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81.
82.
Dr. Yang Zhou Dr. Stéphane Maisonneuve Prof. François Maurel Prof. Juan Xie Dr. Rémi Métivier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(68):e202202071
Multichromophoric systems showing both fluorescence and photoisomerization are fascinating, with complex interchromophoric interactions. The experimental and theoretical study of a series of compounds, bearing a variable number of 4-dicyanomethylene-2-tert-butyl-6-(p-(N-(2-azidoethyl)-N-methyl)aminostyryl)-4H-pyran (DCM) units are reported. The photophysical properties of multi-DCM derivatives, namely 2DCM and 3DCM , were compared to the single model azido-functionalized DCM , in the E and Z isomers. The (EE)- 2DCM and (EEE)- 3DCM were synthesized via the click reaction. Steady-state spectroscopy and photokinetics experiments under UV or visible irradiation indicated the presence of intramolecular energy transfer processes among the DCM units. Homo- and hetero-energy transfer processes between adjacent chromophores were confirmed by fluorescence anisotropy and decays. Molecular dynamics simulations for 2DCM were carried out and analyzed using a Markov state model, providing geometrical parameters (orientation and distance between chromophores) and energy transfer efficiency. This work contributes to a better understanding and rationalization of multiple energy transfer processes occuring within multichromophoric systems. 相似文献
83.
High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene 下载免费PDF全文
Dr. Marie Betou Nicolas Kerisit Esme Meledje Dr. Yann R. Leroux Dr. Claudine Katan Dr. Jean‐François Halet Dr. Jean‐Claude Guillemin Dr. Yann Trolez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9553-9557
A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings. 相似文献
84.
Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals 下载免费PDF全文
Paschalis D. Paraskevas Dr. Maarten K. Sabbe Prof. Marie‐Françoise Reyniers Prof. Dr. Nikos Papayannakos Prof. Dr. Guy B. Marin 《Chemphyschem》2014,15(9):1849-1866
Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS‐QB3 ab initio (AI) calculations by using conventional transition‐state theory within the high‐pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group‐additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α‐hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon‐centered radicals, 15 GA values (ΔGAVos) are obtained for both the forward and reverse reactions. Among them, four ΔGAVos refer to primary contributions, and the remaining 11 ΔGAVos refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross‐resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAVos are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre‐exponential factors (log A) and activation energies (Ea) for the forward reaction at 300 K are 0.238 log(m3 mol?1 s?1) and 1.5 kJ mol?1, respectively, whereas the mean factor of deviation <ρ> between the GA‐predicted and the AI‐calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA‐predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α‐hydrogen‐abstraction reactions between a broad range of oxygenates and oxygenate radicals. 相似文献
85.
Back Cover: Assessment of DNA Binding to Human Rad51 Protein by using Quartz Crystal Microbalance and Atomic Force Microscopy: Effects of ADP and BRC4‐28 Peptide Inhibitor (ChemPhysChem 17/2014) 下载免费PDF全文
86.
Tran Thu Ha Nguyen Hong Phong François-Xavier Le Dimet Hong Son Hoang 《Comptes Rendus Mecanique》2019,347(5):423-444
This article presents a correction method for a better resolution of the problem of estimating and predicting pollution, governed by Burgers' equations. The originality of the method consists in the introduction of an error function into the system's equations of state to model uncertainty in the model. The initial conditions and diffusion coefficients, present in the equations for pollution and concentration, and also those in the model error equations, are estimated by solving a data assimilation problem. The efficiency of the correction method is compared with that produced by the traditional method without introduction of an error function.Three test cases are presented in this study in order to compare the performances of the proposed methods. In the first two tests, the reference is the analytical solution and the last test is formulated as part of the “twin experiment”.The numerical results obtained confirm the important role of the model error equation for improving the prediction capability of the system, in terms of both accuracy and speed of convergence. 相似文献
87.
Françoise Maugé Jean-Paul Gallas Jean-Claude Lavalley Guido Busca Gianguido Ramis Vincenzo Lorenzelli 《Mikrochimica acta》1988,95(1-6):57-61
In the far IR region at low molybdenum loadings, Mo-SiO2 catalysts present a pseudomolybdate or a polymolybdate species, while bulk-like MoO3 appears at loadings close to the geometrical monolayer coverage. W-SiO2 and V-SiO2 spectra show bands close to those observed on the corresponding bulk oxides.In the case of TiO2, Al2O3, ZrO2 supported catalysts, a band is observed near 1000 cm–1 which is assigned to the Mo=O stretching vibration of coordinatively unsaturated Mo
n+ ions showing a stronger interaction with the support than one observed on silica. 相似文献
88.
Monitoring and Quantifying the Passive Transport of Molecules Through Patch–Clamp Suspended Real and Model Cell Membranes 下载免费PDF全文
Dr. Pierluca Messina Dr. Frédéric Lemaître Prof. François Huet Dr. Kieu An Ngo Dr. Vincent Vivier Prof. Eric Labbé Dr. Olivier Buriez Prof. Christian Amatore 《Angewandte Chemie (International ed. in English)》2014,53(12):3192-3196
Transport of active molecules across biological membranes is a central issue for the success of many pharmaceutical strategies. Herein, we combine the patch–clamp principle with amperometric detection for monitoring fluxes of redox‐tagged molecular species across a suspended membrane patched from a macrophage. Solvent‐ and protein‐free lipid bilayers (DPhPC, DOPC, DOPG) patched from single‐wall GUV have been thoroughly investigated and the corresponding fluxes measurements quantified. The quality of the patches and their proper sealing were successfully characterized by electrochemical impedance spectroscopy. This procedure appears versatile and perfectly adequate to allow the investigation of transport and quantification of the transport properties through direct measurement of the coefficients of partition and diffusion of the compound in the membrane, thus offering insight on such important biological and pharmacological issues. 相似文献
89.
Dr. Tao Liu Dr. Aline Nonat Dr. Maryline Beyler Dr. Martín Regueiro‐Figueroa Dr. Katia Nchimi Nono Dr. Olivier Jeannin Dr. Franck Camerel Dr. François Debaene Dr. Sarah Cianférani‐Sanglier Prof. Raphaël Tripier Dr. Carlos Platas‐Iglesias Dr. Loïc J. Charbonnière 《Angewandte Chemie (International ed. in English)》2014,53(28):7259-7263
Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C2‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM . 相似文献
90.
Sébastien Aumaître Kirone Mallick François Pétrélis 《Journal of statistical physics》2006,123(4):909-927
A bifurcating system subject to multiplicative noise can exhibit on–off intermittency close to the instability threshold. For a canonical system, we discuss the dependence of this intermittency on the Power Spectrum Density (PSD) of the noise. Our study is based on the calculation of the Probability Density Function (PDF) of the unstable variable. We derive analytical results for some particular types of noises and interpret them in the framework of on-off intermittency. Besides, we perform a cumulant expansion (N. G. van Kampen, 24, 171 (1976).) for a random noise with arbitrary power spectrum density and we show that the intermittent regime is controlled by the ratio between the departure from the threshold and the value of the PSD of the noise at zero frequency. Our results are in agreement with numerical simulations performed with two types of random perturbations: colored Gaussian noise and deterministic fluctuations of a chaotic variable. Extensions of this study to another, more complex, system are presented and the underlying mechanisms are discussed.
PACS Number: 05.40.-a, 05.45.-a, 91.25.-r 相似文献