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Reaction Constants (reaction + constant)
Selected AbstractsHigh-throughput system for determining dissolution kinetics of inclusion bodiesBIOTECHNOLOGY JOURNAL, Issue 5 2009Astrid Dürauer Dr. Abstract Efficient solubilization is a crucial step during inclusion body processing and dissolving conditions were usually empirically established. Here we describe a new methodology for rapid screening of solubilization conditions and evaluation of dissolution kinetics in microtiter plates. Increase of protein in solution over time was directly related to decrease of turbidity measured by absorbance at 600 nm. Dissolution kinetics of inclusion bodies were described by a first-order reaction kinetics, which was used for drug dissolution modeling. Reaction constants were in the range of 0.01,0.03 s,1 for buffer conditions providing sufficient solubilization power. This method is not limited to the screening of optimal buffer conditions for solubilization and can be applied for studying other parameters involved in the solubility of IBs, such as pI of the protein, influence of fermentation conditions, influence of initial protein concentration, and more. [source] Kinetics and mechanism of the oxidative regeneration of carbonyl compounds from oximes by pyridinium bromochromateINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2006Pradeep K. Sharma The oxidative deoximination of several aldo- and keto-oximes by pyridinium bromochromate (PBC), in dimethylsulfoxide, exhibited a first-order dependence on both the reductant (oxime) and the oxidant (PBC). The oxidation of ketoximes is slower than that of aldoximes. The rates of oxidation of aldoximes correlated well in terms of the Pavelich,Taft dual substituent-parameter equation. The low positive value of polar reaction constant indicated a nucleophilic attack by a chromate-oxygen on the carbon. The reaction is subject to steric hindrance by the alkyl groups. The reaction of acetaldoxime has been studied in 19 different organic solvents. The solvent effect has been analyzed by Taft's and Swain's multiparametric equations. A mechanism involving the formation of a cyclic intermediate, in the rate-determining step, has been proposed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 364,368, 2006 [source] Comprehensive Modeling of Ion Conduction of Nanosized CaF2/BaF2 Multilayer HeterostructuresADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Xiangxin Guo Abstract Molecular beam epitaxy-grown CaF2/BaF2 heterolayers are a demonstration of the potential of nanoionics. It has been shown that ion conductivities both parallel and perpendicular to the interfaces increase with decrease in interfacial spacing. This size effect was attributed to the thermodynamically necessary redistribution of the mobile fluoride ions (N. Sata, K. Eberl, K. Eberman, J. Maier, Nature 2000, 408, 946; X. X. Guo, I. Matei, J.-S. Lee, J. Maier, Appl. Phys. Lett. 2007, 91, 103102). On this basis, the striking phenomenon of an upward bending in the effective parallel conductivity as a function of inverse interfacial spacing for low temperatures (T,,,593,K) has been satisfactorily explained by application of a modified Mott,Schottky model for BaF2 (X.X. Guo, I. Matei, J. Jamnik, J.-S. Lee, J. Maier, Phys. Rev. B 2007, 76, 125429). This model was further confirmed by measurements perpendicular to the interfaces that offer complementary information on the more resistive parts. Here a successful comprehensive modeling of parallel and perpendicular conductivities for the whole parameter range, namely for interfacial spacings ranging from 6 to 200,nm and investigated temperatures ranging from 455 to 833,K, is presented. The model is based on literature data for carrier mobilities and Frenkel reaction constants and the assumption of a pronounced F, redistribution. Given the fact that an impurity content that was experimentally supported is taken into account and apart from minor assumptions concerning profile homogeneity, the only fit parameter is the space charge potential. In particular, it is worth mentioning that in BaF2 the low temperature Mott,Schottky space charge zone which is determined by impurities changes over, at high temperatures, into a Gouy,Chapman situation owing to increased thermal disorder. (The situation in CaF2 is of Gouy,Chapman type at all temperatures.) [source] Correlation analysis of reactivity in the oxidation of anilines by nicotinium dichromate in nonaqueous mediaINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2006D. S. Bhuvaneshwari The kinetics of oxidation of 15 para- and meta-substituted anilines by nicotinium dichromate (NDC) in different organic solvent media in the presence of p -toluenesulfonic acid (TsOH) has been investigated. The rate of the reaction is zero order with respect to substrate, first order in NDC, and is found to increase with increase in [TsOH]. The various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of the isokinetic relationship. The specific rate of oxidizing species-anilines reaction (k2) correlates with Hammett's substituent constants affording negative reaction constants. The effect of para- and meta-substituents on the oxidation rates confirms to Swain et al.'s substituent constants F and R, both with negative reaction constants. The rate data failed to correlate with macroscopic solvent parameters such as ,r and E while showing satisfactory correlation with Kamlet,Taft's solvatochromic parameters (,, ,, and ,*). © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 657,665, 2006 [source] Studies on the kinetics of imidazolium fluorochromate oxidation of some meta - and para -substituted anilines in nonaqueous mediaINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2006D. S. Bhuvaneshwari The imidazolium fluorochromate (IFC) oxidation of meta - and para -substituted anilines, in seven organic solvents, in the presence of p -toluenesulfonic acid (TsOH) is first order in IFC and TsOH and is zero order with respect to substrate. The IFC oxidation of 15 meta - and para -substituted anilines at 299,322 K complies with the isokinetic relationship but not to any of the linear free energy relationships; the isokinetic temperature lies within the experimental range. The specific rate of oxidizing species-anilines reaction (k2) correlates with substituent constants affording negative reaction constants. The rate data failed to correlate with macroscopic solvent parameters such as ,r and ENT. A correlation of rate data with Kamlet,Taft solvatochromic parameters (,, ,, ,*) suggests that the specific solute,solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute,solvent complexation. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 166,175, 2006 [source] Theoretical Study of Remote Substituent Effects on X,H(X=CH2, NH, O) Bond Dissociation Energies of AzuleneCHINESE JOURNAL OF CHEMISTRY, Issue 7 2007Yi-Yun Yu Abstract In the study, the X,H (XCH2, NH, O) bond dissociation energies (BDE) of para -substituted azulene (Y-C10H8X-H) were predicted theoretically for the first time using Density Functronal Theory (DFT) methods at UB3LYP/6-311++g(2df,2p)// UB3LYP/6-31+g(d) level. It was found that the substituents exerted similar effects on the X,H BDE of azulene as those on benzene, except for 6-substituted 2-methylazulene. Owing to the substituent-dipole interaction, the reaction constants (,+) of 2- and 6-Y-C10H8X-H (XNH and O only) varied violently. The origin of the substituent effects on the X,H BDE of azulene was found, by both GE/RE and SIE theory, to be directly associated with variation of the radical effects, although the ground effects also played a modest role in determining the net substituent effects. [source] Evaluation of Intrinsic Ionization and Complexation Constants of TiO2 and Mg-Fe Hydrotalcite-like CompoundsCHINESE JOURNAL OF CHEMISTRY, Issue 10 2006Wan-Guo Hou Abstract The intrinsic surface reaction constants, pKinta1, pKinta2, p*KintC and p*KintA, were evaluated by a modified double extrapolation (MDE) for TiO2 without structural charge and Mg-Fe hydrotalcite-like compounds (HTlc) with structural charge, respectively. The results of intrinsic surface reaction constants for TiO2 were compared with those obtained by class double extrapolation (CDE) in literature. Furthermore, the values of intrinsic surface reaction constants obtained by MDE were used to simulate the charging behaviors of the materials. The following conclusions were obtained. For TiO2 without structural charge, the pKinta1 and pKinta2 evaluated by MDE are equal to those by CDE, however the p*KintC and p*KintA evaluated by MDE are much different from those by CDE. In principle, the results of the p*KintC and p*KintA evaluated by MDE are more accurate than those by CDE. The values of intrinsic surface reaction constants obtained by MDE can excellently simulate the charging curves for TiO2 with the triple layer model (TLM). For HTlc with positive structural charge, the results of *KintC=0 and *KintA,, were obtained by MDE, which means the inert electrolyte chemical binding does not exist; the point of zero net charge (PZNC) of c -independence also exist as the same as solid without structural charge, and the pHPZNC obtained by the acid-base titration can excellently be simulated and the surface charging tendency can be simulated to a great extent using the pKinta1 and pKinta2 evaluated by MDE and the diffuse layer model (DLM). [source] | ||||||||||