Radical and anionic response of N-(Bromomethanesulfonyl)-substituted alpha,alpha'-bridged piperidine substrates

The N-(bromomethanesulfonyl) azabicyclic ketones 2a-c and their exo-methylene analogues 1a-c were prepared. Our examination of the radical-induced behavior of the latter triad provided experimental evidence for the propensity of the b and c systems to engage in 7-endo cyclization. For 1a, only reductive debromination was observed. In no instance was ring closure by the 6-exo radical mode seen. As concerns ketones 2a-c, all three showed a remarkable facility for engaging in intramolecular S(N)2 displacement in the presence of KHMDS. Yields at the mid-80% level were realized irrespective of the value of n. Molecular mechanics calculations of the Monte Carlo type were performed on several conformational isomers and product classes in an effort to provide support for the explanatory conclusions offered as rationale for the collective experimental observations.     

Simulation of ozone depletion using ambient irradiance supplemented with UV lamps

In studies of the biological effects of UV radiation, ozone depletion can be mimicked by performing the study under ambient conditions and adding radiation with UV-B lamps. We evaluated this methodology at three different locations along a latitudinal gradient: Rimouski (Canada), Ubatuba (Brazil) and Ushuaia (Argentina). Experiments of the effect of potential ozone depletion on marine ecosystems were carried out in large outdoor enclosures (mesocosms). In all locations we simulated irradiances corresponding to 60% ozone depletion, which may produce a 130-1900% increase in 305 nm irradiance at noon, depending on site and season. Supplementation with a fixed percentage of ambient irradiance provides a better simulation of irradiance increase due to ozone depletion than supplementation with a fixed irradiance value, particularly near sunrise and sunset or under cloudy skies. Calculations performed for Ushuaia showed that, on very cloudy days, supplementation by the square-wave method may produce unrealistic irradiances. Differences between the spectra of the calculated supplementing irradiance and the lamp for a given site and date will be a function of the time of day and may become more or less pronounced according to the biological weighting function of the effect under study.     

UV effects on marine planktonic food webs: A synthesis of results from mesocosm studies

UV irradiance has a broad range of effects on marine planktonic organisms. Direct and indirect effects on individual organisms have complex impacts on food-web structure and dynamics, with implications for carbon and nutrient cycling. Mesocosm experiments are well suited for the study of such complex interrelationships. Mesocosms offer the possibility to conduct well-controlled experiments with intact planktonic communities in physical, chemical and light conditions mimicking those of the natural environment. In allowing the manipulation of UV intensities and light spectral composition, the experimental mesocosm approach has proven to be especially useful in assessing the impacts at the community level. This review of mesocosm studies shows that, although a UV increase even well above natural intensities often has subtle effects on bulk biomass (carbon and chlorophyll), it can significantly impact the food-web structure because of different sensitivity to UV among planktonic organisms. Given the complexity of UV impacts, as evidenced by results of mesocosm studies, interactions between UV and changing environmental conditions (e.g. eutrophication and climate change) are likely to have significant effects on the function of marine ecosystems.     

Vertical mixing and ecological effects of ultraviolet radiation in planktonic communities

We present a mathematical model for a phytoplankton-zooplankton system, based on a predator-prey scheme. The model considers the effects of sinking in the phytoplankton, vertical mixing and attenuation of photosynthetically active radiation (PAR) and ultraviolet radiation (UVR) in the water column. In a first approach, the model was studied under conditions of average PAR irradiance and shows fluctuations and stable equilibrium points. Secondly, we introduced the effects of photoperiod and photoinhibition by UVR and vertical mixing. Under these conditions, the phytoplankton biomass oscillates depending on the combined effects of UVR and mixing. Higher inhibition by UVR and longer mixing periods can induce strong fluctuations in the system but can also produce higher plankton peaks.