Femtosecond spectroscopy on the photochemistry of ortho-nitrotoluene.

The photo tautomerisations of ortho-nitrotoluene (oNT) and its methylated derivative ortho-ethylnitrobenzene (oENB) have been studied by means of femtosecond spectroscopy and (TD)-DFT computations. In UV/Vis transient absorption spectroscopy a band peaking at 400 nm is seen to rise in a bi-modal manner with time constants of 1-10 ps and 1500 ps. Femtosecond stimulated Raman experiments clearly identify aci-nitro forms as the spectroscopic carriers of the 400 nm band. The assignment of the Raman spectra is based on TD-DFT computations. The quantum yields of the aci-nitro forms after 3 ns are 0.08 (oNT) and 0.3 (oENB). The aci-nitro forms are formed via a singlet channel (1-10 ps) and a triplet channel (1500 ps). There are indications that the triplet channel involves a bi-radical intermediate. In between 3 ns and 1 ms the spectrum of the aci-nitro form shifts from 400 to 390 nm. This could indicate a tautomerisation from Z-aci-nitro to an E form.

The ketene intermediate in the photochemistry of ortho-nitrobenzaldehyde.

The first intermediate of the photochemical transformation of ortho-nitrobenzaldehyde to ortho-nitrosobenzoic acid in acetonitrile solvent has been characterized by femtosecond spectroscopy and time-dependent density functional theory (TDDFT) calculations. Femtosecond stimulated Raman spectroscopy (FSRS) indicates that this intermediate adopts a ketene structure. This assignment is supported by the TDDFT results. A kinetic analysis of FSRS and transient absorption data points to two channels for the formation of the ketene. For the predominating first channel the formation takes 0.4 ps. For the second channel it is much slower and takes 220 ps. We assign the first channel to a reaction via an excited singlet state. The second one might involve a triplet state.

Helminth communities of the barbel Barbus barbus from large river systems in Austria.

The composition and diversity of the total and intestinal component endohelminth communities were determined in the cyprinid barbel from three study areas in two large river systems in Austria. Two sample sites in the Danube and one site in the River Drau are the only free flowing stretches of these rivers in Austria. Nine helminth species were identified, with the acanthocephalan Pomphorhynchus laevis being dominant in the Danube, with up to 100% prevalence. In the Drau, where the dominant species was the cestode Bathybothrium rectangulum, species diversity was higher than in the Danube.

Excited-state dynamics of bacteriorhodopsin probed by broadband femtosecond fluorescence spectroscopy.

The impact of varying excitation densities (approximately 0.3 to approximately 40 photons per molecule) on the ultrafast fluorescence dynamics of bacteriorhodopsin has been studied in a wide spectral range (630-900 nm). For low excitation densities, the fluorescence dynamics can be approximated biexponentially with time constants of <0.15 and approximately 0.45 ps. The spectrum associated with the fastest time constant peaks at 650 nm, while the 0.45 ps component is most prominent at 750 nm. Superimposed on these kinetics is a shift of the fluorescence maximum with time (dynamic Stokes shift). Higher excitation densities alter the time constants and their amplitudes. These changes are assigned to multi-photon absorptions.

Fish macroparasites as indicators of heavy metal pollution in river sites in Austria.

This paper describes two approaches to evaluate the use of fish macroparasites as bioindicators of heavy metal pollution at selected river stretches in Austria. Firstly changes in the diversity and richness of endoparasites of the cyprinid barbel, Barbrus barbuls (L.), were tested in relation to heavy metal contents in the aquatic system. Secondly, the bioaccumulation potential of cadmium, lead and zinc was assessed in the acanthocephalan, Pomphorhynchus laevis (Miller, 1776), and compared with that in the muscle, liver and intestine of its barbel host. The present results indicated that in order to validate the role of parasite community patterns related to heavy metal pollution, more investigations on food web dynamics, interelationships between parasites and the presence/absence of intermediate hosts will be essential. Heavy metal concentrations differed significantly between the organs of barbel and P. laevis (P=0.001) with levels up to 2860 fold in the parasite. The high level of heavy metal accumulation in P. laevis compared with that in its barbel host, suggests that despite variability in the parasite infrapopulation, host mobility and feeding behaviour, P. laevis is a most sensitive indicator of heavy metals in aquatic ecosystems.