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

Prognostic model to predict postoperative acute kidney injury in patients undergoing major gastrointestinal surgery based on a national prospective observational cohort study.

Background: Acute illness, existing co-morbidities and surgical stress response can all contribute to postoperative acute kidney injury (AKI) in patients undergoing major gastrointestinal surgery. The aim of this study was prospectively to develop a pragmatic prognostic model to stratify patients according to risk of developing AKI after major gastrointestinal surgery. Methods: This prospective multicentre cohort study included consecutive adults undergoing elective or emergency gastrointestinal resection, liver resection or stoma reversal in 2-week blocks over a continuous 3-month period. The primary outcome was the rate of AKI within 7 days of surgery. Bootstrap stability was used to select clinically plausible risk factors into the model. Internal model validation was carried out by bootstrap validation. Results: A total of 4544 patients were included across 173 centres in the UK and Ireland. The overall rate of AKI was 14·2 per cent (646 of 4544) and the 30-day mortality rate was 1·8 per cent (84 of 4544). Stage 1 AKI was significantly associated with 30-day mortality (unadjusted odds ratio 7·61, 95 per cent c.i. 4·49 to 12·90; P < 0·001), with increasing odds of death with each AKI stage. Six variables were selected for inclusion in the prognostic model: age, sex, ASA grade, preoperative estimated glomerular filtration rate, planned open surgery and preoperative use of either an angiotensin-converting enzyme inhibitor or an angiotensin receptor blocker. Internal validation demonstrated good model discrimination (c-statistic 0·65). Discussion: Following major gastrointestinal surgery, AKI occurred in one in seven patients. This preoperative prognostic model identified patients at high risk of postoperative AKI. Validation in an independent data set is required to ensure generalizability

Gas-phase kinetics of the N + C2N reaction at low temperature

The rate of the gas-phase N(4S) + C2N(2Πi) reaction has been measured in a continuous supersonic flow reactor down to 54 K through the relative-rate method using the N(4S) + OH(X2Π) → H(2S) + NO(X2Π) reaction as a reference. The microwave discharge technique was employed to produce high concentrations of atomic nitrogen. Pulsed laser photolysis of precursor molecules Cl3C2N and H2O2 at 212 nm in situ led to C2N and OH radical formation, respectively. The rate constant is shown to be approximately independent of temperature, in contrast to previous studies of atom-radical reactions involving atomic nitrogen. While the reaction rate is faster than previously estimated, astrochemical simulations indicate that this reaction is probably only a minor source of CN radicals in dense interstellar clouds