.archives-ouvertes.fr/hal-01412663
DOI : 10.1016/j.pepi.2016.08.005

Éditeur(s) : HAL CCSD Wiley-Blackwell
Résumé : International audience
Absolute Mα x-ray production cross sections have been measured and calculated for heavy elements Au, Pb, Bi, and U for electron incident energies from the ionization threshold up to 38 keV. The experimental cross sections were deduced from M x-ray intensities emitted from ultrathin samples of the elements of interest deposited onto self-supporting C films. The measurements were performed using two electron microprobes and several wavelength-dispersive spectrometers. X-ray intensities were converted into x-ray production cross sections by using estimated values of the number of incident electrons, target thickness, and spectrometer efficiency. Experimental results are compared with calculated cross sections using different predictive formulae. Good agreement is found between the measured cross sections and the predictions from the distorted-wave Born approximation, which indicates that this approximation is suited for the calculation of M-shell ionization cross sections of heavy elements.
ISSN: 0142-2421

hal-01122839
https://hal.archives-ouvertes.fr/hal-01122839
DOI : 10.1002/sia.5561

Éditeur(s) : HAL CCSD
Résumé : International audience
Philodendron acutatum (Araceae) is a hemiepiphyte common to the Atlantic Forest of northeastern Brazil. In two localities, we studied the species’ breeding system and associations with flower-visiting insects, along with an analysis of its floral scent composition. The fruit set of self-incompatible P. acutatum was high, more than 90%, and inflorescences were exclusively pollinated by one species of scarab beetle, Cyclocephala celata (Scarabaeidae, Dynastinae). Pollinators are drawn toward the inflorescences at dusk by strong floral fragrancesgiven off during the female phase of anthesis, along with endogenous heating of the spadix, whose temperatures were recorded at more than 11C above ambient air. Two other species of flower-visiting Cyclocephala were also consistently recovered in blacklight trappings during the flowering period of P. acutatum. The fact that only C. celata was found in association with P. acutatum suggests a local reproductivedependence of the plant to this scarab beetle species. Dihydro-b-ionone and 2-hydroxy-5-methyl-3-hexanone, a rare volatile molecule so far unreported as a floral compound, together accounted for more than 97% of the unique scent composition of P. acutatum and might be involved in specific attraction of C. celata.
International Journal of Plant Sciences

hal-01094225
https://hal-agroparistech.archives-ouvertes.fr/hal-01094225
DOI : 10.1086/654846

Éditeur(s) : HAL CCSD Portland Press
Résumé : International audience
CP12 is a small chloroplastic protein involved in the Calvin cycle that was shown to bind copper, a metal ion involved in modulation of its transition from reduced to oxidized state. In order to describe CP12 copper binding properties, copper-IMAC experiments and site-directed mutagenesis based on computational modeling, were coupled to top-down mass spectrometry (ESI-MS and MSMS). Copper-IMAC experiments allowed the primary characterization of mutation effects upon copper binding. Top-down MSMS experiments carried out under non-denaturing conditions on wild-type and mutant CP12/Cu2+ complexes then allowed fragment ions specifically liganding the copper ion to be determined. Comparison of MSMS datasets defined three regions involved in metal ion binding: residues D16 to D23, D38 to K50 and D70 to E76, with the two first regions containing selected residues for mutation. These data confirmed that copper ligands involved glutamic and aspartic residues in contrast to typical protein copper chelators. We propose that copper might play a role in regulation of CP12 biological activity.
ISSN: 0264-6021

hal-00479106
https://hal.archives-ouvertes.fr/hal-00479106
https://hal.archives-ouvertes.fr/hal-00479106/document
https://hal.archives-ouvertes.fr/hal-00479106/file/PEER_stage2_10.1042%252FBJ20082004.pdf
DOI : 10.1042/BJ20082004

Éditeur(s) : HAL CCSD American Geophysical Union (AGU)
Résumé : International audience
Subduction of a narrow slab of oceanic lithosphere beneath a tightly curved orogenic arc requires the presence of at least one lithospheric scale tear fault. While the Calabrian subduction beneath southern Italy is considered to be the type example of this geodynamic setting, the geometry, kinematics and surface expression of the associated lateral, slab tear fault offshore eastern Sicily remain controversial. Results from a new marine geophysical survey conducted in the Ionian Sea, using high-resolution bathymetry and seismic profiling reveal active faulting at the seafloor within a 140 km long, two-branched fault system near Alfeo Seamount. The previously unidentified 60 km long NW trending North Alfeo Fault system shows primarily strike-slip kinematics as indicated by the morphology and steep-dipping transpressional and transtensional faults. Available earthquake focal mechanisms indicate dextral strike-slip motion along this fault segment. The 80 km long SSE trending South Alfeo fault system is expressed by one or two steeply dipping normal faults, bounding the western side of a 500+ m thick, 5 km wide, elongate, syntectonic Plio-Quaternary sedimentary basin. Both branches of the fault system are mechanically capable of generating magnitude 6–7 earthquakes like those that struck eastern Sicily in 1169, 1542, and 1693.
ISSN: 0278-7407

insu-01256887
https://hal-insu.archives-ouvertes.fr/insu-01256887
https://hal-insu.archives-ouvertes.fr/insu-01256887/document
https://hal-insu.archives-ouvertes.fr/insu-01256887/file/GutscherEtal_2015_Tectonics.pdf
DOI : 10.1002/2015TC003898

Éditeur(s) : HAL CCSD IM Publications
Résumé : The preparation of tropical wood surface sections for time-of-flight secondary ion mass spectrometry imaging is described, and the use of delayed extraction of secondary ions and its interest for the analysis of vegetal surface are shown. The method has been applied to the study by time-of-flight secondary ion mass spectrometry imaging with a resolution of less than one micron of a tropical wood species, Dicorynia guianensis, which is one of the most exploited wood in French Guiana for its durable heartwood. The heartwood of this species exhibits an economical importance, but its production is not controlled in forestry. Results show an increase of tryptamine from the transition zone and a concomitant decrease of inorganic ions and starch fragment ions. These experiments lead to a better understanding of the heartwood formation and the origin of the natural durability of D. guianensis.
ISSN: 1469-0667

hal-01532634
https://hal.archives-ouvertes.fr/hal-01532634
DOI : 10.1002/jms.3762
PRODINRA : 383376

Éditeur(s) : HAL CCSD MDPI AG, Basel, Switzerland
Résumé : International audience
Abstract View references (46)This work shows the preparation of silica membranes by a two-step sol-gel method using tetraethyl orthosilicate in ethanolic solution by employing nitric acid and ammonia as co-catalysts. The sols prepared in pH 6 resulted in the lowest concentration of silanol (Si-OH) species to improve hydrostability and the optimized conditions for film coating. The membrane was tested to desalinate 0.3-15 wt % synthetic sodium chloride (NaCl) solutions at a feed temperature of 22 °C followed by long term membrane performance of up to 250 h in 3.5 wt % NaCl solution. Results show that the water flux (and salt rejection) decrease with increasing salt concentration delivering an average value of 9.5 kg m-2 h-1 (99.6%) and 1.55 kg m-2 h-1 (89.2%) from the 0.3 and 15 wt % saline feed solutions, respectively. Furthermore, the permeate salt concentration was measured to be less than 600 ppm for testing conditions up to 5 wt % saline feed solutions, achieving below the recommended standard for potable water. Long term stability shows that the membrane performance in water flux was stable for up to 150 h, and slightly reduced from thereon, possibly due to the blockage of large hydrated ions in the micropore constrictions of the silica matrix. However, the integrity of the silica matrix was not affected by the long term testing as excellent salt rejection of >99% was maintained for over 250 h. © 2013 by the authors; licensee MDPI, Basel, Switzerland.
ISSN: 2077-0375

hal-01683203
https://hal.univ-antilles.fr/hal-01683203
DOI : 10.3390/membranes3030136

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This work relates to the characterisation of the predominant gill protein of the white clam, Codakia orbicularis (Linné, 1758), which harbours endosymbiotic sulphur-oxidising chemoautotrophic bacteria. Total RNA was extracted from the clam to perform 3'rapid amplification of cDNA ends (3'RACE) using degenerate oligonucleotides prepared from a partial sequence of a predominant protein of about 14kDa, termed codakine. The partial peptide sequence was obtained by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and Edman degradation. Clones isolated from the cDNA library and containing the gene of interest were used in polymerase chain reaction (PCR). The PCR and RACE-PCR products were sequenced to determine the entire coding DNA sequence of codakine. BLAST analysis revealed about 23% to 29% sequence identity between codakine and various animal C-type lectins that are often involved in symbiosis and immune defences. Codakine also contains the motifs and domains of Ca(2+)-dependent C-type lectins, and in particular the tripeptide EPN motif frequently found in mannose-binding lectins (MBLs). Analysis of the protein by affinity chromatography on a mannose-agarose column is consistent with the findings that codakine is a dimeric Ca(2+)-dependent MBL of about 29kDa. Based on the present results, it is hypothesised that this novel C. orbicularis gill protein is involved in the recognition of symbiotic and pathogenic bacteria.
ISSN: 1050-4648

hal-00746015
https://hal.univ-antilles.fr/hal-00746015
DOI : 10.1016/j.fsi.2006.06.013
PUBMED : 17169576

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 IOP Publishing
Résumé : Radioactive pollutants are naturally present in microelectronic device materials and can be an issue for the reliability of devices. The main concern is alpha emitters that produce high-energy particles (a few MeV) that ionize the semiconductor and then trigger soft errors. The question is to know what kinds of radionuclides are present in the device, their location in the device and the abundance of each species. In this paper we describe tools that are required to address the issue of radioactive pollutants in electronic devices.
ISSN: 0268-1242

hal-01504448
https://hal.archives-ouvertes.fr/hal-01504448
DOI : 10.1088/1361-6641/aa5479

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 Wiley
Résumé : International audience
CP12 is a small chloroplast protein involved in the Benson-Calvin cycle. Since it was demonstrated that the CP12 protein shared different conformational properties between reduced and oxidized states we took advantage of the segregational properties of the Traveling Wave Ion Mobility (TWIM) guide to study subtle conformational changes related to redox changes. Electrospray ionization mass (ESI-MS) spectra of the CP12 protein were recorded in the positive ion mode using an ESI source fitted on a quadrupole time-of-flight (QToF) hybrid mass spectrometer equipped with a TWIM cell (Synapt HDMS G1, Waters Corp., Manchester) under non-denaturing conditions. Non-covalent experiments were performed using the same instrument without the use of the TWIM device. Whatever the CP12 form studied, our results showed that CP12 protein was represented by two conformers in equilibrium that displayed very slight differences. These observations led us to propose that CP12 protein structure is rather undergoing transient subtle structural changes than having two different conformational populations in solution. In addition, using non-denaturing experiments, NAD and CP12 stoichiometry were determined with respect to the GAPDH tetramer and the redox state of CP12. In this study we showed that the use of the segregational property of the ion mobility (TWIM, Synapt G1 HDMS, Waters, Manchester, UK) allowed differentiation of subtle conformational changes between redox states of the CP12 protein. Standard non-denaturing experiments revealed different binding stoichiometry according to the redox state of the CP12 protein.
ISSN: 0951-4198

hal-01122181
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01122181
DOI : 10.1002/rcm.6442
PUBMED : 23239332

Éditeur(s) : HAL CCSD Wiley-Blackwell
Résumé : International audience
Heterocyclic aromatic amines (HAA) are formed in cooked meat, poultry and fish but also arise in tobacco smoke and exhaust gases. HAA are potential human carcinogens, which require metabolic activation to exert their genotoxicity. Human tissues can bioactivate HAA to produce reactive intermediates that bind to DNA. HAA DNA adduct formation occurs in human hepatocytes; however, the potential of HAA to form DNA adducts has not been investigated in human T lymphocytes. In this study, we investigated the ability of human T lymphocytes activated with PMA/Ionomycin or CD3/CD28 to express functional CYP1 activity and bioactivate three major HAA: 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), and 2-amino-9H-pyrido[2,3-b]indole (AαC) to form DNA adducts. Adducts were measured by ultraperformance liquid chromatography-electrospray ionization/multistage scan mass spectrometry. The highest level of DNA adducts occurred for AαC (16 adducts per 109 nucleotides), followed by PhIP (9 adducts per 109 nucleotides). In contrast, DNA adducts formed from MeIQx and the structurally related aromatic amine 4-aminobiphenyl, a known human carcinogen, were below the limit of detection (< 3 adducts per 109 nucleotides). Moreover, we demonstrate that AαC is a potent inducer of CYP1A1 and CYP1B1 activity through a transcriptional mechanism involving the AhR pathway. Overall, our results highlight the capacity of activated human T lymphocytes to more efficiently bioactivate AαC to form DNA adducts than other prominent HAA or 4-ABP. Environ. Mol. Mutagen. 57:656-667, 2016.
ISSN: 0893-6692

hal-01400486
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01400486
DOI : 10.1002/em.22059
PUBMED : 27801952