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121.
Anne-Lise Marie Elena Dominguez-Vega François Saller Jean-Luc Plantier Rémi Urbain Delphine Borgel N. Thuy Tran Govert W. Somsen Myriam Taverna 《Analytica chimica acta》2016
Antithrombin (AT) is a plasma glycoprotein which possesses anticoagulant and anti-inflammatory properties. AT exhibits various forms, among which are native, latent and heterodimeric ones. We studied the potential of capillary electrophoresis-mass spectrometry (CE-MS) using a sheath liquid interface, electrospray ionization (ESI), and a quadrupole-time-of-flight (Q-TOF) mass spectrometer to separate and quantify the different AT forms. For CE separation, a neutral polyvinyl alcohol (PVA) coated capillary was employed. The protein conformation was preserved by using a background electrolyte (BGE) at physiological pH. A sheath liquid of isopropanol-water 50:50 (v/v) with 14 mM ammonium acetate delivered at a flow rate of 120 μL h−1 resulted in optimal signal intensities. Each AT form exhibited a specific mass spectrum, allowing unambiguous distinction. Several co-injection experiments proved that latent AT had a higher electrophoretic mobility (μep) than native AT, and that these conformers could associate to form a heterodimer during the CE analysis. The developed CE-MS method enabled the detection and quantitation of latent and heterodimeric forms in a commercial AT preparation stored at room temperature for three weeks. 相似文献
122.
123.
Lignier P Morfin F Mangematin S Massin L Rousset JL Caps V 《Chemical communications (Cambridge, England)》2007,(2):186-188
The gold reference catalyst Au/TiO(2) exhibits high activity in the stereoselective epoxidation of trans-stilbene in methylcyclohexane in the presence of 5 mol% TBHP, by taking part in a chain reaction involving the activation of molecular oxygen by a radical produced from methylcyclohexane. 相似文献
124.
Odom SA Lancaster K Beverina L Lefler KM Thompson NJ Coropceanu V Brédas JL Marder SR Barlow S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(34):9637-9646
Five diamines with thiophene-based bridges--(E)-1,2-bis{5-[bis(4-butoxyphenyl)amino]-2-thienyl}ethylene (1), 5,5'-bis[bis(4-methoxyphenyl)amino]-2,2'-bithiophene (2), 2,6-bis[bis(4-butoxyphenyl)amino]dithieno[3,2-b:2',3'-d]thiophene (3), N-(4-tert-butylphenyl)-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 a) and N-tert-butyl-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 b)--have been synthesised. The syntheses make use of the palladium(0)-catalysed coupling of brominated thiophene species with diarylamines, in some cases accelerated by microwave irradiation. The molecules all undergo facile oxidation, 4 b being the most readily oxidised at about -0.4 V versus ferrocenium/ferrocene, and solutions of the corresponding radical cations were generated by addition of tris(4-bromophenyl)aminium hexachloroantimonate to the neutral species. The near-IR spectra of the radical cations show absorptions characteristic of symmetrical delocalised species (that is, class III mixed-valence species); analysis of these absorptions in the framework of Hush theory indicates strong coupling between the two amine redox centres, stronger than that observed in species with phenylene-based bridging groups of comparable length. The strong coupling can be attributed to high-lying orbitals of the thiophene-based bridging units. ESR spectroscopy indicates that the coupling constant to the amino nitrogen atoms is somewhat reduced relative to that in a stilbene-bridged analogue. The neutral species and the corresponding radical cations have been studied with the aid of density functional theory and time-dependent density functional theory. The DFT-calculated ESR parameters are in good agreement with experiment, while calculated spin densities suggest increased bridge character to the oxidation in these species relative to that in comparable species with phenylene-based bridges. 相似文献
125.
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
126.
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
127.
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
128.
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
129.
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
130.
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