Photochemistry of the PAH pyrene in water ice: the case for ion-mediated solid-state astrochemistry

Context. Icy dust grains play an important role in the formation of complex inter- and circumstellar molecules. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are abundantly present in the ISM in the gas phase. It is likely that these non-volatile species freeze out onto dust grains as well and participate in the astrochemical solid-state network, but experimental PAH ice studies are largely lacking. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, \water and CO. Pyrene ionisation is found to be most efficient in \water ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py^+ and PyH are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionised in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are put in an astrophysical context by determining the importance of PAH ionisation in a molecular cloud. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.Comment: 11 pages, 8 figures, accepted for publication in A&

Laboratory Determination of the Infrared Band Strengths of Pyrene Frozen in Water Ice: Implications for the Composition of Interstellar Ices

Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 microns) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10%-20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate the search for frozen interstellar PAHs, laboratory experiments were conducted to determine the positions and strengths of the bands of pyrene mixed with H2O and D2O ices. The D2O mixtures are used to measure pyrene bands that are masked by the strong bands of H2O, leading to the first laboratory determination of the band strength for the CH stretching mode of pyrene in water ice near 3.25 microns. Our infrared band strengths were normalized to experimentally determined ultraviolet band strengths, and we find that they are generally ~50% larger than those reported by Bouwman et al. based on theoretical strengths. These improved band strengths were used to reexamine YSO spectra published by Boogert et al. to estimate the contribution of frozen PAHs to absorption in the 5-8 micron spectral region, taking into account the strength of the 3.25 micron CH stretching mode. It is found that frozen neutral PAHs contain 5%-9% of the cosmic carbon budget, and account for 2%-9% of the unidentified absorption in the 5-8 micron region.Comment: Accepted for publication in ApJ on 14 Feb 201

Detection of Trojan horse by Analysis of System Behavior and Data Packets

Trojan horse is said to be one of the most serious threats to computer security. A Trojan horse is an executable file in the Windows operating system. These executable files will have certain static and runtime characteristics. Multiple Windows system process will be called whenever a Trojan horse tries to execute any operation on the system. In this paper a new Trojan horse detection method by using Windows dynamic link libraries to identify system calls from a Trojan horses is explicated. Process explorer is used to identify the malicious executable and to determine whether it is a Trojan or not. Further, an attempt is made to study the network behavior after a Trojan horse is executed using wire shark

A Quantitative, High-Throughput Reverse Genetic Screen Reveals Novel Connections between Pre–mRNA Splicing and 5′ and 3′ End Transcript Determinants

Here we present the development and implementation of a genome-wide reverse genetic screen in the budding yeast, Saccharomyces cerevisiae, that couples high-throughput strain growth, robotic RNA isolation and cDNA synthesis, and quantitative PCR to allow for a robust determination of the level of nearly any cellular RNA in the background of 5,500 different mutants. As an initial test of this approach, we sought to identify the full complement of factors that impact pre–mRNA splicing. Increasing lines of evidence suggest a relationship between pre–mRNA splicing and other cellular pathways including chromatin remodeling, transcription, and 3′ end processing, yet in many cases the specific proteins responsible for functionally connecting these pathways remain unclear. Moreover, it is unclear whether all pathways that are coupled to splicing have been identified. As expected, our approach sensitively detects pre–mRNA accumulation in the vast majority of strains containing mutations in known splicing factors. Remarkably, however, several additional candidates were found to cause increases in pre–mRNA levels similar to that seen for canonical splicing mutants, none of which had previously been implicated in the splicing pathway. Instead, several of these factors have been previously implicated to play roles in chromatin remodeling, 3′ end processing, and other novel categories. Further analysis of these factors using splicing-sensitive microarrays confirms that deletion of Bdf1, a factor that links transcription initiation and chromatin remodeling, leads to a global splicing defect, providing evidence for a novel connection between pre–mRNA splicing and this component of the SWR1 complex. By contrast, mutations in 3′ end processing factors such as Cft2 and Yth1 also result in pre–mRNA splicing defects, although only for a subset of transcripts, suggesting that spliceosome assembly in S. cerevisiae may more closely resemble mammalian models of exon-definition. More broadly, our work demonstrates the capacity of this approach to identify novel regulators of various cellular RNAs

Reduced production of bacterial membrane vesicles predicts mortality in ST45/USA600 methicillin-resistant Staphylococcus aureus bacteremia

Immune biomarkers can stratify mortality risk in staphylococcal bacteremia. Microbial biomarkers may provide more consistent signals during early infection. We demonstrate that in ST45/USA600 bacteremia, bacterial membrane vesicle production in vitro predicts clinical mortality (773 vs. 116 RFU, survivors vs. decedents, p \u3c 0.0001). Using a threshold of 301 relative fluorescence units (RFU), the sensitivity and specificity of the membrane vesicles to predict mortality are 78% and 90%, respectively. This platform is facile, scalable and can be integrated into clinical microbiology lab workflows

Lack of PAH emission toward low-mass embedded young stellar objects

PAHs have been detected toward molecular clouds and some young stars with disks, but have not yet been associated with embedded young stars. We present a sensitive mid-IR spectroscopic survey of PAH features toward a sample of low-mass embedded YSOs. The aim is to put constraints on the PAH abundance in the embedded phase of star formation using radiative transfer modeling. VLT-ISAAC L-band spectra for 39 sources and Spitzer IRS spectra for 53 sources are presented. Line intensities are compared to recent surveys of Herbig Ae/Be and T Tauri stars. The radiative transfer codes RADMC and RADICAL are used to model the PAH emission from embedded YSOs consisting of a PMS star with a circumstellar disk embedded in an envelope. The dependence of the PAH feature on PAH abundance, stellar radiation field, inclination and the extinction by the surrounding envelope is studied. The 3.3 micron PAH feature is undetected for the majority of the sample (97%), with typical upper limits of 5E-16 W/m^2. Compact 11.2 micron PAH emission is seen directly towards 1 out of the 53 Spitzer Short-High spectra, for a source that is borderline embedded. For all 12 sources with both VLT and Spitzer spectra, no PAH features are detected in either. In total, PAH features are detected toward at most 1 out of 63 (candidate) embedded protostars (<~ 2%), even lower than observed for class II T Tauri stars with disks (11-14%). Assuming typical class I stellar and envelope parameters, the absence of PAHs emission is most likely explained by the absence of emitting carriers through a PAH abundance at least an order of magnitude lower than in molecular clouds but similar to that found in disks. Thus, most PAHs likely enter the protoplanetary disks frozen out in icy layers on dust grains and/or in coagulated form.Comment: 13 pages, 9 figures, accepted for publication in A&

Systematic Dissection of Roles for Chromatin Regulators in a Yeast Stress Response

Packaging of eukaryotic genomes into chromatin has wide-ranging effects on gene transcription. Curiously, it is commonly observed that deletion of a global chromatin regulator affects expression of only a limited subset of genes bound to or modified by the regulator in question. However, in many single-gene studies it has become clear that chromatin regulators often do not affect steady-state transcription, but instead are required for normal transcriptional reprogramming by environmental cues. We therefore have systematically investigated the effects of 83 histone mutants, and 119 gene deletion mutants, on induction/repression dynamics of 170 transcripts in response to diamide stress in yeast. Importantly, we find that chromatin regulators play far more pronounced roles during gene induction/repression than they do in steady-state expression. Furthermore, by jointly analyzing the substrates (histone mutants) and enzymes (chromatin modifier deletions) we identify specific interactions between histone modifications and their regulators. Combining these functional results with genome-wide mapping of several histone marks in the same time course, we systematically investigated the correspondence between histone modification occurrence and function. We followed up on one pathway, finding that Set1-dependent H3K4 methylation primarily acts as a gene repressor during multiple stresses, specifically at genes involved in ribosome biosynthesis. Set1-dependent repression of ribosomal genes occurs via distinct pathways for ribosomal protein genes and ribosomal biogenesis genes, which can be separated based on genetic requirements for repression and based on chromatin changes during gene repression. Together, our dynamic studies provide a rich resource for investigating chromatin regulation, and identify a significant role for the “activating” mark H3K4me3 in gene repression

Volatiles in the H2_2O and CO2_2 ices of comet 67P/Churyumov-Gerasimenko

ESA's Rosetta spacecraft at comet 67P/Churyumov-Gerasimenko (67P) was the first mission that accompanied a comet over a substantial fraction of its orbit. On board was the ROSINA mass spectrometer suite to measure the local densities of the volatile species sublimating from the ices inside the comet's nucleus. Understanding the nature of these ices was a key goal of Rosetta. We analyzed the primary cometary molecules at 67P, namely H$_2$O and CO$_2$, together with a suite of minor species for almost the entire mission. Our investigation reveals that the local abundances of highly volatile species, such as CH$_4$ and CO, are reproduced by a linear combination of both H$_2$O and CO$_2$ densities. These findings bear similarities to laboratory-based temperature programmed desorption experiments of amorphous ices and imply that highly volatile species are trapped in H$_2$O and CO$_2$ ices. Our results do not show the presence of ices dominated by these highly volatile molecules. Most likely, they were lost due to thermal processing of 67P's interior prior to its deflection to the inner solar system. Deviations in the proportions co-released with H$_2$O and CO$_2$ can only be observed before the inbound equinox, when the comet was still far from the sun and the abundance of highly volatile molecules associated with CO$_2$ outgassing were lower. The corresponding CO$_2$ is likely seasonal frost, which sublimated and lost its trapped highly volatile species before re-freezing during the previous apparition. CO, on the other hand, was elevated during the same time and requires further investigation.Comment: This is a pre-copyedited, author-produced PDF of an article accepted for publication in Monthly Notices of the Royal Astronomical Society following peer review. The version of record is available online at: https://doi.org/10.1093/mnras/stad300

Volatiles in the H2O and CO2 ices of comet 67P/Churyumov–Gerasimenko

European Space Agency’s Rosetta spacecraft at comet 67P/Churyumov–Gerasimenko (67P) was the first mission that accompanied a comet over a substantial fraction of its orbit. On board was the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis mass spectrometer suite to measure the local densities of the volatile species sublimating from the ices inside the comet’s nucleus. Understanding the nature of these ices was a key goal of Rosetta. We analysed the primary cometary molecules at 67P, namely H2O and CO2, together with a suite of minor species for almost the entire mission. Our investigation reveals that the local abundances of highly volatile species, such as CH4 and CO, are reproduced by a linear combination of both H2O and CO2 densities. These findings bear similarities to laboratory-based temperature-programmed desorption experiments of amorphous ices and imply that highly volatile species are trapped in H2O and CO2 ices. Our results do not show the presence of ices dominated by these highly volatile molecules. Most likely, they were lost due to thermal processing of 67P’s interior prior to its deflection to the inner solar system. Deviations in the proportions co-released with H2O and CO2 can only be observed before the inbound equinox, when the comet was still far from the sun and the abundance of highly volatile molecules associated with CO2 outgassing were lower. The corresponding CO2 is likely seasonal frost, which sublimated and lost its trapped highly volatile species before re-freezing during the previous apparition. CO, on the other hand, was elevated during the same time and requires further investigation