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showing 10 items of 13546 documents
New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure.
2010
International audience; The "water-silicalite-1" system is known to act as a molecular spring. The successive intrusion-extrusion cycles of liquid water in small crystallites (6 × 3 × 0.5 μm(3)) of hydrophobic silicalite-1 were studied by volumetric and calorimetric techniques. The experiments displayed a decrease of the intrusion pressure between the first intrusion-extrusion cycle and the consecutive ones, whereas the extrusion pressures remained unchanged. However, neither XRD studies nor SEM observations revealed any structural and morphological modifications of silicalite-1 at the long-range order. Such a shift in the value of the intrusion pressure after the first water intrusion-extr…
First signals of electrochemically oxidized species of TTF and TMT-TTF : a study by in situ spectroelectrochemical FTIR and DFT calculations
2003
A first study by in situ FTIR spectroelectrochemistry of TTF and TTM-TTF has been undertaken. The oxidation, in this case, is caused only by electrochemistry, which constitutes a clear advantage over chemical oxidation since no side products are present in the solution. In this context, we obtained the signals of neutral, radical cation, and dication species of TTF and TTM-TTF. The experimental conditions were chosen in order to avoid the possible formation of π-dimer species and to obtain a satisfactory signal-to-noise ratio. A weak signal was detected for TTF and a stronger one for TTM-TTF. The changes induced by the oxidation process in the IR spectra of TTF and TTM-TTF have been analyze…
FT-Raman and QM/MM study of the interaction between histamine and DNA
2006
The interaction between histamine and highly polymerized calf-thymus DNA has been investigated using FT-Raman spectroscopy and the hybrid QM/MM (quantum mechanics/molecular mechanics) methodology. Raman spectra of solutions containing histamine and calf-thymus DNA, at different molar ratios, were recorded. Solutions were prepared at physiological settings of pH and ionic strength, using both natural and heavy water as the solvent. The analysis of the spectral changes on the DNA Raman spectra when adding different concentrations of histamine allowed us to identify the reactive sites of DNA and histamine, which were used to built two minor groove and one intercalated binding models. They were…
Nitroanilines as Quenchers of Pyrene Fluorescence
2012
The quenching of pyrene and 1‐methylpyrene fluorescence by nitroanilines (NAs), such as 2‐, 3‐, and 4‐nitroaniline (2‐NA, 3‐NA, and 4‐NA, respectively), 4‐methyl‐3‐nitroaniline (4‐M‐3‐NA), 2‐methyl‐4‐nitroaniline (2‐M‐4‐NA), and 4‐methyl‐3,5‐dinitroaniline (4‐M‐3,5‐DNA), are studied in toluene and 1,4‐dioxane. Steady‐state fluorescence data show the higher efficiency of the 4‐NAs as quenchers and fit with a sphere‐of‐action model. This suggests a 4‐NA tendency of being in close proximity to the fluorophore, which could be connected with their high polarity/hyperpolarizability. In addition, emission and excitation spectra evidence the formation of emissive pyrene—NA ground‐state complexes in…
Effect of sodium to barium substitution on the space charge implementation in thermally poled glasses for nonlinear optical applications
2009
Thermally poled niobium borophosphate glasses in the system 0.55(0.95-y) NaPO{sub 3}+y/2 Ba(PO{sub 3}){sub 2}+0.05Na{sub 2}B{sub 4}O{sub 7})+0.45Nb{sub 2}O{sub 5} were investigated for second order optical nonlinear (SON) properties. Bulk glasses were studied by Raman spectroscopy, thermal analysis, optical and dielectric measurements. The sodium to barium substitution does not lead to significant changes in optical properties, crystallization of glasses and coordination environment of polarizable niobium atoms. However, the ionic conductivity decreases drastically with the increase of barium concentration. Secondary ion mass spectroscopy has been used to determine the element distribution …
Relationship between particle size and dissolution rate of bulk powders and sieving characterized fractions of two qualities of orthoboric acid
1996
Drug Dev. Ind. Pharm. ISI Document Delivery No.: VN279 Times Cited: 1 Cited Reference Count: 22 Tromelin, A Habillon, S Andres, C Pourcelot, Y Chaillot, B; International audience; We have carried out a study of the particle size distribution and aqueous dissolution rate of two commercially available qualities of orthoboric acid, labeled ''crystal'' (ABC) and ''powder'' (ABP). In a previous work, we have shown that the two commercial qualities of orthoboric acid chosen as model compound (''powder'' and ''crystal'') are related to the same crystal network in spite of their different names. However, these two qualities have very different size particle distributions, as previously determined b…
Investigation into the reaction of (t-BuC5H4)2Nb(η2-Te2)H with CH3Li: Hydride abstraction versus telluride methylation
2007
Abstract The reaction of [ Cp 2 ′ Nb ( Te 2 ) H ] ( 1 ) (Cp′ = t -BuC 5 H 4 ) with CH 3 Li in THF was examined by variable temperature 1 H NMR, ESR and mass spectroscopic means. From these methods it is evident that the diamagnetic compounds [ Cp 2 ′ NbH 2 ( TeCH 3 ) ] ( 2 ) and [ Cp 2 ′ Nb ( Te ) CH 3 ] ( 3 ) as well as the paramagnetic compound [ Cp 2 ′ Nb ( TeCH 3 ) 2 ] ( 4 ) form simultaneously. In the subsequent reaction of the intermediate solution with [Co 2 (CO) 8 ] compound 4 was consumed and the compound [ Cp 2 ′ Nb ( μ - TeCH 3 ) 2 Co(CO) 2 ] ( 5 ) formed in good yield. Complex 5 was characterized by IR and variable temperature 1 H NMR spectroscopies. Electrochemical two-electro…
Spectroscopic Detection and Structure of Hydroxidooxidosulfur (HOSO) Radical, An Important Intermediate in the Chemistry of Sulfur-Bearing Compounds
2013
The rotational spectrum of hydroxidooxidosulfur, HOSO, an intermediate of particular interest in the combustion of sulfur-rich fuels, has been determined to high accuracy from gas-phase measurements. Detection of specific isotopic species using isotopically enriched gases suggests that HOSO is formed in our discharge nozzle via the reaction H + SO2 (+M) → HOSO (+M). A precise experimental r0 geometry has also been derived from the isotopic analysis; HOSO has a cis configuration, but the subtle structural question of its planarity remains unresolved. From the derived spectroscopic constants, in situ and remote sensing for this fundamental radical can now be undertaken in a variety of environ…
FT-ICR MS studies of ion-molecule reactions of Ru+ and Os+ with oxygen
2005
Abstract The reactions of stored ruthenium and osmium cations with oxygen have been studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. In case of osmium the reaction products OsO+ and OsO 2 + have been observed and corresponding reaction-rate constants have been determined. In addition, there is an unreactive fraction of Os+ ions due to the presence of a slightly endothermic reacting ground state. Only the excited states react with oxygen. For ruthenium no spontaneous reaction with oxygen has been observed unless the cyclotron motion of Ru+ was excited. The results are discussed with respect to a similar investigation in a Penning trap-TOF mass spectrometer […
TASCAを用いたCn, Nh, Fl化学実験のためのHg, Tl, PbのSiO2及びAu表面に対するオンライン化学吸着研究
2018
Online gas-solid adsorption studies with single atom quantities of Hg, Tl, and Pb on SiO$_{2}$ and Au surfaces were carried out using short-lived radioisotopes with half-lives in the range of 4-49 s. This is a model study to measure adsorption enthalpies of superheavy elements Cn, Nh, and Fl. The short-lived isotopes were produced and separated by the gas-filled recoil separator TASCA at GSI. The products were stopped in He gas, and flushed into gas chromatography columns made of Si detectors whose surfaces were covered by SiO$_{2}$ or Au. The short-lived Tl and Pb were successfully measured by the Si detectors with the SiO$_{2}$ surface at room temperature. On the other hand, the Hg did no…