Oxygen diffusion in poly(dimethyl siloxane) using fluorescence quenching. II. Filled samples

The method of fluorescence quenching has been used to measure the transport properties of oxygen in poly(dimethyl siloxane) (PDMS) filled with small weight fractions of fumed silica. The experimental results show that the diffusion coefficient of oxygen and the pre-exponential term in the Arrhenius relationship are reduced, but the activation energy is not affected. In the pressure and temperature ranges used in these experiments, the diffusion coefficient was found to be independent of both the oxygen and fluorophor concentrations. A discussion concerning the effect of fillers on the pre-exponential term is presented.     

Druckmessung

Ohne Zusammenfassung     

Electron tunneling through sensitizer wires bound to proteins

We report a quantitative theoretical analysis of long-range electron transfer through sensitizer wires bound in the active-site channel of cytochrome P450cam. Each sensitizer wire consists of a substrate group with high binding affinity for the enzyme active site connected to a ruthenium-diimine through a bridging aliphatic or aromatic chain. Experiments have revealed a dramatic dependence of electron transfer rates on the chemical composition of both the bridging group and the substrate. Using combined molecular dynamics simulations and electronic coupling calculations, we show that electron tunneling through perfluorinated aromatic bridges is promoted by enhanced superexchange coupling through virtual reduced states. In contrast, electron flow through aliphatic bridges occurs by hole-mediated superexchange. We have found that a small number of wire conformations with strong donor–acceptor couplings can account for the observed electron tunneling rates for sensitizer wires terminated with either ethylbenzene or adamantane. In these instances, the rate is dependent not only on electronic coupling of the donor and acceptor but also on the nuclear motion of the sensitizer wire, necessitating the calculation of average rates over the course of a molecular dynamics simulation. These calculations along with related recent findings have made it possible to analyze the results of many other sensitizer-wire experiments that in turn point to new directions in our attempts to observe reactive intermediates in the catalytic cycles of P450 and other heme enzymes.     

Observation of size-dependent thermalization in CdSe nanocrystals using time-resolved photoluminescence spectroscopy

We report heat dissipation times in semiconductor nanocrystals of CdSe. Specifically, a previously unresolved, subnanosecond decay component in the low-temperature photoluminescence decay dynamics exhibits longer decay lifetimes (tens to hundreds of picoseconds) for larger nanocrystals as well as a size-independent, ~25-meV spectral shift. We attribute the fast relaxation to transient phonon-mediated relaxation arising from nonequilibrium acoustic phonons. Following acoustic phonon dissipation, the dark exciton state recombines more slowly via LO-phonon assistance resulting in the observed spectral shift. The measured relaxation time scales agree with classical calculations of thermal diffusion, indicating that interfacial thermal conductivity does not limit thermal transport in these semiconductor nanocrystal dispersions.     

Extracting BB′IW Inhabitants of Simple Types From Proofs in the Sequent Calculus {LT_\to^{t}} for Implicational Ticket Entailment

The decidability of the logic of pure ticket entailment means that the problem of inhabitation of simple types by combinators over the base { B, B′, I, W } is decidable too. Type-assignment systems are often formulated as natural deduction systems. However, our decision procedure for this logic, which we presented in earlier papers, relies on two sequent calculi and it does not yield directly a combinator for a theorem of ${T_\to}$ . Here we describe an algorithm to extract an inhabitant from a sequent calculus proof—without translating the proof into another proof system.     

Halogen

Ohne Zusammenfassung