Ultrafast proton-coupled electron-transfer dynamics in pyrene-modified pyrimidine nucleosides: model studies towards an understanding of reductive electron transport in DNA.

5-(Pyren-1-yl)-2'-deoxyuridine (PydU) and 5-(Pyren-1-yl)-2'-deoxycytidine (PydC) were used as model nucleosides for DNA-mediated reductive electron transport (ET) in steady-state fluorescence and femtosecond time-resolved transient absorption spectroscopy studies. Excitation of the pyrene moiety in PydU and PydC leads to an intramolecular electron transfer that yields the pyrenyl radical cation and the corresponding pyrimidine radical anion (dU.- and dC.-. By comparing the excited state dynamics of PydC and PydU, we derived information about the energy difference between the two pyrimidine radical anion states. To determine the influence of protonation on the rates of photoinduced intramolecular ET, the spectroscopic investigations were performed in acetonitrile, MeCN, and in water at different pH values. The results show a significant difference in the basicity of the generated pyrimidine radical anions and imply an involvement of proton transfer during electron hopping in DNA. Our studies revealed that the radical anion dC.- is being protonated even in basic aqueous solution on a picosecond time scale (or faster). These results suggest that protonation of dC.- may also occur in DNA. In contrast, efficient ET in PydU could only be observed at low pH values (< 5). In conclusion, we propose--based on the free energy differences and the different basicities--that only dT.- but not dC.- can participate as an intermediate charge carrier for excess electron migration in DNA.     

Reaction-diffusion problems in electrolysis

Supported in part by Schweizerischer Nationalfonds (20-25263.88) and European Community (Science Plan, Project Evolutionary Systems)     

Intramolecular carboxylic acid trapping of pyran-4-one derived zwitterions: A novel synthesis of fused bicyclic lactones

Pyran-4-ones bearing carboxylic acid side chains were prepared either by direct carboxylation with carbon dioxide or through oxidative cleavage of side chain olefins. Irradiation in a non-nucleophilic solvent yielded fused bicyclic lactones. The efficiency of the reaction was not dependent on ring substitution.     

Giant improvement of time-delayed feedback control by spatio-temporal filtering

Control of spatio-temporal chaos by the time-delay autosynchronization method is improved by several orders of magnitude. Unstable time periodic patterns are efficiently stabilized if one employs filters and couplings which originate from the Floquet eigenvalue problem of the unstable orbit. We illustrate our scheme by an application to a globally coupled reaction-diffusion model which describes charge transport in semiconductor devices.     

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Ohne Zusammenfassung     

Semilinear parabolic equations involving measures and low regularity data

A detailed study of abstract semilinear evolution equations of the form is undertaken, where generates an analytic semigroup and is a Banach space valued measure depending on the solution. Then it is shown that the general theorems apply to a variety of semilinear parabolic boundary value problems involving measures in the interior and on the boundary of the domain. These results extend far beyond the known results in this field. A particularly new feature is the fact that the measures may depend nonlinearly and possibly nonlocally on the solution.

     

Analysis of exhaled breath from smokers,passive smokers and non‐smokers by solid‐phase microextraction gas chromatography/mass spectrometry

In this study, 38 samples of expired air were collected and analyzed from 20 non‐smoking volunteers, four passive smokers and 14 smokers (21 women and 17 men). Measurements were carried out using solid‐phase microextraction (SPME) as an isolation and preconcentration technique. The determination and identification were accomplished by gas chromatography coupled with mass spectrometry (GC/MS). Our data showed that ca 32% of all identified compounds in the breath of healthy non‐smokers were saturated hydrocarbons. In the breath of smoking and passive smoking volunteers hydrocarbons were predominant, but also present were more exogenous analytes such as furan, acetonitrile and benzene than in the breath of non‐smokers. Acetonitrile, furan, 3‐methylfuran, 2,5‐dimethylfuran, 2‐butanone, octane and decane were identified in breath of smoking and passive smoking persons. Copyright © 2008 John Wiley & Sons, Ltd.     

Multi-harmonic detection in wavelength modulation spectroscopy systems

Two multi-harmonic detection methods for wavelength modulation spectroscopy (WMS) systems are presented and compared. The two possibilities discussed in this paper are: simultaneous curve fitting of multiple harmonic spectra, and reconstruction of the transmission from harmonic coefficients. The optimum number of harmonics is four and 25 harmonics, respectively. Compared with standard single-harmonic curve fitting, the methods give about a factor of 3 better performance than standard second-harmonic curve fitting. Concluding, multi-harmonic detection is better than single-harmonic detection and should be used if the system bandwidth is high enough to allow for proper detection of the higher harmonics.