Probing carbonyl-water hydrogen-bond interactions in thin polyoxazoline brushes.

Temperature-responsive oxazoline-based polymer brushes have gained increased attention as biocompatible surfaces. In aqueous environment, they can be tuned between hydrophilic and hydrophobic behavior triggered by a temperature stimulus. This transition is connected with changes in molecule-solvent interactions and results in a switching of the brushes between swollen and collapsed states. This work studies the temperature-dependent interactions between poly(2-oxazoline) brushes and water. In detail, thermoresponsive poly(2-cyclopropyl-2-oxazoline), nonresponsive hydrophilic poly(2-methyl-2-oxazoline), as well as a copolymer of the two were investigated with in situ infrared ellipsometry. Focus was put on interactions of the brushes' carbonyl groups with water molecules. Different polymer-water interactions could be observed and assigned to hydrogen bonding between C=O groups and water molecules. The switching behavior of the brushes in the range of 20-45 °C was identified by frequency shifts and intensity changes of the amide I band.

Biomarkers as diagnostic tools for evaluating effects of unknown past water quality conditions on stream organisms.

The following biomarkers were investigated in stream populations of juvenile brown trout (Salmo trutta f. fario) and gammarids (Gammarus pulex) to determine if crayfish mortality could have been confounded by pollutants: (1) alterations of fish liver ultrastructure, (2) fish gill and kidney histopathology, (3) stress protein (hsp70) expression in fish liver and gills and in gammarids, and (4) changes in various blood parameters of brown trout. In addition, the following measurements were conducted in parallel with the biological sampling: (a) chemical analyses including several pesticides, organochlorines, PCBs, and PAHs in sediment and tissue samples of brown trout and crayfish (Astacus astacus), and (b) limnochemical analyses of nutrients, electrolytes, dissolved oxygen content, temperature and pH. Biomarkers together with chemical and limnochemical analyses concomitantly indicated moderate pollution of the stream at all sampling sites. Biological data indicated a transient, episodic event at one sampling site resulting (a) in altered stress protein levels in gills and livers of trout and in whole gammarids as well as (b) in elevated numbers of macrophages in liver tissue. Biomarker responses provided spatial and temporal evidence that a contaminant release was associated with the crayfish mortalities observed in this stream system.