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22 pags., 8 figs., 1 tab., Massive stars disrupt their natal molecular cloud material through radiative and mechanical feedback processes. These processes have profound effects on the evolution of interstellar matter in our Galaxy and throughout the universe, from the era of vigorous star formation at redshifts of 1-3 to the present day. The dominant feedback processes can be probed by observations of the Photo-Dissociation Regions (PDRs) where the far-ultraviolet photons of massive stars create warm regions of gas and dust in the neutral atomic and molecular gas. PDR emission provides a unique tool to study in detail the physical and chemical processes that are relevant for most of the mass in inter-and circumstellar media including diffuse clouds, proto-planetary disks, and molecular cloud surfaces, globules, planetary nebulae, and star-forming regions. PDR emission dominates the infrared (IR) spectra of star-forming galaxies. Most of the Galactic and extragalactic observations obtained with the James Webb Space Telescope (JWST) will therefore arise in PDR emission. In this paper we present an Early Release Science program using the MIRI, NIRSpec, and NIRCam instruments dedicated to the observations of an emblematic and nearby PDR: the Orion Bar. These early JWST observations will provide template data sets designed to identify key PDR characteristics in JWST observations. These data will serve to benchmark PDR models and extend them into the JWST era. We also present the Science-Enabling products that we will provide to the community. These template data sets and Science-Enabling products will guide the preparation of future proposals on star-forming regions in our Galaxy and beyond and will facilitate data analysis and interpretation of forthcoming JWST observations., Support for JWST-ERS program ID 1288 was provided through grants from the STScI under NASA contract NAS5-03127 to STScI (K.G., D.V.D.P., M.R.), Univ. of Maryland (M.W., M.P.), Univ. of Michigan (E.B., F.A.), and Univ. of Toledo (T.S.-Y.L.). O.B. and E.H. are supported by the Programme National “Physique et Chimie du Milieu Interstellaire” (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES, and through APR grants 6315 and 6410 provided by CNES. E. P. and J.C. acknowledge support from the National Science and Engineering Council of Canada (NSERC) Discovery Grant program (RGPIN-2020-06434 and RGPIN-2021-04197 respectively). E.P. acknowledges support from a Western Strategic Support Accelerator Grant (ROLA ID 0000050636). J.R.G. and S.C. thank the Spanish MCINN for funding support under grant PID2019-106110GB-I00. Work by M.R. and Y.O. is carried out within the Collaborative Research Centre 956, subproject C1, funded by the Deutsche Forschungsgemeinschaft (DFG)—project ID 184018867. T.O. acknowledges support from JSPS Bilateral Program, grant No. 120219939. M.P. and M.W. acknowledge support from NASA Astrophysics Data Analysis Program award #80NSSC19K0573. C.B. is grateful for an appointment at NASA Ames Research Center through the San José State University Research Foundation (NNX17AJ88A) and acknowledges support from the Internal Scientist Funding Model (ISFM) Directed Work Package at NASA Ames titled: “Laboratory Astrophysics—The NASA Ames PAH IR Spectroscopic Database.”

Introduction: Ceres is the largest object of the Solar System main belt with a complex geological and chemical history, which experienced extensive water related processes and geochemical differentiation [1]. Ceres’ surface is characterized by dark materials, phyllosilicates, ammonium-bearing minerals, carbonates, water ice, and salts. In addition to a global presence of carbon-bearing chemistry, local concentration of aliphatic organics has been detected by Dawn mission [2]. The mission, thanks to the data collected by the Italian instrument VIR [3], showed clear evidence of a high amount of aliphatic organic material on the surface of Ceres [4, 5, 6]. This has raised new questions about the origin and preservation of this material, especially when considering its high estimated abundance (Fig 1). We started a series of laboratory studies on physicochemical evolution of organic material interacting with minerals thought to be present on Ceres. The goal is to understand the transformations induced on these samples by processing with ultraviolet radiation. Fig. 1 Ceres spectra of the organic-rich area in Ernutet crater (label “Organics”); of a background organic-poor area from a region southeast of Ernutet (label “Background”); and Occator bright material (label “Carbonate”) [4]. Results: In this study, we mixed organic material with a mixture of minerals considered a spectral analog of the Ceres surface. Specifically, we mixed undecanoic acid and solid material made of serpentine, magnetite, carbonate and ammonium bearing montmorillonite with a ratio of 1:80 (organic:mineral). Diffuse FTIR reflectance spectra were acquired in vacuum. Spectra of simulant are resembling the Ceres surface composition (Fig. 2) organic rich area, even if the proportions between the bands of clays, carbonates and organics are not the same as seen on Ceres. We irradiated the sample in the vacuum chamber at room temperature using an UV lamp to simulate the solar radiation. The photon flux was 2.75x1017 ph. cm-2s-1 in the 200-400 nm spectral range as measured through a single monochromator Spectro 320 spectrometer. The simulant was irradiated at increasing fluence up to irradiation time of about 7 hours and the degradation process was monitored in real time with FTIR spectroscopy by measuring the changes in the spectral features (band areas). In Fig. 4 the reflectance spectra of the simulant as prepared and after UV irradiation at 180, 2280, and 21180 s are showed. The bands area of NH3 at 3 μm and aliphatic CH2/CH3 at 3.4 μm are decreasing as the irradiation fluence increases with time. Fig. 2 Average spectrum of Ceres Ernutet organic-rich ares (black) compared to laboratory simulant (blue). Spectra are normalized at 2.6 μm. Each band area, which is proportional to the number of functional groups, was evaluated at different irradiation time and the degradation rate was obtained by fitting the band areas vs irradiation time using an exponential function. This method permits to determine the degradation cross section of each band, which is the probability that chemical bonds are broken by UV radiation. In particular, for the aliphatic band at 3.4 μm it was possible to obtain the degradation cross section of the whole band, 5.85x10-21 cm2. and of every single band component distinguishing between CH2 and CH3 bonds behavior under irradiation. In presence of mineral simulant, the degradation rate of aliphatic compounds extrapolated to the estimated UV flux at the surface of Ceres gives a half-lifetime of 215 days. This result coupled with resurfacing process time scale of million years could justify the absence of detectable organics on most of the Ceres’ surface. However, this result would not be able to explain the presence of organics in the organic-rich area in Ernutet crater. Furthermore, as can be seen from Fig. 3, UV radiation not only degrades the CH bonds but also affects the NH bonds present in the ammoniated silicates. In this latter case the degradation cross section for the whole band is 2.05x10-21 cm2 which is responsible of a less effective photodegradation process giving a degradation half-lifetime of about 613 days. This result also seems to be in contrast with the ubiquity of the presence of ammoniated silicates on Ceres. We have to recall that the experiments reported in this work have been done at room temperature. It is not excluded that photoprocessing at cryogenic temperature typical of Ceres surface can be less effective further reducing the degradation cross sections of CH and NH bonds. Discussion: As showed by VIR, the ammoniated band is ubiquitous on Ceres, which is in contrast with the fact that we expected the ammoniated band to be completely degraded. However, photodegradation acts on the first molecular layers of the surface exposed to the radiation. Furthermore, the visible and near infrared spectra detected by VIR are diffused by the first millimeters of the surface at a depth that cannot be affected by UV radiation. Therefore, the spectra are a combination of processed superficial material and underlying layers of the Ceres surface, which may retain the primitive characteristics of material rich in organic. However, it should be noted that in addition to UV, the surface is constantly bombarded by solar energetic particles (SEP) and galactic cosmic rays (GCR). This radiation also has the effect of breaking chemical bonds such as UV photons, but penetrating meters into the surface can alter deeper layers. These results suggest that there must be a resurfacing mechanism able to expose organic rich material that acts on a much shorter time scale than the geological one. Fig. 3 Diffuse reflectance spectra of the simulant as prepared (0 s) and after UV irradiation at 180, 2280, and 21180 s. Acknowledgements: This work is supported by INAF Main Stream program, grant “Evolution and alteration of organic material on Ceres”. References: [1] De Sanctis et al., 2016, Nature 536, 54–57 [2] Marchi et al., 2019, Nature Astr. 3, 140-145 [3] De Sanctis et al., 2011, Space Science Reviews 163, 329-369. [4] De Sanctis et al., 2017, Science 355, 719-722 [5] Pieters et al., 2018, Meteoritics and Planetary Science 53 (9), 1983-1998 [6] De Sanctis et al., 2019, MNRAS 482 (2), 2407–2421

The origin of organic compounds detected in meteorites and comets, some of which could serve as precursors of life on Earth, still remains an open question. The aim of the present study is to make one more step in revealing the nature and composition of organic materials of extraterrestrial particles by comparing infrared spectra of laboratory-made refractory organic residues to the spectra of cometary particles returned by the Stardust mission, interplanetary dust particles, and meteorites. Our results reinforce the idea of a pathway for the formation of refractory organics through energetic and thermal processing of molecular ices in the solar nebula. There is also the possibility that some of the organic material formed already in the parental molecular cloud before it entered the solar nebula. The majority of the IR "organic" bands of the studied extraterrestrial particles can be reproduced in the spectra of the laboratory organic residues. We confirm the detection of water, nitriles, hydrocarbons, and carbonates in extraterrestrial particles and link it to the formation location of the particles in the outer regions of the solar nebula. To clarify the genesis of the species, high-sensitivity observations in combination with laboratory measurements like those presented in this paper are needed. Thus, this study presents one more piece of the puzzle of the origin of water and organic compounds on Earth and motivation for future collaborative laboratory and observational projects., accepted for publication in ApJ

Summary Ceres is the largest object in the Solar System main belt. Clearly, Ceres experienced extensive water-related processes and geochemical differentiation and nowadays it is a body with a complex geological and chemical history [1]. Its surface is characterized by dark materials, phyllosilicates, ammonium-bearing minerals, carbonates, water ice, and salts. In addition to a global presence of carbon bearing chemistry, local concentration of aliphatic organics has been detected by Dawn [2]. In this context, we have started a series of laboratory spectroscopy measurements targeted to study the physicochemical interactions between organic material and minerals possibly present on Ceres. The goal is to understand the transformations induced on these samples by ultraviolet radiation, neutral atoms, and fast ions, under experimental conditions that simulate the environment of Ceres. The spectroscopic data obtained in laboratory experiments allow, through the comparison with the observations of the VIR spectrometer aboard the Dawn mission, to clarify the nature and origin of organic material identified on Ceres. Introduction Organic material in the minor bodies of the Solar System is an important component to understand planetary evolution and, eventually, the origin of life. Nevertheless, our knowledge on the subject is still limited. Recently the Dawn mission, thanks to the data collected by the Italian instrument VIR [3], showed clear evidence of a high amount of aliphatic organic material on the surface of Ceres [4, 5, 6] (Fig 1). This evidence has raised new questions about the origin and preservation of this material, especially when considering its high estimated abundance and the mineralogical context. Fig 1 Ceres spectra of the organic-rich area in Ernutet crater (label “Organics”); of a background organic-poor area from a region southeast of Ernutet (label “Background”); and of Occator bright material (label “Carbonate”) [4]. In order to understand the organic chemical species and in particular their abundance on Ceres, laboratory studies were performed [7]. The importance of having a direct comparison between laboratory and remote sensing data can provide a further investigation clues to shed light on the origin and evolution of Ceres. Through this project, we intend to study, through dedicated experiments, the interaction between minerals, water, and organic concerning the environmental conditions of Ceres. Making a synergistic use of complementary and indispensable skills present within INAF (Italian National Institute of Astrophysics) laboratories we investigated a complex issue such as that concerning the origin and preservation of organic molecules on planetary surfaces. Within INAF, complementary and unique realities coexist which, thanks to joint and coordinated work, can give a new interpretation of the physical-chemical processes active on Ceres. Project development and results In this study, we prepare mixtures of materials resembling the Ceres surface composition [8, 9] adding organic molecules in order to: (i) understand how organic molecules behave and eventually degrade on Ceres, in particular, how aliphatic molecules degrade by energetic processing with fast ions (keV-MeV) and UV photons [10, 11]. Moreover, the physico-chemical properties of the materials exposed to a flux of neutral atoms are investigated [12, 13]. (ii) evaluate the interaction between ammoniated minerals and simple organic molecules that may lead to the synthesis of complex compounds. In the presence of ultraviolet (UV) radiation, these minerals present on the surface of Ceres can show photocatalytic effects accelerating the photo-reactions, which generally destroy the original organic molecule and in the synthesis of new complex organic molecules [14]. (iii) evaluate the role of minerals in the protection or degradation of organic compounds. Some studies indicated a fundamental role of clays in the catalysis and preservation of organic materials [15]. Ceres is rich in clays and other hydrated minerals, making the interactions with the observed organics of particular interest. The project is carried out by several INAF institutes and laboratories. In detail: INAF-IAPS Istituto di Astrofisica e Planetologia Spaziali prepared the analog mineral mixtures taking into account the compositional information gained by VIR observations. INAF - Osservatorio Astrofisico di Arcetri subsequently doped the mixture with several organic investigating UV photostability in Ceres analog conditions and the influence of temperature. INAF -Osservatorio Astronomico di Capodimonte studied irradiation with atoms and temperature effect while INAF - Osservatorio Astrofisico di Catania performed irradiation with fast ions. Finally, results of laboratory measurements were compared with data obtained by VIR instrument onboard Dawn mission. AcknowledgementsThis work is support by INAF Main Stream programme, grant 1.05.01.86.08 Evoluzione ed alterazione del materiale organico su Cerere (ref. Maria Cristina De Sanctis). References [1] De Sanctis et al., 2016, Nature 536, 54–57 [2] Marchi et al., Nature Astr., 2019 [3] De Sanctis et al., 2011, Space Science Reviews 163, 329-369. [4] De Sanctis et al., science 2017 355, 719 [5] Pieters et al., 2018, Meteoritics and Planetary Science 53 (9), 1983-1998 [6] De Sanctis et al., 2019, 482 (2), 2407–2421 [7] Vinogradoff et al., 2021 [8] Ferrari et al., 2019, Icarus 321, 522-530 [9]De Angelis et al., 2021 JGR Planets doi: 10.1029/2020JE006696 [10] Baratta et al. 2002, A&A, 384, 343-349 [11] Brucato et al. 2006, A&A, 455, 395-399 [12] Mennella et al. 2003, ApJ, 587, 727-738 [13] Palumbo et al 2004, Ad. Sp. Res., 33, 49-56 [14] Fornaro et al. 2013, Icarus, 226(1), 1068–1085 [15] Fornaro et al 2018, Astrobiology, 18, 989-1007

International audience; We describe the results obtained on a set of organic samples that have been part of the experiment "Photochemistry on the Space Station (PSS)" on the EXPOSE-R2 mission conducted on the EXPOSE-R facility situated outside the International Space Station (ISS). The organic samples were prepared in the Catania laboratory by 200 keV He+ irradiation of N2:CH4:CO icy mixtures deposited at 17 K, on vacuum UV (VUV) transparent MgF2 windows. This organic material contains different chemical groups, including triple CN bonds, that are thought to be of interest for astrobiology. It is widely accepted that materials similar to that produced in the laboratory by ion irradiation of frozen ices could be present in some astrophysical environments such as comets. Once expelled from comets, these materials are exposed to solar radiation during their interplanetary journey. In the young Solar System, some of these processed materials could have reached early Earth and contributed to its chemical and prebiotic evolution. The samples were exposed for 16 months to the unshielded solar UV photons. It was found that, if an interplanetary dust particle (IDP) containing organic material (50% vol) is large enough (>20-30 μm), relevant chemical groups, such as those containing the CN triple bond, can survive for many years (>104 years) in the interplanetary medium.

The James Webb Space Telescope (JWST) is expected to be launched in 2021. The JWST’s science instruments will provide high quality spectra acquired in the line of sight to young stellar objects whose interpretation will require a robust database of laboratory data. With this in mind, an experimental work is in progress in the Laboratory for Experimental Astrophysics in Catania to study the profile (shape, width, and peak position) of the main infrared bands of molecular species expected to be present in icy grain mantles. Our study also takes into account the modifications induced on icy samples by low-energy cosmic ray bombardment and by thermal processing. Here we present some recent results on deuterium hydrogen monoxide (HDO), N-bearing species, and carbon dioxide (CO2).

The simultaneous detection of organic molecules of the form C$_2$H$_{\text{n}}$O, such as ketene (CH$_2$CO), acetaldehyde (CH$_3$CHO), and ethanol (CH$_3$CH$_2$OH), toward early star-forming regions offers hints of shared chemical history. Several reaction routes have been proposed and experimentally verified under various interstellar conditions to explain the formation pathways involved. Most noticeably, the non-energetic processing of C$_2$H$_2$ ice with OH-radicals and H-atoms was shown to provide formation routes to ketene, acetaldehyde, ethanol, and vinyl alcohol (CH$_2$CHOH) along the H$_2$O formation sequence on grain surfaces. In this work, the non-energetic formation scheme is extended with laboratory measurements focusing on the energetic counterpart, induced by cosmic rays penetrating the H$_2$O-rich ice mantle. The focus here is on the H$^+$ radiolysis of interstellar C$_2$H$_2$:H$_2$O ice analogs at 17 K. Ultra-high vacuum experiments were performed to investigate the 200 keV H$^+$ radiolysis chemistry of predeposited C$_2$H$_2$:H$_2$O ices, both as mixed and layered geometries. Fourier-transform infrared spectroscopy was used to monitor in situ newly formed species as a function of the accumulated energy dose (or H$^+$ fluence). The infrared (IR) spectral assignments are further confirmed in isotope labeling experiments using H$_2$$^{18}$O. The energetic processing of C$_2$H$_2$:H$_2$O ice not only results in the formation of (semi-) saturated hydrocarbons (C$_2$H$_4$ and C$_2$H$_6$) and polyynes as well as cumulenes (C$_4$H$_2$ and C$_4$H$_4$), but it also efficiently forms O-bearing COMs, including vinyl alcohol, ketene, acetaldehyde, and ethanol, for which the reaction cross-section and product composition are derived. A clear composition transition of the product, from H-poor to H-rich species, is observed as a function of the accumulated energy dose., Comment: 14 pages, 7 figures, 2 tables

Water ice exists on many objects in space. The most abundant icy species, among them water, are present in the icy satellites of the outer Solar System giant planets. The nuclei of comets, which are mainly composed of water ice, give another example of its abundance. In the interstellar medium (ISM), ice mantles, formed by molecular species sticking on dust grains, consist mainly of water ice. All these objects are exposed to ionizing radiation like ions, UV photons, and electrons. Sputtering of atoms, molecules, ions, and radicals from icy surfaces may populate and maintain exospheres of icy objects in the Solar System. In other respects, ionized hydrides such as OH+, H2O+, and H3O+ have been detected in the gas phase in star-forming regions. Interactions with cosmic rays could be an additional explanation to the current models for the formation of those species. In fact, laboratory simulations showed that the main components of the sputtered ionic species from water ice are oxygen hydrides. In this work, water ice targets were irradiated at several temperatures (10-200 K) by 90 keV O6+ ions, yielding an electronic stopping power of about 12 eV/A, when the nuclear stopping power is comparable to the electronic stopping power. Sputtering of secondary ions after bombardment of the ice target was analyzed by time-of-flight mass spectrometry (TOF-SIMS). Besides hydrogen ions (H+, H2+, H3+), also O+, O2+, OH+, (H2O)+, and clusters of (H2O)nH+ with n = 1-8 are emitted. Our results show a progressive yield decrease with increasing temperature of all of the detected species. This is related to the structure of the ice: the ionic sputtering yield for crystalline ice is much lower than for an amorphous ice. For instance, amorphous ice at 10 K exhibits a yield of the order of 2 × 10-6 secondary (H2O)nH+ hydride ions/projectile (with n = 1-8). As the temperature is increasing toward the phase transition to crystalline ice, the yields decrease by about one order of magnitude.

Context. Reliable, directly measured optical properties of astrophysical ice analogues in the infrared and terahertz (THz) range are missing from the literature. These parameters are of great importance to model the dust continuum radiative transfer in dense and cold regions, where thick ice mantles are present, and are necessary for the interpretation of future observations planned in the far-infrared region. Aims: Coherent THz radiation allows for direct measurement of the complex dielectric function (refractive index) of astrophysically relevant ice species in the THz range. Methods: We recorded the time-domain waveforms and the frequency-domain spectra of reference samples of CO ice, deposited at a temperature of 28.5 K and annealed to 33 K at different thicknesses. We developed a new algorithm to reconstruct the real and imaginary parts of the refractive index from the time-domain THz data. Results: The complex refractive index in the wavelength range 1 mm-150 μm (0.3-2.0 THz) was determined for the studied ice samples, and this index was compared with available data found in the literature. Conclusions: The developed algorithm of reconstructing the real and imaginary parts of the refractive index from the time-domain THz data enables us, for the first time, to determine the optical properties of astrophysical ice analogues without using the Kramers-Kronig relations. The obtained data provide a benchmark to interpret the observational data from current ground-based facilities as well as future space telescope missions, and we used these data to estimate the opacities of the dust grains in presence of CO ice mantles. The data plotted in Fig. 6 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/cat/J/A+A/629/A112

Context. C2O and C3O belong to the carbon chain oxides family. Both molecules have been detected in the gas phase towards several star-forming regions, and to explain the observed abundances, ion-molecule gas-phase reactions have been invoked. On the other hand, laboratory experiments have shown that carbon chain oxides are formed after energetic processing of CO-rich solid mixtures. Therefore, it has been proposed that they are formed in the solid phase in dense molecular clouds after cosmic ion irradiation of CO-rich icy grain mantles and released in the gas phase after their desorption. Aims. In this work, we contribute to the understanding of the role of both gas-phase reactions and energetic processing in the formation of simple carbon chain oxides that have been searched for in various low-mass star-forming regions. Methods. We present observations obtained with the Noto-32m and IRAM-30 m telescopes towards star-forming regions. We compare these with the results of a gas-phase model that simulates C2O and C3O formation and destruction, and laboratory experiments in which both molecules are produced after energetic processing (with 200 keV protons) of icy grain mantle analogues. Results. New detections of both molecules towards L1544, L1498, and Elias 18 are reported. The adopted gas phase model is not able to reproduce the observed C2O/C3O ratios, while laboratory experiments show that the ion bombardment of CO-rich mixtures produces C2O/C3O ratios that agree with the observed values. Conclusions. Based on the results obtained here, we conclude that the synthesis of both species is due to the energetic processing of CO-rich icy grain mantles. Their subsequent desorption because of non-thermal processes allows the detection in the gas-phase of young star-forming regions. In more evolved objects, the non-detection of both C2O and C3O is due to their fast destruction in the warm gas.

We present a novel experimental study on solid CH2DOH pure and in astrophysical relevant mixtures. Solid samples were accreted under ultra high vacuum conditions at 17 K and were analyzed by mid-infrared transmission spectroscopy. Refractive index, density, and mid-IR band strength values were measured for pure solid CH2DOH. The refractive index was also measured for CH2DOH:H2O, CH2DOH:CO, and CH2DOH:CH3OH mixtures. For all samples, the thermal evolution of the main band profile was studied. We used the interference laser technique (He Ne laser, λ = 543.5 nm) to measure the samples thickness and a numerical method to measure the refractive index starting from the amplitude of the interference curve. We obtained the ice density through the Lorentz-Lorenz relation. To calculate the band strength values we used the linear fit of the integrated band intensities with respect to the column densities. Samples deposited at 17 K were warmed up to their sublimation temperature. Spectra were taken at selected temperatures to study their thermal evolution. The results are discussed in view of their relevance for the interpretation of astronomical IR spectra.

1,25-Dihydroxyvitamin D3 (1,25(OH)2D3) is known to suppress NF-kB activity by interfering with its pathways. The aim of this study was to investigate the ability of 1,25(OH)2D3 in reducing the reactivation of the HIV virus J-LAT cells, an established model of latently infected cells, which were treated with TNFalpha (100 ng/ml) for 2 h with or without 24 h 1,25(OH)2D3 (100 nM) pretreatment. Reactivation of HIV RNA in J-LAT was evaluated in terms of green fluorescent protein (GFP) expression. The same experimental setting was repeated on T cells from HIV-infected patients. Treatment with TNFalpha was associated with a 16 % increase in GFP+ cells and a five-fold increase in unspliced HIV RNA expression (p

Astronomical observations towards star-forming regions have revealed the presence of molecules with the N-O bond such as NO, N2O, and HNO. These species are considered potential precursors of prebiotic molecules. Thus, understanding nitrogen and oxygen chemistry may help us to better understand the origin and evolution of prebiotic molecules in space. However, species with the N-O bond are poorly studied and laboratory works on the effects induced on them by solar wind and galactic cosmic rays are still scarce. For this, we wanted to study the effects of ion bombardment on molecules with the N-O bond. We focus here on N2O ices and NO2:N2O4 = 1:1 ice mixtures (at 16 and 50/60 K) irradiated with 200 keV protons. Infrared transmission spectroscopy (8000-500 cm-1; 1.25-20 μm) was used to analyse the samples. Irradiation of N2O ices and NO2:N2O4 ice mixtures produces comparable effects independent of the irradiation temperature, NO being the main product. Moreover, we show that the maximum amount of N2O and N2O4 destroyed by irradiation, at the highest dose reached in our experiments, is equal to about 98 and 70 {{ per cent}}, respectively. The dose range covered in the experiments has been compared with the astrophysical time-scale of surface processing in space, showing that irradiation of N2O and NO2:N2O4 mixtures can produce, within 105-108 yr, amounts of solid NO ice detectable towards star-forming regions by the James Webb Space Telescope.

The comparison between astronomical spectra and laboratory experiments is fundamental to spread light on the structure and composition of ices found in interstellar dense molecular clouds and in Solar system bodies. Water is among the most abundant solid-phase species observed in these environments, and several attempts have been made to investigate the presence of its solid-phase isotopologues. In particular, the detection of the O-D stretching mode band at 4.1 μm due to both D2O and HDO within icy grain mantles is still under debate, and no detection has been reported about the presence of these species within icy bodies in the Solar system yet. In the near future, an important contribution could derive from the data acquired in the O-D stretching mode spectral range by the sensitive instruments on board the James Webb Space Telescope. With this in mind, we performed several laboratory experiments to study the O-D stretching mode band in solid mixtures containing water and deuterated water deposited in the temperature range between 17 and 155 K, in order to simulate astrophysical relevant conditions. Furthermore, samples have been studied at various temperature and irradiated with energetic ions (200 keV H^+) in order to study the effects induced by both thermal and energetic processing. Our results provide some constraints on the detection of the 4.1 μm band in astronomical environments.

Icy grain mantles are the main reservoir for volatile elements in star-forming regions across the Universe, as well as the formation site of pre-biotic complex organic molecules (COMs) seen in our Solar System. Through the IceAge Early Release Science program, we will trace the evolution of pristine and complex ice chemistry in a representative low-mass star-forming region through observations of a: pre-stellar core, Class 0 protostar, Class I protostar, and protoplanetary disk. Comparing high spectral resolution (R~1500-3000) and sensitivity (S/N~100-300) observations from 3 to 15 micron to template spectra, we will map the spatial distribution of ices down to ~20-50 AU in these targets to identify when, and at what visual extinction, the formation of each ice species begins. Such high-resolution spectra will allow us to search for new COMs, as well as distinguish between different ice morphologies, thermal histories, and mixing environments.The analysis of these data will result in science products beneficial to Cycle 2 proposers. A newly updated public laboratory ice database will provide feature identifications for all of the expected ices, while a chemical model fit to the observed ice abundances will be released publically as a grid, with varied metallicity and UV fields to simulate other environments. We will create improved algorithms to extract NIRCAM WFSS spectra in crowded fields with extended sources as well as optimize the defringing of MIRI LRS spectra in order to recover broad spectral features. We anticipate that these resources will be particularly useful for astrochemistry and spectroscopy of fainter, extended targets like star forming regions of the SMC/LMC or more distant galaxies.

Context. Multi-year laboratory experiments have demonstrated that frozen icy mixtures containing simple organic and inorganic molecules (such as H2O, N2, CH4, CO, CO2, C2H6, etc.), if exposed to a flux of energetic ions or UV photons, give rise to new more complex molecules at low temperatures (10–50 K). A fraction of the new synthesized molecules is volatile while the remaining fraction is refractory and therefore it is preserved after the warm-up of the substrate to room temperature. Moreover, a part of the refractory material is formed during the annealing to room temperature, when molecules and radicals into the processed ice become mobile and react to form non-volatile molecules. By means of similar mechanisms, complex organic materials may be formed on the icy surfaces of some objects in the outer solar system, such as trans-Neptunian objects, comets and some satellites of the giant planets: in fact the interaction with solar wind and solar flares ions, solar photons and galactic cosmic rays could produce more refractory materials, analogous to those produced in the laboratory. In some cases, the materials thus synthesized may contain functional groups considered relevant to the pre-biotic chemistry in the hypothesis that interplanetary dust particles, comets and meteoroids contributed to seed the early Earth with the building blocks of life. Aims. The aim of this work is to investigate the chemical similarities and differences between some organic residues left over after ion bombardment (200 keV H+) of different ice mixtures followed by subsequent warm up under vacuum to room temperature. Methods. Seven organic residues have been prepared in our laboratory following a procedure involving the proton irradiation of seven different icy mixtures and their warm-up to room temperature. All the organic samples were characterized by FTIR spectroscopy with measurements performed in situ, in the ultra-high vacuum condition preventing any sample degradation. Three of them were selected to be characterized by XPS spectroscopy as well. Results. Among the organic residues presented in this paper, only those containing nitrogen and carbon exhibit the multi-component band centred at 2200 cm−1. This multi-component band presents interest from the astrobiological point of view due to its attribution to nitriles (–C≡N) and isonitriles (–N≡C). Our results demonstrate that this band is present in the IR spectra of organic nitrogen residues regardless the use of oxygen-bearing species in the icy mixture. This finding is of interest since the 2200 cm−1 band has been observed in some extraterrestrial samples (micro-meteorites) collected in the Antarctica.

HIV-associated neurocognitive disorders are common in HIV-infected individuals, even in the combination antiretroviral therapy (c-ART) era. Several mechanisms are involved in neuronal damage, including chronic inflammation immune activation. Mammalian 2'-5'-oligoadenylate synthetase (OAS) genes are produced in response to interferon (IFN), mainly by monocytes, and exert their antiviral functions by activation of RNase L that degrades viral and cellular RNAs. In this study, we aimed at exploring OAS gene family RNA expression in simian immunodeficiency virus encephalitis (SIVE), in HIV-associated neurocognitive disorders (HAND), and in HIV-associate dementia (HAD). We analyzed three microarray datasets obtained from the NCBI in order to assess the expression levels of OAS gene family network in brain biopsies of macaques with SIVE vs uninfected animals, as well as post-mortem brain of individuals with HAND (on or off ART) vs uninfected controls and three brain regions of HIV-infected individuals with both neurocognitive impairment (HAD) and encephalitis (HIVE). All OAS genes were upregulated both in SIVE and in HAND. OAS expression was significantly higher in high-viremic individuals; increased expression levels persisted in cART subjects when compared to healthy controls. OAS gene network analysis showed that several genes belonging to the type I IFN pathway, especially CXCL10 and IFIT3, were similarly upregulated in SIVE/HAND. Furthermore, we identified a significant upregulation of OAS gene family RNA expression in basal ganglia, white matter, and frontal cortex of HIV-1, HAD, and HAD/HIVE patients compared to healthy subjects. OAS gene family expression is increased in brain sections from individuals with HAND, HAD, and HIVE as well as macaques with SIVE. OAS family expression is likely to be induced by IFN as a consequence of viral replication in the CNS. Its long-term upregulation may contribute to the chronic inflammatory status and neurocognitive impairment we still observe in virologically suppressed individuals on c-ART.

Sulfur appears to be depleted by an order of magnitude or more from its elemental abundance in star-forming regions. In the last few years, numerous observations and experiments have been performed in order to to understand the reasons behind this depletion without providing a satisfactory explanation of the sulfur chemistry towards high-mass star-forming cores. Several sulfur-bearing molecules have been observed in these regions, and yet none are abundant enough to make up the gas-phase deficit. Where, then, does this hidden sulfur reside? This paper represents a step forward in our understanding of the interactions among the various S-bearing species. We have incorporated recent experimental and theoretical data into a chemical model of a hot molecular core in order to see whether they give any indication of the identity of the sulfur sink in these dense regions. Despite our model producing reasonable agreement with both solid-phase and gas-phase abundances of many sulfur-bearing species, we find that the sulfur residue detected in recent experiments takes up only ~6 per cent of the available sulfur in our simulations, rather than dominating the sulfur budget., Comment: 13 pages, 6 colourful figures, accepted by MNRAS

Silicates are the dominant surface material of many Solar System objects, which are exposed to ion bombardment by solar wind ions and cosmic rays. Induced physico-chemical processes include sputtering which can contribute to the formation of an exosphere. We have measured sputtering yields and velocity spectra of secondary ions ejected from nepheline, an aluminosilicate thought to be a good analogue for Mercury's surface, as a laboratory approach to understand the evolution of silicate surfaces and the presence of Na and K vapor in the exosphere. Experiments were performed with highly charged ion beams (keV/u–MeV/u) delivered by GANIL using an imaging XY-TOF-SIMS device under UHV conditions. The fluence dependence of sputtering yields gives information about the evolution of surface stoichiometry during irradiation. From the energy distributions N(E) of sputtered particles, the fraction of particles which could escape from the gravitational field of Mercury, and of those falling back and possibly contributing to populate the exosphere can be roughly estimated.

Astrophysical ices are exposed to different radiation fields including photons, electrons and ions. The latter stem from interstellar cosmic rays (CR), the solar and stellar winds, shock waves or are trapped in the magnetospheres of giant planets. We briefly discuss the physics of energy deposition by ion ir radiation in condensed matter and experimental methods to study the induced effects. We then present results on radiation effects such as sputtering, amorphisation and compaction, dissociation of molecules, formation of new molecular species after radiolysis and by implantation of ions. The formation and radio-resistance of organic molecules, related to the question of the initial conditions for the emergence of life, are briefly discussed. This review is not meant to be comprehensive, but rather focusses on recent findings, with special emphasis on experiments with heavy multiply charged ion beams. These experiments aim in particular at simulating the effects of CRs on icy grains in dense molecular clouds, and on the formation of molecules on icy bodies in the Solar System.

Context. Sulfur is an abundant element in the cosmos and it is thus an important contributor to astrochemistry in the interstellar medium and in the solar system. Astronomical observations of the gas and of the solid phases in the dense interstellar/circumstellar regions have evidenced that sulfur is underabundant. The hypothesis to explain such a circumstance is that it is incorporated in some species in the solid phase (I.e. as frozen gases and/or refractory solids) and/or in the gas phase, which for different reasons have not been observed so far. Aims: Here we wish to give a contribution to the field by studying the chemistry induced by thermal and energetic processing of frozen mixtures of sulfur dioxide (one of the most abundant sulfur-bearing molecules observed so far) and water. Methods: We present the results of a series of laboratory experiments concerning thermal processing of different H2O:SO2 mixtures and ion bombardment (30 keV He+) of the same mixtures. We used in situ Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results: The results indicate that ionic species such as HSO, HSO, and S2O are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions: The produced ionic species exhibit spectral features in a region that, in astronomical spectra of dense molecular clouds, is dominated by strong silicate absorption. However, such a dominant feature is associated with some spectral features, some of which have not yet been identified. We suggest adding the sulfur-bearing ionic species to the list of candidates to help explain some of those features. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets.

Laboratory experiments have shown that the energetic processing, i.e. ion bombardment and UV photolysis, of interstellar grain mantles and cometary surfaces is efficient in the production of formamide. To explain its presence in the gas-phase in these astrophysical environments, a desorption mechanism has to be taken into account. In this work we show experimental results on the thermal evolution of formamide when deposited at 17 K as pure and in mixture with water or carbon monoxide. In these samples, we observed formamide desorption at 220 K. Moreover, we discuss its synthesis in a mixture containing molecular nitrogen, methane and water (N2:CH4:H2O) deposited at 17 K and bombarded with 200 keV H+. Heating the sample, we observed that the newly formed formamide remains trapped in the refractory residue produced after the ion bombardment up to 296 K. To analyse the samples we used Fourier transform-infrared spectroscopy (FT-IR) that allowed us to study the infrared spectra between the deposition and the complete desorption of formamide. Here we discuss the experimental results in view of their astrophysical relevance.

The HIV-1 virus activates the complement system, an essential element of the immune system. SERPING1 is a protease inhibitor that disables C1r/C1s in the C1 complex of the classical complement pathway. In this paper, we performed an analysis of several microarrays deposited in GEO dataset to demonstrate that SERPING1 mRNA is modulated in CD14+ monocytes from HIV-1-infected individuals. In addition, data were validated on monocytes isolated from seronegative healthy volunteers, treated with IFNs. Our analysis shows that SERPING1 mRNA is overexpressed in monocytes from HIV-1+ patients and the expression levels correlate positively with viral load and negatively with the CD4+ T-cell count. Of note, anti-retroviral therapy is able to reduce the levels of SERPING1 mRNA, ex vivo. In addition, we found that 30% of the SERPING1 genes network is upregulated in monocytes from HIV-1+ patients. Noteworthy, the expression levels of IFITM1—an antiviral molecule belonging to the genes network—correlate positively with SERPING1 expression. Interestingly, the monocytes treatment with IFN-gamma, IFN-beta and IFN-alpha significantly upregulates the SERPING1 mRNA expression levels. From the outcome of our investigation, it is possible to conclude that SERPING1 and its network serve as important components of the innate immune system to restrict HIV-1 infection.

To examine how prebiotic chemical evolution took place on Earth prior to the emergence of life, laboratory experiments have been conducted since the 1950s. Methane has been one of the key molecules in these investigations. In earlier studies, strongly reducing gas mixtures containing methane and ammonia were used to simulate possible reactions in the primitive atmosphere of Earth, producing amino acids and other organic compounds. Since Earth's early atmosphere is now considered to be less reducing, the contribution of extraterrestrial organics to chemical evolution has taken on an important role. Such organic molecules may have come from molecular clouds and regions of star formation that created protoplanetary disks, planets, asteroids, and comets. The interstellar origin of organics has been examined both experimentally and theoretically, including laboratory investigations that simulate interstellar molecular reactions. Endogenous and exogenous organics could also have been supplied to the primitive ocean, making submarine hydrothermal systems plausible sites of the generation of life. Experiments that simulate such hydrothermal systems where methane played an important role have consequently been conducted. Processes that occur in other Solar System bodies offer clues to the prebiotic chemistry of Earth. Titan and other icy bodies, where methane plays significant roles, are especially good targets. In the case of Titan, methane is both in the atmosphere and in liquidospheres that are composed of methane and other hydrocarbons, and these have been studied in simulation experiments. Here, we review the wide range of experimental work in which these various terrestrial and extraterrestrial environments have been modeled, and we examine the possible role of methane in chemical evolution. Key Words: Methane-Interstellar environments-Submarine hydrothermal systems-Titan-Origin of life. Astrobiology 17, 786-812.

N2 is believed to lock considerable part of nitrogen elemental budget and, therefore, to be one of the most abundant ice constituent in cold dark clouds. This laboratory-based research utilizes high energetic processing of N2 containing interstellar ice analogues using 200 keV H+ and He+ ions that mimics cosmic ray processing of the interstellar icy grains. It aims to investigate the formation of (iso)cyanates and cyanides in the ice mantles at the conditions typical for cold dark clouds and prestellar cores. Investigation of cosmic ray processing as a chemical trigger mechanism is explained by the high stability of N2 molecules that are chemically inert in most of the atom- and radical-addition reactions and cannot be efficiently dissociated by cosmic ray induced UV-field. Two sets of experiments are performed to closer address solid-state chemistry occurring in two distinct layers of the ice formed at different stages of dark cloud evolution, i.e. `H2O-rich' and `CO-rich' ice layers. Formation of HNCO and OCN- is discussed in all of the performed experiments. Corresponding kinetic curves for HNCO and OCN- are obtained. Furthermore, a feature around 2092 cm-1 assigned to the contributions of 13CO, CN-, and HCN is analysed. The kinetic curves for the combined HCN/CN- abundance are derived. In turn, normalized formation yields are evaluated by interpolation of the obtained results to the low irradiation doses relevant to dark cloud stage. The obtained values can be used to interpret future observations towards cold dark clouds using James Webb Space Telescope.

In this paper we present the formation of carbon nanowires (polyynes and polycumulenes) in the solid state by ion irradiation of frozen hydrocarbons (C6H6 and C2H2). Irradiations have been performed using H+ ions in the 100’s keV energy regime using fluences up to 5 × 1014 ions/cm2. Beyond the intrinsic significance of these results in the field of material science, this work has been motivated by the fact that ion beam irradiation of hydrocarbon ices is one of the most important process thought to happen in several extraterrestrial environments where many spectroscopic features of polyyne molecules have been identified.

We present the analyses results of two bulk Terminal Particles, C2112,7,171,0,0 and C2112,9,171,0,0, derived from the Jupiter-family comet 81P/Wild 2 returned by the Stardust mission. Each particle embedded in a slab of silica aerogel was pressed in a diamond cell. This preparation, as expected, made it difficult to identify the minerals and organic materials present in these particles. This problem was overcome using a combination of three different analytical techniques, viz. FE-SEM/EDS, IR, and Raman microspectroscopy that allowed identifying the minerals and small amounts of amorphous carbon present in both particles. TP2 and TP3 were dominated by Ca-free and low-Ca, Mg-rich, Mg,Fe-olivine. The presence of melilite in both particles is supported by IR microspectroscopy, but is not confirmed by Raman microspectroscopy, possibly because the amounts are too small to be detected. TP2 and TP3 show similar silicate mineral compositions, but Ni-free and low-Ni, subsulfur (Fe,Ni)S grains are present in TP2 only. TP2 contains indigenous amorphous carbon hot spots; no indigenous carbon was identified in TP3. These nonchondritic particles probably originated in a differentiated body. This work found an unanticipated carbon contamination following the FE-SEM/EDS analyses. It is suggested that organic materials in the embedding silica aerogel are irradiated during FE-SEM/EDS analyses creating a carbon gas that develops a strong fluorescence continuum. The combination of the selected analytical techniques can be used to characterize bulk Wild 2 particles without the need of extraction and removal of the encapsulating aerogel. This approach offers a relatively fast sample preparation procedure, but compressing the samples can cause spurious artifacts, viz. silica contamination. Because of the combination of techniques, we account for these artifacts.

[1] In this work, we applied infrared spectroscopy to investigate the spectral signature of the volcanic ash particles emitted during the 21–24 July 2001 eruption at Mount Etna, in Italy. We used a Bruker Equinox-55 Fourier transform infrared spectrometer in the range 7000–600 cm−1 (1.43–16.67 µm) and, for every collected spectrum, an image of the volcanic ash particles was recorded in the visible spectral range through the same microscope. These images were then analyzed by standard image analysis software in order to evaluate the main features of the particle: the length of the major and minor axes (Max and Min L), Feret diameter (FD), equivalent diameter (ED), and aspect ratio (AR). We measured transmission spectra in different conditions; spectra of one single particle (Single-Particle Measurement, SPM), spectra of a number of particles from two to ten (Multi-Particle Measurements type 1, MPM1) and of more than a hundred particles (Multi-Particle Measurements type 2, MPM2). For SPM, Max and Min L range between 5 and 24 µm and 3.5 and 15 µm, FD ranges between 5.5 and 25 µm, ED varies between 5 and 19 µm, and AR between 0.45 and 0.95. For MPM1 and MPM2, the mean values of Max and Min L are between 4–17 µm and 3–10 µm, FD and ED between 5 and 19 µm and 3.5 and 23 µm, and AR between 0.3 and 1. The optical depth spectra as a function of the wave number clearly show the presence of the Christiansen effect that produces high transmission at a given frequency in the infrared region (Christiansen frequency). We find that the effect depends on the particle size through a linear relation. Both the Christiansen effect and their relationship with the ash particle effective radius were compared with radiative transfer model simulations using different ash refractive indexes. The combined use of the linear relationship and the spectral position of the Christiansen frequency also indicated the possibility to characterize ash type. All these information can be used to improve the IR remote sensing volcanic ash quantitative estimations.

The detection of Energetic Neutral Particles (ENP) above 10 eV can unequivocally relate a surface-bound exosphere to surface features and can monitor instantaneously the effect of plasma precipitation onto the surface. In the framework of a mission to Jupiter's moons, 2D imaging of plasma precipitation will provide important information on the plasma circulation at the orbits of the moons. Furthermore, a joint measurement of precipitating ions will permit an estimation of the efficiency of the release process. Coupled measurements of ENP and gas composition will improve our knowledge of surface release mechanisms. Ganymede's and Europa's Neutral Imaging Experiment (GENIE) is a high-angular-resolution detector, based on the ToF (Time of Flight) technique, that can detect ENP (energy range >10 eV-few keV) in the Jupiter environment thanks to an innovative design and technology. Its objective is to map the sites of origin of the ENP of the icy moons' exospheres to investigate the interaction between the surface and the environment. Finally, coupling GENIE with an ion sensor and a mass spectrometer will be an outstanding opportunity to better understand the magnetosphere-moon coupling within the Jupiter system and compare the surface interaction with plasma in the diverse moons. In this paper, the scientific objectives and requirements of ENP detection are summarized and the description of the innovative design concept of GENIE is given, together with the signal and background noise simulation.

Inter- and circumstellar ices comprise different molecules accreted on cold dust particles. These icy dust grains provide a molecule reservoir where particles can interact and react. As the grain acts as a third body, capable of absorbing energy, icy surfaces in space have a catalytic effect. Chemical reactions are triggered by a number of possible processes; (i) irradiation by light, typically UV photons from the interstellar radiation field and Ly-α radiation emitted by excited hydrogen, but also X-rays, (ii) bombardment by particles, free atoms (most noticeably hydrogen, but also N, C, O and D-atoms), electrons, low energy ions and cosmic rays, and (iii) thermal processing. All these effects cause ices to (photo)desorb, induce fragmentation or ionization in the ice, and eventual recombination will make molecules to react and to form more and more complex species. The effects of this solid state astrochemistry are observed by astronomers; nearly 180 different molecules (not including isotopologues) have been unambiguously identified in the inter- and circumstellar medium, and the abundances of a substantial part of these species cannot be explained by gas phase reaction schemes only and must involve solid state chemistry. Icy dust grains in space experience different chemical stages. In the diffuse medium grains are barely covered by molecules, but upon gravitational collapse and darkening of the cloud, temperatures drop and dust grains start acting as micrometer sized cryopumps. More and more species accrete, until even the most volatile species are frozen. In parallel (non)energetic processing can take place, particularly during planet and star formation when radiation and particle fluxes are intense. The physical and chemical properties of ice clearly provide a snapshotroot to characterize the cosmological chemical evolution. In order to fully interpret the astronomical observations, therefore, dedicated laboratory experiments are needed that simulate dust grain formation and processing as well as ice mantle chemistry under astronomical conditions and in full control of the relevant parameters; ice morphology (i.e., structure), composition, temperature, UV and particle fluxes, etc., yielding parameters that can be used for astrochemical modeling and for comparison with the observations. This is the topic of the present manuscript. Laboratory experiments simulating the conditions in space are conducted for decades all over the world, but particularly in recent years new techniques have made it possible to study reactions involving inter- and circumstellar dust and ice analogues at an unprecedented level of detail. Whereas in the past “top-down scenarios” allowed to conclude on the importance of the solid state for the chemical enrichment of space, presently “bottom-up approaches” make it possible to fully quantify the involved reactions, and to provide information on processes at the molecular level. The recent progress in the field of “solid state laboratory astrophysics” is a consequence of the use of ultra high vacuum systems, of new radiation sources, such as synchrotrons and laser systems that allow extensions to wavelength domains that long have not been accessible, including the THz domain, and the use of highly sensitive gas phase detection techniques, explicitly applied to characterize the solid state such as fluorescence, luminescence, cavity ring-down spectroscopy and sophisticated mass spectrometric techniques. This paper presents an overview of the techniques being used in astrochemical laboratories worldwide, but it is incomplete in the sense that it summarizes the outcome of a 3-day workshop of the authors in November 2012 (at the Observatoire de Meudon in France), with several laboratories represented, but not all. The paper references earlier work, but it is incomplete with regard to latest developments of techniques used in laboratories not represented at the workshop.

Sulfuric acid has been suggested to be present on the surface of the jovian moon Europa where it is mixed with the dominant water ice. The formation mechanism of sulfuric acid is still under discussion. We present new experimental results on the implantation of S q + ( q = 7, 9, 11) ions at an energy range between 35 and 176 keV in water ice at 80 K. Previous results on 200 keV S + implantation in H 2 O at 80 K have also been included in the data analysis. Experiments with multiply-charged ions at different energies are particularly relevant to simulate the complexity of the irradiation environment to which the surface of Europa is exposed being embedded in the jovian magnetosphere. The experiments were performed at the low energy ion beam facility ARIBE of GANIL in Caen (France). 35–176 keV S q + ( q = 7, 9, 11) ions were implanted in solid H 2 O layers which were frozen at 80 K. Fourier Transform Infrared Spectrometry (FTIR) was used to analyze the sample in the 5000–600 cm −1 (2–16.7 μm) region with a spectral resolution of 1 cm −1 . The results of our experiments indicate that implantation produces hydrated sulfuric acid with yields that increase with ion energy, from 0.12 molecules ion −1 for 35 keV ions to 0.64 molecules ion −1 for 200 keV ions. We have also searched for the production of SO 2 and H 2 S, but we were not able to find any evidence for their synthesis. We conclude that sulfur ion implantation is the dominant formation mechanism of hydrated sulfuric acid at Europa. The suggestion that the observed distribution of sulfuric acid on the surface is well correlated with the local flux of sulfur ions find a full explanation by present experimental data.

We present new experimental results relative to 144 keV S 9 + or Ar 9 + ion implantation in targets made of oxygen rich frozen gases (O2, CO2) and mixtures with water ice. Spectra in the UV (200–400 nm) range have been obtained before and after implantation. The targets have been selected because they can be representative of the parent molecules from which SO2 and O3, observed to be present on the surfaces of Jupiter’s icy Moons, could be formed due to radiolysis induced by the abundant magnetospheric ions. The results indicate that sulfur dioxide is not detectable after sulfur implantation in oxygen bearing species. Ozone is formed after argon and sulfur ion implantation. Sulfur implantation in O2 and CO2 targets also induces the formation of a band centered at about 255 nm (that we tentatively attribute to SO3 − radicals). In the mixtures with water the band appears initially at the same wavelength and shifts to about 247 nm at higher ion fluences possibly indicating the formation of sulfite (HSO3 − ) ions. An absorption band observed on Ganymede is well fitted by using three components: ozone, sulfite ions and a not identified component having an absorption band centered at 298 nm. In all of the studied cases ion implantation produces a spectral reddening over the investigated spectral range (200–400 nm) that well mimics the observed spectral slopes of Jupiter’s icy satellites.

Background Amyotrophic Lateral Sclerosis (ALS) is a rapidly progressive neurodegenerative disease characterized by the degeneration and death of upper (UMN) and lower (LMN) motor neurons. In the last decade, it has been shown that Chitinases are an important prognostic indicator of neuro-inflammatory damage induced by microglia and astrocytes. Materials and methods We analyzed microarray datasets obtained from the Array Express in order to verify the expression levels of CHI3L1 and CHI3L2 in motor cortex biopsies of sALS patients with different survival times. We also divided the sALS patients into smokers and non-smokers. In order to extend our analysis, we explored two additional microarray datasets, GSE833 and GSE26927, of post-mortem spinal cord biopsies from sALS patients. Results The analysis showed that CHI3L1 and CHI3L2 expression levels were significantly upregulated in the motor cortex of sALS patients, compared to the healthy controls. Moreover, their expression levels were negatively correlated with survival time. Interesting results were obtained when we compared the expression levels of Chitinases among smokers. We showed that CHI3L1 and CHI3L2 were significantly upregulated in sALS smokers compared to non-smokers. Furthermore, we found that four genes belonging to the Chitinases network (SERPINA3, C1s, RRAD, HLA-DQA1) were significantly upregulated in the motor cortex of sALS patients and positively correlated with Chitinases expression levels. Similar results were obtained during the exploration of the two-microarray dataset. Conclusions This study suggests that CHI3L1 and CHI3L2 are associated with the progression of neurodegeneration in motor cortex and spinal cord of sALS patients.

Methyl formate is a complex organic molecule considered potentially relevant as precursor of biologically active molecules. It has been observed in several astrophysical environments, such as hot cores, hot corinos, and comets. The processes that drive the formation of molecules in cometary ices are poorly understood. In particular it is not yet clear if molecules are directly accreted from the pre-solar nebula to form comets or are formed after accretion. The present work analyzes the possible role of cosmic ion irradiation and radioactive decay in methyl formate formation in methanol-bearing ices. The results indicate that cosmic ion irradiation can account for about 12% of the methyl formate observed in comet Hale–Bopp, while radioactive decay can account for about 6% of this amount. The need of new data coming from earth based and space observational projects as well as from laboratory experiments is outlined.

Several complex organic molecules are routinely detected in high abundances towards hot cores and hot corinos. For many of them, their paths of formation in space are uncertain, as gas phase reactions alone seem to be insufficient. In this paper, we investigate a possible solid-phase route of formation for methyl formate (HCOOCH3). We use a chemical model updated with recent results from an experiment where simulated grain surfaces were irradiated with 200 keV protons at 16 K, to simulate the effects of cosmic ray irradiation on grain surfaces. We find that this model may be sufficient to reproduce the observed methyl formate in dark clouds, but not that found in hot cores and corinos.

Since many years, the Laboratory for Experimental Astrophysics in Catania (Italy) has given a contribution to a number of experiments with the aim to investigate the physico-chemical effects induced by fast ions irradiating astrophysical relevant materials. Here, we review some of the most recent results, namely irradiation of mixtures of solid CO and S-bearing molecules. In the interstellar medium, two or more icy compounds can coexist to form ice mantles on grains in two different forms: either they can be mixed together or form separated layers (ice segregation). Thus experiments have been performed with targets prepared at low T (15–20 K) both by a co-deposition of a mixture of two gas compounds (CO and SO2 or H2S) and with targets prepared by deposition of CO ices on a previously deposited SO2 or H2S layer. Samples have been irradiated with 200 keV protons with the aim of simulating a cosmic ion bombardment of interstellar ices. The results show that new chemical species are formed; in particular, OCS and CS2. The astrophysical relevance of the results is discussed.

We have studied, by infrared absorption spectroscopy, the profile (shape and peak position) of the OH dangling bond feature in pure porous amorphous solid water (ASW) and in mixtures of water with other species (CO, CO 2 , O 2 , N 2 , H 2 O 2 , CH 4 , SO 2 , and CH 3 OH) at 12–16 K. Furthermore, we have investigated the effects of ion and UV irradiation on the morphology/porosity of amorphous water ice. Thin films (about 0.25–1 μm) of porous amorphous water ice were irradiated with 200 keV H + , 30 keV He + , and 10.2 eV Lyman alpha photons at 12–16 K. We have found that the profile of the OH dangling bond feature depends on the mixture considered and that the intensity of the OH dangling bond feature decreases after irradiation. This latter result indicates that the porosity of amorphous water ice decreases after both ion and UV irradiation.

Context. A better understanding of sulphur chemistry is needed to solve the interstellar sulphur depletion problem. A way to achieve this goal is to study new S-bearing molecules in the laboratory, obtaining accurate rest frequencies for an astronomical search. We focus on dithioformic acid, HCSSH, which is the sulphur analogue of formic acid. Aims: The aim of this study is to provide an accurate line list of the two HCSSH trans and cis isomers in their electronic ground state and a comprehensive centrifugal distortion analysis with an extension of measurements in the millimetre and submillimetre range. Methods: We studied the two isomers in the laboratory using an absorption spectrometer employing the frequency-modulation technique. The molecules were produced directly within a free-space cell by glow discharge of a gas mixture. We measured lines belonging to the electronic ground state up to 478 GHz, with a total number of 204 and 139 new rotational transitions, respectively, for trans and cis isomers. The final dataset also includes lines in the centimetre range available from literature. Results: The extension of the measurements in the mm and submm range lead to an accurate set of rotational and centrifugal distortion parameters. This allows us to predict frequencies with estimated uncertainties as low as 5 kHz at 1 mm wavelength. Hence, the new dataset provided by this study can be used for astronomical search. Frequency lists are only available at the CDS via anonymous ftp to "http://cdsarc.u-strasbg.fr" (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/612/A56

Context. Space infrared observations with ISO-SWS and Spitzer telescopes have clearly shown that solid carbon dioxide (CO2 )i s ubiquitous and abundant along the line of sight to quiescent clouds and star forming regions. Due to the CO2 low gas-phase abundance, it is suggested that CO2 is synthesized on grains after energetic processing of icy mantles and/or surface reactions. Aims. We study quantitatively the abundance of carbon dioxide synthesized from ice mixtures of astrophysical relevance induced by ion irradiation at low temperature. We compare the CO2 stretching and bending-mode band profiles observed towards some young stellar objects (YSOs) for which infrared spectra exist. Methods. Using a high vacuum experimental setup, the effects induced by fast ions (30−200 keV) on several ice mixtures of astrophysical interest are investigated. Chemical and structural modifications of the ice samples that form new molecular species are analyzed using infrared spectroscopy. The formation cross section of solid CO2 is estimated from the increase in column density as a function of the dose fitting of experimental data with an exponential curve. Results. Our laboratory experiments showed that carbon dioxide is formed after irradiation of ice mixtures containing C- and O-bearing molecules. Furthermore, when the same amount of energy is released into the icy sample, a larger amount of CO2 is formed in H2O-rich mixtures in agreement with previous studies. We also found that the CO2 stretching and bending mode band profiles depend on the mixture and temperature of the ice sample. We found that the amount of carbon dioxide formed after ion irradiation can account for the observed carbon dioxide towards YSOs. Furthermore, we discovered that laboratory spectra are a good spectroscopic analogue of the interstellar features. Conclusions. Even if the comparison between laboratory and observed spectra presented here cannot be considered unique and complete, our results quantitatively support the hypothesis that interstellar solid CO2 forms after ion irradiation and UV photolysis of icy mantles.

We studied icy CH4 and its mixtures with N2 (temperature 16-40 K), using near-IR transmittance spectroscopy (1.0-3.6 μm), and monitoring the film growth using interference patterns of two lasers. We measured peak position, full width at half-maximum, and strengths of the methane bands, and density and real refractive index of the icy films. Results confirm and extend but also partially contradict previous studies on similar mixtures. Experimental data can be applied to interpret observations of solar system (trans-Neptunian objects) and interstellar ices, where methane and nitrogen are believed to be present. We predict the optical depths of two methane NIR bands in the line of sight of some dense molecular clouds.

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H+, On+, Sn+, etc.), it can concur to the formation of new molecules. Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices. In this work, we describe some experiments of 15–100 keV H+ and He+ implantation in pure sulfur dioxide (SO2) at 16 and 80 K and carbon dioxide (CO2) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H2CO3) is formed after H-implantation in CO2, vice versa H-implantation in SO2 at both temperatures does not produce measurable quantity of sulfurous acid (H2SO3). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO2 and it is continuously bombarded with H+ ions caught in Jupiter's magnetosphere.

We report combined micro-infrared, micro-Raman, and field emission scanning electron microscope (FESEM) analyses of particles collected by the Stardust spacecraft during its flyby of comet 81P/Wild 2 on 2 January 2004 and successfully returned back to Earth on 15 January 2006. We present mid-infrared (IR) spectra of six of these particles. The CH2/CH3 ratios inferred from the infrared data are greater than those seen in organics in the diffuse interstellar medium, possibly indicating the presence of longer or less branched aliphatic chains. The micro-Raman data offer insights into the state of the order of the carbonaceous component present in the particles. Raman parameters for most of the particles span a similar range to that observed in interplanetary dust particles (IDPs) and the most primitive meteorites. Both the IR and Raman data imply the presence of a very labile carbonaceous component. Hydrated silicates may be present in two particles of Track 35, one of which may also contain carbonates, but further investigations with other techniques need to be performed to confirm these findings. In some cases, the analyses are difficult to interpret because of the presence of compressed aerogel mixed with the grains.

Solid objects in space (interstellar grains, comets, interplanetary dust particles, etc.) are continuously exposed to energetic processes, such as cosmic ion irradiation, that influence their evolution. In this paper we present an experimental study, carried out by Raman spectroscopy, of the effects induced by ion irradiation on frozen ices and refractory materials. If the irradiated ice mixture contains a relevant amount of carbon atoms, the ice is converted into an organic residue (stable at room temperature), which at high irradiation dose evolves toward a hydrogenated amorphous carbon. Here we show that material similar to that produced in the laboratory by ion irradiation of frozen ice mixtures and refractory materials can be formed in space by cosmic ion irradiation. This finding has been recently confirmed by the Stardust mission, which revealed in some of the cometary particles collected in space and returned to earth carbonaceous materials that have been processed by cosmic ion irradiation. Copyright © 2008 John Wiley & Sons, Ltd.

Background The innate immunity plays a predominant role in the early control of HIV infection, before the induction of adaptive immune responses. The cytokine secretion operated by the CD4+ T helper cells is able to induce a response in the innate immunity cells and significantly affect HIV-1 persistence and replication. One of the pathways activated by monocytes to restrain viral infection is the 2′ -5′ -oligoadenylate synthetase (OAS)/RNase L pathway. OAS is activated by dsRNA and IFNs to produce 2′ -5′ oligoadenylates, which are activators of RNase L. This enzyme degrades viral and cellular RNAs, thus restricting viral infection. Materials and methods We analyzed a microarray dataset obtained from the NCBI Gene Expression Omnibus (GEO, http://www.ncbi.nlm.nih.gov/geo/ ) databank (accession number GSE18464 ) in order to verify the modulation of the OAS gene family in CD14 + monocytes isolated from 55 subjects, 22 with HIV-1 HVL (high viral load), and 22 with HIV-1 LVL (low viral load), as well as in 11 HIV-1 seronegative controls. We have validated the data on the expression levels of the OAS genes by performing real-time PCR on monocyte from a cohort of HIV infected patients (n = 20), with clinical characteristics similar to those of the patients recruited in the study present in the microarray. Results Microarray analysis showed that OAS gene family are significantly upregulated in monocyte of HIV-1 patients with HVL, as compared to LVL patients and to healthy donors. Furthermore, we showed a significant correlation between the OAS gene family and the log2 viral load and CD4 count. These results were confirmed by the in vitro validation. Conclusions Data from this study suggest an involvement for the OAS gene family in the control of HIV-1 infection.

Context. It has been confirmed that solid carbon dioxide (CO2) is abundantly present along the line of sight to quiescent clouds and star-forming regions via space IR observations with ISO-SWS and Spitzer Space Telescope. Since CO2 has low abundance in the gas-phase, the assumption is that it is synthesized on grains after energetic processing of icy mantles and surface reactions. Aims: The role of solid carbon is investigated as a reservoir for molecule formation and structural modifications of the material with and without an ice layer upon ion bombardment. Methods: A gas-phase condensation technique was used to prepare a layer of 13C amorphous grains. These grains were covered with H2O and O2 ice and finally bombarded with 200 keV protons. The formation of new molecular species was analyzed using IR spectroscopy. The formation cross sections of solid 13CO and 13CO2 were determined from the increase in the column density as a function of the fluence. In addition, bare carbon grains were bombarded with a comparable fluence of protons to study the processing of the grains without ice layer. Imaging techniques such as transmission electron microscopy were used to monitor the changes in the structure. Results: CO and CO2 were formed efficiently at the interface between ice and solid carbon grains at the expense of solid carbon, leading to strong grain erosion. Given the initial thickness of our C-samples (about 120 nm), this resulted in an erosion of about 50% after 200 keV proton bombardment with 6.76 × 1016 ions/cm2. The column density of CO and CO2 follows an exponential trend as a function of the irradiation fluence. The asymptotic values obtained when O2 ice is deposited on top of the carbon grains are about one order of magnitude higher than the values obtained when H2O ice is deposited on the solid carbon layer. The carbon grains were strongly graphitized upon ion bombardment in a surface layer. Less graphitization accompanied by the formation of fullerene molecules and structures from cage fragments present in the original material were observed beneath the graphitic layer. Conclusions: The formation of CO and CO2 at the expense of solid carbon strongly restricts the lifetime of the solid carbon material and may influence the formation of more complex molecules in astrophysical environments. Graphitization of carbonaceous grains upon ion bombardment affect the spectral properties of the carbon grains in particular in the far-IR range.