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Fluidized bed plasma for pre-treatment of Co-ferrierite catalysts: An approach to NOx abatement
R. Bartolomeu, M. Foix, A. Fernandes, M. Tatoulian, M.F. Ribeiro, C. Henriques, P. Da Costa
CATALYSIS TODAY - 176(1) :234-8 - DOI:10.1016/j.cattod.2010.12.051 - 2011
Replacement of calcination procedures used during catalyst preparation, by a plasma treatment, was studied over a Co-ferrierite (Co-FER) catalyst. The catalyst was tested in the NOx selective catalytic reduction reaction. A combination of UV–Vis spectroscopy and TG analysis revealed the presence of ammonium ions on the untreated and plasma Co-FER samples but not on the calcined one. Therefore, it can be concluded that the plasma treatment was not able to replace the thermal calcination step. The evaluation of catalyst behaviour was performed both under temperature programmed surface reaction (TPSR) and under steady-state conditions at different temperatures. NO oxidation tests showed that, during TPSR runs, calcined catalyst produces more NO2 than plasma catalyst. NOx consumption during TPSR of plasma catalyst confirms that precursors used on the ion-exchange procedure are still present on the catalyst even after the plasma treatment, reacting with NO to produce R-NOx, N2O and N2. Concerning deNOx tests using ethanol as reducing agent, TPSR tests showed higher NOx conversions over untreated and plasma catalysts due to the presence of ammonium and acetate precursors on these catalysts. Untreated, plasma and calcined catalysts present the same NOx and COx conversions in isothermal tests.
Deposition of Cobalt Oxide thin films by PECVD for catalysis application
C. Guyon, A. Barkallah, F. Rousseau, K. Giffard, D. Morvan, M. Tatoulian
Surface & Coatings Technology - 206(7) :1673-9 - DOI:10.1016/j.surfcoat.2011.09.060 - 2011
Plasma-enhanced chemical vapour deposition (PECVD) was used to prepare thin films of cobalt oxide. Cobalt oxide-based (CoO and Co3O4) catalysts were chosen due to their efficiency in mineralisation of organic pollutants achieved by catalytic ozonation. In this work, two types of PECVD processes were used for the production of cobalt oxide thin films. In the first one, a solution of nitrate salt of cobalt was sprayed into a RF low pressure plasma discharge (40 MHz, 600 Pa, 200 W) to obtain CoxOy layers. In the second MOPECVD (metal organic plasma-enhanced chemical vapour deposition) process, cobalt oxide thin films were deposited using a capacitive coupled external electrodes RF plasma reactor (13.56 MHz, 100 Pa, 200 W) with cobalt carbonyl Co2(CO)8 dissolved in hexene as precursor sprayed in a gas carrier (argon and oxygen). In the case of coatings produced from a solution of cobalt nitrate salt, a layer of 1 µm of Co3O4 in crystalline form was obtained after annealing. Considering the thin films obtained from cobalt carbonyl precursor, analyses confirmed the presence of cobalt oxide in a polymeric layer on the surface of the substrate. XRD investigation showed the presence of a crystalline phase of Co3O4 (crystallite size of about 40 nm).
Microchip integrating magnetic nanoparticles for allergy diagnosis
Teste B, Malloggi F, Siaugue JM, Varenne A, Kanoufi F, Descroix S.
Lab. Chip - 11(24) :4207-13 - DOI:10.1039/c1lc20809h - 2011
We report on the development of a simple and easy to use microchip dedicated to allergy diagnosis. This microchip combines both the advantages of homogeneous immunoassays i.e. species diffusion and heterogeneous immunoassays i.e. easy separation and preconcentration steps. In vitro allergy diagnosis is based on specific Immunoglobulin E (IgE) quantitation, in that way we have developed and integrated magnetic core-shell nanoparticles (MCSNPs) as an IgE capture nanoplatform in a microdevice taking benefit from both their magnetic and colloidal properties. Integrating such immunosupport allows to perform the target analyte (IgE) capture in the colloidal phase thus increasing the analyte capture kinetics since both immunological partners are diffusing during the immune reaction. This colloidal approach improves 1000 times the analyte capture kinetics compared to conventional methods. Moreover, based on the MCSNPs' magnetic properties and on the magnetic chamber we have previously developed the MCSNPs and therefore the target can be confined and preconcentrated within the microdevice prior to the detection step. The MCSNPs preconcentration factor achieved was about 35,000 and allows to reach high sensitivity thus avoiding catalytic amplification during the detection step. The developed microchip offers many advantages: the analytical procedure was fully integrated on-chip, analyses were performed in short assay time (20 min), the sample and reagents consumption was reduced to few microlitres (5 µL) while a low limit of detection can be achieved (about 1 ng mL(-1)).
On-chip multi-electrochemical sensor array platform for simultaneous screening of nitric oxide and peroxynitrite
Quinton D., Girard A., Kim LTT., Raimbault V., Griscom L., Razan F., Griveau S., Bedioui F.
Lab. Chip - 11 :1342-50 - DOI:10.1039/c0lc00585a - 2011
In this work we report on the design, microfabrication and analytical performances of a new electrochemical sensor array (ESA) which allows for the first time the simultaneous amperometric detection of nitric oxide (NO) and peroxynitrite (ONOO(-)), two biologically relevant molecules. The on-chip device includes individually addressable sets of gold ultramicroelectrodes (UMEs) of 50 µm diameter, Ag/AgCl reference electrode and gold counter electrode. The electrodes are separated into two groups; each has one reference electrode, one counter electrode and 110 UMEs specifically tailored to detect a specific analyte. The ESA is incorporated on a custom interface with a cell culture well and spring contact pins that can be easily interconnected to an external multichannel potentiostat. Each UME of the network dedicated to the detection of NO is electrochemically modified by electrodepositing thin layers of poly(eugenol) and poly(phenol). The detection of NO is performed amperometrically at 0.8 V vs. Ag/AgCl in phosphate buffer solution (PBS, pH = 7.4) and other buffers adapted to biological cell culture, using a NO-donor. The network of UMEs dedicated to the detection of ONOO(-) is used without further chemical modification of the surface and the uncoated gold electrodes operate at -0.1 V vs. Ag/AgCl to detect the reduction of ONOOH in PBS. The selectivity issue of both sensors against major biologically relevant interfering analytes is examined. Simultaneous detection of NO and ONOO(-) in PBS is also achieved.
Magnetic core shell nanoparticles trapping in a microdevice generating high magnetic gradient
Teste B, Malloggi F, Gassner AL, Georgelin T, Siaugue JM, Varenne A, Girault H, Descroix S.
Lab. Chip - 11(5) :833-40 - DOI:10.1039/c0lc00510j - 2011
Magnetic core shell nanoparticles (MCSNPs) 30 nm diameter with a magnetic weight of 10% are usually much too small to be trapped in microfluidic systems using classical external magnets. Here, a simple microchip for efficient MCSNPs trapping and release is presented. It comprises a bed of micrometric iron beads (6-8 µm diameter) packed in a microchannel against a physical restriction and presenting a low dead volume of 0.8 nL. These beads of high magnetic permeability are used to focus magnetic field lines from an external permanent magnet and generate local high magnetic gradients. The nanoparticles magnetic trap has been characterised both by numerical simulations and fluorescent MCSNPs imaging. Numerical simulations have been performed to map both the magnetic flux density and the magnetic force, and showed that MCSNPs are preferentially trapped at the iron bead magnetic poles where the magnetic force is increased by 3 orders of magnitude. The trapping efficiency was experimentally determined using fluorescent MCSNPs for different flow rates, different iron beads and permanent magnet positions. At a flow rate of 100 µL h(-1), the nanoparticles trapping/release can be achieved within 20 s with a preconcentration factor of 4000.
Determination of binding parameters between lysozyme and its aptamer by frontal analysis continuous microchip electrophoresis (FACMCE)
Girardot M, Li HY, Descroix S, Varenne A.
J. Chrom. A - 1218 :4052-8 - DOI:10.1016/j.chroma.2011.04.077 - 2011
An original and simple methodology based on microchip electrophoresis (MCE) in a continuous frontal analysis mode (named frontal analysis continuous microchip electrophoresis, FACMCE) was developed for the simultaneous determination of the binding parameters, i.e. ligand-site dissociation constant (k(d)) and number of binding sites on the substrate (n). This simultaneous determination was exemplified with the interaction between an aptamer and its target. The selected target is a strongly basic protein, lysozyme, as its quantification is of great interest due to its antimicrobial and allergenic properties. A glass microdevice equipped with a fluorescence detection system was coated with hydroxypropylcellulose, reducing the electroosmotic flow and adsorption onto the channel walls. This microdevice allowed the continuous electrokinetic injection of a mixture of fluorescently labelled aptamer and non-labelled lysozyme. By determining the concentration of the free fluorescently labelled aptamer thanks to its corresponding plateau height, mathematical linearization methods allowed to determine a k(d) value of 48.4±8.0 nM, consistent with reported results (31 nM), while the average number of binding sites n on lysozyme, never determined before, was 0.16±0.03. These results seem to indicate that the buffer nature and the SELEX process should influence the number and affinity of the binding sites. In parallel it has been shown that the binding between lysozyme and its aptamer presents two sites of different binding affinities.
Microelectrochemical patterning of gold surfaces using 4-azidobenzenediazonium and scanning electrochemical microscopy
Coates M., Cabet E., Griveau S., Nyokong T., Bedioui F.
Electrochemistry Communications - 13 :150-3 - DOI:10.1016/j.elecom.2010.11.037 - 2011
This work describes for the first time the possibility of performing local micro electrochemical grafting of a gold substrate by 4-azidobenzenediazonium by SECM in a single and simple one step without complications from adsorption. The electrografted spots of diazonium were performed by positioning a Pt tip at a given distance above the gold substrate and the SECM was used in a three-electrode configuration (the Pt tip serving as the microanode) in acetonitrile containing 5 mM 4-azidobenzenediazonium and 0.1 M Bu4NBF4 during 10 ms. The dimensions of the derivatized areas of the substrates were finely tuned by using different experimental conditions (tip distance above the substrate, tip diameter, presence or absence of supporting electrolyte). The use of the azido-derivated diazonium molecule and these preliminary results open the gate to important applications and developments devoted to the local micro functionalization of electrodes by thin layers that allow the implementation of the emerging and attractive interfacial click reaction.
External forces control mitotic spindle positioning
Fink J, Carpi N, Betz T, Bétard A, Chebah M, Azioune A, Bornens M, Sykes C,Fetler L, Cuvelier D, Piel M*. (*corresponding authors)
Nat. Cell Biol. - 13(7) :771-8 - DOI:10.1038/ncb2269 - 2011
The response of cells to forces is essential for tissue morphogenesis and homeostasis. This response has been extensively investigated in interphase cells, but it remains unclear how forces affect dividing cells. We used a combination of micro-manipulation tools on human dividing cells to address the role of physical parameters of the micro-environment in controlling the cell division axis, a key element of tissue morphogenesis. We found that forces applied on the cell body direct spindle orientation during mitosis. We further show that external constraints induce a polarization of dynamic subcortical actin structures that correlate with spindle movements. We propose that cells divide according to cues provided by their mechanical micro-environment, aligning daughter cells with the external force field.
Cell migration in confinement: a micro-channel-based assay
Heuzé ML, Collin O, Terriac E, Lennon-Duménil AM, Piel M
Methods Mol Biol. - 769 :415-434 - DOI:10.1007/978-1-61779-207-6_28. - 2011
This chapter describes a method to study cells migrating in micro-channels, a confining environment of well-defined geometry. This assay is a complement to more complex 3D migration systems and provides several advantages even if it does not recapitulate the full complexity of 3D migration. Important parameters such as degree of adhesion, degree of confinement, mechanical properties, and geometry can be varied independently of each other. The device is fully compatible with almost any type of light microscopy and the simple geometry makes automated analysis very easy to perform, which allows screening strategy. The chapters is divided into five parts describing the design of different types of migration chambers, the fabrication of a mold by photolithography, the assembly of the chamber, the loading of cells, and finally the imaging on live or fixed cells.
Dansyl-peptides matrix-assisted laser desorption/ionization mass spectrometric (MALDI-MS) and tandem mass spectrometric (MS/MS) features improve the liquid chromatography/MALDI-MS/MS analysis of the proteome
Chiappetta G, Ndiaye S, Demey E, Haddad I, Marino G, Amoresano A, Vinh J.
Rapid Commun Mass Spectrom - 24(20) :3021-32 - DOI:10.1002/rcm.4734 - 2010
Peptide tagging is a useful tool to improve matrix-assisted laser desorption/ionization tandem mass spectrometric (MALDI-MS/MS) analysis. We present a new application of the use of the dansyl chloride (DNS-Cl). DNS-Cl is a specific primary amine reagent widely used in protein biochemistry. It adds a fluorescent dimethylaminonaphthalene moiety to the molecule. The evaluation of MALDI-MS and MS/MS analyses of dansylated peptides shows that dansylation raises the ionization efficiency of the most hydrophilic species compared with the most hydrophobic ones. Consequently, higher Mascot scores and protein sequence coverage are obtained by combining MS and MS/MS data of native and tagged samples. The N-terminal DNS-Cl sulfonation improves the peptide fragmentation and promotes the generation of b-fragments allowing better peptide sequencing. In addition, we set up a labeling protocol based on the microwave chemistry. Peptide dansylation proved to be a rapid and cheap method to improve the performance of liquid chromatography (LC)/MALDI-MS/MS analysis at the proteomic scale in terms of peptide detection and sequence coverage.


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