排序方式: 共有130条查询结果,搜索用时 13 毫秒
61.
Galatanu AN Rollet AL Porion P Diat O Gebel G 《The journal of physical chemistry. B》2005,109(22):11332-11339
A casting process has been studied for charged polymers: the sulfonated polyimide ionomer membrane. The formation of the membrane has been followed by X-ray reflectivity as a function of temperature. The effect of equivalent weight has been also investigated. The thickness loss presents two regimes: the first one is linear vs time indicating that the models developed for noncharged polymer may be suitable for ionomers in the early period of drying. The second one corresponds to the loss of X-ray reflectivity signal. Moreover, the X-ray reflectivity signal seems to be correlated to the characteristic time of the sample drying. In complement, we have studied the influence of casting on the properties of the dried ionomer membranes. The transport coefficients of N(CH(3))(4)(+) ions confined in two kinds of membranes that were differently cast were measured. The results show that shearing the ionomer solution during casting may lead to an enhancement of the anisotropy of structure and of transport. Moreover, we have studied the effect of both interfaces on the ion transport properties through the dried membranes. 相似文献
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63.
Chiara Danieli Andrea Cornia Claudia Cecchelli Roberta Sessoli Anne-Laure Barra Glauco Ponterini Barbara Zanfrognini 《Polyhedron》2009,28(9-10):2029-2035
Tripods of general formula R’–O–CH2C(CH2OH)3 are excellent site-specific ligands for the preparation of functionalized Fe4 single-molecule magnets. Herein, we describe the synthesis and characterization of two novel complexes designed to bind graphene surfaces, in which the R group consists of an alkyl spacer –(CH2)n– (n = 6 and 10) and a terminal pyrenyl moiety. The site-specific ligand substitution on [Fe4(OMe)6(dpm)6] (Hdpm = dipivaloylmethane) with the new tripods has been studied with 2H NMR on isotopically-enriched samples, revealing that, once formed, these clusters are stable in solution over long timescales. It was not possible to isolate the new compounds as crystalline solids, nevertheless they were chemically characterized by elemental analysis and 1H NMR. The presence of the pyrenyl ending groups prompted us to investigate the effect of metal complexation on fluorescence, and a full pyrene-to-iron cluster excitation energy transfer was observed. The analysis of the magnetic behaviour revealed an S = 5 ground spin state with a negative zero-field splitting parameter D = ?0.42 cm?1. 相似文献
64.
Two major milk whey proteins, β-lactoglobulin and α-lactalbumin, are among the main cow milk allergens and can cause allergy even at a very low concentrations. Therefore, these proteins are interesting targets in food analysis, not only for food quality control but also for highlighting the presence of allergens. Herein, a sensitive analysis for β-lactoglobulin and α-lactalbumin was developed using immunoaffinity capillary electrophoresis hyphenated with MALDI-MS. Magnetic beads functionalized with appropriate antibodies were used for β-lactoglobulin and α-lactalbumin immunocapture inside the capillary. After elution from the beads, analyte focusing and separation were performed by transient isotachophoresis followed by MALDI-MS analysis performed through an automated iontophoretic fraction collection interface. A LOD in the low nanomolar range was attained for both whey proteins. The method developed was further applied to the analysis of different milk samples including fortified soy milk. 相似文献
65.
To deal with their highly variable workload, logistics companies make their task force flexible using multi-skilled employees, flexible working hours or short-term contracts. Together with the legal constraints and the handling equipments’ capacities, these possibilities make personnel scheduling a complex task. This paper describes a model to support their chain of decisions from the weekly timetabling to the daily rostering (detailed task allocation). 相似文献
66.
Anne-Laure Fameau Bérénice Houinsou-Houssou Bruno Novales Laurence Navailles Frédéric Nallet Jean-Paul Douliez 《Journal of colloid and interface science》2010,341(1):38-47
There is a growing interest for constructing supramolecular hollow tubes from amphiphilic molecules. Aqueous solutions of the ethanolamine salt of 12-hydroxystearic acid are known to form tubes of several tens of micrometers in length with a temperature-tunable diameter. However, the phase behavior of this system has not been fully studied. Herein, we report the variation of various physico-chemical parameters on the self-assembling properties of this system. The effects of the ionic strength, ethanol, doping with other lipids, pH, concentration, and the fatty acid/ethanolamine molar ratio R were investigated by both phase-contrast microscopy and DSC. We observed the formation of tubes in a wide range of parameters. For instance, the molar ratio R can be modified from 2/3 to 5/2 without altering the formation of tubes. In some but not all cases, the tube diameter still varied with temperature. These findings show that tubes form under various experimental conditions. This should increase the interest in producing such self-assemblies from low-cost fatty acids. 相似文献
67.
The precipitation of natrojarosite from iron sodium sulfate solutions has been investigated at temperatures close to the atmospheric boiling point, in batch and semi-batch conditions. Semi-batch conditions make it possible to maintain a weaker iron concentration in the stirred reactor, leading to lower supersaturations, closer to those in continuous and possibly seeded MSMPRs or tanks—in series units. In these reactors, primary and secondary nucleations are few, allowing the growth of pure mono-crystalline particles of controlled size and size dispersion. Both modi operandi lead to agglomerates made of crystals of cubic habit. The surface of cauliflower-like particles from the batch modus operandi displays overlaying crystals, of size between 100 and 400 nm. The particles from the semi-batch mode, with moderate iron addition, are rougher and show bigger intergrown constitutive crystals of size up to a few microns, which denotes lesser secondary nucleation and more growth. A model is developed to characterize iron(III) and sulfate speciation with non-ideal behavior in the mother solution. It is used to compare the variations of supersaturation in the reactor between the batch and the semi-batch conditions. During the first 500 min, the supersaturation resulting from a moderate addition of iron is 10,000–10 times lower than during batch kinetics, which agrees with the reduction of secondary nucleation suggested by scanning electron micrographs. The semi-batch technique, which can be combined with the addition of support particles, is worth further work, aiming to reduce secondary nucleation and to determine the crystallite growth rate expression of natrojarosite as a function of supersaturation, using the model of solution developed in this work. 相似文献
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Rebilly JN Catala L Charron G Rogez G Rivière E Guillot R Thuéry P Barra AL Mallah T 《Dalton transactions (Cambridge, England : 2003)》2006,(23):2818-2828
The trinuclear and the tetranuclear complexes [[iPrtacnCr(CN)3]2[Ni(cyclam)]](NO3)2.5H2O 1 (cyclam = 1,4,8,11-tetraazacyclotetradecane, iPrtacn = 1,4,7-tris-isopropyl-1,4,7-triazacyclononane) and [[iPrtacnCr(CN)3Ni(Me2bpy)2]2](ClO4)4.2CH3CN 2 (Me2bpy = 4,4-dimethyl-2,2-bipyridine) were synthesized by reacting (iPrtacn)Cr(CN)3 with [Ni(cyclam)](NO3)2 and [Ni(Me2bpy)2(H2O)2](ClO4)2, respectively. The crystallographic structure of the two compounds was solved. The molecular structure of complex 1 consists of a linear Cr-Ni-Cr arrangement with a central Ni(cyclam) unit surrounded by two Cr(iPrtacn)(CN)3 molecules through bridging cyanides. Each peripheral chromium complex has two pending CN ligands. Complex 2 has a square planar arrangement with the metal ions occupying the vertices of the square. Each Cr(iPrtacn)(CN)3 molecule has two bridging and one non-bridging cyanide ligands. The magnetic properties of the two complexes were investigated by susceptibility vs. temperature and magnetization vs. field studies. As expected from the orthogonality of the magnetic orbitals between Cr(III) (t2g3) and Ni(II) (e(g)2) metal ions, a ferromagnetic exchange interaction occurs leading to a spin ground states S = 4 and 5 for 1 and 2, respectively. The magnetization vs. field studies at T = 2, 3 and 4 K showed the presence of a magnetic anisotropy within the ground spin states leading to zero-field splitting parameters obtained by fitting the data D4 = 0.36 cm(-1) and D5 = 0.19 cm(-1) (the indices 4 and 5 refer to the ground states of complexes 1 and 2, respectively). In order to quantify precisely the magnitude of the axial (D) and the rhombic (E) anisotropy parameters, High-field high frequency electron paramagnetic resonance (HF-HFEPR) experiments were carried out. The best simulation of the experimental spectra (at 190 and 285 GHz) gave the following parameters for 1: D4 = 0.312 cm(-1), E4/D4 = 0.01, g4x = 2.003, g4y = 2.017 and g4z = 2.015. For complex 2 two sets of parameters could be extracted from the EPR spectra because a doubling of the resonances were observed and assigned to the presence of complexes with slightly different structures at low temperature: D5 = 0.154 (0.13) cm(-1), E5/D5 = 0.31 (0.31) cm(-1), g4x = 2.04 (2.05), g4y = 2.05 (2.05) and g4z = 2.03 (2.02). The knowledge of the magnetic anisotropy parameters of the mononuclear Cr(iPrtacn)(CN)3, Ni(cyclam)(NCS)2 and Ni(bpy)2(NCS)2 complexes by combining HF-HFEPR studies and calculation using a software based on the angular overlap model (AOM) allowed to determine the orientation of the local D tensors of the metal ions forming the polynuclear complexes. We, subsequently, show that the anisotropy parameters of the polynuclear complexes computed from the projection of the local tensors are in excellent agreement with the experimental ones extracted from the EPR experiments. 相似文献
69.
The design and performance of two new devices adapted for high-frequency electron paramagnetic resonance (HF-EPR) in a broad frequency range are described. Both systems, a Fabry–Pérot resonator and a rotating sample holder, rely on similar construction schemes and on the use of submicrometer piezoelectric positioners. A study of a single crystal of graphite allows illustrating the operation of these two new systems associated with our quasi-optical HF-EPR spectrometer. 相似文献
70.
We have developed a new experimental setup for the measurement of self-diffusion coefficients at high temperature (up to 1500 K) in corrosive liquids. It is based on pulsed field gradient NMR using a 10 mm liquid probe with two channels F-H/X modified and coupled with laser heating. The values obtained thanks to this setup are in good agreement with the available data obtained using the reference method, i.e., the capillary method. We present here results on 19F, 7Li, 23Na, 27Al in molten fluorides. In alkali fluoride mixtures, the self-diffusion coefficients depend weakly on the composition (nature and concentration of the different alkali) but mainly on temperature. In cryolite (Na3AlF6), the diffusion evidences AlFx3 ? x species. 相似文献