The characterization of silica microparticles by electrophoretic mobility measurements

Summary Electrophoretic mobility measurements in the pH 2‐10 range are described for several commercial HPLC silica microparticles and a laboratory-produced product. The content of metal impurities for the silicas was also determined by AAS. An acidic/hydrothermal treatment was used to generate a more homogenous surface for some of the silicas. The zero points of charge (zpc) for both a native and a treated silica plus several commercial HPLC silicas were compared. The electrophoretic mobility method may be useful in predicting the utility of certain types of silica supports for chromatographic separations.     

Favorskii rearrangement of α,β-epoxy ketones

Reactions of α,β-epoxy ketones with nucleophilic bases generally take one of two courses: (1) α-displacement followed by β-elimination of water or (2) Favorskii rearrangement via a cyclopropanone or zwitterion intermediate. Among the factors that appear to control these reactions, it is suspected that an α′-substituent effect may operate. Such an effect has been confirmed by observing the conversion of 3,5,5,6 - tetramethyl - 2,3 - epoxycyclohexanone (1) to the ring-contracted γ-lactone 3, together with other Favorskii rearrangement products, on treatment with refluxing methanolic potassium hydroxide. The α′-methyl substituted steroid 2 under similar reaction conditions was transformed into roughly equal amounts of 4, 5 and 4 (all rationalized by a Favorskii-like mechanism). In each case the analogous epoxy ketone lacking an α′-Me substituent failed to give any Favorskii products.     

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.     

Origin of Schottky barriers in gold contacts on GaAs110

Gold contacts on n-type GaAs(110) have been investigated using scanning tunneling microscopy and spectroscopy in cross-sectional configuration. In spatially resolved current voltage spectroscopy the Schottky barrier potential is visible. We find signatures of delocalized gap states at the interface decaying into the semiconductor and observe a defect density at the interface below 3 x 10(13) cm(-2). Both findings support that the Fermi level pinning at the Au/GaAs(110) interface is dominated by metal-induced gap states.     

Experimental evidence for a reduction in electron thermal diffusion due to trapped particles

New high time resolution measurements of the electron thermal diffusion χ(e) throughout the sawtooth cycle of the Madison Symmetric Torus reversed-field pinch have been made by utilizing the enhanced capabilities of the upgraded multipoint, multipulse Thomson scattering system. These measurements are compared to the χ(e) due to magnetic diffusion predicted by using information from a new high spectral resolution zero-β nonlinear resistive magnetohydrodynamic simulation performed, for the first time, at the Lundquist number of high current Madison Symmetric Torus plasmas (S≈4×10(6)). Agreement between the measured and predicted values is found only if the reduction in thermal diffusion due to trapped particles is taken into account.