Fabien Borget

Hydrogenation of solid hydrogen cyanide HCN and methanimine CH2NH at low temperature

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 CH2NH ices are bombarded at room temperature by H-atoms in an ultra-high vacuum experiment. Warm H-atoms are generated in an H2 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 CH3NH2 ,a nd CH 2NH hydrogenation leads to the formation of methylamine CH3NH2, suggesting that CH2NH can be a hydrogenation-intermediate species between HCN and CH3NH2. Conclusions. In cold environments the HCN hydrogenation reaction can produce CH3NH2, which is known to be a glycine precursor, and to destroy solid-state HCN, preventing its observation in molecular clouds ices.

Experimental investigation of aminoacetonitrile formation through the Strecker synthesis in astrophysical-like conditions: reactivity of methanimine (CH2NH), ammonia (NH3), and hydrogen cyanide (HCN)

Astronomy & Astrophysics Experimental investigation of aminoacetonitrile formation through the Strecker synthesis in astrophysical-like conditions: reactivity of methanimine (CH 2 NH), ammonia (NH 3), and hydrogen cyanide (HCN) ABSTRACT 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 astrophysical-like 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 spec-troscopy 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.

Methylammonium methylcarbamate thermal formation in interstellar ice analogs: a glycine salt precursor in protostellar environments

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 (NH2CH2COOH). 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 H2O:CO2:CH3NH2 and CO2:CH3NH2 ice mixtures during both warming processes and VUV photolysis. Results. We first show how carbon dioxide (CO2) and methylamine (CH3NH2) thermally react in water-dominated ice to form methylammonium methylcarbamate [CH3NH + ][CH3NHCOO − ] 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 [CH3NH + ][NH2CH2COO − ] noted G. We propose a scenario explaining how C and subsequently G can be synthesized in interstellar ices and precometary grains. Conclusions. [CH3NH + ][CH3NHCOO − ] 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.

Carbamic acid and carbamate formation in NH

Context. We study carbamic acid [ NH 2 COOH] and ammonium carbamate [ NH 2 COO - ] [ NH 4 + ] formation in interstellar ice analogs. Aims. We demonstrate how carbamic acid [ NH 2 COOH] and ammonium carbamate [ NH 2 COO - ] [ NH 4 + ] can be formed from both thermal reactions and energetic photons in an NH 3 :CO 2 ice mixture. Methods. 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.

_{\sf 3}

This contribution is focused on the concurrent pathway to the Strecker synthesis of amino acids in an astrophysicallike environment. We indeed use experimental and modeling simulations to investigate the possibility to form the aminomethanol (HOCH2NH2) in concurrence with the hydroxyacetonitrile (HOCH2CN) from ices containing at 40 K formaldehyde (CH2O), ammonia (NH3), and cyanide ion (CN − ). We demonstrate using infrared spectroscopy and mass spectrometry that the formation of the aminomethanol (Ea = 4.5 kJ mol −1 ) is competing with the hydroxyacetonitrile formation (Ea = 3.9 kJ mol −1 ). The ratio between aminomethanol and hydroxyacetonitrile depends on the initial ratio in the ice between ammonia and cyanide. An increase of cyanide ion provides a decrease in aminomethanol formation. Since the aminomethanol is the first step through the formation of glycine in astrophysical environments, these data are important for understanding the possibility of forming glycine in such environments. Furthermore, using a reduced kinetic model, we evaluate the astrophysical environments in which the aminomethanol and hydroxyacetonitrile can be formed and evolved without degradation. The results suggest that these two molecules could be formed in molecular clouds or protostellar disks, and subsequently incorporated inside comets or asteroids. Therefore, hydroxyacetonitrile and aminomethanol could be formed before the formation of the solar system, which suggests that hydroxyacids and amino acids, such as those detected inside meteorites, have been formed in various astrophysical environments.

:CO

Context. The study of the chemical reactivity in interstellar ices in astrophysical environments is an important tool for understanding the origin of the organic matter in molecular clouds, in protoplanetary disks, and possibly, as a final destination, in our solar system. The laboratory simulations of the reactivity in ice analogs provide important information for understanding the reactivity in these environments. Here, we used these experimental simulations to trace some formation pathways of two nitriles, acetonitrile and amino acetonitrile, which are two potential precursors of amino acids in astrophysical environments. Aims. The purpose of this work is to present the first experimental approach for the formation of acetonitrile and amino acetonitrile in interstellar-like conditions. Methods. We use Fourier Transform InfraRed (FTIR) spectroscopy and mass spectrometry to study the formation at 20 K of ace-tonitrile CH 3 CN from VUV irradiation of ethylamine and of amino acetonitrile NH 2 CH 2 CN from VUV irradiation of ammonia: acetonitrile mixture. Isotopic substitutions are used to confirm identifications. Results. We demonstrate that acetonitrile can be formed at 20 K from the VUV irradiation of ethylamine with a yield of 4%. Furthermore, in presence of ammonia, at 20 K and under VUV irradiation, the acetonitrile can lead to the amino acetonitrile for-mation. These results suggest that acetonitrile and amino acetonitrile can be formed in astrophysical environments that are submitted to VUV irradiations.

_{\sf 2}

Aims. Aminoalcohol molecules such as alpha-aminoethanol NH 2 CH(CH 3)OH may be aminoacid precursors. We attempt to charac-terize and detect this kind of molecules which is important to establish a possible link between interstellar molecules and life as we know it on Earth. Methods. We use Fourier transform infrared (FTIR) spectroscopy and mass spectrometry to study the formation of alpha-aminoethanol NH 2 CH(CH 3)OH in H 2 O:NH 3 : CH 3 CHO ice mixtures. Isotopic substitution with 15 NH 3 and ab-initio calculation are used to confirm the identification of alpha-aminoethanol. Results. After investigating the thermal reaction of solid NH 3 and acetaldehyde CH 3 CHO at low temperature, we find that this reac-tion leads to the formation of a chiral molecule, the alpha aminoethanol NH 2 CH(CH 3)OH. For the first time, we report the infrared and mass spectra of this molecule. We also report on its photochemical behavior under VUV irradiation. We find that the main photo-product is acetamide (NH 2 COCH 3). Data provided in this work indicates that alpha-aminoethanol is formed in one hour at 120 K and suggests that its formation in warm interstellar environments such as protostellar envelopes or cometary environments is likely.

ices – UV irradiation versus thermal processes

We have investigated by means of HREEL spectroscopy electron induced reactivity in a binary CO2 : NH3 ice mixture. It was shown that the interaction of low energy electrons (9-20 eV) with such mixtures induces the synthesis of neutral carbamic acid NH2COOH and that flashing the sample at 140 K induces the formation of ammonium carbamate. The products have been assigned by FTIR spectroscopy of a CO2 : NH3 mixture heated from 10 K to 240 K. A mechanism involving dissociation of NH3 molecules into NH2* and H* radicals is proposed to explain the product formation.

HYDROXYACETONITRILE (HOCH2CN) FORMATION IN ASTROPHYSICAL CONDITIONS. COMPETITION WITH THE AMINOMETHANOL, A GLYCINE PRECURSOR

HCN is a molecule central to interstellar chemistry, since i t is the simplest molecule containing a carbon-nitrogen bond and its solid state chemistry is r ich. The aim of this work was to study the NH3 + HCN→ NH + CN − thermal reaction in interstellar ice analogues. Laborator y experiments based on Fourier transform infrared spectroscopy and mass spectrometry were performed to characterise the NH + CN − reaction product and its formation kinetics. This reaction is purely thermal and can occur at low temperatures in interstellar ices without requiring non-thermal processing by photons, electrons or cosmic rays. The reaction rate constant has a temperature dependence of k(T ) = 0.016 +0.010 −0.006 s −1 exp( −2.7±0.4 kJ mol −1 RT ) when NH3 is much more abundant than HCN. When both reactants are diluted in water ice, the reaction is slowed down. We have estimated the CN − ion band strength to be ACN − = 1.8±1.5×10 −17 cm molec −1 at both 20 K and 140 K. NH + CN − exhibits zeroth-order multilayer desorption kinetics wit h a rate of kdes(T ) = 10 28 molecules cm −2 s −1 exp( −38.0±1.4 kJ mol −1

Experimental investigation of nitrile formation from VUV photochemistry of interstellar ices analogs: acetonitrile and amino acetonitrile

We focus on low temperature reactivity from 25 to 300 K, in ice containing acetaldehyde, ammonia, and formic acid. We show that the warming of this ice mixture forms the acetaldehyde ammonia trimer (2,4,6-trimethyl-1,3,5-hexahydrotriazine, C(6)H(15)N(3)) after five steps. The reaction is monitored by FTIR spectroscopy and mass spectrometry. We propose a mechanism for its formation that differs from the one proposed in the liquid phase. The reaction intermediates, α-aminoethanol (from 80 K) and ethanimine (formed at 180 K), have been identified by a mechanistic approach: each step of the reaction has been treated separately. The chemical implications and the astrophysical relevance of the study are also discussed.