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High-frequency sinusoidal oscillations of a coarse-grained polymer model are used to calculate the local dynamic mechanical properties (DMPs) of free-standing polymer thin films. The storage modulus G(') and loss modulus G(") are examined as a function of position normal to the free surfaces. It is found that mechanically soft layers arise near the free surfaces of glassy thin films, and that their thickness becomes comparable to the entire film thickness as the temperature approaches the glass transition T(g). As a result, the overall stiffness of glassy thin films decreases with film thickness. It is also shown that two regions coexist in thin films just at the bulk T(g); a melt-like region (G(')G(")) in the middle of the film. Our findings on the existence of a heterogeneous distribution of DMPs in free-standing polymer thin films provide insights into recent experimental measurements of the mechanical properties of glassy polymer thin films. 相似文献
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Pure manganese dioxide, prepared synthetically, has been used for the oxidative decomposition of chrome ores. The usual constituents of the ores, viz. Cr(2)O(3) FeO, Al(2)O(3), MgO, CaO and SiO(2) have been estimated and the results compare favourably with those obtained by standard methods. 相似文献
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Soluble complex-formation of mercury(II) thiocyanate has been studied oscillometrically. The titration of mercury(II) nitrate with thiocyanate gives one inflection corresponding to the formation of Hg(SCN)2, while in the reverse titration the formation of Hg(SCN)+ is also indecated. The method is useful for a rapid determination of very small quantities of mercury or thiocyanate in highly dilute solutions. The titrations can be effected in presence of nitric acid provided its total acidity in the system does not exceed about N. Further Work on the mercury(II) -halide and mercury(II)-cyanide reactions is in progress. 相似文献
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An interesting transformation during the oxidation of 3,4-epoxy alcohols 1a-d, derived from the corresponding homoallylic alcohols, led to the formation of 4-hydroxy-2,3-unsaturated carbonyls 2a-d in very good yields. One of these products 2c was transformed into the functionalised carboxylic acid 5, an advanced stage intermediate from which the total synthesis of macrosphelide A has been reported. 相似文献
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Dimers of the pyrrole amino acid (Paa), 5-(aminomethyl)pyrrole-2-carboxylic acid, and its derivatives having Lys anchored on N- and C-termini bind in the minor groove of DNA with considerable apparent binding affinities. When the Lys unit is attached to the C-terminus, the resulting ligand binds to ds-DNA with twice the affinity, of the order of 105, than the one carrying two positive charges at the same end. 相似文献
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Syntheses of Boc-protected 4-amino- and 5-amino-pyrrole-2-carboxylic acid methyl esters have been achieved and the structures of these compounds have been fully characterized by detailed NMR studies. 相似文献
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B. R. Sant 《Fresenius' Journal of Analytical Chemistry》1955,145(4):257-260
Summary The oxidation of hydroxylamine by alkaline ferricyanide has been studied. It is observed that in presence of sodium hydroxide the molar ratio of NH2OH to K3Fe(CN)6 varies between 11.3 to 11.6. Quantitative oxidation to N2 is therefore carried out in weakly alkaline medium using borax-boric acid buffer. Hydroxylamine is estimated by titrating the ferrocyanide formed with standard ceric sulphate. Accurate and reproducible results are obtained if too large an excess of ferricyanide is avoided. Application of the present procedure to the determination of oximes and their metal complexes is suggested.Grateful thanks of the author are due to Prof. S. S. Joshi for facilities and encouragement and to Dr. G. S. Deshmukh for kind interest in the work. 相似文献