Abiotic reductive deiodination of iodinated organic compounds and X-ray contrast media catalyzed by free corrinoids.

Iodinated X-ray contrast media are known for their stability concerning deiodination in the aquatic environment under aerobic conditions. In this study, we demonstrate the abiotic reductive deiodination of the iodinated contrast media iopromide, iopamidol and diatrizoate in the presence of corrinoids. In addition, triiodinated benzoic acid derivatives with iodine atoms bound at different positions were investigated. Corrinoids like cyanocobalamin (vitamin B12) and dicyanocobinamide served as electron shuttles and as catalysts between the reducing agent (e.g., titanium (III) citrate) and the electron accepting iodinated compound. The concentration decrease of the iodinated compounds followed first-order kinetics with rate constant kobs depending on the iodinated compound. A linear correlation between the rate of iodide release and the corrinoid concentration was observed, with deiodination rates for dicyanocobinamide twice as high as for vitamin B12. Reducing agents with a less negative standard redox potential like dithiothreitol or cysteine caused slower deiodination as the cobalt center was only reduced to its CoII oxidation state. With a temperature increase from 11 to 23 °C, the concentrations of released iodide doubled. A complete deiodination was only observed for the iodinated contrast media but not for structurally similar iodinated benzoic acid derivatives.

Toxicity of hydroquinone to different freshwater phototrophs is influenced by time of exposure and pH.

The interaction of natural organic matter with phytoplankton communities in freshwater ecosystems is an intensively studied subject matter. Previous studies showed that apparently plant-derived phenols were able to inhibit algal and cyanobacterial growth. Furthermore, it was also assumed that humic substances (HS), which comprise the major part of dissolved organic carbon in freshwater ecosystems, directly interact with freshwater phototrophs. For example, quinoid building blocks of HS were thought to be algicidal. To identify key environmental variable for the toxic action of potential quinone algicides, we tested the toxicity of hydroquinone (HQ) to different eukaryotic and prokaryotic freshwater phototrophs in terms of growth performance and investigated also the effect of HQ oxidation at different pH values on its algicidal potential. It was shown that cyanobacterial species were much more susceptible to hydroquinone than coccal green algal species were, with Microcystis aeruginosa being the most sensitive species by far. In addition, it was obvious that the aging of hydroquinone-stock solution at pH 11 led to polymerization and, by this process, to a total loss of toxicity; whereas the algicidal potential sustained if the polyphenol was kept at pH 7. Since most lakes with heavy blooms of phototrophs possess pH values clearly above 7.0, it is questionable, if polyphenols in general and quinones in particular are the effective chemicals and if litter and straw leachates are applied as means to combat algal and cyanobacterial blooms.

Enrichment of humic material with hydroxybenzene moieties intensifies its physiological effects on the nematode Caenorhabditis elegans.

Dissolved humic substances are taken up by organisms and interact on various molecular and biochemical levels. In the nematode Caenorhabditis elegans, such material can promote longevity and increase its reproductive capacity; moreover, the worms tend to stay for longer in humic-enriched environments. Here, we tested the hypothesis that the chemical enrichment of humic substances with hydroxybenzene moieties intensifies these physiological effects. Based on the leonardite humic acid HuminFeed (HF), we followed a polycondensation reaction in which this natural humic substance and a dihydroxybenzene (hydroquinone or benzoquinone) served as reaction partners. Several analytical methods showed the formation of the corresponding copolymers. The chemical modification boosted the antioxidant properties of HF both in vitro and in vivo. Humic substances enriched with hydroxybenzene moieties caused a significantly increased tolerance to thermal stress in C. elegans and extended its lifespan. Exposed nematodes showed delayed linear growth and onset of reproduction and a stronger pumping activity of the pharynx. Thus, treated nematodes act younger than they really are. In this feature the modified HF replicated the biological impact of hydroquinone-homopolymers and various plant polyphenol monomers, thereby supporting the hydroxybenzene moieties of humic substances as major effective structures for the physiological effects observed in C. elegans.

Treatment of pharmaceuticals and diagnostic agents using zero-valent iron--kinetic studies and assessment of transformation products assay.

This research examined whether treatment with zero-valent iron in the presence of oxygen is a suitable process for the degradation of pharmaceuticals (antibiotics, cytostatic drugs) and diagnostic agents. It was shown that the concentration of all selected compounds was decreased efficiently by treatment with iron. The compounds exhibited a pseudo-first-order decay with a linear dependence on ln(c/c(0)) on time. The observed reaction rate strongly depended on pH, the amount of added iron, and the stirring speed. The influence of temperature on the reaction rate was small. Comparison of detected transformation products with those obtained after catalytic hydrogenation and treatment with Fenton's reagent revealed that reductive and oxidative processes are responsible for the transformations observed.