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61.
Alkynyl ruthenium colorimetric sensors: optimizing the selectivity toward fluoride anion 总被引:1,自引:0,他引:1
Fillaut JL Andriès J Perruchon J Desvergne JP Toupet L Fadel L Zouchoune B Saillard JY 《Inorganic chemistry》2007,46(15):5922-5932
We report on the synthesis of alkynyl ruthenium colorimetric sensors whose receptors are constituted by thiazolidinedione, rhodanine, or barbituric heads as recognition centers for anions. As modifications in the charge density at these recognition centers affect the whole molecule, through the alkynyl ligand acting as a communicating wire, the effects of hydrogen-bonding interactions with the anions were observed with the naked eye and monitored by UV-vis absorption spectrometry. The selectivity of the sensors was improved through electronic modifications of the alkynyl ruthenium subunit: the higher the electron density at the receptor head, the higher the selectivity is. TD-DFT calculations rationalize the long-range electronic communication as a main characteristic of the alkynyl ruthenium species and as a key to improve the selectivity of alkynyl ruthenium-based sensors toward anions. 相似文献
62.
Segut O Lakard B Herlem G Rauch JY Jeannot JC Robert L Fahys B 《Analytica chimica acta》2007,597(2):313-321
A new type of pH biosensor was developed for biological applications. This biosensor was fabricated using silicon microsystem technology and consists in two platinum microelectrodes. The first microelectrode was coated by an electrosynthesized polymer and acted as the pH sensitive electrode when the second one was coated by a silver layer and was used as the reference electrode. Then, this potentiometric pH miniaturized biosensor based on electrosynthesized polypyrrole or electrosynthesized linear polyethylenimine films was tested. The potentiometric responses appeared reversible and linear to pH changes in the range from pH 4 to 9. More, the responses were fast (less than 1 min for all sensors), they were stable in time since PPy/PEI films were stable during more than 30 days, and no interference was observed. The influence of the polymer thickness was also studied. 相似文献
63.
64.
Christel Roux Wladimir Gorecki Jean-Yves Sanchez Elie Belorizky 《Macromolecular Symposia》1997,114(1):211-216
High molecular weight polymers have been prepared by ring-opening polymerization of propylene oxide PO using a Vandenberg initiator. Polymer electrolytes based on this polymer and an imide salt LiTFSI have been investigated. We present the results concerning the synthesis of the polymer and the glass transition temperatures evolution of the complexes with respect to salt composition. Diffusion constants of 19F and 7Li nuclei are determined by NMR techniques and a value of the cationic transport number t+ = 0.1 is obtained. 相似文献
65.
Alessandra Ciapponi Stéphanie Palmier Jean-Yves Natoli Laurent Gallais 《Journal of luminescence》2009,129(12):1786-1789
Hafnia thin films for high-power optical coatings have been characterized by photoluminescence pumped by 4.66 eV photons and photothermal deflection measurements. These data are compared to the statistical laser damage behavior in order to find correlations between destructive and non-destructive characterizations. Thin films have been produced at two thicknesses and using different thin-film deposition techniques typically employed for optical coating fabrication: EBD (HfO2 target), EBD (Hf target), RLVIP and DIBS. The photoluminescence spectra show significant differences depending on the deposition techniques and thicknesses. EBD films show significant luminescence but the luminescence of ion-assisted films could not be distinguished from the uncoated substrate. All EBD coating spectra could be described by a linear combination of four bands. Further, XRD measurements show that the 255-nm-thick films had a relatively high crystallinity: EBD films contained the monoclinic phase and the ion-assisted films contained oriented nanocrystals of orthorhombic hafnia. The presence of orthorhombic phases indicates high compressive strain quenching the photoluminescence of these samples. 相似文献
66.
Corral I Mó O Yáñez M Salpin JY Tortajada J Moran D Radom L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(26):6787-6796
The gas-phase reactions between Ca(2+) and glycine ([Ca(gly)](2+)) have been investigated through the use of mass spectrometry techniques and B3-LYP/cc-pWCVTZ density functional theory computations. The major peaks observed in the electrospray MS/MS spectrum of [Ca(gly)](2+) correspond to the formation of the [Ca,C,O(2),H](+), NH(2)CH(2) (+), CaOH(+), and NH(2)CH(2)CO(+) fragment ions, which are produced in Coulomb explosion processes. The computed potential energy surface (PES) shows that not only are these species the most stable product ions from a thermodynamic point of view, but they may be produced with barriers lower than for competing processes. Carbon monoxide is a secondary product, derived from the unimolecular decomposition of some of the primary ions formed in the Coulomb explosions. In contrast to what is found for the reactions of Ca(2+) with urea ([Ca(urea)](2+)), minimal unimolecular losses of neutral fragments are observed for the gas-phase fragmentation processes of [Ca(gly)](2+), which is readily explained in terms of the topological differences between their respective PESs. 相似文献
67.
68.
Jean-Christophe Novelli Thierry Paul David Sauzin Jean-Yves Thibon 《Letters in Mathematical Physics》2018,108(7):1583-1600
We derive new expressions for the Rayleigh–Schrödinger series describing the perturbation of eigenvalues of quantum Hamiltonians. The method, somehow close to the so-called dimensional renormalization in quantum field theory, involves the Birkhoff decomposition of some Laurent series built up out of explicit fully non-resonant terms present in the usual expression of the Rayleigh–Schrödinger series. Our results provide new combinatorial formulae and a new way of deriving perturbation series in quantum mechanics. More generally we prove that such a decomposition provides solutions of general normal form problems in Lie algebras. 相似文献
69.
Mariem Miladi Chaabane Régis Plateaux Jean-Yves Choley Chafik Karra Alain Rivière Mohamed Haddar 《Comptes Rendus Mecanique》2014,342(8):466-477
The present work tackled the modeling of frame structures using a topological approach based on the concepts of topological collections and transformations. The topological collections are used to specify the interconnection law between the frame structures and the transformations that are used to describe their behavior. As a language allowing the application of this approach, we applied the MGS (Modeling of General System) language. To validate this approach, we studied the case of two- and three-dimensional frame structures. Then, the results obtained using the MGS language are presented and compared to those obtained by the structural calculation software by the finite-element method RDM6. For both studied cases, we find that the results obtained by MGS language based on the notions of topological collections and transformations and those obtained by the RDM6 software based on the finite element method are very close, which validates our approach. Using this topological approach, any structure can be characterized by local relations between its elements, thus making it possible to dissociate its topology and its physics. Indeed, in our topological approach, we separately define the topology of the studied frame structure and the local behavior law as well as the equilibrium equations of its various components. Therefore, this topological approach might be generalized to model complex systems which can be considered as a set of local elements linked by a neighborhood relationship. 相似文献
70.
R Spezia A Cimas MP Gaigeot JY Salpin K Song WL Hase 《Physical chemistry chemical physics : PCCP》2012,14(33):11724-11736
In this paper we report different theoretical approaches to study the gas-phase unimolecular dissociation of the doubly-charged cation [Ca(urea)](2+), in order to rationalize recent experimental findings. Quantum mechanical plus molecular mechanical (QM/MM) direct chemical dynamics simulations were used to investigate collision induced dissociation (CID) and rotational-vibrational energy transfer for Ar + [Ca(urea)](2+) collisions. For the picosecond time-domain of the simulations, both neutral loss and Coulomb explosion reactions were found and the differences in their mechanisms elucidated. The loss of neutral urea subsequent to collision with Ar occurs via a shattering mechanism, while the formation of two singly-charged cations follows statistical (or almost statistical) dynamics. Vibrational-rotational energy transfer efficiencies obtained for trajectories that do not dissociate during the trajectory integration were used in conjunction with RRKM rate constants to approximate dissociation pathways assuming complete intramolecular vibrational energy redistribution (IVR) and statistical dynamics. This statistical limit predicts, as expected, that at long time the most stable species on the potential energy surface (PES) dominate. These results, coupled with experimental CID from which both neutral loss and Coulomb explosion products were obtained, show that the gas phase dissociation of this ion occurs by multiple mechanisms leading to different products and that reactivity on the complicated PES is dynamically complex. 相似文献