Abstract. Laboratory experiments involving vacuum ultraviolet (VUV) irradiation of solid isocyanic acid (HNCO) at 10 K, followed by infrared spectroscopy (FTIR), are used to interpret the complex spectra associated with Interstellar Medium (ISM) dust grains, particularly the spectra associated with the icy phase observed toward dense molecular clouds. The comparison of the infrared spectra of the photolysis products with spectra recorded from the protostellar source NGC 7538 IRS9 shows that the "unexplained" 1700 cm −1 feature can be attributed to the contribution of several species H 2 CO (formaldehyde), HCONH 2 (formamide) and H 2 NCONH 2 (urea) mixed with H 2 O as the main contributor. Urea, formaldehyde and NH− (ammonium cyanate) may also contribute to a band at 1470 cm −1 , widely observed in many protostellar infrared sources and which remains up to now poorly explained in numerous ISO-SWS spectra. Isocyanic acid could be a precursor of formamide and urea in interstellar ices.
Context. Hydrogenation reactions dominate grain surface chemistry in dense molecular clouds and lead to the formation of complex saturated molecules in the interstellar medium. Aims. We investigate in the laboratory the hydrogenation reaction network of hydrogen cyanide HCN. Methods. Pure hydrogen cyanide HCN and methanimine CH 2 NH ices are bombarded at room temperature by H-atoms in an ultra-high vacuum experiment. Warm H-atoms are generated in an H 2 plasma source. The ices are monitored with Fourier-transform infrared spectroscopy in reflection absorption mode. The hydrogenation products are detected in the gas phase by mass spectroscopy during temperature-programmed desorption experiments. Results. HCN hydrogenation leads to the formation of methylamine CH 3 NH 2 , and CH 2 NH hydrogenation leads to the formation of methylamine CH 3 NH 2 , suggesting that CH 2 NH can be a hydrogenation-intermediate species between HCN and CH 3 NH 2 . Conclusions. In cold environments the HCN hydrogenation reaction can produce CH 3 NH 2 , which is known to be a glycine precursor, and to destroy solid-state HCN, preventing its observation in molecular clouds ices.
ContextMethods. Infrared and mass spectroscopy are used to monitor NH 3 :CO 2 ice mixture evolution during both warming and VUV photon irradiation.Results. Carbamic acid and ammonium carbamate can be produced thermally in a 1:1 ratio from NH 3 and CO 2 above 80 K. They can be also formed in a 28:1 ratio by less efficient processes such as energetic photons. Our study and its results provide fresh insight into carbamic acid formation in interstellar ices. Conclusions. We demonstrate that care is required to separate irradiation-induced reactivity from purely thermal reactivity in ices in which ammonia and carbon dioxide are both present. From an interstellar chemistry point of view, carbamic acid and ammonium carbamate are readily produced from the ice mantle of a typical interstellar grain and should therefore be a detectable species in molecular clouds.
Context. Studing chemical reactivity in astrophysical environments is an important means for improving our understanding of the origin of the organic matter in molecular clouds, in protoplanetary disks, and possibly, as a final destination, in our solar system. Laboratory simulations of the reactivity of ice analogs provide important insight into the reactivity in these environments. Here, we use these experimental simulations to investigate the Strecker synthesis leading to the formation of aminoacetonitrile in astrophysicallike conditions. The aminoacetonitrile is an interesting compound because it was detected in SgrB2, hence could be a precursor of the smallest amino acid molecule, glycine, in astrophysical environments. Aims. We present the first experimental investigation of the formation of aminoacetonitrile NH 2 CH 2 CN from the thermal processing of ices including methanimine (CH 2 NH), ammonia (NH 3 ), and hydrogen cyanide (HCN) in interstellar-like conditions without VUV photons or particules. Methods. We use Fourier Transform InfraRed (FTIR) spectroscopy to monitor the ice evolution during its warming. Infrared spectroscopy and mass spectroscopy are then used to identify the aminoacetonitrile formation. Results. We demonstrate that methanimine can react with − CN during the warming of ice analogs containing at 20 K methanimine, ammonia, and [NH + 4− CN] salt. During the ice warming, this reaction leads to the formation of poly(methylene-imine) polymers. The polymer length depend on the initial ratio of mass contained in methanimine to that in the [NH + 4− CN] salt. In a methanimine excess, long polymers are formed. As the methanimine is progressively diluted in the [NH + 4− CN] salt, the polymer length decreases until the aminoacetonitrile formation at 135 K. Therefore, these results demonstrate that aminoacetonitrile can be formed through the second step of the Strecker synthesis in astrophysical-like conditions.
We study low temperature reactivity of methylamine (CH3NH2) and carbon dioxide (CO2) mixed within different ratios, using FTIR spectroscopy and mass spectrometry. We report experimental evidence that the methylammonium methylcarbamate [CH3NH3(+)][C3NHCO2(-)] and methylcarbamic acid (CH3NHCOOH) are formed when the initial mixture CH3NH2:CO2 is warmed up to temperatures above 40 K. An excess of CH3NH2 favors the carbamate formation while an excess of CO2 leads to a mixture of both methylammonium methylcarbamate and methylcarbamic acid. Quantum calculations show that methylcarbamic acid molecules are associated into centrosymmetric dimers. Above 230 K, the carbamate breaks down into CH3NH2 and CH3NHCOOH, then this latter dissociates into CH3NH2 and CO2. After 260 K, it remains on the substrate a solid residue made of a well-organized structure coming from the association between the remaining methylcarbamic acid dimers. This study shows that amines can react at low temperature in interstellar ices rich in carbon dioxide which are a privileged place of complex molecules formation, before being later released into "hot core" regions.
The ice giants Uranus and Neptune are the least understood class of planets in our solar system but the most frequently observed type of exoplanets. Presumed to have a small rocky core, a deep interior comprising ∼70% heavy elements surrounded by a more dilute outer envelope of H 2 and He, Uranus and Neptune are fundamentally different from the better-explored gas giants Jupiter and Saturn. Because of the lack of dedicated exploration missions, our knowledge of the composition and atmospheric processes of these distant worlds is primarily derived from remote sensing from Earth-based observatories and space telescopes. As a result, Uranus's and Neptune's physical and atmospheric properties remain poorly constrained and their roles in the evolution of the Solar System not well understood. Exploration of an ice giant system is therefore a highpriority science objective as these systems (including the magnetosphere, satellites, rings, atmosphere, and interior) challenge our understanding of planetary formation and evolution. Here we describe the main scientific goals to be addressed by a future in situ exploration of an ice giant. An atmospheric entry probe targeting the 10-bar level, about 5 scale heights beneath the tropopause, would yield insight into two broad themes : i) the formation history of the ice giants and, in a broader extent, that of the Solar System, and ii) the processes at play in planetary atmospheres. The probe would descend under parachute to measure composition, structure, and dynamics, with data returned to Earth using a Carrier Relay Spacecraft as a relay station. In addition, possible mission concepts and partnerships are presented, and a strawman ice-giant probe payload is described. An ice-giant atmospheric probe could represent a significant ESA contribution to a future NASA ice-giant flagship mission.
Context. Analyses of dust cometary grains collected by the Stardust spacecraft have shown the presence of amines and amino acids molecules, and among them glycine (NH 2 CH 2 COOH). We show how the glycine molecule could be produced in the protostellar environments before its introduction into comets. Aims. We study the evolution of the interstellar ice analogues affected by both thermal heating and vacuum ultraviolet (VUV) photons, in addition to the nature of the formed molecules and the confrontation of our experimental results with astronomical observations. Methods. Infrared spectroscopy and mass spectrometry are used to monitor the evolution of the H 2 O:CO 2 :CH 3 NH 2 and CO 2 :CH 3 NH 2 ice mixtures during both warming processes and VUV photolysis. Results. We first show how carbon dioxide (CO 2 ) and methylamine (CH 3 NH 2 ) thermally react in water-dominated ice to form methylammonium methylcarbamate [CH 3 NH + 3 ][CH 3 NHCOO − ] noted C. We then determine the reaction rate and activation energy. We show that C thermal formation can occurs in the 50-70 K temperature range of a protostellar environment. Secondly, we report that a VUV photolysis of a pure C sample produces a glycine salt, methylammonium glycinate [CH 3 NH + 3 ][NH 2 CH 2 COO − ] noted G. We propose a scenario explaining how C and subsequently G can be synthesized in interstellar ices and precometary grains. Conclusions. [CH 3 NH + 3 ][CH 3 NHCOO − ] could be readily formed and would act as a glycine salt precursor in protostellar environments dominated by thermal and UV processing. We propose a new pathway leading to a glycine salt, which is consistent with the detection of glycine and methylamine within the returned samples of comet 81P/Wild 2 from the Stardust mission.
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