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91.
Michle Fontaine Joseph Delhalle Mireille Defranceschi Grard Lcayon Jacques Boissel 《International journal of quantum chemistry》1993,46(1):171-181
3-21G RHF calculations on (CF3)2O and (CF3)2OH+ molecules are carried out to assess the changes induced in the molecular properties of ether links in poly (perfluoro ethers) interacting with acid sites at contact surfaces. Geometry of the species, vibrational frequencies, proton affinity, and energetics of the (CF3)2OH+ fragmentation provide a preliminary basis to understand problems raised by lubricant degradation. © 1993 John Wiley & Sons, Inc. 相似文献
92.
Ab initio calculations using 6-311G**, cc-pVDZ, and aug-cc-pVDZ, with (MP2, QCISD, CCSD(T)) and without (UHF) electron correlation, and density functional methods (BHandHLYP and B3LYP) predict that cyclization of the 5-aza-5-hexenoyl and (E)-6-aza-5-hexenoyl radicals proceed to afford the 5-exo products. At the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory, energy barriers (deltaE(double dagger)) of 36.1 and 47.0 kJ mol(-1) were calculated for the 5-exo and 6-endo pathways for the cyclization of the 5-aza-5-hexenoyl radical. On the other hand, at the same level of theory, deltaE(double dagger) of 38.9 and 45.4 kJ mol(-1) were obtained for the 5-exo and 6-endo cyclization modes of (E)-6-aza-5-hexenoyl radical, with exothermicities of about 27 and 110 kJ mol(-1) calculated for the exo and endo modes, respectively. Under suitable experimental conditions, the 6-endo cyclization product is likely to dominate. Analysis of the molecular orbitals involved in these ring-closure reactions indicate that both reactions at nitrogen are assisted by dual orbital interactions involving simultaneous SOMO-pi* and LP-pi* overlap in the transitions states. Interestingly, the (Z)-6-aza-5-hexenoyl radical, that cannot benefit from these dual orbital effects is predicted to ring-close exclusively in the 5-exo fashion. 相似文献
93.
Laser processing for bio-microfluidics applications (part I) 总被引:1,自引:0,他引:1
Khan Malek CG 《Analytical and bioanalytical chemistry》2006,385(8):1351-1361
This paper reviews applications of laser-based techniques to the fabrication of microfluidic devices for biochips and addresses
some of the challenges associated with the manufacture of these devices. Special emphasis is placed on the use of lasers for
the rapid prototyping and production of biochips in particular for applications in which silicon is not the preferred material
base. Part I of this review addresses applications and devices using UV lasers for laser ablation and surface treatment of
microchannels, in particular in polymers. 相似文献
94.
Jean-Loïc Rose Alain Lalande Olivier Bouchot El-Bey Bourennane Paul M. Walker Patricia Ugolini Chantal Revol-Muller Raymond Cartier François Brunotte 《Magnetic resonance imaging》2010
Magnetic resonance imaging (MRI) is particularly well adapted to the evaluation of aortic distensibility. The calculation of this parameter, based on the change in vessel cross-sectional area per unit change in blood pressure, requires precise delineation of the aortic wall on a series of cine-MR images. Firstly, the study consisted in validating a new automatic method to assess aortic elasticity. Secondly, aortic distensibility was studied for the ascending and descending thoracic aortas in 26 healthy subjects. Two homogeneous groups were available to evaluate the influence of sex and age (with an age limit value of 35 years). The automatic postprocessing method proved to be robust and reliable enough to automatically determine aortic distensibility, even on artefacted images. In the 26 healthy volunteers, a marked decrease in distensibility appears with age, although this decrease is only significant for the ascending aorta (8.97±2.69 10−3 mmHg−1 vs. 5.97±2.02 10−3 mmHg−1). Women have a higher aortic distensibility than men but only significantly at the level of the descending aorta (7.20±1.61 10−3 mmHg−1 vs. 5.05±2.40 10−3 mmHg−1). Through our automatic contouring method, the aortic distensibility from routine cine-MRI has been studied on a healthy subject population providing reference values of aortic stiffness. The aortic distensibility calculation shows that age and sex are causes of aortic stiffness variations in healthy subjects. 相似文献
95.
Disorder in colloid crystals was induced by doping them with a different number of large or small guest particles, which had a different deviation in size from the host colloids. The change in optical properties of the guest-host colloid crystals was assessed by using optical transmission spectroscopy while the variation in crystal structure was examined using scanning electron microscopy (SEM). The disruption in the crystalline lattices depended on the relative deviation in sizes of the guest and host particles and the concentration of the guest colloids. In parallel with experiments, the packing of spheres in guest-host crystals was modeled with a simulated annealing algorithm. A good correlation was found between the changes in crystal structure observed by SEM imaging and the simulated sphere packing. The experimental and simulated changes in the transmission spectra of guest-host colloid crystals were in good agreement. 相似文献
96.
Aharonian F Akhperjanian AG Barres de Almeida U Bazer-Bachi AR Becherini Y Behera B Beilicke M Benbow W Bernlöhr K Boisson C Bochow A Borrel V Braun I Brion E Brucker J Brun P Bühler R Bulik T Büsching I Boutelier T Carrigan S Chadwick PM Charbonnier A Chaves RC Chounet LM Clapson AC Coignet G Costamante L Dalton M Degrange B Deil C Dickinson HJ Djannati-Ataï A Domainko W Drury LO Dubois F Dubus G Dyks J Egberts K Emmanoulopoulos D Espigat P Farnier C Feinstein F Fiasson A Förster A Fontaine G 《Physical review letters》2008,101(17):170402
In the past few decades, several models have predicted an energy dependence of the speed of light in the context of quantum gravity. For cosmological sources such as active galaxies, this minuscule effect can add up to measurable photon-energy dependent time lags. In this Letter a search for such time lags during the High Energy Stereoscopic System observations of the exceptional very high energy flare of the active galaxy PKS 2155-304 on 28 July 2006 is presented. Since no significant time lag is found, lower limits on the energy scale of speed of light modifications are derived. 相似文献
97.
AbstractHigh performance and high temperature polymers are a class of polymeric materials exhibiting high thermal stability and their resistance to fire makes them valuable assets for many applications. Those applications include as typical examples high temperature gas separation membranes, automotive and aerospace industry as well as the construction industry. The high performance polymers have been synthesized since the early 1960s, and have developed rapidly over the past few decades. Most high performance polymers comprise a highly aromatic backbone, linear chains, and strong inter-chain interactions. This review deals mostly with commercial polymeric materials. Studies regarding their thermal behavior, degradation mechanism and their reaction to fire have been synthetically combined in order to bring out potential insight concerning the effect of the thermal decomposition and thermal behavior on the fire properties of those polymers. 相似文献
98.
Dr. Simon Pascal Léo Bucher Dr. Nicolas Desbois Dr. Christophe Bucher Dr. Chantal Andraud Prof. Dr. Claude P. Gros 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4971-4979
The synthesis of dyad and triad aza‐BODIPY‐porphyrin systems in two steps starting from an aryl‐substituted aza‐BODIPY chromophore is described. The properties of the resulting aza‐BODIPY‐porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination. 相似文献
99.
100.
Henri-Joël Sedjame Rachid Brahmi Gwendoline Lafaye Jacques Barbier Céline Fontaine 《Comptes Rendus Chimie》2018,21(3-4):182-193
Monolithic catalysts are prepared by washcoating cordierite monoliths with different sols (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3CeO2, Pt/Al2O3ZrO2, and Pt/CeO2ZrO2). These sols are prepared by a sol–gel process and characterized by specific surface area (SBET), inductively coupled plasma, hydrogen chemisorption, high-resolution transmission electron microscopy, field emission scanning electron microscopy, oxygen storage capacity, X-ray diffraction, temperature-programmed reduction, CO2 chemisorption, and the model reaction of 3,3-dimethylbutene isomerization. The catalytic performances of the monolithic catalysts are then evaluated for the acetic acid oxidation. The nature of catalyst coating has been found to influence the adherence with the cordierite monolith and the presence of cerium in the catalyst appears to increase the adherence of the latter. Pt/CeO2, Pt/Al2O3CeO2, and Pt/CeO2ZrO2 are found to be the most reducible catalysts (oxygen storage capacity and temperature-programmed reduction) and to have the lowest acidities (3,3-dimethylbutene isomerization). CO2 chemisorption shows that these catalysts possess a good basicity. From the relation established between the catalytic activity and the redox and acid–base properties it has been concluded that the reducibility is the key factor for a good catalytic activity although the basicity has a significant influence on the catalytic performance. 相似文献