Interstellar grain chemistry and organic molecules

The detection of prominant infrared absorption bands at 3250, 2170, 2138, 1670 and 1470 cm(-1) (3.08, 4.61, 4.677, 5.99 and 6.80 micron m) associated with molecular clouds show that mixed molecular (icy) grain mantles are an important component of the interstellar dust in the dense interstellar medium. These ices, which contain many organic molecules, may also be the production site of the more complex organic grain mantles detected in the diffuse interstellar medium. Theoretical calculations employing gas phase as well as grain surface reactions predict that the ices should be dominated only by the simple molecules H2O, H2CO, N2, CO, O2, NH3, CH4, possibly CH3OH, and their deuterated counterparts. However, spectroscopic observations in the 2500 to 1250 cm(-1)(4 to 8 micron m) range show substantial variation from source reactions alone. By comparing these astronomical spectra with the spectra of laboratory-produced analogs of interstellar ices, one can determine the composition and abundance of the materials frozen on the grains in dense clouds. Experiments are described in which the chemical evolution of an interstellar ice analog is determined during irradiation and subsequent warm-up. Particular attention is paid to the types of moderately complex organic materials produced during these experiments which are likely to be present in interstellar grains and cometary ices

Aromatic components in cometary materials

The Raman spectra of interplanetary dust particles (IDPs) collected in the stratosphere show that two bands at about 1350 and 1600 delta/cm and a broader feature between 2200 and 3300 delta/cm that are characteristic of aromatic molecular units with ordered domains smaller than 25 A in diameter. This suggests that the carbonaceous material in IDPs may be similar to the polymeric component seen in meteorites, where this material is thought to consist of aromatic molecular units that are randomly interlinked by short aliphatic bridges. The features in the Raman spectra of IDPs are similar in position, and relative strength to interstellar infrared emission features that have been attributed to vibrational transitions in free molecular polycyclic aromatic hydrocarbons. Taken together, these observations suggest that some fraction of the carbonaceous materials in IDPs may have been produced in circumstellar dust shells and only slightly modified in interstellar space

Interstellar grain chemistry and the composition of comets

During the past 15 years considerable progress in observational techniques has been achieved in the middle infrared, the spectral region most diagnostic of molecular vibrations. Spectra of many different astronomical infrared sources are now available. By comparing these astronomical spectra with the spectra of lab ices, one can determine the composition and abundance of the icy materials frozen on the cold dust grains present in the interior of molecular clouds. In the experiments described, the assumption is made that cometary ices are similar to interstellar ices. As an illustration of the processes which can take place as an ice is irradiated and subsequently warmed, the infrared spectra is presented of the mixture H2O:CH3OH:CO:NH3:C6H14 (100:50:10:10:10). Apart from the last species, the ratio of these compounds is representative of the simplest ices found in interstellar clouds

Methanol in the sky with diamonds

The present of gas phase methanol in dense interstellar molecular clouds was established by radio detection of its rotational emission lines. However, the position, width, and profile of a absorption band near 1470 cm(exp -1) in the IR spectra of many dense molecular clouds strongly suggests that solid methanol is an important component of interstellar ices. In an attempt to better constrain the identification of 1470 cm(exp -1) feature, we began a program to search for other characteristic absorption bands of solid state methanol in the spectra of objects known to produce this band. One such feature is now identified in the spectra of several dense molecular clouds and its position, width, and profile fit well with those of laboratory H2O:CH3OH ices. Thus, the presence of methanol-bearing ices in space is confirmed

Clathrate type 2 hydrate formation in vacuo under astrophysical conditions

The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K

A multicomponent model of the infrared emission from Comet Halley

A model based on a mixture of coated silicates and amorphous carbon grains produces a good spectral match to the available Halley data and is consistent with the compositional and morphological information derived from interplanetary dust particle studies and Halley flyby data. The dark appearance of comets may be due to carbonaceous coatings on the dominant (by mass) silicates. The lack of a 10 micrometer feature may be due to the presence of large silicate grains. The optical properties of pure materials apparently are not representative of cometary materials. The determination of the optical properties of additional silicates and carbonaceous materials would clearly be of use

Hydrogenated Polycyclic Aromatic Hydrocarbons and the 2940 and 2850 Wavenumber (3.40 and 3.51 micron) Infrared Emission Features

The 3150-2700/cm (3.17-3.70 micron) range of the spectra of a number of Ar-matrix-isolated PAHs containing excess H atoms (H(sub n)-PAHS) are presented. This region covers features produced by aromatic and aliphatic C-H stretching vibrations as well as overtone and combination bands involving lower lying fundamentals. The aliphatic C-H stretches in molecules of this type having low to modest excess H coverage provide excellent fits to a number of the weak emission features superposed on the plateau between 3080 and 2700/cm (3.25 and 3.7 micron) in the spectra of many planetary nebulae, reflection nebulae, and H II regions. Higher H coverage is implied for a few objects. We compare these results in context with the other suggested identifications of the emission features in the 2950-2700/cm (3.39-3.70 micron) region and briefly discuss their astrophysical implications

Spectral structure near the 11.3 micron emission feature

If the 11.3 micron emission feature seen in the spectra of many planetary nebulae, H II regions, and reflection nebulae is attributable to polycyclic aromatic hydrocarbons (PAHs), then additional features should be present between 11.3 and 13.0 microns. Moderate resolution spectra of NGC 7027, HD 44179, BD+30 deg 3639, and IRAS 21282+5050 are presented which show evidence for new emission features centered near 12.0 and 12.7 microns. These are consistent with an origin from PAHs and can be used to constrain the molecular structure of the family of PAHs responsible for the infrared features. There is an indication that coronene-like PAHs contribute far more to the emission from NGC 7027 than to the emission from HD 44179. The observed asymmetric profile of the 11.3 micron band in all the spectra is consistent with the slight anharmonicity expected in the C-H out-of-plane bending mode in PAHs. A series of repeating features between 10 and 11 microns in the spectrum of HD 44179 suggests a simple hydride larger than 2 atoms is present in the gas phase in this object

Dual Antiplatelet Therapy Prior to Expedited Carotid Surgery Reduces Recurrent Events Prior to Surgery without Significantly Increasing Peri-operative Bleeding Complications

ObjectiveA daily Rapid-Access TIA Clinic was introduced in 2008, where symptomatic patients were started on 75 mg aspirin + 40 mg simvastatin by the referring doctor, before attending the clinic. Following clinic assessment, patients with 50–99% stenoses were transferred to the vascular unit for carotid endarterectomy (CEA). In two audits (n = 212 patients), the median delay from transfer to the vascular unit to undergoing CEA was 3 days, during which time 28 patients (13%) suffered recurrent neurological events. It was hypothesized that early introduction of dual antiplatelet therapy (by adding clopidogrel 75 mg once parenchymal haemorrhage was excluded in the TIA clinic) might significantly reduce recurrent events between transfer to the surgical unit and undergoing CEA.MethodsProspective audit in 100 consecutive, recently symptomatic patients receiving dual antiplatelet therapy. Endpoints were: prevalence of recurrent events between transfer from the TIA clinic and undergoing CEA; rates of spontaneous embolization prior to undergoing CEA; and prevalence of haemorrhagic complicationsResultsThe median delay from symptom to CEA was 8 days (IQR 5–15). The median delay between transfer from the TIA clinic to CEA was 3 days (IQR 2–5), during which time three patients (3%) suffered recurrent TIAs. This represents a fivefold reduction compared with previous audit data (OR 4.9, 95% CI 1.5–16.6, p = .01) and was matched by a fourfold reduction in the prevalence of spontaneous embolization from 39/189 (21%) previously to 5/83 (5%) in the current audit (OR 4.1, 95% CI 1.5–10.7, p = .0047). The 30-day death/stroke rate was 1%. There were three haemorrhagic complications: stroke caused by haemorrhagic transformation of an infarct; exploration for neck haematoma; and debridement and skin grafting for spontaneous shin haematoma.ConclusionEarly introduction of dual antiplatelet therapy was associated with a significant reduction in recurrent neurological events and spontaneous embolization prior to CEA, without incurring a significant increase in major peri-operative bleeding complications

Formation of Nucleobases from the UV Photo-Irradiation of Pyrimidine in Astrophysical Ice Analogs

Astrochemistry laboratory simulations have shown that complex organic molecules including compounds of astrobiological interest can be formed under interstellarl/circumstellar conditions from the vacuum UV irradiation of astrophysical ice analogs containing H2O, CO, CO2, CH3OH, NH13, etc. Of all prebiotic compounds, the formation of amino acids under such experimental conditions has been the most extensively studied. Although the presence of amino acids in the interstellar medium (ISM) has yet to be confirmed, they have been detected in meteorites, indicating that biomolecules and/or their precursors can be formed under extraterrestrial, abiotic conditions. Nucleobases, the building blocks of DNA and RNA, as well as other 1V-heterocycles, have also been detected in meteorites, but like amino acids, they have yet to be observed in the ISM. In this work, we present an experimental study of the formation of pyrimidine-based compounds from the UV photo-irradiation of pyrimidine in ice mixtures containing H2O, NH3, and/or CH3OH at low temperature and pressure