排序方式: 共有76条查询结果,搜索用时 43 毫秒
1.
Dr. Jean-Noël Rebilly Wenli Zhang Dr. Christian Herrero Dr. Hachem Dridi Dr. Katell Sénéchal-David Dr. Régis Guillot Prof. Frédéric Banse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):659-668
Rieske dioxygenases are metalloenzymes capable of achieving cis-dihydroxylation of aromatics under mild conditions using O2 and a source of electrons. The intermediate responsible for this reactivity is proposed to be a cis-FeV(O)(OH) moiety. Molecular models allow the generation of a FeIII(OOH) species with H2O2, to yield a FeV(O)(OH) species with tetradentate ligands, or {FeIV(O); OH.} pairs with pentadentate ones. We have designed a new pentadentate ligand, mtL42, bearing a labile triazole, to generate an “in-between” situation. Two iron complexes, [(mtL42)FeCl](PF6) and [(mtL42)Fe(OTf)2]), were obtained and their reactivity towards aromatic substrates was studied in the presence of H2O2. Spectroscopic and kinetic studies reflect that triazole is bound at the FeII state, but decoordinates in the FeIII(OOH). The resulting [(mtL42)FeIII(OOH)(MeCN)]2+ then lies on a bifurcated decay pathway (end-on homolytic vs. side-on heterolytic) depending on the addition of aromatic substrate: in the absence of substrate, it is proposed to follow a side-on pathway leading to a putative (N4)FeV(O)(OH), while in the presence of aromatics it switches to an end-on homolytic pathway yielding a {(N5)FeIV(O); OH.} reactive species, through recoordination of triazole. This switch significantly impacts the reaction regioselectivity. 相似文献
2.
We perform numerical simulations of hexagonal quantum dots of AlGaN semiconductors. We show that the competition between surface mass diffusion and evaporation rules the morphology of the quantum dots. The system displays three different behaviors: presence of separated islands without a wetting layer, islands dissolving into the wetting layer, or islands that do not evolve. The first behavior is of special interest because its optoelectrical properties are significantly improved in comparison with quantum dots with a wetting layer. 相似文献
3.
Storm processes and stochastic geometry 总被引:1,自引:0,他引:1
This paper is devoted to a prototype of max-stable models called the storm process. At first its spatial distribution is given
in association with different observation supports. Then the compatibility relationships between extremal coefficients at
various supports are completely characterized. Particular attention is paid to the special case where the storms are indicator
functions of Poisson polytopes. Explicit formulae are found for the extremal coefficients with finite or convex supports.
A new algorithm for exactly simulating the Poisson storm process in continuous space is also provided. Overall, the storm
process can be used as a benchmark for comparing the performances of several estimators of extremal coefficients, or for model
selection. 相似文献
4.
Elise Deunf Olivier Buriez Eric Labbé Jean-Noël Verpeaux Christian Amatore 《Electrochemistry communications》2009,11(1):114-117
The electrochemical behavior of a new cobalt–cyclodextrin (CD) complex was investigated, in dimethylformamide, from CoX2 (X = Br and BF4) in the presence of 1 equiv. 6-Deoxy-6-N-(2-methyliminopyridine)-β-cyclodextrin as ligand. Under these conditions, it was demonstrated for the first time, that the electrogenerated cobalt(I) species can be kinetically and thermodynamically stabilized. The electrochemical study of CoX2 in the presence of a related iminopyridine ligand (2-pyridyl-N-benzylmethylimine), in which the cyclodextrin (CD) group was replaced by a simple aryl moiety, allowed to highlight the crucial role of the CD in this unexpected stabilization. Importantly, this unprecedented result was only observed when both the iminepyridine and the CD moieties were together covalently attached. Importantly, the supramolecular stabilized low-valent cobalt species remained fairly reactive towards aromatic halides despite its intrinsic stability. This original work opens new opportunities for the development of more selective catalytic processes both in organic and aqueous media. 相似文献
5.
Jean-Noël Marsat Frank Stahlhut André Laschewsky Hans v. Berlepsch Christoph Böttcher 《Colloid and polymer science》2013,291(11):2561-2567
An amphiphilic linear ternary block copolymer was synthesised in three consecutive steps via reversible addition–fragmentation chain transfer polymerisation. Oligo(ethylene glycol) monomethyl ether acrylate was engaged as a hydrophilic building block, while benzyl acrylate and 3-tris(trimethylsiloxy)silyl propyl acrylate served as hydrophobic building blocks. The resulting “triphilic” copolymer consists thus of a hydrophilic (A) and two mutually incompatible “soft” hydrophobic blocks, namely, a lipophilic (B) and a silicone-based (C) block, with all blocks having glass transition temperatures well below 0 °C. The triphilic copolymer self-assembles into spherical multicompartment micellar aggregates in aqueous solution, where the two hydrophobic blocks undergo local phase separation into various ultrastructures as evidenced by cryogenic transmission electron microscopy. Thus, a silicone-based polymer block can replace the hitherto typically employed fluorocarbon-based hydrophobic blocks in triphilic block copolymers for inducing multicompartmentalisation. 相似文献
6.
The first synthesis of “α-methylene-γ-phostones” (propylphostonates) using dimethyl bromo-3-propen-2 ylphosphonate and ketones and aldehydes, in the presence of zinc, is described. 相似文献
7.
The fracture of porous media subjected to a constant load is studied. Contrary to homogeneous solids in which fracture usually happens instantaneously at a well-defined breaking strength, the fracture of a porous medium can occur with a delay, allowing us to quantify the average lifetime of the unbroken material. We show that the average fracture probability, a key property for risk analysis in civil engineering, is given by the probability of crack nucleation. The nucleation process can be understood qualitatively by calculating the activation energy for crack nucleation, taking into account the porosity of the medium. 相似文献
8.
Quirico E Rouzaud JN Bonal L Montagnac G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(10):2368-2377
The present study questions the sensitivity and the accuracy of Raman spectroscopy as a tool for determining the maturity of natural organic matter (NOM). It focuses on the definition of optimized experimental parameters in order to maximize the quality of the Raman signal and control the accuracy and reproducibility of measurements. A series of 11 coals has been investigated, sampling a wide maturity range (2-7% vitrinite reflectance VR). The role of experimental parameters is first investigated. An excitation wavelength of 514.5 nm gives better results than 457.9 and 632.8 nm, minimizing the fluorescence background observed in the spectra of low-rank coals. Both Raman and fluorescence spectra were investigated with time-resolved experiments in air and argon. These data show that fluorescence and Raman spectra are sensitive to acquisition time and laser power parameters, and reveal a physicochemical instability of the samples under laser irradiation, mostly due to photo-oxidation processes. These data clearly show that the experiments, especially in air, should be performed with strictly constant acquisition parameters. In addition, the results of a whole series of coal measurements performed in air under constant experimental conditions show that Raman spectroscopy is definitely sensitive to the maturity of coal samples with VR> approximately 1%. The most sensitive spectral maturity tracers are the width of the D-band (FWHM-D), the ratio of the peak intensities of the D- and G-bands (I(D)/I(G)), the normalized ratio of the band integrated intensities A(D)/[A(D)+A(G)] for the maturity range VR=3-7% and the width of the G-band (FWHM-G) for VR=1-5%. However, the accuracy and reproducibility are definitely weaker in such measurements compared to the standard VR. Future work must solve the problem of sample stability under laser irradiation, and greatly increase the number of samples to improve the statistical significance of the results. 相似文献
9.
A recent result by Ricceri [Ri] states that a ${C^{1,1}_{loc}}$ function ${f : X \to {\mathbb R}}$ , where X is a Hilbert space, attains its minimum on any small closed ball around a point where its derivative does not vanish, and that the unique minimum point belongs to the boundary of the ball. The proof is based on a saddle-point theorem. We show that the result, which we extend to Banach spaces having a norm with modulus of convexity of power type 2, can be obtained by means of a purely variational argument. 相似文献
10.
On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy
Beyssac O Goffé B Petitet JP Froigneux E Moreau M Rouzaud JN 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(10):2267-2276
The applicability of Raman spectroscopy to characterize disordered and heterogeneous carbonaceous materials (CM) is discussed, by considering both natural and synthetic CM. First, different analytical mismatches during the measurement are discussed and technical indications are provided in order to eliminate them. Second, the accuracy and relevance of the different parameters obtained by the decomposition of spectra by conventional fitting procedure, is reviewed. Lastly, a new Raman technique (Raman area mode microspectroscopy) giving an homogeneous repartition of power within a large laser beam is presented, this technique being powerful to study strongly heterogeneous CM and/or photosensitive samples. 相似文献