RESUMO
A series of model oligomers consisting of combinations of a traditional strong donor unit (3,4-ethylenedioxythiophene), a traditional strong acceptor unit (benzo[c][1,2,5]thiadiazole), and the ambipolar unit thieno[3,4-b]pyrazine were synthesized via cross-coupling methods. The prepared oligomers include all six possible dimeric combinations in order to characterize the extent and nature of donor-acceptor effects commonly used in the design of conjugated materials, with particular focus on understanding how the inclusion of ambipolar units influences donor-acceptor frameworks. The full oligomeric series was thoroughly investigated via photophysical and electrochemical studies, in parallel with density functional theory (DFT) calculations, in order to correlate the nature and extent of donor-acceptor effects on both frontier orbital energies and the desired narrowing of the HOMO-LUMO energy gap. The corresponding relationships revealed should then provide a deeper understanding of donor-acceptor interactions and their application to conjugated materials.
RESUMO
Urban ozone (O3) pollution is influenced by the transport of wildfire smoke but observed impacts are highly variable. We investigate O3 impacts from smoke in 18 western US cities during July-September, 2013-2017, with ground-based monitoring data from air quality system sites, using satellite-based hazard mapping system (HMS) fire and smoke product to identify overhead smoke. We present four key findings. First, O3 and PM2.5 (particulate matter <2.5 µm in diameter) are elevated at nearly all sites on days influenced by smoke, with the greatest mean enhancement occurring during multiday smoke events; nitrogen oxides (NOx) are not consistently elevated across all sites. Second, PM2.5 and O3 exhibit a nonlinear relationship such that O3 increases with PM2.5 at low to moderate 24 h PM2.5, peaks around 30-50 µg m-3, and declines at higher PM2.5. Third, the rate of increase of morning O3 is higher and NO/NO2 ratios are lower on smoke-influenced days, which could result from additional atmospheric oxidants in smoke. Fourth, while the HMS product is a useful tool for identifying smoke, O3 and PM2.5 are elevated on days before and after HMS-identified smoke events implying that a significant fraction of smoke events is not detected.