Thermal processing and interactions of ethyl formate in model astrophysical ices containing water and ethanol

Temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) have been used to investigate the interactions between ethyl formate and water and ethyl formate and ethanol in model astrophysical ices adsorbed on a graphitic model grain surface. Experiments show that the ethyl formate forms hydrogen bonds to both water and ethanol via the oxygen lone pairs. This leads to the observation of shifts in the vibrational wavenumber of the C=O and C-O-C modes of ethyl formate, which can potentially be used to identify the environment of this complex organic molecule in astronomical observations. TPD data show that the interaction of ethyl formate with water is stronger than that with ethanol, with an additional species being observed in the TPD spectrum corresponding to the desorption of ethyl formate directly bonded to the water ice surface. The desorption energy of ethyl formate adsorbed on water ice was found to be 48.5 kJ mol-1, compared to 43.2 kJ mol-1 for pure ethyl formate monolayers. Ethyl formate also traps in water ice, and undergoes volcano desorption at the water amorphous to crystalline phase transition temperature. In contrast to the water, ethanol has very little effect on the desorption of ethyl formate, with the two species behaving independently even in a co-deposited ice

A TPD and RAIRS comparison of the low temperature behavior of benzene, toluene, and xylene on graphite

The first comparative study of the surface behavior of four small aromatic molecules, benzene, toluene, p-xylene, and o-xylene, adsorbed on graphite at temperatures ≤30 K, is presented. Intermolecular interactions are shown to be important in determining the growth of the molecules on the graphite surface at low (monolayer) exposures. Repulsive intermolecular interactions dominate the behavior of benzene and toluene. By contrast, stronger interactions with the graphite surface are observed for the xylene isomers, with islanding observed for o-xylene. Multilayer desorption temperatures and energies increase with the size of the molecule, ranging from 45.5 to 59.5 kJ mol−1 for benzene and p-xylene, respectively. Reflection absorption infrared spectroscopy gives insight into the effects of thermal processing on the ordering of the molecules. Multilayer benzene, p-xylene, and o-xylene form crystalline structures following annealing of the ice. However, we do not observe an ordered structure for toluene in this study. The ordering of p-xylene shows a complex relationship dependent on both the annealing temperature and exposure

Using laboratory investigations to aid the identification of small aromatic molecules in water-containing astrophysical ices

Monocyclic aromatic hydrocarbons such as benzene, toluene and xylene are thought to play an important role as precursors to the formation of polycyclic aromatic hydrocarbons (PAHs) and their methylated counterparts in a range of astrophysical environments. Benzene has been detected in two carbon rich objects and models have predicted that it could also be present in the interstellar medium (ISM). It has hence been speculated that small aromatic molecules are present in molecular clouds in the ISM, although they have not been detected to date. If they are present in the ISM, they are likely to exist in water-ice dominated icy mantles on the surface of dust grains. We present a laboratory study of benzene, toluene and two xylene isomers (ortho- and para-xylene) in the presence of water ice on a carbonaceous model dust grain surface (highly oriented pyrolytic graphite, HOPG). Temperature programmed desorption (TPD) shows how the desorption of the molecules is affected by the presence of water ice. The importance of these data for astrophysical situations is demonstrated by the use of TPD-derived kinetic parameters to generate a simple model of desorption in dense molecular clouds on an astrophysical timescale. Since benzene, toluene and xylene have not been detected in water-dominated icy mantles to date, desorption has been simulated in a range of different water-containing environments to show the different behaviour expected depending on ice composition. The simulations demonstrate how future observations of aromatic molecules in dense molecular clouds at known temperatures could reveal which environments the molecules are in. Data from these experiments are also used to predict the behaviour of other, larger, aromatic molecules such as PAHs. Reflection absorption infrared spectroscopy (RAIRS) is also used to record the infrared spectra of the small molecules in different water ice configurations. These spectra can be used to aid identification of these icy aromatics in future observations, such as those that will be possible with the James Webb Space Telescope (JWST). In all cases, spectra of mixed ices consisting of the aromatic molecule and amorphous water ice show evidence of interactions between the water ice and the aromatic species

Peeling the astronomical onion

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H2O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol-1 on the silica surface below 25 K and 0 kJ mol-1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface

Methods for specifying the target difference in a randomised controlled trial : the Difference ELicitation in TriAls (DELTA) systematic review

Peer reviewedPublisher PD

Ten millennia of hepatitis B virus evolution

Hepatitis B virus (HBV) has been infecting humans for millennia and remains a global health problem, but its past diversity and dispersal routes are largely unknown. We generated HBV genomic data from 137 Eurasians and Native Americans dated between ~10,500 and ~400 years ago. We date the most recent common ancestor of all HBV lineages to between ~20,000 and 12,000 years ago, with the virus present in European and South American hunter-gatherers during the early Holocene. After the European Neolithic transition, Mesolithic HBV strains were replaced by a lineage likely disseminated by early farmers that prevailed throughout western Eurasia for ~4000 years, declining around the end of the 2nd millennium BCE. The only remnant of this prehistoric HBV diversity is the rare genotype G, which appears to have reemerged during the HIV pandemic

A laboratory model of Saturn's North Polar hexagon

A hexagonal structure has been observed at ~76°N on Saturn since the 1980s (Godfrey, D. A. [1988]. Icarus 76, 335-356). Recent images by Cassini (Baines, K, Momary, T., Roos-Serote, M., Atreya, S., Brown, R., Buratti, B., Clark, R., Nicholson, P. [2007]. Geophys. Res. Abstr. 9, 02109; Baines, K., Momary, T., Fletcher, L., Kim, J., Showman, A., Atreya, S., Brown, R., Buratti, B., Clark, R., Nicholson, P. [2009]. Geophys. Res. Abstr. 11, 3375] have shown that the feature is still visible and largely unchanged. Its long lifespan and geometry has puzzled the planetary physics community for many years and its origin remains unclear. The measured rotation rate of the hexagon may be very close to that of the interior of the planet (Godfrey, D. A. [1990]. Science 247, 1206-1208; Caldwell, J., Hua, X., Turgeon, B., Westphal, J. A., Barnet, C. D. [1993]. Science 206, 326-329; Sánchez-Lavega, A., Lecacheux, J., Colas, F., Laques, P. [1993]. Science 260, 329-332), leading to earlier interpretations of the pattern as a stationary planetary wave, continuously forced by a nearby vortex (Allison, M., Godfrey, D. A., Beebe, R. F. [1990]. Science 247, 1061-1063). Here we present an alternative explanation, based on an analysis of both spacecraft observations of Saturn and observations from laboratory experiments where the instability of quasi-geostrophic barotropic (vertically uniform) jets and shear layers is studied. We also present results from a barotropic linear instability analysis of the saturnian zonal wind profile, which are consistent with the presence of the hexagon in the North Pole and absence of its counter-part in the South Pole. We propose that Saturn's long-lived polygonal structures correspond to wavemodes caused by the nonlinear equilibrium of barotropically unstable zonal jets

VAMAS interlaboratory study for desorption electrospray ionization mass spectrometry (DESI MS) intensity repeatability and constancy

A VAMAS (Versailles Project on Advanced Materials and Standards) interlaboratory study for desorption electrospray ionization mass spectrometry (DESI MS) measurements has been conducted with the involvement of 20 laboratories from 10 countries. Participants were provided with an analytical protocol and two reference samples: a thin layer of Rhodamine B and double-sided adhesive tape, each on separate glass slides. The studies comprised acquisition of positive ion mass spectra in predetermined m/z ranges. No sample preparation was required. Results for Rhodamine B show that very consistent craters may be generated. However, inadequacies of the spray and sample stage designs often lead to variable crater shapes. The average repeatability for Rhodamine B is 50%. Yet, repeatabilities better than 20% can be achieved. Rhodamine B proved to be an excellent reference sample to check the sample erosion crater, the sample stage movement and memory effects. Adhesive tape samples show that their average absolute intensity repeatability is 30% and the relative repeatability is 9%. The constancy of these spectra from relative intensities gives day-to-day average relative repeatabilities of 31%, three times worse than the short-term repeatability. Significant differences in the spectra from different laboratories arise from the different adventitious adducts observed or from contaminants that may cause the higher day-to-day variations. It is thought that this may be overcome by allowing some 20 ppb of sodium to be always present in the solvent, to be the dominating adduct. Repeatabilities better than 5% may be achieved with adequate control

Correction to VAMAS Interlaboratory Study for Desorption Electrospray Ionization Mass Spectrometry (DESI MS) Intensity Repeatability and Constancy

Correction to VAMAS Interlaboratory Study for Desorption Electrospray Ionization Mass Spectrometry (DESI MS) Intensity Repeatability and Constanc

Analysis of urine, oral fluid and fingerprints by liquid extraction surface analysis coupled to high resolution MS and MS/MS - Opportunities for forensic and biomedical science

Liquid Extraction Surface Analysis (LESA) is a new, high throughput tool for ambient mass spectrometry. A solvent droplet is deposited from a pipette tip onto a surface and maintains contact with both the surface and the pipette tip for a few seconds before being re-aspirated. The technique is particularly suited to the analysis of trace materials on surfaces due to its high sensitivity and low volume of sample removal. In this work, we assess the suitability of LESA for obtaining detailed chemical profiles of fingerprints, oral fluid and urine, which may be used in future for rapid medical diagnostics or metabolomics studies. We further show how LESA can be used to detect illicit drugs and their metabolites in urine, oral fluid and fingerprints. This makes LESA a potentially useful tool in the growing field of fingerprint chemical analysis, which is relevant not only to forensics but also to medical diagnostics. Finally, we show how LESA can be used to detect the explosive material RDX in contaminated artificial fingermarks.OLD ChemE/Organic Materials and Interface