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41.
Reaction of arenesulfonylimines of methyl trifluoropyruvate with 1,3-C,N-and-N,N-binucleophiles led to a variety of N-sulfonylated fluorine-containing heterocycles, including the fused ones.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2171–2175, November, 2007. 相似文献
42.
N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods
in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization
of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly
accepted. Bridged TS are formed by both the substitution mechanism S
N
2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise
N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized
upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates
of N-acylalkylation, as was demonstrated by localization of the corresponding TS.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007. 相似文献
43.
L. Bartosch P. Kopietz 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,28(1):29-36
We consider the effect of Coulomb interactions on the average density of states (DOS) of disordered low-dimensional metals
for temperatures T and frequencies ω smaller than the inverse elastic life-time 1/τ. Using the fact that long-range Coulomb interactions in two dimensions (2d) generate ln2-singularities in the DOS ν(ω) but only ln-singularities in the conductivity σ(ω), we can re-sum the most singular contributions
to the average DOS via a simple gauge-transformation. If σ(ω) > 0, then a metallic Coulomb gapν(ω) ∝ |ω|/e
4 appears in the DOS at T = 0 for frequencies below a certain crossover frequency Ω
2 which depends on the value of the DC conductivity σ(0). Here, - e is the charge of the electron. Naively adopting the same procedure to calculate the DOS in quasi 1d metals, we find ν(ω) ∝ (|ω|/Ω
1)1/2exp(- Ω
1/|ω|) at T = 0, where Ω
1 is some interaction-dependent frequency scale. However, we argue that in quasi 1d the above gauge-transformation method is on less firm grounds than in 2d. We also discuss the behavior of the DOS at finite temperatures and give numerical results for the expected tunneling conductance
that can be compared with experiments.
Received 28 August 2001 / Received in final form 28 January 2002 Published online 9 July 2002 相似文献
44.
DRIFTS study of surface reactivity to NO2 by zinc nanoparticle aggregates and zinc hollow nanofibers
Zinc nanostructures synthesized with different morphologies from the same evaporation/condensation technique are studied with concern to surface reactivity to NO2 by Diffuse Reflectance Infrared Fourier Transformed Spectroscopy (DRIFTS). Synthesis of nanopowders is obtained, according to previous work, by gas flow thermal evaporation at 540 °C of bulk Zn grains. Two types of Zn powders are obtained and studied in experiments. The first one is collected on the cold walls of the reactor as a deposit produced by thermophoretic effect. It is constituted by grains (∼10 μm) originated by the stratification of smaller aggregates (∼200 nm) and isolated primary particles (∼50 nm) born in the gas flow. The second type of powder is grown from the condensation of Zn chemical vapors within the expansion orifice of the quartz reactor after relatively long time (∼1 h) deposition process. It is constituted mainly by hollow Zn nanofibers with external and internal diameter about 100 and 60 nm. Preliminary characterization of the two types of powders is made by SEM, TEM, XRD. Thereafter, the two types of samples are studied by DRIFTS at variable temperature (VT). Comparison is made between the home-synthesized nanopowders with respect to commercial Zn standard dust. The Zn hollow nanofibers when exposed to NO2 are found to exhibit dramatic reactivity, which is not observed at all either in the case of clustered aggregate zinc or of commercial Zn dust powders. Results indicate that, at increasing temperature from RT to 300 °C, the hollow nanofibers surface reacts distinctively with adsorbant gas NO2, with contemporary formation of a progressively growing narrow absorption band at 2500 cm−1 and contemporary depression of a doublet (∼1600-1628 cm−1) band. In order to justify this striking spectral feature, we propose the occurring of a possible polymerization process at nanofibers surface where most probably as a consequence of pre-treatment and exposure to gas NO2 a very thin film of ZnO is formed. The possible role of huge specific surface of hollow nanofibers as inferred by preliminary SEM, TEM, XRD studies is discussed. 相似文献
45.
M. Olivares-Marín C. Fernández-González V. Gómez-Serrano 《Applied Surface Science》2006,252(17):5980-5983
Using cherry stones, the preparation of activated carbon has been undertaken in the present study by chemical activation with potassium hydroxide. A series of KOH-activated products was prepared by varying the carbonisation temperature in the 400-900 °C range. Such products were characterised texturally by gas adsorption (N2, −196 °C), mercury porosimetry, and helium and mercury density measurements. FT-IR spectroscopy was also applied. The carbons prepared as a rule are microporous and macroporous solids. The degree of development of surface area and porosity increases with increasing carbonisation temperature. For the carbon heated at 900 °C the specific surface area (BET) is 1624 m2 g−1, the micropore volume is 0.67 cm3 g−1, the mesopore volume is 0.28 cm3 g−1, and the macropore volume is 1.84 cm3 g−1. 相似文献
46.
We present Hall effect measurements on highly oriented pyrolytic graphite that indicate the occurrence of the integer quantum-Hall-effect. The evidence is given by the observation of regular plateau-like structures in the field dependence of the transverse conductivity obtained in van der Pauw configuration. Measurements with the Corbino-disk configuration support this result and indicate that the quasi-linear and non-saturating longitudinal magnetoresistance in graphite is governed by the Hall effect in agreement with a recent theoretical model for disordered semiconductors. 相似文献
47.
Donald Craig 《Tetrahedron: Asymmetry》1991,2(12):1177-1180
The synthesis and thermally-induced intramolecular Diels-Alder (IMDA) reaction of (S)s-(+)-S-[(1E,7E)-1,7,9-decatrienyl]-S-phenyl-N-(p-tolylsulphonyl)sulphoximine 4 is described. A model is proposed for the cis-selectivity of the cycloaddition based on previous results from the reactions of sulphonyl-substituted trienes. The stereochemistry of the major cis-fused cycloadduct is determined by single-crystal X-ray analysis of that obtained from reaction of racemic 4. 相似文献
48.
R. Souzy B. Ameduri B. Boutevin 《Journal of polymer science. Part A, Polymer chemistry》2004,42(20):5077-5097
The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF2), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by 19F and 1H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004 相似文献
49.
Ajay K. Saini Clifford M. Carlin Howard H. Patterson 《Journal of polymer science. Part A, Polymer chemistry》1992,30(3):419-427
New model compounds for poly[N,N′-bis(phenoxyphenyl)pyromellitimide] have been synthesized in order to investigate the formation of imine bonds which are proposed to form during the curing process and lead to crosslinking in the bulk polymer. Raman studies show that terminal amines can react with imide carbonyls during curing to form C?N bonds. The Raman band due to C?N appears at 1656 cm?1 and the band due to C?O closest to the imine bond is observed at 1742 cm?1. These results are in agreement with previously published results on vapor deposited polyimide films. 相似文献
50.
I. Mohammed-Ziegler B. Por M. Kubinyi A. Grofcsik A. Grün I. Bitter 《Journal of Molecular Structure》2003,650(1-3):39-44
The complex formation between chromogenic capped calix 4 arene derivatives comprising indophenol indicator group(s), and aliphatic amines has been studied by UV/Vis spectroscopy. The equilibrium constants have been determined in ethanol, and—for one ligand—also in dimethylsulfoxide. The results have been interpreted in terms of various types of host–guest interactions and of steric effects. 相似文献