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51.
Ivan Scodeller Samir Mansouri Dr. Didier Morvan Dr. Eric Muller Dr. Karine de Oliveira Vigier Dr. Raphael Wischert Dr. François Jérôme 《Angewandte Chemie (International ed. in English)》2018,57(33):10510-10514
We report the synthesis of biomass‐derived functionalized aromatic chemicals from furfural, a building block nowadays available in large scale from low‐cost biomass. The scientific strategy relies on a Diels–Alder/aromatization sequence. By controlling the rate of each step, it was possible to produce exclusively the meta aromatic isomer. In particular, through this route, we describe the synthesis of renewably sourced meta‐xylylenediamine (MXD). Transposition of this work to other furfural‐derived chemicals is also discussed and reveals that functionalized biomass‐derived aromatics (benzaldehyde, benzylamine, etc.) can be potentially produced, according to this route. 相似文献
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Improvements for ground-based remote sensing of atmospheric aerosol properties by additional polarimetric measurements 总被引:1,自引:0,他引:1
Zhengqiang Li Philippe Goloub Oleg Dubovik Luc Blarel Wenxing Zhang Thierry Podvin Alexander Sinyuk Mikhail Sorokin Hongbin Chen Brent Holben Didier Tanr Marius Canini Jean-Pierre Buis 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(17):1954-1961
We discuss the improvements in the aerosol properties characterization resulting from the additional multi-wavelength polarization measurements measured by a new CIMEL polarized sun/sky-photometer, CE318-DP. In order to process direct-sun, sky and polarization measurements in a wide spectral range (340–1640 nm), we developed new calibration methods and strategies, e.g. using the Langley plot method to calibrate both direct-sun irradiance and sky radiance, as well as combining laboratory facilities with a vicarious method to calibrate the polarized sky measurements. For studying the impact of new polarimetric measurements on the retrievals of aerosol properties, we have processed an extensive record of field measurements using an updated Dubovik and King retrieval algorithm [Dubovik O, Sinyuk A, Lapyonok T, Holben BN, Mishchenko MI, et al. Application of spheroid models to account for aerosol particle nonsphericity in remote sensing of desert dust. J Geophys Res 2006;111:D11208.]. A preliminary analysis shows that adding polarization in the inversion can reduce possible errors (notably for about 30% of our field cases) in the fine mode size distribution, real part of refractive index and particle shape parameter retrievals, especially for small particles. 相似文献
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Mitchell DL Meador J Paniker L Gasparutto D Jeffrey WH Cadet J 《Photochemistry and photobiology》2002,75(3):257-265
We developed a facile, cost-effective competitive binding assay for the analysis of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) in DNA, using a polyclonal rabbit antiserum raised against an 8-oxodGuo hapten coupled to bovine serum albumin and radiolabeled synthetic ligand containing multiple 8-oxodGuo residues. This radioimmunoassay (RIA) displays a high affinity for 8-oxodGuo in DNA, with a detection limit of approximately 1 adduct in 10(5) bases of DNA. 8-oxodGuo standards for RIA were quantified by high-performance liquid chromatography and electrochemical detection in DNA diluted in methylene blue and exposed to visible light. As an initial application we quantified 8-oxodGuo in dosimeters deployed at increasing depths in the Southern Ocean during the austral spring of the 1998 field season or at the surface at Palmer Station, Antarctica, throughout the 1999 field season. Cyclobutane pyrimidine dimers (CPD) were quantified using an established RIA. We found that the frequency of both photoproducts decreased with depth. However, CPD induction was attenuated at a faster rate than 8-oxodGuo, correlating with the differential attenuation of solar ultraviolet wavelengths in the water column. CPD induction was closely related with ultraviolet-B radiation (UVB) attenuation, whereas the lower attenuation of 8-oxodGuo suggests that oxidative damage is more closely related to ultraviolet-A radiation (UVA) irradiance. The ratio of 8-oxodGuo: CPD was also found to covary with changes in stratospheric ozone concentrations at Palmer Station. These data demonstrate the usefulness of these assays for environmental photobiology and the potential for their use in studying the relative impacts of UVB versus UVA, including ozone depletion events. 相似文献
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We provide a rigorous theoretical basis for the artificial magnetic activity of metamaterials near resonances. Our approach is a renormalization-based scheme that authorizes a completely general theory. The major result is an explicit expression of the effective permeability, in terms of resonant frequencies. The theoretical results are checked numerically, and we give applications of our theory to left-handed media and to the solution of the Pokrovski-Efros paradox. 相似文献
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We study in this paper the effect of small-scale irregularities on the quasi-geostrophic model. This study is motivated by some problems related to oceanography, as the Gulf Stream separation, or the impact of the topography on the global circulation. We first consider the role of coastal roughness in the phenomenon of western intensification of boundary currents. We show that the roughness is responsible for a nonlinear dynamics of the boundary layers, governed by a quasilinear elliptic equation. We thus extend substantially the classical derivation of Munk layers [15] and the results of convergence obtained in [10]. We then discuss the effect of a rough topography, by generalizing and justifying some formal computations of [17]. In particular, we derive rigorously a simplified model of oceanic circulation, with a nonlinear and nonlocal dissipative term due to the roughness.Acknowledgement This work has been partially supported by the GDR Amplitude Equations and Qualitative Properties (GDR CNRS 2103: EAQP) and by the IDOPT project in Grenoble. 相似文献
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Escoubet S Gastaldi S Timokhin VI Bertrand MP Siri D 《Journal of the American Chemical Society》2004,126(39):12343-12352
Thiols mediate the radical isomerization of allylic amines into enamines. The reaction results in the cleavage of the allylic C-N bond, after treatment with aqueous HCl. The mechanism involves the abstraction of an allylic hydrogen alpha to nitrogen by thiyl radical, followed by a return hydrogen transfer from the thiol to the carbon gamma to nitrogen in the intermediate allylic radical. The scope and limitations of the reaction with respect to the nature of the thiol, to the structure of the allylic chain, and to the nature of the substituents at nitrogen were investigated. The experimental results were interpreted on the ground of DFT calculations of the C-Halpha BDE in the starting allylic amines, and of the C-Hgamma BDE in the resulting enamines. The efficiency of the initial hydrogen transfer is the first requirement for the reaction to proceed. A balance must be found between the S-H BDE and the two above-mentioned C-H BDEs. The incidence of stereoelectronic factors was analyzed through NBO calculations performed on the optimized geometries of the starting allylic amines. Additional calculations of the transition structures and subsequent tracing of the reaction profiles were performed for the abstraction of Halpha from both the allyl and the prenyl derivatives by p-TolS(*). The latter allowed us to estimate the rate constant for the abstraction of hydrogen by thiyl radical from an N-prenylamine and an N-allylamine. 相似文献
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