2,852 research outputs found
Watching gene expression in color.
A combination of two fluorescent proteins with different half-lives allows gene expression to be followed with improved time resolution
Gas Phase Production and Loss of Isoprene Epoxydiols
Isoprene epoxydiols (IEPOX) form in high yields from the OH-initiated oxidation of isoprene under low-NO conditions. These compounds contribute significantly to secondary organic aerosol formation. Their gas-phase chemistry has, however, remained largely unexplored. In this study, we characterize the formation of IEPOX isomers from the oxidation of isoprene by OH. We find that cis-β- and trans-β-IEPOX are the dominant isomers produced, and that they are created in an approximate ratio of 1:2 from the low-NO oxidation of isoprene. Three isomers of IEPOX, including cis-β- and trans-β, were synthesized and oxidized by OH in environmental chambers under high- and low-NO conditions. We find that IEPOX reacts with OH at 299 K with rate coefficients of (0.84 ± 0.07) × 10^(–11), (1.52 ± 0.07) × 10^(–11), and (0.98 ± 0.05) × 10^(–11) cm^3 molecule^(–1) s^(–1) for the δ1, cis-β, and trans-β isomers. Finally, yields of the first-generation products of IEPOX + OH oxidation were measured, and a new mechanism of IEPOX oxidation is proposed here to account for the observed products. The substantial yield of glyoxal and methylglyoxal from IEPOX oxidation may help explain elevated levels of those compounds observed in low-NO environments with high isoprene emissions
Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds
The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative atmospheric chamber campaign that occurred during January 2014. FIXCIT is the laboratory component of a synergistic field and laboratory effort aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. Approximately 20 principal scientists from 14 academic and government institutions performed parallel measurements at a forested site in Alabama and at the atmospheric chambers at Caltech. During the 4 week campaign period, a series of chamber experiments was conducted to investigate the dark- and photo-induced oxidation of isoprene, α-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX) in a highly controlled and atmospherically relevant manner. Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized and contributed by campaign participants, which enabled explicit exploration into the oxidation mechanisms and instrument responses for these important atmospheric compounds. The present overview describes the goals, experimental design, instrumental techniques, and preliminary observations from the campaign. This work provides context for forthcoming publications affiliated with the FIXCIT campaign. Insights from FIXCIT are anticipated to aid significantly in interpretation of field data and the revision of mechanisms currently implemented in regional and global atmospheric models
Kinetics and Product Yields of the OH Initiated Oxidation of Hydroxymethyl Hydroperoxide
Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C1 Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF3O- chemical ionization mass spectrometry (CIMS) and laser induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [k1;2-butanediol+OH = (27:0 5:6) 10- exp12 cm3 molecule-1s-1]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 1.5) 10-12 cm3 molecule-1s-1, with the formic acid to formaldehyde yield in a ratio of 0:880:21 and independent of NO concentration (31010 1.51013 molecule cm-3). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr-1 (1-3%) of global annual formic acid production
Responding by exclusion in temporal discrimination tasks
Responding by exclusion, one of the most robust phenomena in Experimental
Psychology, consists of choosing an undefined comparison stimulus given an undefined
sample, when the comparison stimulus is presented next to other experimentally defined
stimuli. The goal of the present study was to determine whether responding by
exclusion could be obtained using samples that varied along a single dimension. Using a
double temporal bisection task, ten university students learned to choose visual
comparisons (colored circles) based on the duration of a tone. In tests of exclusion,
sample stimuli with new durations were followed by comparison sets that included one
previously trained, defined comparison (colored circle) and one previously untrained,
undefined comparison (geometric shape). Subjects preferred the defined comparisons
following the defined samples and the undefined comparisons following the undefined
samples, the choice pattern typical of responding by exclusion. The use of samples
varying along a single dimension allows us to study the interaction between stimulus
generalization gradients and exclusion in the control of conditional responding.The first author was supported by a master's degree fellowship by the Ministry of Education (CAPES). Armando Machado was supported by grant PTDC/MHC-PCN/3540/2012 from the Portuguese Foundation for Science and Technology. Camila Domeniconi had a post-doctoral fellowship from the Foundation for Research Support in the State of Sao Paulo (FAPESP, 2009/18479-5). She is currently affiliated with the National Institute of Science and Technology on Behavior, Cognition and Teaching. Grants: FAPESP (08/57705-8) and CNPq (573972/2008-7). She has a research productivity fellowship by the National Council for Scientific and Technological Development (CNPq, 301623/2012-0)
Biochemical properties of Paracoccus denitrificans FnrP:Reactions with molecular oxygen and nitric oxide
In Paracoccus denitrificans, three CRP/FNR family regulatory proteins, NarR, NnrR and FnrP, control the switch between aerobic and anaerobic (denitrification) respiration. FnrP is a [4Fe-4S] cluster containing homologue of the archetypal O2 sensor FNR from E. coli and accordingly regulates genes encoding aerobic and anaerobic respiratory enzymes in response to O2, and also NO, availability. Here we show that FnrP undergoes O2-driven [4Fe-4S] to [2Fe-2S] cluster conversion that involves up to 2 O2 per cluster, with significant oxidation of released cluster sulfide to sulfane observed at higher O2 concentrations. The rate of the cluster reaction was found to be ~6-fold lower than that of E. coli FNR, suggesting that FnrP can remain transcriptionally active under microaerobic conditions. This is consistent with a role for FnrP in activating expression of the high O2 affinity cytochrome c oxidase under microaerobic conditions. Cluster conversion resulted in dissociation of the transcriptionally active FnrP dimer into monomers. Therefore, along with E. coli FNR, FnrP belongs to the subset of FNR proteins in which cluster type is correlated with association state. Interestingly, two key charged residues, Arg140 and Asp154, that have been shown to play key roles in the monomer-dimer equilibrium in E. coli FNR are not conserved in FnrP, indicating that different protomer interactions are important for this equilibrium. Finally, the FnrP [4Fe-4S] cluster is shown to undergo reaction with multiple NO molecules, resulting in iron nitrosyl species and dissociation into monomers
Search for direct production of charginos and neutralinos in events with three leptons and missing transverse momentum in √s = 7 TeV pp collisions with the ATLAS detector
A search for the direct production of charginos and neutralinos in final states with three electrons or muons and missing transverse momentum is presented. The analysis is based on 4.7 fb−1 of proton–proton collision data delivered by the Large Hadron Collider and recorded with the ATLAS detector. Observations are consistent with Standard Model expectations in three signal regions that are either depleted or enriched in Z-boson decays. Upper limits at 95% confidence level are set in R-parity conserving phenomenological minimal supersymmetric models and in simplified models, significantly extending previous results
Measurement of the production of a W boson in association with a charm quark in pp collisions at √s = 7 TeV with the ATLAS detector
The production of a W boson in association with a single charm quark is studied using 4.6 fb−1 of pp collision data at s√ = 7 TeV collected with the ATLAS detector at the Large Hadron Collider. In events in which a W boson decays to an electron or muon, the charm quark is tagged either by its semileptonic decay to a muon or by the presence of a charmed meson. The integrated and differential cross sections as a function of the pseudorapidity of the lepton from the W-boson decay are measured. Results are compared to the predictions of next-to-leading-order QCD calculations obtained from various parton distribution function parameterisations. The ratio of the strange-to-down sea-quark distributions is determined to be 0.96+0.26−0.30 at Q 2 = 1.9 GeV2, which supports the hypothesis of an SU(3)-symmetric composition of the light-quark sea. Additionally, the cross-section ratio σ(W + +c¯¯)/σ(W − + c) is compared to the predictions obtained using parton distribution function parameterisations with different assumptions about the s−s¯¯¯ quark asymmetry
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