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131.
Barlow S Zhang Q Kaafarani BR Risko C Amy F Chan CK Domercq B Starikova ZA Antipin MY Timofeeva TV Kippelen B Brédas JL Kahn A Marder SR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(12):3537-3547
Several hexaazatrinaphthylene derivatives and a tris(thieno)hexaazatriphenylene derivative have been synthesised by reaction of the appropriate diamines with hexaketocyclohexane. The crystal structure of 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene has been determined by X-ray diffraction; this reveals a molecular structure in good agreement with that predicted by density functional theory (DFT) calculations and pi-stacking with an average spacing between adjacent molecular planes of 3.18 A. Solid-state ionisation potentials have been measured by using UV photoelectron spectroscopy and fall in the range of 5.99 to 7.76 eV, whereas solid-state electron affinities, measured using inverse photoelectron spectroscopy, vary in the range -2.65 to -4.59 eV. The most easily reduced example is a tris(thieno)hexaazatriphenylene substituted with bis(trifluoromethyl)phenyl groups; DFT calculations suggest that the highly exothermic electron affinity is due both to the replacement of the outermost phenylene rings of hexaazatrinaphthylene with thieno groups and to the presence of electron-withdrawing bis(trifluoromethyl)phenyl groups. The rather exothermic electron affinities, the potential for adopting pi-stacked structures and the low intramolecular reorganisation energies obtained by DFT calculations suggest that some of these molecules may be useful electron-transport materials. 相似文献
132.
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
133.
Petkova V Benattar JJ Zoonens M Zito F Popot JL Polidori A Jasseron S Pucci B 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4303-4309
The possibility of organizing detergent-solubilized membrane proteins in a plane within the core of Newton black films (NBFs) formed from fluorinated surfactants has been investigated. Fluorinated surfactants have the interesting characteristics of being poorly miscible with detergents and highly surface-active. As a result, when a membrane protein-the transmembrane domain of OmpA (tOmpA)-solubilized by the nonionic detergent C8E4 (tetraethylene glycol monooctyl ether) was injected under a monolayer of fluorinated surfactant, C8E4 and tOmpA/C8E4 complexes remained confined to the subphase. Vertical, macroscopic NBFs were drawn, and their structure was investigated by means of X-ray reflectivity. Depending on experimental conditions, the protein was shown to organize into either one or two monolayers stabilized by two monolayers of fluorinated surfactant. Two different mechanisms of protein insertion were investigated: (i) attachment of polyhistidine-tagged tOmpA/C8E4 complexes to nickel-bearing polar groups born by a fluorinated surfactant and (ii) spontaneous diffusion into the surfactant films. Possible applications are discussed. 相似文献
134.
Three polyphenylene dendrimers were studied by molecular modeling techniques with the goal of better defining the notion of shape persistence often associated with these molecules. We show that despite the rigidity of the monomers, a large variety of dendrimer morphologies is accessible, in large part due to the asymmetrical branching pattern of the monomers (they have nodes in meta and para positions with respect to their anchor point). The folding ability of a branch depends on the number and sequence of the meta and para nodes it contains: while some of the branches are always straight, others can fold back, and the amplitude of that folding increases with generation. As a result, the range of accessible morphologies increases with the generation, from a dense-shell model in low generation to a model intermediate between a dense shell and a dense core in high generation. When the typical A2B monomer is replaced by an A4B monomer, the dense packing limit is reached as early as the second generation because of a higher density and the presence of nodes in the ortho position, which are oriented backward. 相似文献
135.
Bruno Coulomb Fabien Robert-Peillard Najib Ben Ali Gam Salwa Sadok Jean-Luc Boudenne 《Molecules (Basel, Switzerland)》2021,26(19)
This paper presents the development and the application of a multisyringe flow injection analysis system for the fluorimetric determination of the major heat-stable known allergen in shrimp, rPen a 1 (tropomyosin). This muscle protein, made up of 284 amino acids, is the main allergen in crustaceans and can be hydrolyzed by microwave in hydrochloric acid medium to produce glutamic acid, the major amino acid in the protein. Glutamic acid can then be quantified specifically by thermal conversion into pyroglutamic acid followed by chemical derivatization of the pyroglutamic acid formed by an analytical protocol based on an OPA-NAC reagent. Pyroglutamic acid can thus be quantified between 1 and 100 µM in less than 15 min with a detection limit of 1.3 µM. The method has been validated by measurements on real samples demonstrating that the response increases with the increase in the tropomyosin content or with the increase in the mass of the shrimp sample. 相似文献
136.
Jean-Luc Putaux 《Macromolecular Symposia》2005,229(1):66-71
Summary: In this paper, we review recent studies on the morphology and molecular structure of some polysaccharide crystals from amylose, cellulose, and mannan. The data were recorded using combinations of imaging, diffraction, and spectroscopic techniques: scanning and transmission electron microscopy, electron, neutron, and X-ray diffraction, as well as 13C solid-state NMR spectroscopy. Differences were generally found between native crystals, whose features result from in vivo biogenesis and the recrystallized products prepared in vitro. 相似文献
137.
This paper studies the focusing of high-frequency solutions of semilinear hyperbolic equations. In previous papers, we studied two opposite phenomena. First, the focusing of nonlinear waves can force the solutions to blow up, even before reaching the caustics. Second, for strongly dissipative equations, nonlinear oscillations can be completely absorbed when they reach the caustic set. In this paper, we study the intermediate case of equations with globally Lipschitz nonlinearities. The nonlinear oscillations persist after crossing the caustic set. The solutions are described using oscillatory integrals, which are associated with Lagrangian manifolds in the cotangent bundle. The equations of nonlinear geometric optics lift to these manifolds. In contrast to the linear case, the transport equations for amplitudes living above the same points of spacetime are coupled. © 1996 John Wiley & Sons, Inc. 相似文献
138.
The aim of the present work is to show how, using the differential calculus associated to Dirichlet forms, it is possible
to construct non-trivial Fredholm modules on post critically finite fractals by regular harmonic structures (D, r). The modules are (d
S
, ∞)–summable, the summability exponent d
S
coinciding with the spectral dimension of the generalized Laplacian operator associated with (D, r). The characteristic tools of the noncommutative infinitesimal calculus allow to define a d
S
-energy functional which is shown to be a self-similar conformal invariant.
Thiswork has been supported by the project “Teoria ellittica e forme di Dirichlet su spazi frattali” G.N.A.M.P.A. 2008 and
by the G.R.E.F.I.-G.E.N.C.O. French-Italian Research Group. 相似文献
139.
We study the moments and the distribution of the discrete Choquet integral when regarded as a real function of a random sample drawn from a continuous distribution. Since the discrete Choquet integral includes weighted arithmetic means, ordered weighted averaging functions, and lattice polynomial functions as particular cases, our results encompass the corresponding results for these aggregation functions. After detailing the results obtained in [J.-L. Marichal, I. Kojadinovic, Distribution functions of linear combinations of lattice polynomials from the uniform distribution, Statistics & Probability Letters 78 (2008) 985–991] in the uniform case, we present results for the standard exponential case, show how approximations of the moments can be obtained for other continuous distributions such as the standard normal, and elaborate on the asymptotic distribution of the Choquet integral. The results presented in this work can be used to improve the interpretation of discrete Choquet integrals when employed as aggregation functions. 相似文献
140.
While connected arithmetic discrete lines are entirely characterized, only partial results exist for the more general case of arithmetic discrete hyperplanes. In the present paper, we focus on the three-dimensional case, that is on arithmetic discrete planes. Thanks to arithmetic reductions on a vector , we provide algorithms either to determine whether a given arithmetic discrete plane with as normal vector is connected, or to compute the minimal thickness for which an arithmetic discrete plane with normal vector is connected. 相似文献