Four-electron oxygen reduction by tetrathiafulvalene

The four-electron reduction of oxygen by tetrathiafulvalene (TTF) in acidified 1,2-dichloroethane and at the acidified water/1,2-dichloroethane interface has been observed. Spectroscopy and ion transfer voltammetry results suggest that the reaction proceeds by the fast protonation of TTF followed by the 4-electron reduction of oxygen to form water. Electronic structure computations give evidence of the formation of a helical tetramer assembly ([TTF(4)H(2)](2+)) of two protonated TTF and two neutral TTF molecules. The protonated tetramer is potentially able to deliver the four electrons needed for the oxygen reduction. The production of water was corroborated by (1)H NMR analysis.     

Probing Transient Conformational States of Proteins by Solid‐State R1ρ Relaxation‐Dispersion NMR Spectroscopy

The function of proteins depends on their ability to sample a variety of states differing in structure and free energy. Deciphering how the various thermally accessible conformations are connected, and understanding their structures and relative energies is crucial in rationalizing protein function. Many biomolecular reactions take place within microseconds to milliseconds, and this timescale is therefore of central functional importance. Here we show that R_1ρ relaxation dispersion experiments in magic‐angle‐spinning solid‐state NMR spectroscopy make it possible to investigate the thermodynamics and kinetics of such exchange process, and gain insight into structural features of short‐lived states.     

Bioactivity screening and mass spectrometric confirmation for the detection of PPARδ agonists that increase type 1 muscle fibres

Sensitive and robust bioassays able to detect nuclear receptor activation are very useful for veterinary and doping control, pharmaceutical industry and environmental scientists. Here, we used bioassays based on human leukemic monocyte lymphoma U937 and human liver hepatocellular carcinoma HepG2 cell lines to detect the ligand-induced activation of the peroxisome proliferator-activated receptor delta (PPARδ). Exposure of U937 cells to the PPARδ agonist GW501516 resulted in a marked increase in mRNA expression of the PPARδ target gene Angptl4 which was quantified by qRT-PCR analysis. Exposure of HepG2 cells transiently transfected with a PPARδ expression plasmid and a PPAR-response element-driven luciferase reporter plasmid to PPARδ agonists GW501516, GW610742 and L-165041 resulted in clear dose–response curves. Although the qRT-PCR resulted in higher fold inductions, the luciferase assay with transfected HepG2 cells is cheaper and quicker and about ten times more sensitive to GW501516 compared to analysis of Angptl4 mRNA expression in U937 cells by qRT-PCR. The HepG2-based luciferase assay was therefore used to screen GW501516-spiked supplements and feed and water samples. After liquid extraction and clean-up by solid phase extraction using a weak anion exchange column, extracts were screened in the HepG2 bioassay followed by confirmation with a newly developed UPLC-MS/MS method, using two transitions for each compound, i.e., for GW501516, 454.07>188.15 (collision energy (CE) 46 V) and 454.07>257.08 (CE 30 V); for GW610742, 472.07>206.2 (CE 48 V) and 472.07>275.08 (CE 30 V); and for L-165041, 401.2>193.15 (CE 26 V) and 401.2>343.2 (CE 20 V).     

Parallel electromembrane extraction in a multiwell plate

This paper describes the concept of parallel electromembrane extraction (Pa-EME) with flat membranes in a multiwell format for the first time. The setup is based on a multiwell plate and provided simultaneous and selective isolation, cleanup, and enrichment of several human plasma samples as well as LC-MS-compatible extracts within 8 min of extraction. Undiluted human plasma samples spiked with four antidepressant drugs were added to separate wells in the donor plate. Subsequently, the samples were extracted with Pa-EME. The four drugs migrated electrokinetically from undiluted human plasma through a flat polypropylene membrane impregnated with 2-nitrophenyl octyl ether, and were isolated into formic acid. Extraction time, extraction voltage, agitation rate, sample volume, and acceptor solution volume were all optimized with an experimental design. The optimal conditions were as follows: The agitation rate was 1,040 rpm, and an extraction voltage of 200 V was applied. The sample volume and acceptor solution volume was 240 and 70 μL, respectively. The extraction was continued for 8 min. Eventually, the extracts were analyzed by LC-MS/MS. The combination of Pa-EME with LC-MS/MS provided quantitation limits below the therapeutic level and reported relative standard deviations in the range 5–13 %. Linear calibration curves were obtained for all analytes, and the correlation coefficients were above 0.9974 in the range 1–400 ng mL^?1. The drug concentrations from two subjects treated with quetiapine and sertraline were successfully determined with Pa-EME combined with LC-MS/MS. Post-column infusion experiments demonstrated that Pa-EME provided extracts free from interfering matrix components.     

Approximation of an open polygonal curve with a minimum number of circular arcs and biarcs

We present an algorithm for approximating a given open polygonal curve with a minimum number of circular arcs. In computer-aided manufacturing environments, the paths of cutting tools are usually described with circular arcs and straight line segments. Greedy algorithms for approximating a polygonal curve with curves of higher order can be found in the literature. Without theoretical bounds it is difficult to say anything about the quality of these algorithms. We present an algorithm which finds a series of circular arcs that approximate the polygonal curve while remaining within a given tolerance region. This series contains the minimum number of arcs of any such series. Our algorithm takes O(n²logn) time for an original polygonal chain with n vertices. Using a similar approach, we design an algorithm with a runtime of O(n²logn), for computing a tangent-continuous approximation with the minimum number of biarcs, for a sequence of points with given tangent directions.     

The computer as “an exercise and repetition” medium in mathematics lessons: Educational Effectiveness of Tablet PCs

The request of a new educational culture within the classroom goes hand in hand with the introduction of the new Educational Standards. That is they are essentially connected with a paradigm shift. The Project supports this aim via different tasks administered through Tablet PC's within the scope of exercise and repetition phase of learning. The central concern is to find appropriate lesson approaches through computer use in everyday life at school, which are conductive for the math learners and are at the same time easy to effectively implement in other classrooms. In the summer of 2004 the use of Tablet-PCs in school took place in two 9th classes of an Ostalbkreis secondary school in Baden-Württenberg. We report on the effectiveness of this new technology in the classroom.     

Hemin Modified Carbon Fat Electrode for Analyzing Antimalarial Endoperoxide Artemisinin in Artemisia annua

A hemin bulk modified carbon electrode with Adeps neutralis (solid fat) as binder was developed for the determination of antimalarial endoperoxide artemisinin in plant matrix. The hemin modified electrode showed significant catalytic activity for the electrochemical reduction of artemisinin at about ?380 mV vs. Ag/AgCl in phosphate buffer solution of pH 7 by using cyclic and differential pulse voltammetry. Under optimized conditions strict linearity between artemisinin concentration and height of the cathodic catalytic current peak was observed in 4.8×10^?6–7.8×10^?5 M concentration range (R=0.9991) when using differential pulse voltammetry. The detection limit was calculated as 1.4×10^?6 M of artemisinin. The developed electroanalytical device is suitable for the determination of artemisinin in Artemisia annua extracts.     

Strength of convergence and multiplicities in the spectrum of a C*-dynamical system

We consider separable C*-dynamical systems (A, G,) for whichthe induced action of the group G on the primitive ideal spacePrim A of the C*-algebra A is free. We study how the representationtheory of the associated crossed product C*-algebra A G dependson the representation theory of A and the properties of theaction of G on Prim A and the spectrum Â. Our main toolsinvolve computations of upper and lower bounds on multiplicitynumbers associated to irreducible representations of A G. Weapply our techniques to give necessary and sufficient conditions,in terms of A and the action of G, for AG to be (i) a continuous-traceC*-algebra, (ii) a Fell C*-algebra and (iii) a bounded-traceC*-algebra. When G is amenable, we also give necessary and sufficientconditions for the crossed product C*-algebra AG to be (iv)a liminal C*-algebra and (v) a Type I C*-algebra. The resultsin (i), (iii)–(v) extend some earlier special cases inwhich A was assumed to have the corresponding property.     

A new look at reactions of 2-butoxy and 1-butoxy radicals in the presence of oxygen

Under atmospheric conditions, experiments show that 2-butoxy radicals in the presence of oxygen yield acetaldehyde and butanone such that the concentration ratio [acetaldehyde] [O2]/[butanone] shows a linear dependence on oxygen concentration [O2]. [Zabel et al., Phys. Chem. Chem. Phys., 2002, 4, 2579; Cox et al.Phys. Chem. Chem. Phys, 2005, 7, 3702.] A similar oxygen dependence was found by Cox et al. in the reactions of 1-butoxy radicals. These experiments imply a unimolecular rate constant that apparently depends on oxygen pressure. Previously this has been explained by postulating the presence of a small amount of excited radicals assumed to undergo 'prompt' dissociation. We propose an alternative interpretation based on the solution of the time-dependent master equation that does not require the putative presence of excited radicals. We do this by allowing the time to run until the so-called long-time steady-state, and then show that the oxygen dependence arises quite naturally if the transport matrix takes into account that in addition to the principal reaction channel (dissociation into acetaldehyde in the case of 2-butoxy and isomerization in the case of 1-butoxy), there is a small "leak" of alkoxy radicals due to the reaction with oxygen, and provided the calculation takes into account that in the cited experiments there is a continuous incoming flux of butoxy radicals.     

Experimental and theoretical study of temperature dependent exciton delocalization and relaxation in anthracene thin films

The spectroscopy of solid anthracene is examined both experimentally and theoretically. To avoid experimental complications such as self-absorption and polariton effects, ultrathin polycrystalline films deposited on transparent substrates are studied. To separate the contributions from different emitting species, the emission is resolved in both time and wavelength. The spectroscopic data are interpreted in terms of a three-state kinetic model, where two excited states, a high energy state 1 and a low energy state 2, both contribute to the luminescence and are kinetically coupled. Using this model, we analyze the spectral lineshape, relative quantum yield, and relaxation rates as a function of temperature. For state 1, we find that the ratio of the 0-0 vibronic peak to the 0-1 peak is enhanced by roughly a factor of 3.5 at low temperature, while the quantum yield and decay rates also increase by a similar factor. These observations are explained using a theoretical model previously developed for herringbone polyacene crystals. The early-time emission lineshape is consistent with that expected for a linear aggregate corresponding to an edge-dislocation defect. The results of experiment and theory are quantitatively compared at different temperatures in order to estimate that the singlet exciton in our polycrystalline films is delocalized over about ten molecules. Within these domains, the exciton's coherence length steadily increases as the temperature drops, until it reaches the limits of the domain, whereupon it saturates and remains constant as the temperature is lowered further. While the theoretical modeling correctly reproduces the temperature dependence of the fluorescence spectral lineshape, the decay of the singlet exciton appears to be determined by a trapping process that becomes more rapid as the temperature is lowered. This more rapid decay is consistent with accelerated trapping due to increased delocalization of the exciton at lower temperatures. These observations suggest that exciton coherence can play an important role in both radiative and nonradiative decay channels in these materials. Our results show that the spectroscopy of polyacene solids can be analyzed in a self-consistent fashion to obtain information about electronic delocalization and domain sizes.