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A. V. Sokolov A. A. Nikanorov E. M. Pliss E. T. Denisov 《Russian Chemical Bulletin》1985,34(4):705-708
Conclusions The rate constant of the reaction of peroxide radicals of acrylic and methacrylic esters of polyols with nonpolar cumene is not dependent on the number of ester groups, and with polar 2,4,6-tri-tert-butylphenol decreases with an increase in the number of ester groups in the peroxide radical. Both findings are in agreement with the model of a dipole-dipole interaction in reactions of polyfunctional compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 778–781, April, 1985. 相似文献
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Conclusions In methacrylates and acrylates undergoing oxidation, stable nitroxyl radicals react with the alkyl radicals of the monomers. The relative rate constants of the reactions of and O2 with alkyl radicals for the different esters range from 0.36 to 5.20.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 753–756, April, 1977.We thank V. A. Golubev for providing the stable nitroxyl radicals. 相似文献
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E. M. Pliss M. E. Soloviev I. V. Tikhonov D. V. Loshadkin A. L. Buchachenko 《Russian Journal of Physical Chemistry B, Focus on Physics》2016,10(3):417-420
The enthalpy change of disproportionation reaction of nitroxyl and peroxyl radicals was calculated by the DFT B3LYP/cc-pVDZ method. The regeneration of the corresponding hydroxylamine during the oxidation of unsaturated compounds inhibited by nitroxyl radicals is shown to be associated with the disproportionation of the nitroxyl and peroxyl radicals. 相似文献
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Tikhonov I. V. Pliss E. M. Borodin L. I. Sen’ V. D. 《Russian Chemical Bulletin》2016,65(12):2985-2987
Russian Chemical Bulletin - The kinetics of oxidation of methyl linoleate in micelles inhibited by stable nitroxyl radicals in the presence of superoxide dismutase was studied. In the presence of... 相似文献
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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 50, No. 4, pp. 631–639, April, 1989. 相似文献
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P. V. Pliss 《Journal of Optimization Theory and Applications》1992,74(1):171-177
In this note, we consider the mapping which associates a controllability set to each value of the parameter of a system. Sufficient conditions for the existence of breaks of this mapping are obtained. They show that nearly all such mappings have a finite number of breaks.This note was written during the author's stay at the University of Hamburg. He expresses his gratitude to the Institut für Angewandte Mathematik for its warm hospitality. 相似文献
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Ivan V. Tikhonov Vasily D. Sen' Leonid I. Borodin Evgeny M. Pliss Valery A. Golubev Alexander I. Rusakov 《Journal of Physical Organic Chemistry》2014,27(2):114-120
Acid‐catalyzed disproportionation of cyclic nitroxyl radicals R2NO? includes the half‐reactions of their oxidation to oxoammonium cations R2NO+ and reduction to hydroxylamines R2NOH. For many nitroxyl radicals, this reaction is characterized by its ~100% reversibility. Quantitative characteristics of acid–base and redox properties of the whole redox triad may be obtained from research of kinetics and equilibrium of this reaction. Here, we have examined the kinetics for the disproportionation of twenty piperidine‐, pyrroline‐, pyrrolidine‐, and imidazoline nitroxyl radicals in aqueous H2SO4, and interpreted it in terms of the excess acidity function X. The rate‐limiting step of this reaction is R2NO? oxidation by its protonated counterpart R2NOH+?. Kinetic stability of R2NO? in acidic media depends on the basicity of nitroxyl group. This basicity is influenced predominantly by protonation of another, more basic group in radical structure, and its proximity to nitroxyl group. The discovered estimates of pK values for radical cations R2NOH+? (from ?5.8 to ?12.0) indicate a very low basicity of nitroxyl groups in all commonly used R2NO?. For the first time, a linear correlation is obtained between the one‐electron reduction potentials of oxoammonium cations and the basicity of nitroxyl groups of related radicals. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献