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261.
Adriana Predoi−Cross Michel Herman Luciano Fusina Gianfranco Di Lonardo 《Journal of Quantitative Spectroscopy & Radiative Transfer》2012,113(11):1134-1137
The far infrared spectrum of HCOOH was recorded at a high resolution (0.0009 cm?1) and long path length (72 m) at the far-infrared beamline, Canadian Light Source. Spectra were recorded in the region 62–300 cm?1, showing transitions from the trans-isomer.Ground state rotational transitions with Ka up to 30, were identified up to 175 cm?1, extending the observation reported in the literature. A total of 3321 transitions were assigned and fitted together with previous (4149) published data. An improved set of rotational parameters was obtained adopting the symmetric top (A) reduction of the rotational Hamiltonian in the Ir representation. The newly measured far infrared transitions allowed the determination of all diagonal and off diagonal 8th order parameters L and of some of the diagonal 10th order parameters P. 相似文献
262.
Valérie Mancier Céline Rousse-Bertrand Jean Dille Jean Michel Patrick Fricoteaux 《Ultrasonics sonochemistry》2010,17(4):690-696
Cu–Ag core–shell nanopowders have been prepared by ultrasound-assisted electrochemistry followed by a displacement reaction. The composition of the particles has been determined by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). The XRD patterns versus time displacement show that higher are the silver peaks intensities, weaker are the copper ones. That exhibits the progressive recovering of copper by silver. EDX results and quartz crystal microbalance results indicate that various reaction mechanisms are implied in this process. Transmission electron microscopy (TEM) points out variable nanometric diameter grain and some small agglomerates. Elemental mapping obtained by electron energy-loss spectroscopy (EELS) underlines the core–shell structure. 相似文献
263.
Patrick Gougeon Rabih Al Rahal Al Orabi Rgis Gautier Michel Potel 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(5):i25-i28
The structure of scandium dirubidium pentadecamolybdenum nonadecasulfide, Sc0.43 (2)Rb2Mo15S19, constitutes a partially Sc‐filled variant of Rb2Mo15S19 [Picard, Saillard, Gougeon, Noel & Potel (2000), J. Solid State Chem. 155 , 417–426]. In the two compounds, which both crystallize in the Rc space group, the structural motif is characterized by a mixture of Mo6Si8Sa6 and Mo9Si11Sa6 cluster units (`i' is inner and `a' is apical) in a 1:1 ratio. The two components are interconnected through interunit Mo—S bonds. The cluster units are centred at Wyckoff positions 6b and 6a (point‐group symmetries and 32, respectively). The Rb+ cations occupy large voids between the different cluster units. The Rb and the two inner S atoms lie on sites with 3. symmetry (Wyckoff site 12c), and the Mo and S atoms of the median plane of the Mo9S11S6 cluster unit lie on sites with .2 symmetry (Wyckoff site 18e). A unique feature of the structure is a partially filled octahedral Sc site with symmetry. Extended Hückel tight‐binding calculations provide an understanding of the variation in the Mo—Mo distances within the Mo clusters induced by the increase in the cationic charge transfer due to the insertion of Sc. 相似文献
264.
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266.
Frederic Dujols Michel Mulliez 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):165-191
Abstract Derivatives of β aminoacids in form of esters 1 or nitrile 4 (table I) undergo in an alcohol-ate/alcohol medium a rearrangement (Fig. 2), with formation of a β peptide link, resulting in the formation of esters 6 (table II). According to the experimental conditions the six membered ring heterocycles 5 are detected or isolated. They are also synthetized by cyclisation of acids 2 or hydrazide 3 (Fig. 5). While phosphorus easily reacts with alcohols and water, leading respectively to esters 6 and acids 9 (Fig. 7), it remains unaffected by amines. These results are discussed in term of mechanisms of the phosphorylation. The applications for β peptide synthesis and the participation of the p amide group in phosphorylation are limited. 相似文献
267.
Abstract The available data concerning the polymerization of three classes of monomers deemed to yield living polymers, vinyl ethers, styrenic monomers and isobutylene, are discussed from the point of view of transfer and termination reaction. In the case of vinylethers, linearity of [Mbar]n with a yield up to 30,000 has been obtained, but when higher [Mbar]n are planned, there is evidence for the occurrence of transfer reactions. In the case of isobutylene, indene, and p-Me-styrene, the linearity (up to [Mbar]n ~ 105) of [Mbar]n with the amount of monomer polymerized which has been observed (but only at low temperature) is compatible with values of transfer constants to monomer measured in “conventional” systems. In these living systems, irreversible terminations are often not very important but may become significant toward the end of monomer consumption. The main termination process is reversible termination which may lead to narrow molecular weight distributions. The linearity of [Mbar]n with yield is not conclusive evidence for the absence of transfer and termination and for the presence of particular active centers. The control of the polymerizations achieved up to now can be accounted for by the mechanisms of conventional cationic polymerizations, transfer reactions included. 相似文献
268.
Abstract The equilibrium distribution of chloride or nitrate counter-ions of K or NH4 co-ions and of water is determined experimentally at different degrees of ionization X[xbar] of hydrophylic weak-base aminated polyvinyl-alcohol membranes. These data are analyzed and explained in terms of thermodynamics interrelating the molality of fixed-charge densities and of counter-ions to that of the amount of water and of diffused salt in the membrane. Three domains have to be considered: the polyelectrolyte domain with small external concentration compared to the internal net fixed charge concentration (notion of “net-charge” densities), the domain of homogeneous interstitial liquid of the concentrated electrolyte type with sufficiently concentrated salt solution, and the intermediate domain. 相似文献
269.
Abstract Radical copolymerization kinetics of vinyl chloride (VC) and vinyl bromide (VB) lead to the following reactivity ratios rVC=0.825 rVB=1.05 Vinyl bromide acts as a chain transfer agent, more powerful than vinyl chloride, the transfer constant for VC radicals being 8.5 × 10?3 at 40° C. Neither thermal nor ionic degrad-ation produce controlled distribution of short diene sequences in the copolymer. In the ionic process initiated with LiCl or LiBr in dimethylformamide solution, substitution of halogen atoms as well as acid elimination takes place. 相似文献
270.
During several years, we have been involved in the growth and characterization of non-linear optical crystals by the two most common techniques for growing single-crystal fibers from the melt: laser-heated pedestal growth and micro-pulling down. Their specific features are presented in this study and their versatility is demonstrated through two typical examples of incongruently melting materials: K3Li2?xNb5+xO15+2x (solid solution of the ternary system K2O–Li2O–Nb2O5) and Ca5(BO3)3F which can only be grown from a flux. 相似文献