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91.
Filho DA Coropceanu V Fichou D Gruhn NE Bill TG Gierschner J Cornil J Brédas JL 《Philosophical transactions. Series A, Mathematical, physical, and engineering sciences》2007,365(1855):1435-1452
Density functional theory calculations together with highly resolved gas-phase ultraviolet photoelectron spectroscopy have been applied to oligothiophene chains with up to eight thiophene rings. One of the important parameters governing the charge transport properties in the condensed phase is the amount of energy relaxation upon ionization. Here, we investigate the impact on this parameter of the backbone flexibility present in oligothiophenes as a result of inter-ring torsional motions. With respect to oligoacenes that are characterized by a coplanar and rigid backbone, the torsional flexibility in oligothiophenes adds to the relaxation energy and leads to the broadening of the first ionization peak, making its analysis more complex. 相似文献
92.
Nuclear Magnetic Resonance of Physisorbed 129Xe Used as a Probe to Investigate Porous Solids 总被引:1,自引:0,他引:1
Jean-Luc Bonardet Jacques Fraissard Antoine G d on Marie-Anne Springuel-Huet 《Catalysis Reviews》1999,41(2):115-225
Xenon is an inert gas with a large electronic environment that makes it sensitive to any interaction, even physical. In the case of 129Xe isotope (spin 1/2), the resulting electronic perturbation is directly transmitted to the nucleus and, therefore, affects the nuclear magnetic resonance chemical shift. In this review, we report exhaustively up to 1996 the many applications of this technique in both fundamental and applied research in the fields of microporous and mesoporous solids. 相似文献
93.
Long-term behavior of oil-based varnishes and paints I. Spectroscopic analysis of curing drying oils
Jacky Mallégol Jean-Luc Gardette Jacques Lemaire 《Journal of the American Oil Chemists' Society》1999,76(8):967-976
The curing of drying oils at 60°C has been investigated by Fourier transform infrared spectroscopy and Fourier transform Raman
analysis of linseed oil and poppyseed oil. In the first step, hydroperoxides are formed (broad vibration band centered around
3425 cm−1) with concomitant conjugation and cis-trans isomerization of the double bonds (disappearance of cis bands at 3011 and 716 cm−1, appearance of trans conjugated and trans nonconjugated bands at 987 and 970 cm−1). The subsequent decomposition of hydroperoxides in the presence of oxygen leads to the formation of alcohols (nitrite band
at 779 cm−1 after nitrogen monoxide treatment), aldehydes (bands at 2810 and 2717 cm−1 in gas phase), ketones (saturated and unsaturated at 1720 and 1698 cm−1, respectively), carboxylic acids (saturated and unsaturated acid fluorides identified at 1843 and 1810 cm−1 after SF4 treatment), and peresters or γ-lactones (near 1770 cm−1). A rapid decrease in the double-bond concentration is recorded when curing continues, and the formation of epoxides, characterized
by a vibration band at 885 cm−1, is observed. Thermolysis experiments have suggested the proposal of a reaction of addition of peroxyl radicals on the conjugated
double bonds as a probable mechanism. This mechanism explains both the rapid disappearance of conjugated double bonds and
the formation of epoxides as intermediate products observed in the initial step of curing. 相似文献
94.
In this paper we design an interval observer for the estimation of unmeasured variables of uncertain bioreactors. The observer is based on a bounded error observer, as proposed in [Lemesle, V., & Gouzé, J.-L. (2005). Hybrid bounded error observers for uncertain bioreactor models. Bioprocess and Biosystems Engineering, 27, 311-318], that makes use of a loose approximation of the bacterial kinetics. We first show how to generate guaranteed upper and lower bounds on the state, provided that known intervals for the initial condition and the uncertainties are available. These so-called framers depend on a tuning gain. They can be run in parallel and the envelope provides the best estimate. An optimality criterion is introduced leading to the definition of an optimal observer. We show that this criterion provides directly a gain set containing the best framers. The method is applied to the estimation of the total biomass of an industrial wastewater treatment plant, demonstrating its efficiency. 相似文献
95.
There is interest as to whether the electromagnetic fields used in mobile radiotelephony might affect biological processes. Other weak fields such as gravity intervene in a number of physical and biological processes. Under appropriate in vitro conditions, the macroscopic self-organization of microtubules, a major cellular component, is triggered by gravity. We wished to investigate whether self-organization might also be affected by radiotelephone electromagnetic fields. Detecting a possible effect requires removing the obscuring effects triggered by gravity. A simple manner of doing this is by rotating the sample about the horizontal. However, if the external field does not also rotate with the sample, its possible effect might also be averaged down by rotation. Here, we describe an apparatus in which both the sample and an applied radiofrequency electromagnetic field (1.8 GHz) are stationary with respect to one another while undergoing horizontal rotation. The electromagnetic field profile within the apparatus has been measured and the apparatus tested by reproducing the in vitro behavior of microtubule preparations under conditions of weightlessness. Specific adsorption rates of electromagnetic energy within a sample are measured from the initial temperature rise the incident field causes. The apparatus can be readily adapted to expose samples to various other external fields and factors under conditions of weightlessness. 相似文献
96.
Distributed Coordination and Workflow on the World Wide Web 总被引:5,自引:0,他引:5
Antonietta Grasso Jean-Luc Meunier Daniele Pagani Remo Pareschi 《Computer Supported Cooperative Work (CSCW)》1997,6(2-3):175-200
This paper describes WebFlow, an environment thatsupports distributed coordination services on theWorld Wide Web. WebFlow leverages the HTTP Webtransport protocol and consists of a number of toolsfor the development of applications that require thecoordination of multiple, distributed servers.Typical applications of WebFlow include distributeddocument workspaces, inter/intra-enterprise workflow,and electronic commerce. In this paper we describe thegeneral WebFlow architecture for distributedcoordination, and then focus on the environment fordistributed workflow. 相似文献
97.
Stigliani JL Arnaud P Delaine T Bernardes-Génisson V Meunier B Bernadou J 《Journal of molecular graphics & modelling》2008,27(4):536-545
The front-line antituberculosis drug isoniazid (INH) inhibits InhA, the NADH-dependent fatty acid biosynthesis enoyl ACP-reductase from Mycobacterium tuberculosis, via formation of covalent adducts with NAD (INH-NAD adducts). While ring tautomers were found the main species formed in solution, only the 4S chain INH-NAD tautomer was evidenced in the crystallized InhA:INH-NAD complex. In this study we attempted to explore the modes of interaction and energy binding of the different isomers placed in the active site of InhA with the help of various molecular modelling techniques. Ligand and enzyme models were generated with the help of the Vega ZZ program package. Resulting ligands were then docked into the InhA active site individually using computational automated docking package AUTODOCK 3.0.5. The more relevant docked conformations were then used to compute the interaction energy between the ligands and the InhA cavity. The AM1 Hamiltonian and the QM/MM ONIOM methodologies were used and the results compared. The various tautomers were found docked in almost the same place where INH-NAD was present as predicted by earlier X-ray crystallographic studies. However, some changes of ligand conformation and of the interactions ligand-protein were evidenced. The lower binding energy was observed for the 4S chain adduct that probably represents the effective active form of the INH-NAD adducts, as compared to the 4R epimer. The two 4S,7R and 4R,7S ring tautomers show intermediate and similar binding energies contrasting with their different experimental inhibitory potency on InhA. As a possible explanation based on calculated conformations, we formulated the hypothesis of an initial binding of the two ring tautomers to InhA followed by opening of only the ring hemiamidal 4S,7R tautomer (possibly catalyzed by Tyr158 phenolate basic group) to give the 4S chain INH-NAD tight-binding inhibitor. The predictions of ligand-protein interactions at the molecular level can be of primary importance in elucidating the mechanisms of action of isoniazid and InhA-related resistances, in identifying the effective mycobactericidal entities and, in further step, in the design of a new generation of antitubercular drugs. 相似文献
98.
Hsiao-Hsi Wang Kuan-Ching Li Ssu-Hsuan Lu Chun-Chieh Yang Jean-Luc Gaudiot 《International journal of parallel programming》2008,36(6):521-542
In recent years, cluster computing has been widely investigated and there is no doubt that it can provide a cost-effective
computing infrastructure by aggregating computational power, communication, and storage resources. Moreover, it is also considered
to be a very attractive platform for low-cost supercomputing. Distributed shared memory (DSM) systems utilize the physical
memory of each computing node interconnected in a private network to form a global virtual shared memory. Since this global
shared memory is distributed among the computing nodes, accessing the data located in remote computing nodes is an absolute
necessity. However, this action will result in significant remote memory access latencies which are major sources of overhead
in DSM systems. For these reasons, in order to increase overall system performance and decrease this overhead, a number of
strategies have been devised. Prefetching is one such approach which can reduce latencies, although it always increases the
workload in the home nodes. In this paper, we propose a scheme named Agent Home Scheme. Its most noticeable feature, when compared to other schemes, is that the agent home distributes the workloads of each computing
nodes when sending data. By doing this, we can reduce not only the workload of the home nodes by balancing the workload for
each node, but also the waiting time. Experimental results show that the proposed method can obtain about 20% higher performance
than the original JIAJIA, about 18% more than History Prefetching Strategy (HPS), and about 10% higher than Effective Prefetch
Strategy (EPS). 相似文献
99.
Walter P Welcomme E Hallégot P Zaluzec NJ Deeb C Castaing J Veyssière P Bréniaux R Lévêque JL Tsoucaris G 《Nano letters》2006,6(10):2215-2219
Lead-based chemistry was initiated in ancient Egypt for cosmetic preparation more than 4000 years ago. Here, we study a hair-dyeing recipe using lead salts described in text since Greco-Roman times. We report direct evidence about the shape and distribution of PbS nanocrystals that form within the hair during blackening. It is remarkable that the composition and supramolecular organization of keratins can control PbS nanocrystal growth inside a hair. 相似文献
100.
Romaner L Heimel G Gruber M Brédas JL Zojer E 《Small (Weinheim an der Bergstrasse, Germany)》2006,2(12):1468-1475
Density functional theory (DFT) calculations based on band structure are used to investigate the electromechanical properties of a molecular junction consisting of a dithiolbenzene molecule sandwiched between two gold slabs. This represents a prototypical system for the field of molecular electronics; such a system has previously been studied in break-junction measurements and electron-transport calculations. The stretching and breaking behavior of the junction is analyzed for different geometric conformations, and it is found that the breakage occurs through dissociation of one of the sulfur-gold bonds with a maximum force of 1.25 nN. The molecular electronic states shift during stretching, and, at the point of highest stress in the junction, the highest occupied molecular orbital (HOMO) of the molecule is located exactly at the Fermi level. 相似文献