This paper examines the reactive surface dynamics of energy- and angle-selected N2 dissociation on a clean Ru(0001) surface. Presented herein are the first STM images of highly energetic N2 ...dissociation on terrace sites utilizing a novel UHV instrument that combines a supersonic molecular beam with an in situ STM that is in-line with the molecular beam. Atomically resolved visualization of individual N2 dissociation events elucidates the fundamental reactive dynamics of the N2/Ru(0001) system by providing a detailed understanding of the on-surface dissociation dynamics: the distance and angle between nitrogen atoms from the same dissociated N2 molecule, site specificity and coordination of binding on terrace sites, and the local evolution of surrounding nanoscopic areas. These properties are precisely measured over a range of impinging N2 kinetic energies and angles, revealing previously unattainable information about the energy dissipation channels that govern the reactivity of the system. The experimental results presented in this paper provide insight into the fundamental N2 dissociation mechanism that, in conjunction with ongoing theoretical modeling, will help determine the role of dynamical processes such as energy transfer to surface phonons and nonadiabatic excitation of electron–hole pairs (ehps). These results will not only help uncover the underlying chemistry and physics that give rise to the unique behavior of this activated dissociative chemisorption system but also represent an exciting approach to studying reaction dynamics by pairing the angstrom-level spatiotemporal resolution of an in situ STM with nonequilibrium fluxes of reactive gases generated in a supersonic molecular beam to access highly activated chemical dynamics and observe the results of individual reaction events.
Airborne and ground‐based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South ...Coast Air Basin (SoCAB) consistent with previous observations. The well‐known and much‐studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non‐methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground‐based data show an average decrease in NOx of 46 ± 11% and 34 ± 4%, respectively, and an average increase in VOC/NOxratio of 48 ± 8% and 43 ± 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC‐NOxoxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday‐to‐weekend differences in the products of NOx oxidation show 45 ± 13% and 42 ± 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 ± 14% and 22 ± 17% greater ozone production efficiency on weekends in the airborne and ground‐based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.
Key Points
A weekend ozone effect is observed in the South Coast Air Basin
Reductions in NOx emissions drive weekday and weekend differences in ozone
Photochemical ozone production contributes to observed weekend ozone levels
Rapid radio brightening of GRB 210702A Anderson, G E; Russell, T D; Fausey, H M ...
Monthly notices of the Royal Astronomical Society,
06/2023, Letnik:
523, Številka:
4
Journal Article
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ABSTRACT
We observed the rapid radio brightening of GRB 210702A with the Australia Telescope Compact Array (ATCA) just 11 h post-burst, tracking early-time radio variability over a 5 h period on ∼15 ...min time-scales at 9.0, 16.7, and 21.2 GHz. A broken power law fit to the 9.0 GHz light curve showed that the 5 h flare peaked at a flux density of 0.4 ± 0.1 mJy at ∼13 h post-burst. The observed temporal and spectral evolution is not expected in the standard internal–external shock model, where forward and reverse shock radio emission evolves on much longer time-scales. The early-time (<1 d) optical and X-ray light curves from the Neil Gehrels Swift Observatory demonstrated typical afterglow forward shock behaviour, allowing us to use blast wave physics to determine a likely homogeneous circumburst medium and an emitting electron population power-law index of p = 2.9 ± 0.1. We suggest that the early-time radio flare is likely due to weak interstellar scintillation (ISS), which boosted the radio afterglow emission above the ATCA sensitivity limit on minute time-scales. Using relations for ISS in the weak regime, we were able to place an upper limit on the size of the blast wave of ≲6 × 1016 cm in the plane of the sky, which is consistent with the theoretical forward shock size prediction of 8 × 1016 cm for GRB 210702A at ∼13 h post-burst. This represents the earliest ISS size constraint on a gamma-ray burst (GRB) blast wave to date, demonstrating the importance of rapid (<1 d) radio follow-up of GRBs using several-hour integrations to capture the early afterglow evolution and to track the scintillation over a broad frequency range.
In late 2016 and early 2017, the flat spectrum radio quasar CTA 102 exhibited a very strong and long-lasting outburst. The event can be described by a roughly two-month long increase of the baseline ...flux in the monitored energy bands (optical to γ-rays) by a factor 8, and a subsequent decrease over another two months back to pre-flare levels. The long-term trend was superseded by short but very strong flares, resulting in a peak flux that was a factor 50 above pre-flare levels in the γ-ray domain and almost a factor 100 above pre-flare levels in the optical domain. In this paper, we explain the long-term evolution of the outburst by the ablation of a gas cloud penetrating the relativistic jet. The slice-by-slice ablation results in a gradual increase of the particle injection until the center of the cloud is reached, after which the injected number of particles decreases again. With reasonable cloud parameters, we obtain excellent fits of the long-term trend.
Aiming towards the development of novel nootropic therapeutics to address the cognitive impairment common to a range of brain disorders, we set out to develop highly selective small molecule ...inhibitors of HDAC2, a chromatin modifying histone deacetylase implicated in memory formation and synaptic plasticity. Novel
-aminoanilide inhibitors were designed and evaluated for their ability to selectively inhibit HDAC2 versus the other Class I HDACs. Kinetic and thermodynamic binding properties were essential elements of our design strategy and two novel classes of
-aminoanilides, that exhibit kinetic selectivity (biased residence time) for HDAC2 versus the highly homologous isoform HDAC1, were identified. These kinetically selective HDAC2 inhibitors (
and
) increased H4K12 and H3K9 histone acetylation in primary mouse neuronal cell culture assays, in the hippocampus of CK-p25 mice, a model of neurodegenerative disease, and rescued the associated memory deficits of these mice in a cognition behavioural model. These studies demonstrate for the first time that selective pharmacological inhibition of HDAC2 is feasible and that inhibition of the catalytic activity of this enzyme may serve as a therapeutic approach towards enhancing the learning and memory processes that are affected in many neurological and psychiatric disorders.
Although laboratory experiments have shown that organic compounds in both gasoline fuel and diesel engine exhaust can form secondary organic aerosol (SOA), the fractional contribution from gasoline ...and diesel exhaust emissions to ambient SOA in urban environments is poorly known. Here we use airborne and ground‐based measurements of organic aerosol (OA) in the Los Angeles (LA) Basin, California made during May and June 2010 to assess the amount of SOA formed from diesel emissions. Diesel emissions in the LA Basin vary between weekdays and weekends, with 54% lower diesel emissions on weekends. Despite this difference in source contributions, in air masses with similar degrees of photochemical processing, formation of OA is the same on weekends and weekdays, within the measurement uncertainties. This result indicates that the contribution from diesel emissions to SOA formation is zero within our uncertainties. Therefore, substantial reductions of SOA mass on local to global scales will be achieved by reducing gasoline vehicle emissions.
Key Points
Diesel emissions contribute significantly to primary organic aerosol
Gasoline exhaust emissions dominate secondary organic aerosol (SOA) formation
Globally, SOA from gasoline exhaust may reach 16% of biogenic SOA
The inherited peripheral neuropathies (IPNs) are characterized by marked clinical and genetic heterogeneity and include relatively frequent presentations such as Charcot‐Marie‐Tooth disease and ...hereditary motor neuropathy, as well as more rare conditions where peripheral neuropathy is associated with additional features. There are over 250 genes known to cause IPN‐related disorders but it is estimated that in approximately 50% of affected individuals a molecular diagnosis is not achieved. In this study, we examine the diagnostic utility of whole‐exome sequencing (WES) in a cohort of 50 families with 1 or more affected individuals with a molecularly undiagnosed IPN with or without additional features. Pathogenic or likely pathogenic variants in genes known to cause IPN were identified in 24% (12/50) of the families. A further 22% (11/50) of families carried sequence variants in IPN genes in which the significance remains unclear. An additional 12% (6/50) of families had variants in novel IPN candidate genes, 3 of which have been published thus far as novel discoveries (KIF1A, TBCK, and MCM3AP). This study highlights the use of WES in the molecular diagnostic approach of highly heterogeneous disorders, such as IPNs, places it in context of other published neuropathy cohorts, while further highlighting associated benefits for discovery.
We investigate the relationship between a thousand-year history of violent conflict in Europe and various reconstructions of temperature and precipitation. We find that conflict was more intense ...during colder period, just like Zhang et al. (Clim Change 76:459-477, 2006) found for China. This relationship weakens in the industrialized era, and is not robust to the details of the climate reconstruction or to the sample period. As the correlation is negative and weakening, it appears that global warming would not lead to an increase in violent conflict in temperature climates.
The light emitted by stars and accreting compact objects through the history of the universe is encoded in the intensity of the extragalactic background light (EBL). Knowledge of the EBL is important ...to understand the nature of star formation and galaxy evolution, but direct measurements of the EBL are limited by galactic and other foreground emissions. Here, we report an absorption feature seen in the combined spectra of a sample of gamma-ray blazars out to a redshift of z ~1.6. This feature is caused by attenuation of gamma rays by the EBL at optical to ultraviolet frequencies and allowed us to measure the EBL flux density in this frequency band.
Metastasis is the leading cause of morbidity for lung cancer patients. Here we demonstrate that murine tumor propagating cells (TPCs) with the markers Sca1 and CD24 are enriched for metastatic ...potential in orthotopic transplantation assays. CD24 knockdown decreased the metastatic potential of lung cancer cell lines resembling TPCs. In lung cancer patient data sets, metastatic spread and patient survival could be stratified with a murine lung TPC gene signature. The TPC signature was enriched for genes in the Hippo signaling pathway. Knockdown of the Hippo mediators Yap1 or Taz decreased in vitro cellular migration and transplantation of metastatic disease. Furthermore, constitutively active Yap was sufficient to drive lung tumor progression in vivo. These results demonstrate functional roles for two different pathways, CD24‐dependent and Yap/Taz‐dependent pathways, in lung tumor propagation and metastasis. This study demonstrates the utility of TPCs for identifying molecules contributing to metastatic lung cancer, potentially enabling the therapeutic targeting of this devastating disease.
Synopsis
The molecular characterization of tumor‐propagating cells in mouse models of lung cancer reveals CD24+/Sca1+ and increased Yap/Taz activity as predictive for tumor metastasis.
Murine lung TPCs with the markers Sca1 and CD24 are enriched for metastatic potential in orthotopic transplantation assays.
In lung cancer patient data sets, metastatic spread and patient survival could be stratified with a murine lung TPC gene signature.
Knockdown of the Hippo mediators Yap1 or Taz decreased migration and metastatic potential of lung cancer cells.
Yap activation was sufficient for driving tumor progression in the Kras mouse model of lung cancer.
The molecular characterization of tumor‐propagating cells in mouse models of lung cancer reveals CD24+/Sca1+ and increased Yap/Taz activity as predictive for tumor metastasis.
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