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Results for “disproportionation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Suppressing phase disproportionation in quasi-2D perovskite light-emitting diodes

Electroluminescence efficiencies and stabilities of quasi-two-dimensional halide perovskites are restricted by the formation of multiple-quantum-well structures with broad and uncontrollable phase distributions. Here, we report a ligand design strategy to substantially suppress diffusion-limited phase disproportionation, thereby enabling better phase control. We demonstrate that extending the π-conjugation length and increasing the cross-sectional area of the ligand enables perovskite thin films with dramatically suppressed ion transport, narrowed phase distributions, reduced defect densities, and enhanced radiative recombination efficiencies. Consequently, we achieved efficient and stable deep-red light-emitting diodes with a peak external quantum efficiency of 26.3% (average 22.9% among 70 devices and cross-checked) and a half-life of ~220 and 2.8 h under a constant current density of 0.1 and 12 mA/cm 2 , respectively. Our devices also exhibit wide wavelength tunability and improved spectral and phase stability compared with existing perovskite light-emitting diodes. These discoveries provide critical insights into the molecular design and crystallization kinetics of low-dimensional perovskite semiconductors for light-emitting devices.

14 SOLAR ENERGY↗
DOE OSTI2021

Disproportionate control on aerosol burden by light rain

Atmospheric aerosols are of great climatic and environmental importance due to their effects on the Earth’s radiative energy balance and air quality. Aerosol concentrations are strongly influenced by rainfall via wet removal. Global climate models have been used to quantify their climate and health effects. However, they commonly suffer from a well-known problem of ‘too much light rain and too little heavy rain’. The impact of simulated rainfall intensities on aerosol burden at the global scale is still unclear. In this study, we show that rainfall intensity has profound impacts on aerosol burden, and light rain has a disproportionate control on it. By improving the representation of convection, the light-rain (1–20 mm d –1 ) frequency in two state-of-the-art global climate models is reduced. As a result, the aerosol burden is increased globally, especially over the tropics and subtropics, by as much as 0.3 in aerosol optical depth in tropical rain belts. It is attributed to the dominant contribution of light rain to the accumulated wet removal by its frequent occurrence despite its weak intensity. The implication of these findings is that understanding the nature of aerosol scavenging by rainfall is critical to aerosol–climate interaction and its impact on climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

The disproportionate impact of enhanced evaporation from melting arctic sea ice on cold-season land precipitation trends

Diminishing Arctic sea ice has led to enhanced evaporation from the Arctic marginal seas (AMS), which is expected to alter precipitation over land. In this work, AMS evaporation is numerically tracked to quantify its contribution to cold-season (October–March) precipitation over land in the Northern Hemisphere during 1980–2021. Results show a significant 32% increase in AMS moisture contribution to land precipitation, corresponding to a 16% increase per million square km loss of sea ice area. Especially over the high-latitude land, despite the fractional contribution of AMS to precipitation being relatively low (8%), the augmented AMS evaporation contributed disproportionately (42%) to the observed upward trend in precipitation. Notably, northern East Siberia exhibited a substantial rise in both the amount and fraction of extreme snowfall sourced from the AMS. Our findings underscore the importance of the progressively ice-free Arctic as an important contributor to the escalating levels of cold-season precipitation and snowfall over northern high-latitude land.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Charge disproportionation in the spin-liquid candidate κ – ( ET ) 2 Cu 2 ( CN ) 3 at 6 K revealed by Cu 63 NQR measurements

The spin-liquid candidate κ – ( ET ) 2 Cu 2 ( CN ) 3 [ET: bis(ethylenedithio)tetrathiafulvalene] does not exhibit magnetic ordering down to a very low temperature, but shows a mysterious anomaly at 6 K. The origin of the so-called 6-K anomaly is still under debate. We carried out nuclear quadrupole resonance (NQR) measurements on the copper sites of the insulating layers, which are sensitive to the charge dynamics unlike conventional spin- 1 / 2 nuclear magnetic resonance (NMR). The main finding of this Rapid Communication is that the observation of a sharp peak behavior in the nuclear spin-lattice relaxation rate T 1 – 1 of Cu 63 NQR at 6 K while T 1 – 1 of both C 13 and H 1 NMR show no clear anomaly. This behavior can be understood as a second-order phase transition related to charge disproportionation in the ET layers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mutagenesis of Human Cytomegalovirus Glycoprotein L Disproportionately Disrupts gH/gL/gO over gH/gL/pUL128-131

Herein, cell-free and cell-to-cell spread of herpesviruses involves a core fusion apparatus comprised of the fusion protein glycoprotein B (gB) and the regulatory factor gH/gL. The human cytomegalovirus (HCMV) gH/gL/gO and gH/gL/pUL128-131 facilitate spread in different cell types. The gO and pUL128-131 components bind distinct receptors, but how the gH/gL portions of the complexes functionally compare is not understood. We previously characterized a panel of gL mutants by transient expression and showed that many were impaired for gH/gL-gB-dependent cell-cell fusion but were still able to form gH/gL/pUL128-131 and induce receptor interference. Here, the gL mutants were engineered into the HCMV BAC clones TB40/e-BAC4 (TB), TR, and Merlin (ME), which differ in their utilization of the two complexes for entry and spread. Several of the gL mutations disproportionately impacted gH/gL/gO-dependent entry and spread over gH/gL/pUL128-131 processes. The effects of some mutants could be explained by impaired gH/gL/gO assembly, but other mutants impacted gH/gL/gO function. Soluble gH/gL/gO containing the L201 mutant failed to block HCMV infection despite unimpaired binding to PDGFRα, indicating the existence of other important gH/gL/gO receptors. Another mutant (L139) enhanced the gH/gL/gO-dependent cell-free spread of TR, suggesting a “hyperactive” gH/gL/gO. Recently published crystallography and cryo-electron microscopy studies suggest structural conservation of the gH/gL underlying gH/gL/gO and gH/gL/pUL128-131. However, our data suggest important differences in the gH/gL of the two complexes and support a model in which gH/gL/gO can provide an activation signal for gB.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Disproportionate impacts of COVID-19 in a large US city

COVID-19 has disproportionately impacted individuals depending on where they live and work, and based on their race, ethnicity, and socioeconomic status. Studies have documented catastrophic disparities at critical points throughout the pandemic, but have not yet systematically tracked their severity through time. Using anonymized hospitalization data from March 11, 2020 to June 1, 2021 and fine-grain infection hospitalization rates, we estimate the time-varying burden of COVID-19 by age group and ZIP code in Austin, Texas. During this 15-month period, we estimate an overall 23.7% (95% CrI: 22.5–24.8%) infection rate and 29.4% (95% CrI: 28.0–31.0%) case reporting rate. Individuals over 65 were less likely to be infected than younger age groups (11.2% [95% CrI: 10.3–12.0%] vs 25.1% [95% CrI: 23.7–26.4%]), but more likely to be hospitalized (1,965 per 100,000 vs 376 per 100,000) and have their infections reported (53% [95% CrI: 49–57%] vs 28% [95% CrI: 27–30%]). We used a mixed effect poisson regression model to estimate disparities in infection and reporting rates as a function of social vulnerability. We compared ZIP codes ranking in the 75th percentile of vulnerability to those in the 25th percentile, and found that the more vulnerable communities had 2.5 (95% CrI: 2.0–3.0) times the infection rate and only 70% (95% CrI: 60%-82%) the reporting rate compared to the less vulnerable communities. Inequality persisted but declined significantly over the 15-month study period. Our results suggest that further public health efforts are needed to mitigate local COVID-19 disparities and that the CDC’s social vulnerability index may serve as a reliable predictor of risk on a local scale when surveillance data are limited.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF-Supported Mononuclear Copper Site

Dianionic hyponitrite (N 2 O 2 2- ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases. In this work, we examine the gas-solid reaction of nitric oxide with the metal–organic framework Cu I -ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 .- intermediate. These results highlight the advantage provided by site-isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one-electron couple in these enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site

Abstract Dianionic hyponitrite (N 2 O 2 2− ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme‐copper oxidases and nitric oxide reductases. In this work, we examine the gas‐solid reaction of nitric oxide with the metal–organic framework Cu I ‐ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 .− intermediate. These results highlight the advantage provided by site‐isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one‐electron couple in these enzymes.

Sun, Chenyue↗
DOE OSTI2024

The Median Isn’t the Message: soil nutrient hot spots have a disproportionate influence on biogeochemical structure across years, seasons, and depths

Abstract Soil nutrient distribution is heterogeneous in space and time, potentially altering nutrient acquisition by trees and microorganisms. Ecologists have distinguished “hot spots” (HSs) as areas with enhanced and sustained rates of nutrient fluxes relative to the surrounding soil matrix. We evaluated the spatial and temporal patterns in nutrient flux HSs in two mixed-conifer forest soils by repeatedly sampling the soil solution at the same spatial locations (horizontally and vertically) over multiple seasons and years using ion exchange resins incubated in situ. The climate of these forests is Mediterranean, with intense fall rains occurring following summers with little precipitation, and highly variable winter snowfall. Hot spots formed most often for NO 3 − and Na + . Although nutrient HSs often occurred in the same spatial location multiple times, HSs persisted more often for PO 4 3− NH 4 + , and NO 3 − , and were more transient for Ca 2+ , Mg 2+ , and Na + . Sampling year (annual precipitation ranged from 558 to 1223 mm) impacted the occurrence of HSs for most nutrients, but season was only significant for PO 4 3− , NH 4 + , NO 3 − , and Na + , with HSs forming more often after fall rains than after spring snowmelt. The frequency of HSs significantly decreased with soil depth for all nutrients, forming most commonly immediately below the surficial organic horizon. Although HSs accounted for less than 17% of the sampling volume, they were responsible for 56–88% of PO 4 3− , NH 4 + , and NO 3 − resin fluxes. Our results suggest that macronutrient HSs have a disproportional contribution to soil biogeochemical structure, with implications for vegetation nutrient acquisition strategies and biogeochemical models. Graphical abstract

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Anion-induced disproportionation of Th( iii ) complexes to form Th( ii ) and Th( iv ) products

Here, a new synthesis of Th(II) complexes has been identified involving addition of simple MX salts (M = Li, Na, K; X = H, Cl, Me, N 3 ) to Cp" 3 Th III [Cp" = [C 5 H 3 (SiMe 3 ) 2 ] in the presence of 18-crown-6 or 2.2.2-cryptand, forming [M(chelate)][Cp" 3 Th II ] and Cp'' 3 Th IV X. Cp tet 3 Th III (Cp tet = C 5 Me 4 H) reacts with KH to form Cp tet 3 Th IV H and the C–H bond activation product, [K(crypt)]{[Cp tet 2 Th IV H[η 1 :η 5 -C 5 Me 3 H(CH 2 )]}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The Challenge of Disproportionate Importance of Temporal Features in Predicting HPC Power Consumption

In this work, we demonstrate the challenges in predicting HPC cluster power consumption in the face of significant temporal skew in power consumption behavioral patterns. Predicting large power swings that extend several megawatts has significant operational value for HPC centers, however, prediction is challenging due to the relative rarity of such events and also due to the abrupt or disjoint deviation from the average power consumption levels. To study the impact of this challenge, we have trained a recurrent neural network (RNN) as a reasonably sophisticated model to predict power consumption of the one-year worth of node power consumption data from the Summit supercomputer located in the Oak Ridge Leadership Computing Facility. By studying the prediction results, we have found that although simple usage of RNN models can provide good results on average power consumption levels, it would fail at predicting the power swings that have more operational value. With such results, we discuss potential next steps in addressing such issues aiming towards a robust usage of power prediction techniques in HPC operations.

Li, Chengcheng↗