Exploring Refractory Organics in Extraterrestrial Particles

The origin of organic compounds detected in meteorites and comets, some of which could have served as precursors of life on Earth, 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 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 had 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

Cosmic ray processing of N2-containing interstellar ice analogues at dark cloud conditions

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

Solid deuterated water in space: detection constraints from laboratory experiments

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

Mid-IR band strength, density, refractive index, and thermal evolution study for solid CH2DOH pure and in astrophysical relevant mixtures

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 (Hesbnd 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

Organic samples produced by ion bombardment of ices for the EXPOSE-R2 mission on the International Space Station

We describe the preparation and characterization (by UV-vis-IR spectroscopy) of a set of organic samples, stable at room temperature and above, that are part of the experiment "Photochemistry on the Space Station (PSS)" planned to be enclosed in the EXPOSE-R2 mission, which will be conducted on the EXPOSE-R facility. The core facility is placed outside the International Space Station (ISS) on the Universal Platform D (URM-D platform) of the Russian module Zvezda. The organic materials are prepared in the Catania laboratory after 200 keV He+ irradiation of icy mixtures, namely N2:CH4:CO deposited at 16 K on MgF2 windows furnished by the European Space Agency. It is widely accepted that such a kind of materials produced by energetic processing are representative of organic material in some astrophysical environments as comets. Once expelled from comets these materials are exposed to solar radiation during their interplanetary journey before they eventually land on Earth and other planetary objects where they might give a contribution to the chemical and pre-biotical evolution. In particular our residues contain different chemical groups, including triple CN bonds that are considered relevant to pre-biotic chemistry. Therefore the samples will be exposed, for several months, to the solar ultraviolet photons that are a major source of energy to initiate chemical evolution in the solar system. This will allow analysis of their destruction or modification and evaluation of their lifetime in the interplanetary medium. The samples have three different thicknesses that will allow estimation of the depth profile of destruction. This experiment overcomes the limits of ground tests which do not reproduce exactly the space parameters

Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells

The chiral cationic complex [Ru(η1-OAc)(CO)((R,R)-Skewphos)(phen)]OAc (2R), isolated from reaction of [Ru(η1-OAc)(η2-OAc)(R,R)-Skewphos)(CO)] (1R) with phen, reacts with NaOPiv and KSAc affording [RuX(CO)((R,R)-Skewphos)(phen)]Y (X=Y=OPiv 3R; X=SAc, Y=OAc 4R). The corresponding enantiomers 2S-4S have been obtained from 1S containing (S,S)-Skewphos. Reaction of 2R and 2S with (S)-cysteine and NaPF6 at pH=9 gives the diastereoisomers [Ru((S)-Cys)(CO)(PP)(phen)]PF6 (PP=(R,R)-Skewphos 2R-Cys; (S,S)-Skewphos 2S-Cys). The DFT energetic profile for 2R with (S)-cysteine in H2O indicates that aquo and hydroxo species are involved in formation of 2R-Cys. The stability of the ruthenium complexes in 0.9 % w/v NaCl solution, PBS and complete DMEM medium, as well as their n-octanol/water partition coefficient (logP), have been evaluated. The chiral complexes show high cytotoxic activity against SW1736, 8505 C, HCT-116 and A549 cell lines with EC50 values of 2.8–0.04 μM. The (R,R)-Skewphos derivatives show higher cytotoxicity compared to their enantiomers, 4R (EC50=0.04 μM) being 14 times more cytotoxic than 4S against the anaplastic thyroid cancer 8505 C cell line

Infrared study on the thermal evolution of solid state formamide

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

Combined IR and XPS characterization of organic refractory residues obtained by ion irradiation of simple icy mixtures

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

Photoprocessing of Organic Material on Ceres: Laboratory Studies on Chemical Evolution of the Inner Dwarf Planet

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. 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. The mission, thanks to the data collected by the Italian instrument VIR, showed clear evidence of a high amount of aliphatic organic material on the surface of Ceres. This has raised new questions about the origin and preservation of this material, especially when considering its high estimated abundance. 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