Biomedical subjects

R Weinkauf

Publications and source records attributed to R Weinkauf.

5 recordsLinked to original sources

PubMed2001

Ethnic variation in the skin irritation response.

There is a widespread, but largely unsubstantiated, view that certain skin types may be more susceptible to the effect of skin irritants than others. One expression of this would be that certain ethnic groups may also be more likely to experience skin irritation. As a consequence, when evaluating the skin compatibility of substances/preparations, these differences may need to be taken into account. However, other evidence indicates that, within any particular group, inter-individual variation is likely to be much larger than the differences between means for distinct groups. In this study, we have investigated 2 carefully matched panels of Caucasian and Japanese women volunteers to determine their topical irritant reaction, both acute and cumulative, to a range of materials. The results indicated that the acute irritant response tended to be greater in the Japanese panel and this reached statistical significance with the stronger irritants. Cumulative irritation was investigated only with the weaker irritants and, although again the trend was to a higher response in Japanese compared to Caucasian panelists, this rarely reached significance. Nevertheless, where risk assessment for skin irritation was critical, then at the population level, these differences might be relevant, both for safety in use of substances and products and for skin acceptability.

Adult↗

PubMed2000

Investigation of charge localization and charge delocalization in model molecules by multiphoton ionization photoelectron spectroscopy and DFT calculations.

In this work we focus on the question to which degree a surplus charge is localized or delocalized in extended molecular systems. Molecules consisting of a flexible tail and the benzene chromophore, such as n-propylbenzene, 2-phenylethyl alcohol and 2-phenylethylamine, are used as model molecules. Their S0-S1 resonance enhanced multiphoton ionization (MPI) spectra containing origin transitions of different conformers appear at similar wavelengths. This shows, that in the neutral the electronic excitation is localized at the benzene chromophore. Geometry differences between the neutral and the cation can be qualitatively derived from intensities of vibrational transitions or the onset behavior in MPI high-resolution photoelectron (MPI-PE) spectra. We identify two possible reasons for structural changes: Charge-dipole interaction and charge delocalization. Whereas both effects can be active for the folded gauche conformers, the charge-dipole interaction is expected to be small for the extended anti conformers and geometry changes are attributed to charge delocalization. Density functional calculations of structures and energies qualitatively confirm the experimental results for all molecules and their conformers. They predict charge delocalization into the end group of below 20% for n-propylbenzene and 2-phenylethyl alcohol. In the case of 2-phenylethylamine the charge is equally shared by the near-isoenergetic charge sites of the benzene chromophore and the amine group.

Benzene Derivatives↗

PubMed1999

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.

Journal Article↗

PubMed1998

Dynamical principles in biological processes.

The purpose of this paper is to propose certain dynamical principles in biological systems, which can be used to explain the effectiveness of charge transfer or excitation transfer in biological systems. Some of these systems are accessible experimentally.

Electron Transport↗

PubMed1997

Energetics of photoinduced electron transfer in the indole.O2 cluster in gas phase: possible consequences for photoexcited tryptophan in solution.

A direct process for an activationless electron transfer from photoexcited tryptophan to molecular oxygen is proposed. By photodetachment of mass-selected indole+.O2- clusters in gas phase a neutral indole+.O2- charge-separated exciplex state is found at 2.25 +/- 0.2 eV above the neutral ground state. By theory also, the existence of an excited charge separated state at 3.05 +/- 0.2 eV is postulated. In gas phase both charge-separated cluster states are energetically below the first singlet states 1Lb and 1La and the lower even below the first triplet state T1 of indole. In gas-phase clusters these energetics imply a very efficient quenching of photoexcited indole by fast electron transfer to oxygen. We discuss a similar mechanism for tryptophan.O2 in aqueous environment and find it without activation barrier and presumably extremely fast. In the collisional tryptophan*-O2 complex the efficiency and the time scale of the charge transfer process should be mostly solvent independent. In polar solvent a complete charge separation and free superoxide formation are expected. We correlate this model with previous fluorescence and phosphorescence quenching data of excited tryptophan by O2 and propose electron transfer to be the relevant process.

Electron Transport↗