Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Lattice instabilities in Cs2MFe(CN)6 (M = Mg2+, Ca2+, and Sr2+): The crystal structure of Cs2BaFe(CN)6·2H2O

The room temperature Raman spectra of Cs₂MFe(CN)₆ (M = Mg²⁺, Ca²⁺, and Sr²⁺) suggest that these salts undergo phase transformations similar to those found in Cs₂LiCr(CN)₆ where the distortion from the high-symmetry phase proceeds primarily along two modes of vibration. The distortion involves an antiferroelectric rotation of the hexacyanide moiety and a cesium translation. On the basis of the spectra a correlation has been made between the size of M and the apparent transition temperature. In going down the alkaline earths, the apparent transition temperature increases. The structure of the barium salt determined at room temperature shows the crystal latitce contains two waters of hydration. Many similarities have been found between Cs₂BaFe(CN)₆·2H₂O and the low-symmetry phase structure of Cs₂LiCr(CN)₆.     

Satellite phenomena in the X-ray photoelectron spectra of lanthanide trihydroxides

Using the direct CI method perturbation corrections to the Koopmans ionization energies have been obtained up to order 10 for the molecules CN^? and H₂O. The results are compared with those from the fully converged CI and B_k-type calculations. The convergence of the perturbation series is found to be quite slow although substantial improvement is possible using a variation-perturbation method.