Effects of atrazine, agricultural runoff, and selected effluents on antimicrobial activity of skin peptides in Xenopus laevis.

Atrazine (technical and formulation), agricultural runoff containing atrazine, and treated sewage and landfill effluents were evaluated for their potential to modulate antimicrobial activity of Xenopus laevis skin secretions against the chytrid fungus, Batrachochytrium dendrobatidis. This chytrid fungus is implicated in several localized mass mortality events, yet the cause of the susceptibility of amphibians to this newly emergent pathogen is unknown. Antimicrobial peptides secreted from dermal glands are thought to provide critical protection against this pathogen. Chronic exposure of X. laevis larvae to agricultural runoff decreased protein content of collected secretions, while treated wastewater effluents increased protein content. However, the in vitro bioactivity was decreased in treatments with both increased and decreased protein. No differences were observed in protein or bioactivity following laboratory exposures of technical atrazine or a typical atrazine formulation (AAtrex(®) 4L/Top Surf(®)). These findings demonstrate that exposure of an amphibian model to agricultural runoff or effluent from municipal sewage treatment plants and landfills alters peptide production and in vitro activity of protective peptides. Although evidence suggests peptide production and bioactivity is a critical part of amphibian resistance to pathogens such as the chytrid fungus, the implications of observed effects for immunity and infection are not clear.

A study of electronic effects on the kinetics of thermal deamination of N-nitrosoamides.

N-4-R-Benzyl-N-nitrosopivalamides (1a-d; R = MeO, Me, H, NO(2)) were allowed to decompose at 18 degrees C in C(6)D(12), CDCl(3), CD(3)CN, and d(6)-DMSO, and the rates of decomposition were followed by (1)H NMR spectroscopy. The half-lives of the nitrosoamides were found to vary in a systematic way with the nature of the R group on the aromatic nucleus. Electron-releasing groups were found to decrease the stability of the starting nitrosoamide, whereas electron-withdrawing ones increased the nitrosoamides' thermal stability. A Hammett-type plot of log(rate constants of deamination) vs sigma(p) was linear (R(2) = 0.986) with a rho-type value of -0.90 indicating development of significant positive charge at the benzylic position in the transition state of the rate-determining step. The thermal stability of the nitrosoamides was also found to be systematically affected by the polarity of the solvent: as the solvent polarity increased, so did the lability of the nitrosoamides. This observation of intra- and intermolecular electronic perturbations of the kinetics of nitrosoamide decomposition appears to be novel. A closer look at the rate-determining step of nitrosoamide thermolysis is made, and a mechanistic framework is proposed that accounts for both steric and electronic modulation of nitrosoamide stability as well as the greater thermal stabilities of the related N-nitrocarboxamides and N-nitrosotosylamides.

Boundary conditions on the partitioning of deaminatively generated benzyl cations.

Nitrogenous entity-separated ion pairs (NESIPs) containing benzyl cations, nitrogen gas, and pivalate anions were generated via thermal deamination of N-benzyl-N-nitrosopivalamide. Some decompositions were performed in methanolic solutions saturated with selected nucleophiles: acetate, azide, or cyanide ions. Trace amounts of benzyl cyanide and tolunitriles were observed; no corresponding products were detected in the acetate and azide cases. Other decompositions were performed in the absence of traditional solvent but in the presence of the nucleophilic salts; again only poor cyanide interception of the cation was observed. The poor showing of the nucleophilic ions, when present, is discussed in the context of the lifetime of the cation, effective nucleophilicity, and cage effects in deamination.