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排序方式: 共有549条查询结果,搜索用时 31 毫秒
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.
It is well known that laser scattered-light applicators when applied for laser-induced tumor therapy allow the precise thermal destruction of metastases. Using laser radiation in the NIR spectral range (usually, Nd:YAG laser systems λ = 1064 nm), a penetration depth of 5–10 cm (1/e is the decrease in radiation intensity) is achieved in biological tissues. The major tissue-optical parameters, i.e., absorption coefficient μa, scattering coefficient μs, and the anisotropy factor g, show biological tissues to be strongly scattering media which have a so-called optical window in the NIR. As a consequence, the therapeutic laser radiation is scattered and absorbed at a deeper level, leading to a virtual enlargement of the laser applicator. The thermal sclerotization and the thermal cell damage originate within the absorbing volume of the laser radiation and spread outward by thermal diffusion. There are three dosimetrically relevant zones of thermal and biological damage: (1) a zone of thermal coagulation; (2) a threshold of partial necrosis (destruction of all metabolic processes in the cell is the maintenance of essential parts of the cytoskeleton and the plasma membrane); this is characterized by a specific temperature range, the so-called phase transition, which refers to the transition from the gel phase of the biomembrane to the fluid phase; the determination of this temperature zone is an integral part of the following experimental investigations on MX1 cells; (3) an external zone of thermal effects made up of partial and multiple damage with a statistical chance of survival. This paper describes the investigations on heat stress in cancer cells to verify the maximum phase transition of the outer MX1 cell membranes and the related results. For this purpose, a novel method of quantum dot fluorescence dosimetry was developed. The evaluation of the measured laser-induced fluorescences yields a first approximation of the determination of the phase transition on MX1 cells. 相似文献
3.
Jacquet Philippe Minet Pascale Mühlethaler Paul Rivierre Nicolas 《Wireless Personal Communications》1997,4(1):51-63
Radio LANs are emerging in the computing world. They are supported by distinct configurations: on the one hand radio LANs with base stations and a wired backbone, on the other hand radio LANs implementing Intra-forwarding. Adding a new node in a radio LAN with Intra-forwarding, increases the reliability, while this reliability decreases with ad hoc or hub configurations. This advantage of Intra-forwarding is quantified. Intra-forwarding, as defined in the HIPERLAN standard, is based on a hop-by-hop policy and link check procedures. It is shown how point-to-point packets and broadcast packets are forwarded. The three basic components of Intra-forwarding needed to build and update the Intra-forwarding database are described. The originality of this approach is the use of multipoint relays which enable better scalability. The correctness of the Intra-forwarding protocol is proved and its cost is evaluated. 相似文献
4.
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
5.
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
6.
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
7.
Guy Bouchoux Yannik Hoppiiliard Pascale Jaudon 《Journal of mass spectrometry : JMS》1987,22(2):98-102
Dissociative ionization of 1,2-epoxy n-alkanes gives rise to abundant [C4H7O]+ ions of structure [CH3OCHCHCH2]+. This conclusion is drawn from metastable ion analysis and from collisional activation spectra. This fragmentation involves the C? C ring opening and a 1,4-H migration leading to the corresponding enol ether [CH3OCHCHCH2R]+. precursor of [CH3OCHCHCH2]+ fragment. The same isomerization scheme applies to 1,2-epoxy methyl substituted alkanes and 2,3-epoxy n-alkanes. 相似文献
8.
Determination of ochratoxin A in domestic and imported beers in italy by immunoaffinity clean-up and liquid chromatography 总被引:4,自引:0,他引:4
A method first developed to quantify ochratoxin A in wine has been applied to the analysis of domestic and imported beers in Italy. The method uses commercial immunoaffinity columns for clean-up and high-performance liquid chromatography for quantification of the toxin. Beer was degassed, then diluted with a polyethylene glycol-sodium hydrogencarbonate solution and applied to an OchraTest immunoaffinity column. Ochratoxin A was eluted from the immunoaffinity column with methanol and quantified by reversed-phase HPLC with fluorometric detector. Average recoveries of ochratoxin A from blank beer spiked at levels from 0.04 to 1.0 ng/ml ranged from 93.8% to 100.4%, with relative standard deviations between 3.3% and 5.7%. The detection limit was 0.01 ng/ml based on a signal-to-noise ratio of 3:1. The analysis of 61 samples of domestic (10) and imported (51) beers showed ochratoxin A levels ranging from <0.01 to 0.135 ng/ml with an incidence of contamination of 50% and no substantial difference between strong and pale beers. 相似文献
9.
Bonnet C Gadelle A Pécaut J Fries PH Delangle P 《Chemical communications (Cambridge, England)》2005,(5):625-627
The cyclodextrin derivative (hexakis (2-O-carboxymethyl-3,6-anhydro)-alpha-cyclodextrin) forms mono- and bimetallic complexes with lutetium(III) in aqueous solution; the X-ray structure of the binuclear complex [Lu2(ACX)(H2O)2] is the first example of a lanthanide-cyclodextrin inclusion complex. 相似文献
10.
Frédéric Lefebvre Pascale Dupont Aline Auroux 《Reaction Kinetics and Catalysis Letters》1995,55(1):3-9
H3PW12O40/activated carbon catalysts have been studied by microcalorimetry and by the dehydration of methanol to dimethyl ether. It has been shown that the acidity of the polyacid is greatly reduced upon grafting on activated carbon. The decrease is so high that, at low polyanion loadings, the catalysts are relatively inactive in the dehydration of methanol to dimethyl ether. 相似文献