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991.
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A polyacrylonitrile (PAN) homopolymer and a copolymer with methyl acrylate were analyzed by differential scanning calorimetry (DSC) in order to establish a method for the kinetic analysis of the stabilization reaction steps during heat treatment. The application of a program rarely used for the study of the chemical transformation of PAN and its copolymers resulted in five separate steps, which can be assigned with large probability to various cyclization and oxidation reactions. A more exact identification of the reactions needs further measurements and considerations. Overlapping peaks appearing in the DSC traces were deconvoluted and then quantitatively analyzed to obtain kinetic parameters. The kinetics of the processes were described by the Kissinger model. The model could be fitted well to four of the five processes that may indicate that these belong to individual reactions of the first order. The parameters obtained agree well with the few values of similar investigations published in the literature up to now. The results have large practical relevance, since the kinetic parameters obtained can be used in the preparation of intermediates and for the optimization of the stabilization process. 相似文献
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Diffuse double layers merge in narrow electrochemical cells. The distribution of ions, and the accompanying electrical properties, are predicted under static conditions that are mild enough not to engender electrochemical reactions. The predictions rest on assumptions that are not egregiously unreasonable. The potential and concentration profiles are respectively described by Legendre elliptic integrals and Jacobian elliptic functions. The special case of pure water is examined and the relevance of this study to water desalination is briefly addressed. 相似文献
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Farzaneh Sarrami Li-Juan Yu Amir Karton 《Journal of computer-aided molecular design》2017,31(10):905-913
During a respiratory burst the enzyme myeloperoxidase generates significant amounts of hypohalous acids (HOX, X?=?Cl and Br) in order to inflict oxidative damage upon invading pathogens. However, excessive production of these potent oxidants is associated with numerous inflammatory diseases. It has been suggested that the endogenous antioxidant carnosine is an effective HOCl scavenger. Recent computational and experimental studies suggested that an intramolecular Cl+ transfer from the imidazole ring to the terminal amine might play an important role in the antioxidant activity of carnosine. Based on high-level ab initio calculations, we propose a similar reaction mechanism for the intramolecular Br+ transfer in carnosine. These results suggest that carnosine may be an effective HOBr scavenger. On the basis of the proposed reaction mechanism, we proceed to design systems that share similar structural features to carnosine but with enhanced HOX scavenging capabilities for X?=?Cl and Br. We find that (i) elongating the β-alanyl-glycyl side chain by one carbon reduces the reaction barriers by up to 44%, and (ii) substituting the imidazole ring with strong electron-donating groups reduces the reaction barriers by similar amounts. We also show that the above structural and electronic effects are largely additive. In an antioxidant candidate that involves both of these effects the reaction barriers are reduced by 71%. 相似文献
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