Transverse field dependence of muonium relaxation: Spin exchange and chemical reaction

It has been shown experimentally that the muonium relaxation due to spin exchange is 1.5 times faster in intermediate transverse fields (say, atB=50 G, where the so-called two-frequency muonium signal is observed) than in low fields (say, atB=5 G), in agreement with an earlier theoretical prediction. It has also been confirmed experimentally that this distinct field dependence is totally absent in the case of chemical reaction.     

The Role of Pressure During Shearing, Dissipative Collapse

We analyse a new family of solutions to the Einstein field equations describing the collapse of a fluid sphere in the presence of heat flux and shear. These solutions ensure that the collapsing fluid is accelerating and provide a generalisation of the geodesic fluid models studied in earlier treatments. In particular, we demonstrate the role played by pressure in the dynamics of the collapse process.     

Activated barrier crossing: Comparison of experiment and theory

Photochemical isomerization in stilbene and diphenyl butadiene has been studied as a model for activated barrier crossing. Experiments have been carried out from isolated molecule conditions up to 3000 atm pressure in solution-phase samples. The qualitative features predicted by Kramers theory are observed. The system undergoes a transition from energy-controlled to diffusion-controlled behavior in the high-pressure gas phase. The influences of multidimensionality, intramolecular vibrational relaxation, and frequency dependent friction are discussed.Camille and Henry Dreyfus Teacher Scholar.     

In situ thermoset molecular composites

The polymerization of rigid rod polymer precursors in a reactive matrix precursor, which is later cured in the mold, constitutes the in situ process. A poly-azomethine (PAM) was used as the rigid rod molecule. The resin used was an epoxy. We discuss the prediction of mechanical properties using micromechanics equations for chopped fiber composites. The chemistry used to synthesize the rigid rod polymer PAM in the epoxy precursor is reviewed. Approaches to better control the cure of these epoxy systems through cure kinetics and cure rheology studies completes the thermoset in situ molecular composite process. There was a 71% increase in tensile modulus in comparison to that of the neat epoxy resin. Molecular modeling simulations and continuum mechanics are used to help understand these findings. PAM/epoxy systems were used as a matrix material in the fabrication of unidirectional glass fiber/(PAM/epoxy) structural composites. © 1994 John Wiley & Sons, Inc.     

Carbonium ion rearrangements controlled by the presence of a silyl group

Tertiary alcohols with a λ-silyl group (3) generally undergo a simple carbonium ion rearrangement in acid giving a single alkene product (4) with loss of the silyl group.     

Temperature Dependence of Solubility for Ibuprofen in Some Organic and Aqueous Solvents

The thermodynamic functions—Gibbs energy, enthalpy, and entropy of solution—were evaluated from the solubilities of ibuprofen determined at several temperatures in the pure solvents: octanol, isopropyl myristate, chloroform, cyclohexane, and water. The organic solvent-saturated aqueous media and water-saturated organic solvents were also studied, except for cyclohexane. In aqueous media, the solubility was determined at pH = 7.4 and an ionic strength 0.15 mol-L^–1 (physiological values). The excess Gibbs energy and the activity coefficients of the solutes were also determined. The solubilities are higher in organic media such as chloroform and octanol than in aqueous media and cyclohexane.     

A by-product using TIPS protection--a warning

The TIPS derivatives of alcohols are contaminated with more or less of the diisopropyl(n-propyl)silyl derivative, which can be a major product when a bad batch of reagent is used, a large excess of reagent is used, and/or the reaction is not taken to completion.