THE EFFECTS OF ION IRRADIATION ON THE EVOLUTION OF THE CARRIER OF THE 3.4 MICRON INTERSTELLAR ABSORPTION BAND

Carbon grains in the interstellar medium evolve through exposure to UV photons, heat, gas, and cosmic rays. Understanding their formation, evolution, and destruction is an essential component of evaluating the composition of the dust available for newly forming planetary systems. The 3.4 lm absorption band, attributed to the aliphatic C"H stretch vibration, is a useful probe of the degree to which energetic processing affects hydrogenated carbon grains. Here we report on the effects of ion bombardment of two different kinds of nano-size hydrogenated carbon grains with different hydrogen content. Grain samples, both with and without a mantle of H2O ice, were irradiated with 30 keV He + to simulate cosmic-ray processing in both diffuse and dense interstellar medium conditions. The ion fluences ranged between 1:5 � 10 13 and 7:9 � 10 15 ions cm � 2 . Infrared and Raman spectroscopy were used to study the effects of ion irradiation on grains. In both the dense and diffuse interstellar medium simulations, ion bombardment led to a reduction of the 3.4 lm band intensity. To discuss the effects of cosmic-ray irradiation of interstellar hydrogenated carbon materials we adopt the approximation of 1 MeV monoenergetic protons. An estimate of the C"H bond destruction cross section by 1 MeV protons was made based on experiments using 30 keV He + ions and model calculations. In combination with results from our previous studies, which focused on UV irradiation and thermal H atom bombardment, the present results indicate that the C"H bond destruction by fastcolliding charged particles is negligible with respect to that of UV photons in the diffuse ISM. However, in dense cloud regions, cosmic-ray bombardment is the most significant C"H bond destruction mechanism when the optical depth corresponds to values of the visual extinction larger than � 5 mag. The results presented here strengthen the new interpretation of the evolution of the interstellar aliphatic component (i.e., the C"H bonds in the CH2 and CH3 groups) as evidenced by the presence of the 3.4 lm absorption band in the diffuse medium and the absence of such a signature in the dense cloud environment. The evolutionary transformation of carbon grains, induced by H atoms, UV photons, and cosmic rays, indicates that C"H bonds are readily formed, in situ, in the diffuse interstellar medium and are destroyed in the dense cloud environment

Synthesis of CO and CO2 Molecules by UV Irradiation of Water Ice-covered Hydrogenated Carbon Grains

We present the results of UV irradiation with Lyα photons of carbon grains with a water ice cap at 11 K. Formation of CO and CO2 molecules takes place during irradiation. An estimation of the formation cross section of these molecules by Lyα photons has been obtained from the intensity increase of their infrared stretching bands as a function of the photon fluence. The fraction of carbon in the grains converted to CO and CO2 by UV photons is 0.06 and 0.05, respectively. The spectral profile of the CO stretching feature and that of the CO2 bending mode indicate a polar environment for these molecules. On the basis of the present laboratory results and those obtained in previous work on ion irradiation of similar samples, it has been possible to estimate the contribution of polar CO and CO2 produced on carbon grains by energetic processing to the observed column densities of these molecules for dense clouds whose visual extinction is known. A significant amount of polar CO and CO2 is produced through the mechanism we have studied. Furthermore, we have found that the laboratory profile of the bending band of CO2 produced on carbon grains is compatible with that observed toward the field star Elias 16

Solid CO_2 in low-mass young stellar objects: Comparison between Spitzer and laboratory spectra

Context. Solid interstellar CO_2 is an abundant component of ice dust mantles. Its ubiquity towards quiescent molecular clouds, as well as protostellar envelopes, has recently been confirmed by the IRS (InfraRed Spectrograph) aboard the Spitzer Space Telescope. Although it has been shown that CO_2 cannot be efficiently formed in the gas phase, the CO_2 surface formation pathway is still unclear. To date several CO_2 surface formation mechanisms induced by energetic (e.g., UV photolysis and cosmic ray irradiation) and non-energetic (e.g., cold atom addition) input have been proposed. Aims. Our aim is to investigate the contribution of cosmic ray irradiation to the formation of CO_2 in different regions of the interstellar medium (ISM). To achieve this goal we compared quantitatively laboratory data with the CO_2 bending mode band profile observed towards several young stellar objects (YSOs) and a field star by the Spitzer Space Telescope. Methods. All the experiments presented here were performed at the Laboratory for Experimental Astrophysics in Catania (Italy). The interstellar relevant samples were all irradiated with fast ions (30−200 keV) and subsequently annealed in a stainless steel high vacuum chamber (P < 10^(-7) mbar). Chemical and structural modifications of the ice samples were monitored by means of infrared spectroscopy. Laboratory spectra were then used to fit some thirty observational spectra. Results. A qualitative analysis shows that a good fit can be obtained with a minimum of two components. The choice of the laboratory components is based on the chemical-physical condition of each source. A quantitative analysis of the sources with known visual extinction (A_V) and methanol abundances highlights that the solid carbon dioxide can be efficiently and abundantly formed after ion irradiation of interstellar ices in all the selected YSOs in a time compatible with cloud lifetimes (3 × 10^7 years). Only in the case of field stars can the expected CO_2 column density formed upon energetic input not explain the observed abundances. This result, to be confirmed along the line of sight to different quiescent clouds, gives an indirect indication that CO_2 can also be formed in an early cloud stage through surface reactions induced by non-energetic mechanisms. In a later stage, when ices are exposed to higher UV and cosmic ray doses, the CO_2 total abundance is strongly affected by energetic formation mechanisms. Conclusions. Our results indicate that energetic processing of icy grain mantles significantly contribute to the formation of solid phase interstellar CO_2

High Resolution 4.7 um Keck/NIRSPEC Spectra of Protostars. I: Ices and Infalling Gas in the Disk of L1489 IRS

We explore the infrared M band (4.7 um) spectrum of the class I protostar L1489 IRS in the Taurus Molecular Cloud. This is the highest resolution wide coverage spectrum at this wavelength of a low mass protostar observed to date (R=25,000; Dv=12 km/s). Many narrow absorption lines of gas phase 12CO, 13CO, and C18O are detected, as well as a prominent band of solid 12CO. The gas phase 12CO lines have red shifted absorption wings (up to 100 km/s), likely originating from warm disk material falling toward the central object. The isotopes and the 12CO line wings are successfully fitted with a contracting disk model of this evolutionary transitional object (Hogerheijde 2001). This shows that the inward motions seen in millimeter wave emission lines continue to within ~0.1 AU from the star. The colder parts of the disk are traced by the prominent CO ice band. The band profile results from CO in 'polar' ices (CO mixed with H2O), and CO in 'apolar' ices. At the high spectral resolution, the 'apolar' component is, for the first time, resolved into two distinct components, likely due to pure CO and CO mixed with CO2, O2 and/or N2. The ices have probably experienced thermal processing in the upper disk layer traced by our pencil absorption beam: much of the volatile 'apolar' ices has evaporated and the depletion factor of CO onto grains is remarkably low (~7%). This study shows that high spectral resolution 4.7 um observations provide important and unique information on the dynamics and structure of protostellar disks and the evolution of ices in these disks.Comment: 11 pages, 6 figures Scheduled to appear in ApJ 568 n2, 1 April 200

Novel measurements of refractive index, density and mid-infrared integrated band strengths for solid O2, N2O and NO2: N2O4 mixtures

We present novel measurements of the refractive index, density and integrated band strengths of mid-infrared features of solid N2O at 16 K and of NO2 and N2O4 in two frozen NO2: N2O4 mixtures deposited at 16 and 60 K. The refractive index and density measurements were performed also for frozen O2 deposited at 16 K. In this case, the integrated band strength values could not be determined since O2 is a homonuclear molecule and therefore its fundamental mode is not infrared active. The solid samples were analysed by infrared spectroscopy in the 8000÷800 cm-1 range. The sample thickness was measured by the interference curve obtained using a He-Ne laser operating at 543 nm. The refractive index at this laser wavelength was obtained, by numerical methods, from the measured amplitude of the interference curve. The density values were obtained using the Lorentz-Lorenz relation. Integrated band strength values were then obtained by a linear fit of the integrated band intensities plotted versus column density values. The astrophysical relevance of these novel measurements is briefly discusse

Evaluation of polygenic determinants of non-alcoholic fatty liver disease (NAFLD) by a candidate genes resequencing strategy

NAFLD is a polygenic condition but the individual and cumulative contribution of identified genes remains to be established. To get additional insight into the genetic architecture of NAFLD, GWAS-identified GCKR, PPP1R3B, NCAN, LYPLAL1 and TM6SF2 genes were resequenced by next generation sequencing in a cohort of 218 NAFLD subjects and 227 controls, where PNPLA3 rs738409 and MBOAT7 rs641738 genotypes were also obtained. A total of 168 sequence variants were detected and 47 were annotated as functional. When all functional variants within each gene were considered, only those in TM6SF2 accumulate in NAFLD subjects compared to controls (P = 0.04). Among individual variants, rs1260326 in GCKR and rs641738 in MBOAT7 (recessive), rs58542926 in TM6SF2 and rs738409 in PNPLA3 (dominant) emerged as associated to NAFLD, with PNPLA3 rs738409 being the strongest predictor (OR 3.12, 95% CI, 1.8-5.5, P 0.28 was associated with a 3-fold increased risk of NAFLD. Interestingly, rs61756425 in PPP1R3B and rs641738 in MBOAT7 genes were predictors of NAFLD severity. Overall, TM6SF2, GCKR, PNPLA3 and MBOAT7 were confirmed to be associated with NAFLD and a score based on these genes was highly predictive of this condition. In addition, PPP1R3B and MBOAT7 might influence NAFLD severity

Mild N-Alkylation of Amines with Alcohols Catalyzed by Acetate Ruthenium Complexes

The formation of C-N bonds for the preparation of amines compounds is a reaction of high relevance for the synthesis of bulk and fine chemicals (1). The preparation of several drug molecules involves N-substitution transformations that are usually performed by reaction of amines with alkylating agents or via reductive amination. In this context, the catalytic Nalkylation of amines using environmentally friendly alcohols as alkylating reagents and affording water as only byproduct, is an attractive atom-economic way for the C-N bond formation (2,3). We report here the straightforward synthesis of the carboxylate ruthenium complexes of formula Ru(OAc)2(diphosphane)(CO)n (n = 0, 1). These compounds are efficient catalysts for the N-alkylation of amines using primary alcohols under mild reaction conditions, with an alcohol / amine molar ratio of 10-100. Evidence has been provided that in catalysis a monohydride species is formed through an equilibrium reaction