Engineering topics

MacKenzie, Ian A.

Publications and source records attributed to MacKenzie, Ian A..

3 records

DOE OSTI2020

Discovery and characterization of an acridine radical photoreductant

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2017

Future Global Mortality from Changes in Air Pollution Attributable to Climate Change

Ground-level ozone and fine particulate matter (PM (sub 2.5)) are associated with premature human mortality; their future concentrations depend on changes in emissions, which dominate the near-term, and on climate change. Previous global studies of the air-quality-related health effects of future climate change used single atmospheric models. However, in related studies, mortality results differ among models. Here we use an ensemble of global chemistry-climate models to show that premature mortality from changes in air pollution attributable to climate change, under the high greenhouse gas scenario RCP (Representative Concentration Pathway) 8.5, is probably positive. We estimate 3,340 (30,300 to 47,100) ozone-related deaths in 2030, relative to 2000 climate, and 43,600 (195,000 to 237,000) in 2100 (14 percent of the increase in global ozone-related mortality). For PM (sub 2.5), we estimate 55,600 (34,300 to 164,000) deaths in 2030 and 215,000 (76,100 to 595,000) in 2100 (countering by 16 percent the global decrease in PM (sub 2.5)-related mortality). Premature mortality attributable to climate change is estimated to be positive in all regions except Africa, and is greatest in India and East Asia. Most individual models yield increased mortality from climate change, but some yield decreases, suggesting caution in interpreting results from a single model. Climate change mitigation is likely to reduce air-pollution-related mortality.

Atmohspheric chemistry↗

NASA NTRS2012

The Influence of Ozone Precursor Emissions from Four World Regions on Tropospheric Composition and Radiative Climate Forcing

Ozone (O3) precursor emissions influence regional and global climate and air quality through changes in tropospheric O3 and oxidants, which also influence methane (CH4) and sulfate aerosols (SO4 (sup 2-)). We examine changes in the tropospheric composition of O3, CH4, SO4 (sup 2-) and global net radiative forcing (RF) for 20% reductions in global CH4 burden and in anthropogenic O3 precursor emissions (NOx, NMVOC, and CO) from four regions (East Asia, Europe and Northern Africa, North America, and South Asia) using the Task Force on Hemispheric Transport of Air Pollution Source-Receptor global chemical transport model (CTM) simulations, assessing uncertainty (mean plus or minus 1 standard deviation) across multiple CTMs. We evaluate steady state O3 responses, including long-term feedbacks via CH4. With a radiative transfer model that includes greenhouse gases and the aerosol direct effect, we find that regional NOx reductions produce global, annually averaged positive net RFs (0.2 plus or minus 0.6 to 1.7 2 mWm(sup -2)/Tg N yr(sup -1), with some variation among models. Negative net RFs result from reductions in global CH4 (-162.6 plus or minus 2 mWm(sup -2) for a change from 1760 to 1408 ppbv CH4) and regional NMVOC (-0.4 plus or minus 0.2 to 0.7 plus or minus 0.2 mWm(sup -2)/Tg C yr(sup -1) and CO emissions (-0.13 plus or minus 0.02 to -0.15 plus or minus 0.02 mWm(sup-2)/Tg CO yr(sup-1). Including the effect of O3 on CO2 uptake by vegetation likely makes these net RFs more negative by -1.9 to- 5.2 mWm(sup -2)/Tg N yr(sup -1), -0.2 to -0.7 mWm(sup -2)/Tg C yr(sup -1), and -0.02 to -0.05 mWm(sup -2)/ Tg CO yr(sup -1). Net RF impacts reflect the distribution of concentration changes, where RF is affected locally by changes in SO4 (sup -2), regionally to hemispherically by O3, and globally by CH4. Global annual average SO4 2 responses to oxidant changes range from 0.4 plus or minus 2.6 to -1.9 plus or minus 1.3 Gg for NOx reductions, 0.1 plus or minus 1.2 to -0.9 plus or minus 0.8 Gg for NMVOC reductions, and -0.09 plus or minus 0.5 to -0.9 plus or minus 0.8 Gg for CO reductions, suggesting additional research is needed. The 100-year global warming potentials (GWP(sub 100)) are calculated for the global CH4 reduction (20.9 plus or minus 3.7 without stratospheric O3 or water vapor, 24.2 plus or minus 4.2 including those components), and for the regional NOx, NMVOC, and CO reductions (18.7 plus or minus 25.9 to 1.9 plus or minus 8.7 for NOx, 4.8 plus or minus 1.7 to 8.3 plus or minus 1.9 for NMVOC, and 1.5 plus or minus 0.4 to 1.7 plus or minus 0.5 for CO). Variation in GWP(sub 100) for NOx, NMVOC, and CO suggests that regionally specific GWPs may be necessary and could support the inclusion of O3 precursors in future policies that address air quality and climate change simultaneously. Both global net RF and GWP100 are more sensitive to NOx and NMVOC reductions from South Asia than the other three regions.

ozone↗