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51.
Virginie Gueu Hongpeng You Tomokatsu Hayakawa Masayuki Nogami 《Journal of Sol-Gel Science and Technology》2007,41(3):231-236
Fluorescence and spectral hole burning properties of Eu3+ ions were studied in nanocrystals-precipitated SnO2-SiO2 glasses. The glasses were prepared to contain various amount of Eu2O3 using the sol-gel method, in which SnO2 nanocrystals were precipitated by heating in air. In the glasses containing Eu2O3 less than 1%, the Eu3+ ions were preferentially doped in the SnO2 nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons
and holes excited in SnO2 crystals. The SnO2 nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence
intensities of the Eu3+ ions. With the increasing Eu2O3 concentration, the amount of SnO2 nanocrystals decreased and the Sn4+ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities
and the hole depth to decrease. 相似文献
52.
Van Lokeren L Maheut G Ribot F Escax V Verbruggen I Sanchez C Martins JC Biesemans M Willem R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(24):6957-6966
Diffusion-ordered NMR spectroscopy (DOSY NMR) is presented as a tool for the determination of the diffusion coefficients of organic ligands in suspensions of titanium dioxide nanoparticles. The nanoparticles were prepared by a sol-gel process by hydrolysis and condensation reactions of titanium tetra-n-butoxide in the presence of pentane-2,4-dione (acacH: acetylacetone), as well as para-toluenesulfonic acid (pTsA) and n-butanol (nBuOH). NMR spectroscopic studies were performed in various deuterated solvents, on both dispersed xerosols and diluted sols. The bipolar-pulsed field gradient longitudinal eddy-current delay (LED) pulse sequence was used for data acquisition. The data were processed by inverse Laplace transformation (ILT), by using a maximum entropy algorithm, to afford 2D DOSY spectra. Different diffusion regimes for organic ligands in the bound and unbound states were successfully discriminated, more particularly in [D3]acetonitrile, thus allowing assessment of their interactions with the nanoparticles. 相似文献
53.
Gérald S. Remaud Virginie Silvestre Serge Akoka 《Accreditation and quality assurance》2005,10(8):415-420
The choice of the reference, either as internal or external is not straightforward in quantitative NMR. In this context ERETIC™
methodology appears as an universal referencing technique. An electronic signal, generated by the NMR spectrometer during
the acquisition time, operates as a virtual working standard. The processes for ensuring a traceability to primary standards
is illustrated on the official method devoted to (D/H)i ratios measurement on ethanol, using quantitative 2H-NMR. The ERETIC approach is shown to be equivalent to its official homologue, in terms of accuracy and precision. Finally,
its performance could be beneficial to other analytes, matrices and nuclei. 相似文献
54.
Destructive adsorption of CCl4 over lanthanum-based solids: linking activity to acid-base properties
van der Heijden AW Bellière V Alonso LE Daturi M Manoilova OV Weckhuysen BM 《The journal of physical chemistry. B》2005,109(50):23993-24001
The relative activities of a low-surface crystalline and high-surface amorphous LaOCl, further denoted as S1 and S2, have been compared for the destructive adsorption of CCl4. It was found that the intrinsic activity of S2 is higher than that of S1. Both samples were characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2-physisorption, and Raman and infrared (IR) spectroscopy. IR was used in combination with CO2, CO, and methanol as probe molecules. The CO2 experiments showed that different carbonate species are formed on both materials. For S1, a high surface concentration of bidentate carbonate species and a lower concentration of monodentate carbonate were observed. In the case of S2, bulk carbonates were present together with bridged carbonates. CO adsorption shows that S2 and S1 have very similar Lewis acid sites. However, methanol adsorption experiments showed that S2 had a higher number of stronger Lewis acid sites than S1 and that twofold coordinated methoxy species were more strongly bound than threefold coordinated methoxy species. Because of the analogy between methanol dissociation and the removal of the first chlorine atom in the destructive adsorption of CCl4, the sites enabling twofold coordination were likely to be the same Lewis acid sites actively involved in the destructive adsorption of CCl4. La2O3 was less active than the two LaOCl materials, and therefore, the intrinsic activity of the catalyst increases as the strength of the Lewis acid sites increases. S2 contains more chlorine at the surface than S1, which is expressed by the higher number of sites enabling twofold coordination. Moreover, this explains the difference in destructive adsorption capacity for CCl4 that was observed for the samples S1 and S2. Since LaCl3, being the most acidic phase, is not active for the destructive adsorption of CCl4, basic oxygen atoms, however, remain needed to stabilize the reaction intermediate CCl3 as La-O-CCl3. 相似文献
55.
Recent crystal structures of nicotine bound to the acetylcholine binding protein (AChBP) ended a long debate confirming that the pyridine nitrogen of nicotine is indeed hydrogen-bonded to receptor residues through a bridging water molecule. Here, we describe the first direct experimental evaluation of the hydrogen-bond affinity of the nicotinium pyridine nitrogen. The equilibrium constant of its association with a phenol is 1 order of magnitude greater than the association of the acetylcholine carbonyl oxygen. 相似文献
56.
Lhiaubet-Vallet V Encinas S Miranda MA 《Journal of the American Chemical Society》2005,127(37):12774-12775
Time-resolved measurements using nanosecond laser flash photolysis have revealed significant enantiodifferentiation in the interaction between ketoprofen (a chiral benzophenone derivative) and two relevant nucleosides, namely, thymidine and 2'-deoxyguanosine. In both cases, the highest quenching rate constants have been observed for (R)-ketoprofen, the enantiomer with lower pharmacological activity. Photoproduct studies performed in the case of thymidine suggest that the enantiodifferentiating process corresponds to a Paterno-Büchi reaction, leading to the formation of oxetanes. With 2'-deoxyguanosine, the quenching is associated with an electron-transfer process monitored through the generation of a ketyl radical. 相似文献
57.
58.
Luis E. Piñero Carmelo García Virginie Lhiaubet‐Vallet Rolando Oyola Miguel A. Miranda 《Photochemistry and photobiology》2009,85(4):895-900
Chlorprothixene (CPTX, Taractan®) is a low potency antipsychotic mainly used for the treatment of psychotic disorders (e.g. schizophrenia) and acute mania occurring as part of bipolar disorders. As in the case of other numerous drugs used in the treatment of psychiatric disorders, CPTX presents geometric isomerism. Therefore, in vitro irradiation induces a rapid Z/E isomerization, which can affect its pharmacokinetic properties. This photoisomerization is not dependent on the oxygen concentration. The Z/E quantum yields determined for zCPTX in acetonitrile are 0.22 and 0.21 in anaerobic and aerobic environments, respectively. In the presence of water, both isomers decompose to produce 2‐chlorothioxanthone (CTX) after prolonged irradiation. This process strongly depends on the water concentration and the irradiation time, i.e. it is autocatalyzed by the CTX through a triplet‐energy transfer mechanism. The protonation state of the terminal amino group, on the other hand, has no effect on the isomerization process, but inhibits the formation of CTX. These results indicate that the phototoxicity of zCPTX is somehow affected by the formation of CTX. 相似文献
59.
60.
Virginie André 《Tetrahedron letters》2008,49(34):5059-5062
Reaction of non-conjugated acetylenic phosphonate monoesters with (bis-collidine) bromo and iodo hexafluorophosphates was found to lead to the formation of halo enol phostones. Depending on the size of the heterocyclic compounds formed (6-8-membered compounds), endo or a mixture of endo and exo cyclization products were obtained. 相似文献