Electric Field Effects on Internal Conversion: An Alternative Mechanism for Field-Induced Fluorescence Quenching of MEH-PPV and Its Oligomers in the Low Concentration Limit

In a previously published study (J. Phys. Chem. B 2006, 110, 7732−7742), we reported field-induced fluorescence quenching in both poly[2-methoxy,5-(2‘-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and several model oligomers in solvent glass matrices at high dilution (<0.1% by weight). The observed quenching is not readily explained by field-induced exciton dissociation or by the presence of free charges, two mechanisms that have been invoked to explain this phenomenon by previous authors. A model is developed here that ascribes the observed fluorescence quench in dilute samples to an energetic shift of the relaxed excited state caused by the electric field resulting in increased nonradiative relaxation. To determine whether the relevant nonradiative pathway is intersystem crossing or internal conversion, analytical expressions are derived for each of these two mechanisms. Only the expression derived for the Stark effect on the rate of internal conversion quantitatively predicts the magnitude of quench observed in MEH-PPV and in the oligomeric species

Effects of Spatial Scale on Life Cycle Inventory Results

Efforts to compile life cycle inventory (LCI) data at more geographically refined scales or resolutions are growing. However, it remains poorly understood as to how the choice of spatial scale may affect LCI results. Here, we examine this question using U.S. corn as a case study. We compile corn production data at two spatial scales, state and county, and compare how their LCI results may differ for state and national level analyses. For greenhouse gas (GHG) emissions, estimates at the two scales are similar (<20% of difference) for most state-level analyses and are basically the same (<5%) for national level analysis. For blue water consumption, estimates at the two scales differ more. Our results suggest that state-level analyses may be an adequate spatial scale for national level GHG analysis and for most state-level GHG analyses of U.S. corn, but may fall short for water consumption, because of its large spatial variability. On the other hand, although county-based LCIs may be considered more accurate, they require substantially more effort to compile. Overall, our study suggests that the goal of a study, data requirements, and spatial variability are important factors to consider when deciding the appropriate spatial scale or pursuing more refined scales

Effects of Spatial Scale on Life Cycle Inventory Results

Efforts to compile life cycle inventory (LCI) data at more geographically refined scales or resolutions are growing. However, it remains poorly understood as to how the choice of spatial scale may affect LCI results. Here, we examine this question using U.S. corn as a case study. We compile corn production data at two spatial scales, state and county, and compare how their LCI results may differ for state and national level analyses. For greenhouse gas (GHG) emissions, estimates at the two scales are similar (<20% of difference) for most state-level analyses and are basically the same (<5%) for national level analysis. For blue water consumption, estimates at the two scales differ more. Our results suggest that state-level analyses may be an adequate spatial scale for national level GHG analysis and for most state-level GHG analyses of U.S. corn, but may fall short for water consumption, because of its large spatial variability. On the other hand, although county-based LCIs may be considered more accurate, they require substantially more effort to compile. Overall, our study suggests that the goal of a study, data requirements, and spatial variability are important factors to consider when deciding the appropriate spatial scale or pursuing more refined scales

Optimizing Eco-Efficiency Across the Procurement Portfolio

Manufacturing organizations’ environmental impacts are often attributable to processes in the firm’s upstream supply chain. Environmentally preferable procurement (EPP) and the establishment of environmental purchasing criteria can potentially reduce these indirect impacts. Life-cycle assessment (LCA) can help identify the purchasing criteria that are most effective in reducing environmental impacts. However, the high costs of LCA and the problems associated with the comparability of results have limited efforts to integrate procurement performance with quantitative organizational environmental performance targets. Moreover, environmental purchasing criteria, when implemented, are often established on a product-by-product basis without consideration of other products in the procurement portfolio. We develop an approach that utilizes streamlined LCA methods, together with linear programming, to determine optimal portfolios of product impact-reduction opportunities under budget constraints. The approach is illustrated through a simulated breakfast cereal manufacturing firm procuring grain, containerboard boxes, plastic packaging, electricity, and industrial cleaning solutions. Results suggest that extending EPP decisions and resources to the portfolio level, recently made feasible through the methods illustrated herein, can provide substantially greater CO₂e and water-depletion reductions per dollar spend than a product-by-product approach, creating opportunities for procurement organizations to participate in firm-wide environmental impact reduction targets

High-Resolution Environmentally Extended Input–Output Model to Assess the Greenhouse Gas Impact of Electronics in South Korea

South Korea is a global leader in electronics, but little is known about their climate change impact. Here, we estimate the direct and indirect greenhouse gas (GHG) emissions of Korean electronics by developing a new and high-resolution (∼380 sectors) environmentally extended input–output model, named KREEIO. We find that final demand for Korean electronics led to nearly 8% of national GHG emissions in 2017, mostly because of indirect emissions embodied in the electronics supply chain. Notably, the semiconductor and display sectors contributed 3.2% and 2.4% to national emissions, with capital investment accounting for 17% of the two sectors’ total emissions or nearly 1% of national emissions. For other electronic products, scope 1, scope 2, and upstream scope 3 emissions on average accounted for 3%, 10%, and 87% of a sector’s GHG intensity, respectively. Detailed contribution analysis suggests that reducing Korean electronics GHG emissions would benefit most from the transition to a low-carbon electricity grid, but mitigation efforts in many other sectors such as metals and chemicals are also important. Overall, our study underscores the significance of electronics GHG emissions in South Korea, especially those from semiconductors and displays, and the mitigation challenges these sectors face as demand continue to grow globally

Stereoselective Umpolung Tandem Addition of Heteroatoms to Phenol

Stereoselective Umpolung Tandem Addition of Heteroatoms to Pheno

Stereoselective Umpolung Tandem Addition of Heteroatoms to Phenol

Stereoselective Umpolung Tandem Addition of Heteroatoms to Pheno

Stereoselective Umpolung Tandem Addition of Heteroatoms to Phenol

Stereoselective Umpolung Tandem Addition of Heteroatoms to Pheno

Chain Length and Substituent Effects on the Formation of Excimer-Like States in Nanoaggregates of CN-PPV Model Oligomers

The effects of aggregate formation on the photophysical properties of alkoxy and cyano-substituted polyphenylene phenylene vinylene oligomers (CN-PPVs) were studied in bulk solution to better understand the consequences of aggregation for the emission properties of the polymer. Nanoaggregates of oligomers from 5 to 13 repeat units in length were formed using a solvent reprecipitation method. The propensity for these aggregates to exhibit excimer-like emission in solution was found to be a strong function of oligomer chain length and the solvents used in the reprecipitation process. Short-chain oligomers produced nanoaggregates with absorption and fluorescence spectra and emission lifetimes essentially identical to those of the monomer. The aggregates of long-chain oligomers have broad and red-shifted emission spectra and relatively long emission lifetimes, both of which are characteristic of excimer states. However their absorption spectra are also perturbed suggesting that the oligomer chains in these aggregates interact strongly in their electronic ground states as well. For intermediate chain lengths, dual monomer-like (green) and excimer-like (red) emission is observed. Single aggregate dispersed emission spectra from aggregates deposited onto glass coverslips demonstrate that, in the absence of solvent, the predominant emitters are monomer-like rather than excimer-like. Moreover, the monomer-like emitters are found to be far more photostable than the analogous non-CN substituted aggregates, whereas the photostability of the excimer-like emitters is exceptionally poor under the illumination conditions used for microscopy. Comparisons between the properties of these nanoaggregates and the corresponding CN-substituted polymer are drawn