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271.
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
272.
Ignacio Villanueva 《Mathematische Nachrichten》2003,250(1):98-103
We clarify and prove in a simpler way a result of Taskinen about symmetric operators on C(Kn), K an uncountable metrizable compact space. To do this we prove that, for any compact space K and any n ∈ ?, the symmetric injective n–tensor product of C(K), , is complemented in C(BC(K)*), a result of independent interest. The techniques we develop allow us to extend the result in several directions. We also show that the hypothesis of metrizability and uncountability cannot be removed. 相似文献
273.
M. Dubé C. Daneault V. Vuorinen M. Alava M. Rost 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,56(1):15-26
We investigate the structure and dynamics of the interface between
two immiscible liquids in a three-dimensional disordered porous
medium. We apply a phase-field model that includes explicitly
disorder and discuss both spontaneous and forced imbibition.
The structure of the interface is dominated by a length scale
ξ× which arises from liquid conservation. We further show
that disorder in the capillary and permeability act on different
length scales and give rise to different scalings and
structures of the interface properties. We conclude with a
range of applications. 相似文献
274.
Xiao‐Hui Liu Yan‐Guo Li Ying Lin Yue‐Sheng Li 《Journal of polymer science. Part A, Polymer chemistry》2007,45(7):1272-1281
The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. 1H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 2007 相似文献
275.
We propose objectives consisting of two mirrors with central holes for passage of a light beam. The optical layout ensures
multiple reflection of rays from both mirrors. We consider several approaches to calculating the design parameters for which
three and four aberrations do not occur. The objectives can be used in optical devices operating in the UV and IR regions
of the spectrum.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 267–270, March–April, 2007. 相似文献
276.
N. S. Oliveira J. Dorgan J. A. P. Coutinho A. Ferreira J. L. Daridon I. M. Marrucho 《Journal of Polymer Science.Polymer Physics》2007,45(5):616-625
The sorption of carbon dioxide in glassy Poly(lactic acid) (PLA) films was studied by quartz crystal microbalance (QCM) at high pressures. Two thermal treatments, melted and quenched, were performed in PLA with two different L:D contents, 80:20 and 98:2, films and compared with a third thermal protocol, annealed, and used in a previous work. The results obtained show that for pressures higher than 2 MPa, the carbon dioxide solubility is larger in PLA 80:20 than in PLA 98:2, indicating that the L:D plays a dominant role on this property. The thermal treatments only affect the gas solubility in PLA 98:2. Sorption isotherms at temperatures 303, 313, and 323 K, below the glass transition temperature of the polymer, and pressures up to 5 MPa were measured and analyzed with three different models, the dual‐mode sorption model, the Flory–Huggins equation, and a modified dual‐mode sorption model where the Henry's law term was substituted by the Flory–Huggins equation. This last model performs especially well for CO2 in PLA 80:20, due to the convex upward curvature of the solubility isotherms for that system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 616–625, 2007 相似文献
277.
The spin coating method was used to assemble polymer (Poly (2,5-dibutoxy-1,4-phenylenevinylene)) (DBO-PPV) into the pores of porous alumina which was prepared by anodization. Four peaks in the photoluminescence (PL) spectra of the composite, with contributions from the DBO-PPV and porous alumina, were found. It was also found that the light emitting from the porous alumina could excite the photoluminescence of DBO-PPV. The nanometer effect of the porous alumina can lead to a blue shift of 90 nm of the PL peaks of DBO-PPV. 相似文献
278.
J. Haglund 《Advances in Mathematics》2003,175(2):319-334
We introduce the distribution function Fn(q,t) of a pair of statistics on Catalan words and conjecture Fn(q,t) equals Garsia and Haiman's q,t-Catalan sequence Cn(q,t), which they defined as a sum of rational functions. We show that Fn,s(q,t), defined as the sum of these statistics restricted to Catalan words ending in s ones, satisfies a recurrence relation. As a corollary we are able to verify that Fn(q,t)=Cn(q,t) when t=1/q. We also show the partial symmetry relation Fn(q,1)=Fn(1,q). By modifying a proof of Haiman of a q-Lagrange inversion formula based on results of Garsia and Gessel, we obtain a q-analogue of the general Lagrange inversion formula which involves Catalan words grouped according to the number of ones at the end of the word. 相似文献
279.
The oxidation of aminoethanethiol (1) was investigated in acid solutions on a glass carbon anode. It was shown that at relatively low anode potentials thiyl radicals RS· are released into the solution, but this does not lead to binding of the oxygen in the solution. Raising the anode potential leads to binding of oxygen, which is probably due to the formation of the intermediate RS+. The oxidation of 1 was studied in Ce(SO4)2+H2SO4 solution. It was shown that under certain conditions the intermediate is RS+, which subsequently converts to a product that could not be identified as any previously described product of the oxidation of thiols. Proposals are made regarding its structure and conversion pathways.B. P. Konstantinov Institute of Nuclear Physics, Russian Academy of Sciences, 188350 Leningrad. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 278–288, February, 1992. 相似文献
280.
提出了Ru(phen) 32 +-SO32 - -KClO3(phen =1 ,1 0菲咯啉 )体系化学发光法测定溶液中亚硫酸盐含量的方法 .SO32 - 浓度与化学发光强度在 1 .0× 1 0 - 6~ 1 .0× 1 0 - 3 mol/L范围内成正比 ,检出限为 2 .32× 1 0 - 6mol/L (S/N =3) ,1 .0× 1 0 - 4 mol/LSO32 - 溶液重复 6次测定结果的相对标准偏差为 3.8% .该方法成功地用于白葡萄酒中的亚硫酸盐总含量的测定 ,结果令人满意 . 相似文献