MacMillan Ahmed (hoseviolin3)
The exposure order may strongly affect the impact of stressors, yet is largely ignored for the frequently occurring combinations of toxicants with natural stressors. We tested how exposure order shaped the interactive effects of serial exposure to the pesticide chlorpyrifos and to a heat spike in the larvae of the mosquito Culex pipiens. Notably, the chlorpyrifos-induced mortality was much more magnified by the heat spike and a synergism was already detected at the low concentration when exposure to chlorpyrifos followed the heat spike. This suggests that the preceding heat spike weakened the larvae as reflected in their lower net energy budget, moreover the chlorpyrifos-induced inhibition of its target enzyme (acetylcholinesterase) was only magnified by the heat spike when it was the first stressor. Also the chlorpyrifos-induced reduction in heat tolerance was stronger when the pesticide pulse followed the heat spike, and was buffered by the heat spike when this was the second stressor. Our results provide the first evidence that the exposure order can strongly change the magnifying effect of an important climate change factor on the toxicity of a pesticide. This highlights the importance of exposure order in ecological risk assessment of toxicants under realistic combinations with natural stressors."Smart" biomaterials that are responsive to physiological or biochemical stimuli have found many biomedical applications for tissue engineering, therapeutics, and molecular imaging. In this work, we describe in situ polymerization of activatable biorthogonal small molecules in response to a reducing environment change in vivo. We designed a carbohydrate linker- and cyanobenzothiazole-cysteine condensation reaction-based small molecule scaffold that can undergo rapid condensation reaction upon physiochemical changes (such as a reducing environment) to form polymers (pseudopolysaccharide). The fluorescent and photoacoustic properties of a fluorophore-tagged condensation scaffold before and after the transformation have been examined with a dual-modality optical imaging method. These results confirmed the in situ polymerization of this probe after both local and systemic administration in living mice.We report a DNA-compatible protocol for synthesizing amides from DNA-bound aldehydes and non-nucleophilic arylamines including aza-substituted anilines, 2-aminobenzimidazoles, and 3-aminopyrazoles. The reactions were carried out at room temperature and provided reasonable conversions and wide functional group compatibility. The reactions were also successful when employing aryl and aliphatic aldehydes. KN-62 In addition, qPCR and NGS data suggested no negative impact on DNA integrity after the copper-mediated oxidative amidation reaction.Here, we investigated the photoreduction of Hg(II) (Hg(NO3)2) mediated by dissolved black carbon (DBC, less then 0.45 μm size fraction) collected from water extracts of biochar derived by pyrolyzing crop residues (rice, soybean, and peanut). Under simulated sunlight conditions, the presence of 5 mg C/L DBC significantly facilitated the production of Hg(0) from Hg(II) (initially at 10 nmol/L) with a reduction ratio of 73 ± 4% in 5.3 h. Inhibition of photolysis-induced reactive oxygen species by a quencher or removal of dissolved oxygen indicated that Hg(II) was mainly reduced by superoxide anion (O2•-). Reduction by electrons transferred from photoexcited DBC components or by organic free radicals produced from photo-Fenton-like reactions was also proposed to play a role. Contrary to dissolved humic substances, the DBC-mediated photoreduction of Hg(II) led to unique positive mass-independent isotopic fractionation (MIF) of Hg(0) (Δ199Hg = 1.8 ± 0.3‰), which was attributed to the dominance of secondary Hg(II) reduction by O2•-. The leachate from soil amended with rice biochar at 1-5% mass ratios exhibited significantly higher photocatalytic efficiency than that from unamended soil (wherein the reduced