998 resultados para PROTON RELAXATION


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The structural relaxation process of an inorganic glass (Li(2)O2SiO(2)) at different cooling rates has been studied by differential scanning calorimetry. A four-parameter model-Tool-Narayanaswamy-Moynihan (TNM) model was applied to simulate the normalized specific heat curve measured. Four parameters, Delta h*/R, beta, In A, and x were obtained and compared with the values obtained from the isothermal approach. (C) 1999 Kluwer Academic Publishers.

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Persistent spectral hole burning spectroscopy is applied to evaluate the low-temperature relaxation around the dye molecules doped in several types of polymers. The doped dye is tetraphenylporphine, and the measured polymers are vinyl polymers and main chain aromatic polymers. The changes of microscopic environments around the dye are evaluated from the changes in the hole profiles during temperature cycling experiments. The relaxation behavior of the polymers is discussed in relation to their chemical structures. (C) 1999 John Wiley & Sons, Inc.

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The structural relaxation process of an inorganic glass (Li(2)O2SiO(2)) has been studied by differential scanning calorimetry. The sample is subjected to different thermal ageing histories with isothermal stages at an ageing temperature of T-g - 30 degrees C for different ageing times and at an ageing time of 16 h for different ageing temperatures. A four-parameter Tool-Narayanaswamy-Moynihan (TNM) model, is applied to simulate the normalized specific-heat curves measured. The ageing-temperature and ageing-time dependence of the structural relaxation parameters in the TNM model is obtained. (C) 1998 Elsevier Science S.A. All rights reserved.

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The effect of lanthanum ions on the structural and conformational change of yeast tRNA(Phe) was studied by H-1 NMR. The results suggest that the tertiary base pair (G-15)(C-48), which was located in the terminal in the augmented dihydrouridine helix (D-helix), was markedly affected by adding La3+ and shifted 0.33 downfield. Based pair (U-8)(A-14), which is associated with a tertiary interaction, links the base of the acceptor stem to the D-stem and anchors the elbow of the L structure, shifted 0.20 upfield. Another imino proton that may be affected by La3+ in tRNA(Phe) is the tertiary base pair (G-19)(C-56). The assignment of this resonance is tentative since it is located in the region of highly overlapping resonances between 12.6 and 12.2. This base pair helps to anchor the D-loop to the T psi C loop.

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The main characteristics of structural relaxation and the associated Tool-Narayanaswamy-Moynihan (TNM) model are thoroughly introduced, The structural relaxation of an inorganic glass (Li2O . 2SiO(2)) at different aging temperatures and aging times is found to be well modeled by the TNM model.

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The electron impact mass spectrum (EIMS) of 3-phenyl-1-butyn-3-ol was reported in this paper. Collision-induced dissociation (CID) was used to study the gas phase ion structure of [C8H7](+) formed by the fragmentation of ionized 3-phenyl-1-butyn-3-ol, and that it has the same structure as m/z 103 ions generated by cinnamic acid and alpha-methylstyrene. Deuterium labelling, metastable ion (MI) and CID experimental results indicate the formation of m/z 103 ion resulting from molecular ion of 3-phenyl-1-butyn-3-ol, which is a stepwise procedure via twice proton transfers, rather than concerted process during the successive elimination of methyl radical and neutral carbon monoxide accompanying hydrogen transfer. Moreover, in order to rationalized these fragmentation processes, the bimolecular proton bound complex between benzyne and acetylene intermediate has been proposed.

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Electrochemical behavior of the transfer of H+ across polypyrrole membrane (PPM) was studied. The transfer process was quasi-reversible and mainly diffusion-controlled. PPM electropolymerized in water solution has better reversibility than that in CH3CN solution for the transfer of H+. The transfer process of H+ across the two kinds of PPM indicated that the PPM electrochemically polymerized was of asymmetry.

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The structural relaxation process of an inorganic glass (Li2O . 2SiO(2)) at an ageing temperature of 703 K for an ageing time of 1 h has been studied by differential scanning calorimetry. A four-parameter model-the Tool-Narayanaswamy-Moynihan (TNM)-model was applied to simulate the normalized specific heat curve measured. A set of optimized parameters, Delta h*/R,beta,InA, and x was obtained. Then the effects of variation of each adjustable parameter on the calculated specific heat were summarized. (C) 1997 Elsevier Science S.A.

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The miscibility and specific interactions in poly (beta-hydroxybutyrate) (PHB)/poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry(DSC) , fourier transform infrared(FTIR) spectrometer and high resolution solid state C-13 NMR, A single composition-dependent glass transition temperatures were obtained by DSC which indicate the blends of PHB/PVPh were miscible in the melt state, The experimental glass transition temperatures were fitted quite well with those obtained from Couchman-Karasz equation. The FTIR study shows that the strong intermolecular hydrogen bonding exists in blends of PHB with strong proton acceptor and PVPh with strong proton donor and is the origin of its compatibility. The CPMAS C-13 NMR spectra also show that the strong hydrogen bonding exists in PHB/PVPh blends. From the T-1 rho(H) relaxation time it follows that the blends of PHB/PVPh(40/60, 20/80) studied are completely homogeneous on the scale of about 3.2 nm.

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The thermosetting polyimide PMR-I5 and its blends with thermoplastic polyimides have been studied by dynamic mechanical analysis. The results obtained indicate that the level of beta relaxations in PMR-15 are increased with an increase in cross-linking density. This phenomenon is interpreted as a change of chemical structure during the cross-linking process. Addition of thermoplastic polyimide makes the magnitude of beta relaxations increase when PMR-15 is the major component. This might be due to the strong intermolecular charge-transfer interaction between PI and PI or PMR-15 and PMR-15 molecular chains being partly replaced by the weak intermolecular interaction between PI and PMR-15 in PMR-15/PI blends, resulting in some phenylene rings or imide groups in PIs and PMR-15 chains being able to participate in beta relaxation. However, this increment in beta relaxation magnitude can be reduced by heat treatment of the sample, as a result of phase separation. Hence, it is concluded that the beta relaxation magnitude is determined by the number of groups which can participate in relaxation per unit length, i.e. the magnitude of beta relaxation increases with decreasing interaction between the molecular chains. Copyright (C) 1996 Elsevier Science Ltd

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According to stress relaxation curves of phenolphthalein polyether ketone (PEK-C) at different temperatures and the principle of the time-temperature equivalence, the master curve of PEK-C at arbitrary reference temperature is obtained. A coupling model is applied to explain quantitatively stress relaxation behaviour of PEK-C at different temperatures. The parameters obtained from the coupling model have important physical meaning. Copyright (C) 1996 Elsevier Science Ltd.

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The aqueous complexation of lanthanide ions with citrate in pH 7.4 solution has been investigated with use of the lanthanide-induced shift and paramagnetic relaxation rate enhancement methods. The results show that citrate coordinates via hydroxyl and central carboxylate groups with lanthanide ions and forms 1:2 (Ln/cit) isostructural complexes through the lanthanide series. A new possible coordination geometry deduced from our experimental data is suggested and discussed.

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The developments of physical aging in phenolphthalein poly(aryl-ether-ketone) (PEK-C) and poly(aryl-ether-sulfone) (PES-C) with time at two aging temperatures up to 20 K below their respective glass transition temperatures (T-g = 495 and 520 K) have been studied using differential scanning calorimetry (DSC). Substantial relaxation within the aging course of several hours were observed by detecting T-g decreasing during physical aging process at the two aging temperatures. The relaxation processes of both polymers are extremely nonlinear and self-retarding. The time dependencies of their enthalpies during the initial stages of annealing were approximately modeled using the Narayanaswamy-Tool model. The structure relaxation parameters obtained from this fitting were used to predict the possibility of physical aging occurring at their respective using temperatures. (C) 1995 John Wiley and Sons, Inc.

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According to stress relaxation curves of phenolphthalein poly(ether ketone) (PEK-C) at different temperatures and the principle of time-temperature equivalence, the master curves of PEK-C at arbitrary reference temperatures are obtained. A coupling model (Kohlrausch-Williams-Watts) is applied to explain quantitatively the different temperature dependence of stress relaxation behavior and the relationship between stress relaxation and yield phenomenon is established through the coupling model.