Inter versus intra-molecular photoinduced charge separation in solid films of donor-acceptor molecules

We report on photoinduced charge separation in solid films of two perylene diimides; intramolecular charge separation and recombination is correlated with a reduction in the yield of long-lived, intermolecular charge-separated species.     

Poly(dimethylsiloxane) microchip: microchannel with integrated open electrospray tip

A polymer microchip with an open tip for electrospray mass spectrometry is presented. The tip consists of a groove with parallel walls where a droplet can form at the end surface. A lid covers the whole chip except at the microchannel tip, which is left open. Poly(dimethylsiloxane) (PDMS) microchips were cast using a nickel mould which in turn was replicated from a dry etched silicon wafer. Tips with microchannel widths of around 50 microm could easily be replicated. Since the tip had no cover, the assembly of microchip and cover was simplified. A total ion current variation of 5% during 300 s was achieved for a 1 microM myoglobin solution. The non-complex design of the cover makes it suitable for versatile tests of chip prototypes. The nickel mould was found to be useful for PDMS microstructure fabrication. Also, such a robust mould allows casting electrospray tips in more rigid thermoset materials.     

A Soluble Donor–Acceptor Double-Cable Polymer: Polythiophene with Pendant Fullerenes

Summary.  We report the synthesis and the spectroscopic properties of a novel soluble thiophene-based copolymer carrying pendant fullerene moieties (donor–acceptor double-cable polymer). Photoinduced absorption (PIA) experiments on spin cast films reveal a photoinduced electron transfer from the polythiophene chain onto the fullerene moieties. The performance of photovoltaic devices produced with this copolymer is also discussed. Corresponding author. E-mail: antonio.cravino@jku.at Received August 16, 2002; accepted (revised) August 26, 2002     

Temperature dependence of electronic coupling through oligo-p-phenyleneethynylene bridges

A series of donor-bridge-acceptor (D-B-A) systems with varying donor-acceptor distances has been studied with respect to the temperature dependence of the triplet excitation energy transfer (TEET) rates. The donor and acceptor, zinc(II) and free-base porphyrin, respectively, were separated by oligo-p-phenyleneethynylene (OPE) bridges, where the number of phenyleneethynylene groups was varied between two and five, giving rise to edge-to-edge separations ranging between 12.7 and 33.4 A. The study was performed in 2-MTHF between room temperature and 80 K. It was found that the distance dependence was exponential, in line with the McConnell model, and the attenuation factor, beta, was temperature dependent. The experimentally determined temperature dependence of beta was evaluated by using a previously derived model for the conformational dependence of the electronic coupling based on results from extensive quantum chemical, DFT and time-dependent DFT (TD-DFT), calculations. Two regimes in the temperature interval could be identified: one high-temperature, low-viscosity regime, and one low-temperature, high-viscosity regime. In the first regime, the temperature dependence of beta was, according to the model, well described by a Boltzmann conformational distribution. In the latter, the molecular motions that govern the electronic coupling are slowed down to the same order of magnitude as the TEET rates. This, in effect, leads to a distortion of the conformational distribution. In the high-temperature regime the model could reproduce the temperature dependence of beta, and the extracted rotational barrier between two neighboring phenyl units of the bridge structure, E(i)=1.1 kJ mol(-1), was in line with previous experimental and theoretical studies. After inclusion of parameters that take the viscosity of the medium into account, successful modeling of the experimentally observed temperature dependence of the distance dependence was achieved over the whole temperature interval.     

The split network analysis for exploring composition-structure correlations in multi-component glasses: I. Rationalizing bioactivity-composition trends of bioglasses

We present a strategy, referred to as “split network” analysis, for assessing the average network polymerization (r_F) and mean number of bridging oxygen (BO) atoms (N?_BO^F) for each individual network former F in multi-component oxide-based glasses, primarily targeting those involving Al, B, P and Si. This requires a priori knowledge about the parameters {r_F, N?_BO^F} of all network builders, but one, whose values are deduced by the split network procedure. We illustrate split-network concepts for establishing composition/structure/bioactivity correlations in Na-Ca-Si-P-O glasses. The cooperating influences on the bioactivity from the average polymerization degree of the silicate network and the amounts of orthophosphate and sodium ions are discussed.     

Beyond the speed of light on Finsler spacetimes

As a prototypical massive field theory we study the scalar field on the recently introduced Finsler spacetimes. We show that particle excitations exist that propagate faster than the speed of light recognized as the boundary velocity of observers. This effect appears already in Finsler spacetime geometries with very small departures from Lorentzian metric geometry. It switches on for a sufficiently large ratio of the particle four-momentum and mass, and is the consequence of a modified version of the Coleman–Glashow velocity dispersion relation. The momentum dispersion relation on Finsler spacetimes is shown to be the same as on metric spacetimes, which differs from many quantum gravity models. If similar relations resulted for fermions on Finsler spacetimes, these generalized geometries could explain the potential observation of superluminal neutrinos claimed by the Opera Collaboration.