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1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Using the symbolic computation program MAPLE, we compute several terms of an asymptotic expansion for the distribution function of the logistic midrange. 相似文献
3.
Azuelos G. Benslama K. Costanzo D. Couture G. Garcia J.E. Hinchliffe I. Kanaya N. Lechowski M. Mehdiyev R. Polesello G. Ros E. Rousseau D. 《The European Physical Journal C - Particles and Fields》2004,39(2):13-24
The European Physical Journal C - We discuss possible searches for the new particles predicted by Little Higgs Models at the LHC. By using a simulation of the ATLAS detector, we demonstrate how the... 相似文献
4.
This article describes a professional development course intended to improve the content understanding of middle school mathematics teachers. The design of the course included three professional learning strategies: problem solving, examination of student thinking, and discussion of research. The concepts studied in the course included multi‐digit subtraction, multi‐digit multiplication, operations with fractions, and concepts of area and perimeter. Results from pre‐ and post‐tests administered to the nineteen participants indicate a significant increase in the mean score for each concept and document growth in the teachers' content understanding. In particular, their solutions moved from primarily procedural to more conceptual. Responses to an open‐ended survey indicate other important aspects of the professional development. Examples of teachers' work and comments are included. 相似文献
5.
The reaction of various alcohols with N-fluorodibenzenesulfonimide and triphenylphosphine leads to the corresponding dibenzenesulfonylated amines in high yields. 相似文献
6.
V. Katchkanov J.F.W. Mosselmans S. Dalmasso K.P. ODonnell S. Hernandez K. Wang R.W. Martin O. Briot N. Rousseau G. Halambalakis K. Lorenz E. Alves 《Superlattices and Microstructures》2004,36(4-6):729
The local structure of Tm3+ ions incorporated into GaN epilayers was studied by means of Extended X-ray Absorption Fine Structure. The samples were doped either in situ during growth by Molecular Beam Epitaxy or by ion implantation of layers grown by Metal Organic Chemical Vapour Deposition. The implantation was done at ion energy of 300 keV and different nominal fluences of 3×1015, 4×1015 cm−2 and 5×1015 cm−2. The concentration of Tm in the samples studied was measured by Wavelength Dispersive X-ray analysis. For the in situ doped sample with concentration of 0.5%, and for all of the implanted samples, Tm was found on the Ga site in GaN. The ion implanted sample and an in situ doped sample with a similar concentration of Tm showed the same local structure, which suggests that the lattice site occupied by Tm does not depend on the doping method. When the average Tm concentration for in situ doped samples is increased to 1.2% and 2.0%, Tm is found to occupy the Ga substitutional site and the presence of a substantial number of Tm ions in the second coordination sphere indicates dopant clustering in the films. The formation of pure TmN clusters was found in an in situ doped sample with a dopant concentration of 3.4%. 相似文献
7.
Ginette Ratovo Jean‐Pierre Souchard Pascale Urizzi Yvon Coulais Franoise Nepveu Etienne Hollande 《应用有机金属化学》2004,18(1):1-8
Pancreatic cancer has an extremely poor prognosis, due, in part, to lack of methods for early diagnosis. The present study was designed to evaluate the potential of labeling low‐density lipoprotein (LDL) with a radionuclide using a lipid chelating agent, bis(stearylamide) of diethylenetriaminepentaacetic acid (L), to detect pancreatic tumors by gamma‐scintigraphy. Previous studies indicated that the difficulty of visualization of pancreatic tumors was due to their poor vascularization. This study compares the ability of two radiotracers, 111In–L–LDL and 153Gd–L–LDL to target highly vascularized rat pancreatic tumors (AR4‐2J) implanted in nude mice. Biodistribution studies showed that the tumor uptake of 111In–L–LDL and 153Gd–L–LDL tracers was twofold and fivefold higher respectively than with the controls (111In citrate and 153Gd citrate respectively). These tracers would thus be suitable for scintigraphic imaging. We show here that LDL could be employed as a delivery system for tracers such as 111In or 153Gd when these two radionuclides are complexed by a lipid‐chelating anchor, and that 111In–L–LDL and 153Gd–L–LDL enabled better visualization of the pancreatic tumor tissues, with a better result with 153Gd–L–LDL. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
8.
G. Halambalakis N. Rousseau O. Briot S. Ruffenach R.L. Aulombard P.R. Edwards K.P. ODonnell T. Wojtowicz P. Ruterana 《Superlattices and Microstructures》2004,36(4-6):721
We have studied the optical properties of Eu doped GaN thin films. We have grown high quality Eu doped GaN thin films by using Gas Source Molecular Beam Epitaxy (GSMBE), with 1.4% Eu concentration. The Full Width at Half Maximum (FWHM) of the X-ray diffraction in an omega scan was found to be 288 arcsecs. Low Eu concentration (0.08%) doped GaN thin films were grown, where Eu-related photoluminescence at 622 and 613 nm was detected using above band-gap excitation at 2 K. For high Eu concentration of 30% GaN:Eu crystal photoluminescence (PL) and cathodoluminescence (CL) spectra show strong and intense transitions at 622 and 664 nm, but also at 593 nm for CL spectra, with a similar transition observed from the low Eu concentration sample. 相似文献
9.
Pascale F Catti M Damin A Orlando R Saunders VR Dovesi R 《The journal of physical chemistry. B》2005,109(39):18522-18527
The vibrational spectrum of Ca3Fe2Si3O12 andradite is calculated at the Gamma point by using the periodic ab initio CRYSTAL program that adopts an all-electron Gaussian-type basis set and the B3LYP Hamiltonian. The full set of frequencies (17 IR active, 25 Raman active, and 55 inactive modes) is calculated. The effect of the basis set on the calculated frequencies is discussed. The modes are characterized by direct inspection of the eigenvectors and isotopic substitution. The present calculations permit us to clarify some of the assignment problems raised by experiments. The mean absolute differences of the various modes with respect to the available experimental IR and Raman data are as small as 9 and 5 cm(-1), respectively. 相似文献
10.
Pascale F Ugliengo P Civalleri B Orlando R D'Arco P Dovesi R 《The Journal of chemical physics》2004,121(2):1005-1013
The structure of the Si-free katoite hydrogarnet (116 atoms in the unit cell) has been investigated at the periodic ab initio quantum mechanical level with the CRYSTAL program, by using a Gaussian type basis set and both the HF and the hybrid B3-LYP Hamiltonians. The structure has been fully optimized at various pressures in the 0-46 GPa range; the modifications of the structure, and in particular of the (OH)4 group, as a function of pressure are analyzed. At the B3-LYP level and P greater than 15 GPa, a O-H...O interaction of increasing strength appears, with important modifications in the local geometry of the tetrahedral site. The calculated omega01(O-H) fundamental vibrational frequency at zero pressure is in excellent agreement with experiment (3674 and 3663 cm(-1), respectively); the omega01(O-H) stretching frequency remains essentially constant in the 0-15 GPa interval, whereas it dramatically decreases at higher pressures with a corresponding anharmonicity increase, as a consequence of the formation of a strong hydrogen bond. The hydration energy of grossular and the formation energy of Si-free katoite have also been computed, and the B3-LYP results are in quite good agreement with experiment. 相似文献