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271.
Hygrothermal aging of Nafion 总被引:1,自引:0,他引:1
Floraine M. Collette Chantal Lorentz Grard Gebel Francette Thominette 《Journal of membrane science》2009,330(1-2):21-29
The membrane durability is a critical issue for the development of Proton Exchange Membrane Fuel Cells (PEMFC). Since PEMFC in situ tests were not conclusive to determine Nafion® membrane degradation mechanism, ex situ aging tests were performed on Nafion® 112 in practical fuel cell usage conditions. The polymer chemical structure evolution was investigated by infrared spectroscopy (IR) and Nuclear Magnetic Resonance (NMR) while its hydrophilicity, directly linked to its protonic conductivity, is established through sorption isotherms by Dynamical Vapour Sorption (DVS). Durability studies over a period of 400 days revealed membrane degradation through a modification of sulfonic acid end-groups. Formation of sulfonic anhydride (from the condensation of sulfonic acids) was strongly demonstrated by IR spectroscopy and, indirectly, by NMR. The substitution of ionic end-groups by less hydrophilic anhydrides leads to a significant decrease of water uptake and thus of its hydrophilicity. Surprisingly, kinetic study reveals that the hygrometric level accelerates this condensation reaction. 相似文献
272.
van Gruijthuijsen K Rufier C Phou T Obiols-Rabasa M Stradner A 《Langmuir : the ACS journal of surfaces and colloids》2012,28(28):10381-10388
Steric stabilization of colloids forms a robust mechanism to obtain colloids that are stable in a variety of environments, and that can be used to study the phase behavior of hard or soft spheres. We report the synthesis of sterically stabilized colloids in an aqueous environment using readily dissolvable surfactants, with an unsaturated hydrophobic tail. We synthesized a new surfactant by esterification of a poly(ethylene glycol) (PEG) chain of 4.1 kg/mol with oleic acid, called PEG4OA. The micellization of PEG4OA was characterized by light and neutron scattering, which yielded values for the aggregation number and the overall size that are in excellent agreement with a comparable surfactant with a saturated octadecane chain, Brij 700. We successfully used PEG4OA in the emulsion polymerization of polystyrene colloids. In comparison with the smaller surfactant Tween 80, PEG4OA yielded smaller colloids with radii around 50 nm, and the addition of 1-dodecanethiol reduced the formation of aggregates during the synthesis. A contrast variation study with small angle neutron scattering (SANS) showed that a dense PEG layer was grafted to the colloid surface. 相似文献
273.
Paquet C Ryan S Zou S Kell A Tanha J Hulse J Tay LL Simard B 《Chemical communications (Cambridge, England)》2012,48(4):561-563
The synthesis of magnetic and fluorescent particles is described. The particles are biofunctionalized by binding pathogen-specific proteins to the particles via interactions between His-tags of proteins and zinc of the quantum dots. Detection of Salmonella and Staphylococcus aureus (S. aureus) by these particles is demonstrated. 相似文献
274.
Lanoë PH Gallavardin T Dupin A Maury O Baldeck PL Lindgren M Monnereau C Andraud C 《Organic & biomolecular chemistry》2012,10(31):6275-6278
A molecular engineering strategy based on rational variations of the bromine substitution pattern in two-photon absorbing singlet oxygen sensitizers allows studying the relations that exist between the positioning of an inter-system crossing promoter on the charge-transfer chromophore and its ability to generate singlet oxygen. 相似文献
275.
Chantal Gondran Maylis Orio David Rigal Bruno Galland Laurent Bouffier Tioga Gulon Serge Cosnier 《Electrochemistry communications》2010,12(2):311-314
We describe herein the synthesis and electrochemical polymerization of a viologen monomer functionalized by a biotin group and the use of its redox properties for the impedimetric sensing of protein binding. The electrochemical oxidation of the pyrrole group at 0.85 V in CH3CN led to a biotinylated polypyrrole film allowing the successive anchoring of an avidin layer and a biotinylated cholera toxin layer. EIS performed at ?0.45 V/SCE without redox probe in solution showed the specific immobilization of the anti-cholera toxin antibody. 相似文献
276.
Ross McVinish Kerrie Mengersen Darfiana Nur Judith Rousseau Chantal Guihenneuc-Jouyaux 《Journal of computational and graphical statistics》2013,22(1):215-228
Since its introduction in the early 1990s, the idea of using importance sampling (IS) with Markov chain Monte Carlo (MCMC) has found many applications. This article examines problems associated with its application to repeated evaluation of related posterior distributions with a particular focus on Bayesian model validation. We demonstrate that, in certain applications, the curse of dimensionality can be reduced by a simple modification of IS. In addition to providing new theoretical insight into the behavior of the IS approximation in a wide class of models, our result facilitates the implementation of computationally intensive Bayesian model checks. We illustrate the simplicity, computational savings, and potential inferential advantages of the proposed approach through two substantive case studies, notably computation of Bayesian p-values for linear regression models and simulation-based model checking. Supplementary materials including the Appendix and the R code for Section are available online. 相似文献
277.
Barsu C Fortrie R Nowika K Baldeck PL Vial JC Barsella A Fort A Hissler M Bretonnière Y Maury O Andraud C 《Chemical communications (Cambridge, England)》2006,(45):4744-4746
The design of new chromophores presenting simultaneous SHG and TPEF properties is reported. 相似文献
278.
279.
The series of dinitrogen reduction intermediates (N(2)H(2), N(2)H(4), and NH(3)) coordinated to the Fe(DMeOPrPE)(2)H(+)(DMeOPrPE = 1,2-[bis(dimethoxypropyl)phosphino]ethane) scaffold has been synthesized or generated. The synthesis of trans-[Fe(DMeOPrPE)(2)(NH(3))H][BPh(4)] and generation of trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H][BPh(4)] were achieved by substitu tion of the dinitrogen ligand on trans-[Fe(DMeOPrPE)(2)(N(2))H][BPh(4)]. The trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H](+) complex and its deprotonated conjugate base, trans-Fe(DMeOPrPE)(2)(N(2)H)H, were observed by (31)P and (1)H NMR from decomposition of trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H](+) in the presence of excess hydrazine. Attempts to chemically oxidize trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H](+) to trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H][BPh(4)] with a variety of oxidizing agents yielded only decomposition products consistent with the intermediate formation of trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H](+) prior to decomposition. 相似文献
280.
We propose a parameter-free algorithm for the identification of nearest neighbors. The algorithm is very easy to use and has a number of advantages over existing algorithms to identify nearest-neighbors. This solid-angle based nearest-neighbor algorithm (SANN) attributes to each possible neighbor a solid angle and determines the cutoff radius by the requirement that the sum of the solid angles is 4π. The algorithm can be used to analyze 3D images, both from experiments as well as theory, and as the algorithm has a low computational cost, it can also be used "on the fly" in simulations. In this paper, we describe the SANN algorithm, discuss its properties, and compare it to both a fixed-distance cutoff algorithm and to a Voronoi construction by analyzing its behavior in bulk phases of systems of carbon atoms, Lennard-Jones particles and hard spheres as well as in Lennard-Jones systems with liquid-crystal and liquid-vapor interfaces. 相似文献