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41.
Martina Schwager Emil Roduner Ivan D. Reid Paul W. Percival Jean-Claude Brodovitch Stanislaw Wlodek Robert F. Marzke 《Hyperfine Interactions》1994,87(1):859-864
SR spectra of the ethyl radical adsorbed on porous silica were observed in transverse and in longitudinal magnetic fields in the temperature range 190–298 K. The line widths reflect the dynamic partial averaging of the hyperfine anisotropy due to reorientation and surface diffusion. 相似文献
42.
Based on the similarity in properties of arsenate and phosphate, the colorimetric method using the molybdene blue complex was tested in order to determine low As(V) concentration in waters. The influence of complex formation time, daylight, temperature and competitive anions (silicate and sulphate) upon complex formation was determined. Optimal complex formation was reached in 1 h at 20±1 °C and was slightly favoured when developed in daylight. The formation rate declined with decreasing reaction temperature and no influence of any of the competitive anions tested (at concentrations usually found in natural waters of granitic areas) was noted. The detection limit of this method was 20 μg As(V) l−1. This simple, fast and sensitive arsenic determination method is suitable for field analysis, especially for waters containing low levels of phosphate and organic matter. Through arsenate determination, this colorimetric method allowed the arsenite oxidation efficiency of five common industrial oxidants to be compared. H2O2 and MnO2(s) were not considered as effective oxidants as a high excess was necessary to ensure As(III) oxidation. NaOCl and KMnO4 were promising oxidants as they allowed complete arsenite oxidation with a small excess for NaOCl or even less than the electron stoichiometric ratio in the case of KMnO4. FeCl3 was the most effective oxidant among the reagents tested here. 相似文献
43.
We present in this paper two new effects observed in the state of molecular iodine: a very high diamagnetic correction in the vibrational level υ′ = 62 and an important orientation of the optically excited molecules due to predissociation. Both effects can be interpreted by taking into consideration the perturbation of the B state by other electronic states. 相似文献
44.
Nlate S Nieto Y Blais JC Ruiz J Astruc D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):171-176
Phenol tri- and nonaallyl dendrons (3 and 7, respectively) were functionalized at the focal position to give the new triallyl dendrons 4 and 6 and the nonaallyl dendrons 11 and 13 that contain a iodoalkyl or a bromobenzyl termini. All these dendrons were used for the [FeCp]+-induced hexafunctionalization of hexamethylbenzene in [FeCp(eta6-C6Me6)][PF6] (1) under mild conditions in the presence of KOH. These reactions directly yielded the 18-allyl and 54-allyl dendrimers 9, 10, and 14 with a [FeCp(eta6-arene)]+ unit located at the dendrimer core. Cyclic voltammetry studies were recorded in THF and DMF with these metallodendrimers and compared with those of analogous dendrimers or complexes of smaller size that contain a [FeCp(eta6-arene)]+ unit at the core. The decreased rate of heterogeneous electron transfer when the dendritic size increases first disclosed by Diederich and Gross is confirmed. The variation of the redox potential of the Fe(II/I) redox system with increasing dendritic size is negligible even in a solvent of high dielectric constant such as DMF. This trend is attributed to fact that the involved "redox" orbital is buried on the metal center, well protected by the shell of alkyl chains (electron-reservoir nature), unlike in ferrocene. The chemical irreversibility increases in THF as the dendrimer size increases, due to more facile ligand substitution with THF at the 19-electron level when the chain bulk increases. 相似文献
45.
Anna Chrostowska Véronique Métail Geneviève Pfister-Guillouzo Jean-Claude Guillemin 《Journal of organometallic chemistry》1998,570(2):5188
Primary vinylic and acetylenic germanes and stannanes, synthesized by a chemoselective reduction of the corresponding trichloro derivatives, were investigated by ab initio quantum chemical methods and photoelectron spectroscopy. In particular, the PE spectra display very well-resolved bands which show the increasing destabilizing effect of 14 group heteroatom α-substitution of double or triple carbon–carbon bonds. 相似文献
46.
Paul Boullanger Jean-Claude Martin Grard Descotes 《Journal of heterocyclic chemistry》1975,12(1):91-93
The synthesis of 3,4,6 tri-O-benzyl-D-glucal (4) has been accomplished by direct benzylation of triacetylglucal (yield 55%) and by zinc reduction of 3,4,6-tri-O-henzyl-2-acetoxy-1-bromoglucose (yield 26%). The nmr spectra of tribenzyl- and triacetyl-D-glucal in the presence of lanthanide shift reagents were reported. 相似文献
47.
Céline Pascal Claude Merlet Rose-Marie Marin-Ayral Jean-Claude Tedenac Bernard Boyer 《Mikrochimica acta》2004,145(1-4):147-151
The phases formed at the interface between an intermetallic (NiAl) and a nickel base superalloy joined by combustion synthesis were investigated, particularly the eutectic phases. Owing to their small size, the characterisation of these phases using a Castaings electron microprobe encounters difficulties. The analysis volume size is generally too large to differentiate the phases from their surrounding matrix, even by using low accelerating voltage. Moreover, the eutectic phases contain boron, which is difficult to characterise by EPMA. Independently of the phases shape, the characterisation can be solved by viewing this complex system as a surrounding matrix and a multi layer system. The results of these simulations revealed the presence of two categories of borides: the eutectic boride MM2B2 (M=Mo and M=Co, Cr) and the solid solution boride [Cr1–x (Mo, W)x]B. 相似文献
48.
Bajor G Veszprémi T Riague el H Guillemin JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3649-3656
Vinyl, allyl, and homoallyl selenols were easily prepared by a chemoselective reduction of the corresponding selenocyanates with aluminum hydrides. Two stable vinyl and five stable allyl conformers of both series were predicted on the potential-energy surface. The interaction of SeH or SeCN groups with the vinyl group has been investigated with UV photoelectron spectroscopy and quantum chemical calculations, using the MP2/cc-pVTZ and B3LYP/cc-pVTZ levels. In the vinyl derivatives, a surprisingly strong direct conjugation of the selenium lone electron pair and the C=C double bond was observed. On the other hand, in allyl position the selenium lone pair is independent on the C=C double bond, and the hyperconjugation between the Se-C bond and the double bond is the ruling effect. Thus is clarified the type and extent of the interaction between the SeH or SeCN group and the unsaturated moiety. 相似文献
49.
Jean-Claude Jacquesy 《Journal of fluorine chemistry》2006,127(11):1484-1487
This is a summary of a lecture presented at the 100th Anniversary, Moissan Symposium in Paris on Friday 10th November 2006.In HF/SbF5, Vinca alkaloids react selectively at the D’ring of the molecule. In the presence of CHCl3 (or CCl4), vinorelbine yields 20′,20′-difluoro-3′,4′-dihydrovinorelbine (vinflunine), presently in phase III experimentation for treatment of bladder cancer and non small cell lung cancer. 相似文献
50.