Study of oxygen transport in glassy polymers on a nanometer length scale utilizing the kinetic Monte Carlo simulations.

Diffusion-controlled deactivation of excited phenanthrene and oxidation of triplet aryl-nitrene by molecular oxygen were used to determine the energetics of oxygen jump rates in the set of glassy polymers: poly(methyl methacrylate), poly(n-butyl methacrylate), polycarbonate, polystyrene, and polysulfone. To interpret experimental results, a simple model based on the transition state theory of diffusion jump has been used. The kinetic Monte Carlo simulations of phenanthrene deactivation and nitrene oxidation were carried out in a cubic lattice that modeled a polymer matrix.

Mechanism of photochromic transformations and photodegradation of an asymmetrical 2,3-diarylcyclopentenone.

A mechanistic study of the photochromic properties and photodegradation processes of an asymmetrical diarylcyclopentenone bearing thiophene and benzothiophene units using stationary photolysis, nanosecond laser flash photolysis and time-resolved luminescence was performed. It was found that the light-induced reversible isomerization of (3-(2,5-dimethyltiophen-3-il)-2-(2-methyl-1-benzylthiophen-3-il)cyclopent-2-en-1-one, compound 1) from open to closed form is a common photochromic transformation inherent to diarylethenes, while the photodegradation process proceeds in two ways. The first is a formal 1,2-dyotropic rearrangement, proceeding without the participation of oxygen.

Length and time scales of structural heterogeneities in deeply supercooled propylene carbonate.

Deactivation of excited phenanthrene by molecular oxygen is utilized to probe the structural heterogeneity of supercooled propylene carbonate. The diffusion rate of oxygen molecules in different regions varies over two orders of magnitude. The size of the regions of different oxygen mobility was determined to be 1.

Kinetics of azobenzene nitrene oxidation by molecular oxygen in glassy propylene carbonate.

The kinetics of azobenzene nitrene oxidation by molecular oxygen dissolved in a matrix was studied in glassy propylene carbonate. The reaction was carried out in excess oxygen within its concentration range 0.008 to 0.

Length scale of heterogeneities in glassy propylene carbonate probed by oxygen diffusion.

A new method using the quenching of guest molecule phosphorescence by molecular oxygen is proposed for determination of heterogeneity size in glassy matrixes. The method is based on the high sensitivity of the diffusion of oxygen molecules to spatial density fluctuations. Phenanthrene phosphorescence decay was monitored at different concentrations of molecular oxygen in propylene carbonate below T(g).