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1.
α-Fe_2O_3纳米微粒/硬脂酸交替L-B膜的结构表征 总被引:1,自引:0,他引:1
纳米微粒(NP)是一个新的物质层次,它具有一系列新异的物理、化学特性,涉及到大块样品中所忽略的,或根本不具有的基本物理、化学问题.用NP 制造新型的人工功能材料具有广泛的潜在应用.一个有意义的挑战是能否对NP 进行有序的组装.Zhao andFendler 等曾利用Fe_3O_4NP 进行有序组装的尝试.我们也在前期的初步研究中利用Langmuir-Blodgett(LB)技术对7nm 的α-Fe_2O_3 NP 进行了有序组装的探索,获得了α-Fe_2O_3 NP-硬脂酸交替LB 多层膜(FNSLF).然而这种交替膜的有序情况还不十分清楚. 相似文献
2.
2-Pyridylethylation of benzazothiones-2 which are potential mercapto compounds (benzothiazolethione-2, benzoxazolethione-2, 1-methylbenzoimidazolethione-2, benzoimidazolethione-2, 5, 6-dimethylbenzoimidazolethione-2), is described, as well as preparation of 5, 6-dimethylbenzoimidazolethione-2 by direct oxidation of 5, 6-dimethylbenzoimidazole. 相似文献
3.
Using high-level ab initio MO methods, we have identified two reaction pathways with different thermodynamic and kinetic properties for the thermal decomposition of the three-membered heterocycle thiirane (C2H4S) and related derivatives. A homolytic ring opening, followed by attack of the generated diradical on another thiirane molecule, and subsequent elimination of ethene in a fast radical chain reaction results in the formation of disulfur molecules in their triplet ground state (3S2) and requires activation enthalpies of deltaH#(298) = 222 kJ mol(-1) and deltaG#(298) = 212 kJ mol(-1). This reaction mechanism would result in a first-order rate law in agreement with one reported gas-phase experiment but does neither match the experimental activation energy nor does it explain the observed retention of the stereochemical configuration in the thermal decomposition of certain substituted thiiranes. Alternatively, sulfur atoms can be transferred from one thiirane moleculeto another with the intermediate formation of thiirane 1-sulfide (C2H4S2). This molecule can either decompose unimolecularly to ethene and disulfur in its excited singlet state (1S2) or, by means of spin crossover, S2 in its triplet ground state may be formed. On the other hand, the thiirane 1-sulfide may react with itself and transfer one sulfur atom from one molecule to another with formation of thiirane 1,1-disulfide (C2H4S3), which is an analogue of thiirane sulfone; thiirane is formed as the second product. The 1,1-disulfide may then decompose to ethene and S3. In still another bimolecular reaction, the thiirane 1-sulfide may react with itself in a strongly exothermic reaction to give S4 and two equivalents of ethene. This series of reactions results in a second-order rate law and requires activation enthalpies of deltaH#(298) = 109 kJ mol(-1) and deltaG#(298) = 144 kJ mol(-1) for the formation of thiirane 1-sulfide, while the consecutive reactions require less activation enthalpy. Elemental sulfur (S8) is eventually formed by oligomerization of either S2, S3, or S4 in spin-allowed reactions. These findings are in agreement with most experimental data on the thermal desulfurization of thiirane and its substituted derivatives. Thiirane 1-persulfide (C2H4S3) with a linear arrangement of the three sulfur atoms as well as zwitterions and radicals derived from thiirane are not likely to be intermediates in the thermal decomposition of episulfides. 相似文献
4.
I. Ya. Postovskii N. N. Vereshchagina S. L. Mertsalov 《Chemistry of Heterocyclic Compounds》1966,2(1):94-97
2-R-Quinazolones have been synthesized (R=Me, Ph,-pyridyl,-furyl), and subsequently the 4-chlorides and the corresponding 2-R-4-hydrazinoquinazolines were obtained. By the reaction of orthoformic ester and nitric acid on the hydrazines, 5-R- [3, 4-c]-s-triazoloquinazolines and 5-R- [1, 5-c] tetrazoloquinazolines were prepared, respectively. The compounds in which R=Me differ considerably from compounds with other groups, both in color and stability of intermediate reaction products. 5-R- [1, 5-c] tetrazoloquinazolines are hydrolyzed by HCl into quinazol-4-ones.For Part IV see [1]. 相似文献
5.
In this work a novel graphical method is applied to the presentation of intercomparison results. This is demonstrated with
the results of a recent intercomparison in measuring the 137Cs, 40K, and 90Sr activity concentration in milk powder. The “PomPlot”, an intuitive graphical method, is used for producing a summary overview
of the participants’ results of a common measurand. The “PomPlot” displays (relative) deviations of individual results from
the reference value on the horizontal axis and (relative) uncertainties on the vertical axis. 相似文献
6.
Vera A. Vil' Yana A. Barsegyan Leah Kuhn Maria V. Ekimova Egor A. Semenov Alexander A. Korlyukov Alexander O. Terent'ev Igor V. Alabugin 《Chemical science》2020,11(20):5313
How far can we push the limits in removing stereoelectronic protection from an unstable intermediate? We address this question by exploring the interplay between the primary and secondary stereoelectronic effects in the Baeyer–Villiger (BV) rearrangement by experimental and computational studies of γ-OR-substituted γ-peroxylactones, the previously elusive non-strained Criegee intermediates (CI). These new cyclic peroxides were synthesized by the peroxidation of γ-ketoesters followed by in situ cyclization using a BF3·Et2O/H2O2 system. Although the primary effect (alignment of the migrating C–Rm bond with the breaking O–O bond) is active in the 6-membered ring, weakening of the secondary effect (donation from the OR lone pair to the breaking C–Rm bond) provides sufficient kinetic stabilization to allow the formation and isolation of stable γ-hydroperoxy-γ-peroxylactones with a methyl-substituent in the C6-position. Furthermore, supplementary protection is also provided by reactant stabilization originating from two new stereoelectronic factors, both identified and quantified for the first time in the present work. First, an unexpected boat preference in the γ-hydroperoxy-γ-peroxylactones weakens the primary stereoelectronic effects and introduces a ∼2 kcal mol−1 Curtin–Hammett penalty for reacquiring the more reactive chair conformation. Second, activation of the secondary stereoelectronic effect in the TS comes with a ∼2–3 kcal mol−1 penalty for giving up the exo-anomeric stabilization in the 6-membered Criegee intermediate. Together, the three new stereoelectronic factors (inverse α-effect, misalignment of reacting bonds in the boat conformation, and the exo-anomeric effect) illustrate the richness of stereoelectronic patterns in peroxide chemistry and provide experimentally significant kinetic stabilization to this new class of bisperoxides. Furthermore, mild reduction of γ-hydroperoxy-γ-peroxylactone with Ph3P produced an isolable γ-hydroxy-γ-peroxylactone, the first example of a structurally unencumbered CI where neither the primary nor the secondary stereoelectronic effect are impeded. Although this compound is relatively unstable, it does not undergo the BV reaction and instead follows a new mode of reactivity for the CI – a ring-opening process.Protecting stereoelectronic effects prevent Baeyer–Villiger rearrangement and stabilize γ-OX-γ-peroxylactones (X = H, OH), the previously elusive non-strained Criegee intermediates. 相似文献
7.
T. N. Vereshchagina V. A. Lopyrev M. S. Pevzner L. M. Kogan 《Chemistry of Heterocyclic Compounds》1969,5(5):681-682
By oxidation of 3,5-dimethyl-1,2,4-triazole the monopotassium salt of 1,2,4-triazole-3,5-dicarboxylic acid was obtained. The mononitryl of 1,2,4-triazole-3,5-dicarboxylic acid was isolated during the reaction between 3-diazo-1,2,4-triazole-5-carboxylic acid and potassium cyanide in the presence of copper cyanide. Acid hydrolysis of 3-cyano-1,2,4-triazole-5-carboxylic acid leads to the formation of 3-carbamido-5-carboxy-1,2,4-trlazole, which on esterification with methanol gives rise to 3-carbamido-5-carbomethoxy-1,2,4-triazole. 相似文献
8.
Natalia Fridman Moshe Kapon Yana Sheynin Menahem Kaftory 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):153-157
1,3-Benzenediamine,N,N′-bis(4,6-dichloro-1,3,5-triazine-2-yl) and 1,3,5-Triazine,2,2′-[2-methyl-1,3-phenylenebis(oxy)] bis(4,6-dichloro) were synthesized as host molecules. The inclusion compound of 1,3-Benzenediamine,N,N′-bis(4,6-dichloro-1,3,5-triazine-2-yl) crystallizes in the monoclinic crystal system in space group C2/c. The host molecule occupies the space group 2-fold special position and packed in the crystal lattice in such a manner as to leave channels running along the c axis of a rectangular cross-section. It crystallizes with two molecules of acetone that are hydrogen bonded to the amino nitrogen atoms. Molecules of 1,3,5-Triazine,2,2′-[2-methyl-1,3-phenylene bis(oxy)]bis(4,6-dichloro) are packed in the crystal in such a manner as to leave channels of a trapezoid cross-section that are running along the a axis. Guest molecules such as metanol, ethanol, and ethyl acetate can be used to fill the channels. The crystal structures of two inclusion compounds are described. 相似文献
9.
10.
Vereshchagina Ya. A. Ismagilova R. R. Chachkov D. V. 《Russian Journal of Organic Chemistry》2019,55(2):227-233
Russian Journal of Organic Chemistry - According to DFT calculations, hydrolysis of 1,1,1-trisubstituted hyposilatranes and hypogermatranes proceed in one stage and have lower activation energies... 相似文献