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101.
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The stability constants for the Tc(IV) and V(IV) complexation with the polyamino polycarboxylate ligands IDA, NTA, HEDTA and DTPA were determined using liquid–liquid extraction techniques. These stability constants were then used to evaluate the validity of using V(IV) as a chemical analogue for Tc(IV). Results suggest that Tc(IV), as TcOOH+, will form β 1?11 complexes with the selected ligands, while V(IV), as VO2+, will form β 101 complexes. The values for these determined stability constants are (in log10 unit) 10.9 ± 0.1, 11.4 ± 0.1, 14.9 ± 0.1, and 20.1 ± 0.1 for Tc(IV) in 0.5 mol·L?1 NaCl at 25 °C, for IDA, NTA, HEDTA and DTPA, respectively, they are 9.3 ± 0.1, 11.6 ± 0.2, 15.8 ± 0.1, and 20.8 ± 0.1 for V(IV) in 0.5 mol·L?1 NaCl at 25 °C, for the same suite of ligands. The incorporation of a hydroxide into the metal ligand complexes formed by Tc(IV) is proposed as the largest factor differentiating the apparent stability constants of Tc(IV) and V(IV). This work shows that V(IV) is a poor analog for Tc(IV); however, despite the differences in complexation mechanism between V(IV) and Tc(IV), V(IV) still appears to have some use for predicting Tc(IV) complexation behavior. 相似文献
104.
Marion Collinet-Fressancourt Nathalie Azaroual Jean-Marie Aubry Véronique Nardello-Rataj 《Tetrahedron letters》2010,51(50):6531-6534
The kinetic booster effect of dimethylsulfoxide on the chemical generation of singlet oxygen, 1O2, from the disproportionation of hydrogen peroxide catalyzed by molybdate ions in methanol has been evidenced by detection of the IR luminescence of 1O2 at 1270 nm and by 95Mo NMR spectroscopy. DMSO interacts rapidly, through a direct oxygen transfer with the stable tetraperoxomolybdate , leading to DMSO2 and to the unstable triperoxomolybdate , which releases 1O2. The procedure was applied to accelerate the dark singlet oxygenation of β-citronellol and α-terpinene. 相似文献
105.
Mei Wang Nathalie Simon Gaelle Charrier Muriel Bouttemy Arnaud Etcheberry Musen Li Rabah Boukherroub Sabine Szunerits 《Electrochemistry communications》2010,12(3):351-354
While it is clearly established that oxidation of as-grown boron-doped diamond (BDD) interfaces results in the introduction of different surface oxygen functions such as ether, carbonyl and hydroxyl groups, there is no reported approach which can clearly distinguish between the different surface functions. For further surface functionalization, it is important to quantify the presence of each group on the diamond surface. In this paper, the presence and amount of surface hydroxyl groups is identified using esterification of the COH groups with trifluoroacetic acid. The presence of CF3 group in the acid allowed the identification and estimation of the amount of surface hydroxyl groups using X-ray photoelectron spectroscopy (XPS). 相似文献
106.
Gomila A Le Poul N Cosquer N Kerbaol JM Noël JM Reddy MT Jabin I Reinaud O Conan F Le Mest Y 《Dalton transactions (Cambridge, England : 2003)》2010,39(48):11516-11518
We report the self-induced "electroclick" immobilization of the [Cu(II)(6-ethynyl-TMPA)(H(2)O)](2+) complex, by its simple electro-reduction, onto a mixed azidoundodecane-/decane-thiol modified gold electrode. The redox response of the grafted [Cu(II/I)(TMPA)] at the modified electrode is fully reversible indicating no Cu coordination change and a fast electron transfer. 相似文献
107.
Nathalie Calin Anne Galarneau Thomas Cacciaguerra Renaud Denoyel François Fajula 《Comptes Rendus Chimie》2010,13(1-2):199-206
Mesoporous silica supports are proposed as an alternative to polymeric stationary phases for fast affinity chromatography due to their better mechanical strength compared to polymers. Ideal supports should combine high surface area and large pore size to allow a high loading capacity of large molecules, such as proteins, and favor their accessibility. Increasing the pore size of large-surface area micelle-templated silicas (SBA-15, KIT-6) has been achieved by swelling the micelles by the addition of organic molecules and increasing synthesis time and temperature. The pore size of hexagonal silica mesostructured SBA-15 has been increased up to 35 nm. These materials could find therefore application as affinity chromatography for immunoextraction. 相似文献
108.
Gomes P Wingert NR Paim CS Schapoval EE Steppe M 《Journal of AOAC International》2010,93(6):1829-1835
A stability-indicating HPLC assay method was developed for the quantitative determination of duloxetine (DLX) in a pharmaceutical dosage form in the presence of its degradation products, and kinetic determinations were evaluated in acid conditions and UV-C radiation exposure. Chromatographic separation was achieved by use of an ACE C18 column (250 x 4.0 mm id, 5 microm particle size). The mobile phase was prepared by mixing aqueous 50 mM potassium phosphate buffer (pH 6.0 containing 0.3% triethylamine) and acetonitrile (60 + 40, v/v). DLX was rapidly degraded in an acid medium and in the presence of hydrogen peroxide and UV-C radiation; it was more stable in alkaline medium. The described method was linear over a range of 4.0-14.0 microg/mL for determination of DLX (r = 0.9998). The precision was demonstrated by the RSD of intraday (0.79-1.07%) and interday (0.85%) studies. The mean recovery was found to be 100.56%. The acid degradation of DLX in 0.1 M HCI solution showed an apparent zero-order kinetics (k = 0.177 microg/mL/min), and the photodegradation demonstrated an apparent first-order kinetics (k = 0.082 microg/mL/min). The developed method was found to be simple, specific, robust, linear, precise, and accurate for the determination of DLX in enteric-coated pellets. 相似文献
109.
Nathalie L. Lévêque Sylvie Héron Alain Tchapla 《Journal of mass spectrometry : JMS》2010,45(3):284-296
Triacylglycerols (TAGs) provide a challenge for mass spectrometry (MS) analysis because of their complexity. In particular, for dietary, nutritional and metabolic purposes, the positional placement of fatty acids on the glycerol backbone of TAGs is a crucial aspect. To solve this problem, we have investigated the TAGs' fragmentation patterns using an ion trap mass spectrometer. A series of pure regioisomeric pairs of TAGs (POP/PPO, POO/OPO and OSO/SOO) were cationized by Ag+ after their separation by non‐aqueous reversed‐phase liquid chromatography (NARP‐LC) before MS to improve MS sensitivity. Electrospray ionization–MS (ESI‐MS) conditions were optimized in order to produce characteristic [M + Ag + AgNO3]+ ions from each TAG, which were then fragmented to produce MS/MS spectra and then fragmented further to produce up to MS5 spectra. The observation of ions produced by LC‐MS5 of on‐line Ag+‐cationized TAG provided unambiguous information on the fatty acid distribution on the glycerol backbone. These strategies of MS to MS5 experiments were applied to identify components and to determine the regiospecificity of TAG within a complex mixture of lipids in natural oils. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
110.
Nathalie Dupré Pauline Rémy Dr. Kévin Micoine Dr. Cécile Boglio Dr. Serge Thorimbert Dr. Emmanuel Lacôte Dr. Bernold Hasenknopf Prof. Max Malacria Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(24):7256-7264
The preparation of new organosoluble Lewis acidic polyoxometalates (POMs) is reported. These complexes were prepared by the incorporation of Zr, Sc, and Y atoms into the corresponding monolacunary Dawson [P2W17O61]10? and Keggin [PW11O39]7? polyoxotungstates. The catalytic activity of these compounds was evaluated for C? C bond formation in the Diels–Alder, Mannich, and Mukaiyama‐type reactions. Comparisons with previously described Lewis acidic POMs are reported. Competitive reactions between imines and aldehydes or between various imines demonstrated that fine tuning of the reactivity could be reached by varying the metal atom incorporated into the polyanionic framework. A series of experiments that employed pyridine derivatives allowed us to distinguish between the Lewis and induced Brønsted acidity of the POMs. These catalysts activate imines in a Lewis acidic way, whereas aldehydes are activated by indirect Brønsted catalysis. 相似文献