Structural, mechanistic and functional insight into gliotoxin bis-thiomethylation in Aspergillus fumigatus.

Gliotoxin is an epipolythiodioxopiperazine (ETP) class toxin, contains a disulfide bridge that mediates its toxic effects via redox cycling and is produced by the opportunistic fungal pathogen Aspergillus fumigatus Self-resistance against gliotoxin is effected by the gliotoxin oxidase GliT, and attenuation of gliotoxin biosynthesis is catalysed by gliotoxin S-methyltransferase GtmA. Here we describe the X-ray crystal structures of GtmA-apo (1.66 Å), GtmA complexed to S-adenosylhomocysteine (1.33 Å) and GtmA complexed to S-adenosylmethionine (2.28 Å), providing mechanistic insights into this important biotransformation. We further reveal that simultaneous elimination of the ability of A. fumigatus to dissipate highly reactive dithiol gliotoxin, via deletion of GliT and GtmA, results in the most significant hypersensitivity to exogenous gliotoxin observed to date. Indeed, quantitative proteomic analysis of ΔgliT::ΔgtmA reveals an uncontrolled over-activation of the gli-cluster upon gliotoxin exposure. The data presented herein reveal, for the first time, the extreme risk associated with intracellular dithiol gliotoxin biosynthesis-in the absence of an efficient dismutation capacity. Significantly, a previously concealed protective role for GtmA and functionality of ETP bis-thiomethylation as an ancestral protection strategy against dithiol compounds is now evident

Major components of atmospheric organic aerosol in southern California as determined by hourly measurements of source marker compounds

We report the first hourly in-situ measurements of speciated organic aerosol (OA) composition in an urban environment. Field measurements were made in southern California at the University of California–Riverside during the 2005 Study of Organic Aerosol at Riverside (SOAR), which included two separate measurement periods: a summer study (15 July–15 August) and a fall study (31 October–28 November). Hourly measurements of over 300 semivolatile and nonvolatile organic compounds were made using the thermal desorption aerosol gas chromatograph (TAG). Positive matrix factorization (PMF) was performed on a subset of these compounds to identify major components contributing to submicron (i.e., PM₁) OA at the site, as measured by an aerosol mass spectrometer (AMS). PMF analysis was performed on an 11-day focus period in each season, representing average seasonal conditions during the summer and a period of urban influence during the fall. As a result of this analysis, we identify multiple types of primary and secondary OA (POA and SOA). Secondary sources contribute substantially to fine OA mass at Riverside, which commonly receives regional air masses that pass through metropolitan Los Angeles during the summer. Four individual summertime SOA components are defined, and when combined, they are estimated to contribute an average 88% of the total fine OA mass during summer afternoons according to PMF results. These sources appear to be mostly from the oxidation of anthropogenic precursor gases, with one SOA component having contributions from oxygenated biogenics. During the fall, three out of four aerosol components that contain SOA are inseparable from covarying primary emissions, and therefore we cannot estimate the fraction of total OA that is secondary in nature during the fall study. Identified primary OA components are attributed to vehicle emissions, food cooking, primary biogenics, and biomass burning aerosol. While a distinction between local and regional vehicle emissions is made, a combination of these two factors accounted for approximately 11% of observed submicron OA during both sampling periods. Food cooking operations contributed ~10% of submicron OA mass during the summer, but was not separable from SOA during the fall due to high covariance of sources. Biomass burning aerosol contributed a larger fraction of fine OA mass during the fall (~11%) than compared to summer (~7%). Primary biogenic aerosol was also identified during the summer, contributing ~1% of the OA, but not during the fall. While the contribution of both local and regional primary vehicle OA accounts for only ~11% of total OA during both seasons, gas-phase vehicle emissions likely create a substantial fraction of the observed SOA as a result of atmospheric processing

Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

In this paper we report chemically resolved measurements of organic aerosol (OA) and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA). The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1) aged biomass burning emissions and oxidized urban emissions, (2) oxidized urban emissions (3) oxidation products of monoterpene emissions, (4) monoterpene emissions, (5) anthropogenic emissions and (6) local methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September) due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October), even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO), consistent with previous observations, while being comprised of mostly non-fossil carbon (>75%). The correlation between OA and an anthropogenic tracer does not necessarily identify the source of the carbon as being anthropogenic but instead suggests a coupling between the anthropogenic and biogenic components in the air mass that might be related to the source of the oxidant and/or the aerosol sulfate. Observations of organosulfates of isoprene and α-pinene provided evidence for the likely importance of aerosol sulfate in spite of neutralized aerosol although acidic plumes might have played a role upwind of the site. This is in contrast to laboratory studies where strongly acidic seed aerosols were needed in order to form these compounds. These compounds together represented only a minor fraction (<1%) of the total OA mass, which may be the result of the neutralized aerosol at the site or because only a small number of organosulfates were quantified. The low contribution of organosulfates to total OA suggests that other mechanisms, e.g. NO_x enhancement of oxidant levels, are likely responsible for the majority of the anthropogenic enhancement of biogenic secondary organic aerosol observed at this site

Correction: Contribution of the Cpx envelope stress system to metabolism and virulence regulation in Salmonella enterica serovar Typhimurium

[This corrects the article DOI: 10.1371/journal.pone.0211584.]

Azimuthal dependence of pion source radii in Pb+Au collisions at 158 A GeV

We present results of a two-pion correlation analysis performed with the Au+Pb collision data collected by the upgraded CERES experiment in the fall of 2000. The analysis was done in bins of the reaction centrality and the pion azimuthal emission angle with respect to the reaction plane. The pion source, deduced from the data, is slightly elongated in the direction perpendicular to the reaction plane, similarly as was observed at the AGS and at RHIC.Comment: 5 pages, 2 figure

Elliptic flow of charged pions, protons and strange particles emitted in Pb+Au collisions at top SPS energy

Differential elliptic flow spectra v2(pT) of \pi-, K0short, p, \Lambda have been measured at \sqrt(s NN)= 17.3 GeV around midrapidity by the CERN-CERES/NA45 experiment in mid-central Pb+Au collisions (10% of \sigma(geo)). The pT range extends from about 0.1 GeV/c (0.55 GeV/c for \Lambda) to more than 2 GeV/c. Protons below 0.4 GeV/c are directly identified by dE/dx. At higher pT, proton elliptic flow v2(pT) is derived as a constituent, besides \pi+ and K+, of the elliptic flow of positive pion candidates. The retrieval requires additional inputs: (i) of the particle composition, and (ii) of v2(pT) of positive pions. For (i), particle ratios obtained by NA49 were adapted to CERES conditions; for (ii), the measured v2(pT) of negative pions is substituted, assuming \pi+ and \pi- elliptic flow magnitudes to be sufficiently close. The v2(pT) spectra are compared to ideal-hydrodynamics calculations. In synopsis of the series \pi- - K0short - p - \Lambda, flow magnitudes are seen to fall with decreasing pT progressively even below hydro calculations with early kinetic freeze-out (Tf= 160 MeV) leaving not much time for hadronic evolution. The proton v2(pT) data show a downward swing towards low pT with excursions into negative v2 values. The pion-flow isospin asymmetry observed recently by STAR at RHIC, invalidating in principle our working assumption, is found in its impact on proton flow bracketed from above by the direct proton flow data, and not to alter any of our conclusions. Results are discussed in perspective of recent viscous dynamics studies which focus on late hadronic stages.Comment: 38 pages, 27 figures, 2 tables. Abstract and parts of introduction made more comprehensible; corrected typos; acknowledgement added. To appear in Nucl.Phys.

Leptonic and charged kaon decay modes of the ϕ\phi meson measured in heavy-ion collisions at the CERN SPS

We report a measurement of $\phi$ meson production in central Pb+Au collisions at E$_{lab}$/A=158 GeV. For the first time in heavy-ion collisions, $\phi$ mesons were reconstructed in the same experiment both in the K$^+$K$^-$ and the dilepton decay channel. Near mid-rapidity, this yields rapidity densities, corrected for production at the same rapidity value, of 2.05 +- 0.14(stat) +- 0.25(syst) and 2.04 +- 0.49(stat)+-{0.32}(syst), respectively. The shape of the measured transverse momentum spectra is also in close agreement in both decay channels. The data rule out a possible enhancement of the $\phi$ yield in the leptonic over the hadronic channel by a factor larger than 1.6 at 95% CL.Comment: 11 pages, 4 figures,submitted to Phys. Rev. Let

Lambda production in 40 A GeV/c Pb-Au collisions

During the 1999 lead run, CERES has measured hadron and electron-pair production at 40 A GeV/c beam momentum with the spectrometer upgraded by the addition of a radial TPC. Here the analysis of lambda and antilambda will be presented.Comment: 8 pages, 8 figures. 6th International Conference on Strange Quarks in Matter, Frankfurt 200

Event-by-event fluctuations at SPS

Results on event-by-event fluctuations of the mean transverse momentum and net charge in Pb-Au collisions, measured by the CERES Collaboration at CERN-SPS, are presented. We discuss the centrality and beam energy dependence and compare our data to cascade calculations.Comment: 4 pages, 4 figures, proceedings to INPC2004 Goteborg, Swede