Context. Formamide (NH 2 CHO) and methylamine (CH 3 NH 2 ) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims. The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods. Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the submonolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations.Results. The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H 2 O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions. More than 95 % of solid NH 2 CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution E des = 7460 − 9380 K, which is measured with the best-fit preexponential factor A=10 18 s −1 . However, the desorption energy distribution of methylamine from the np-ASW ice surface (E des =3850-8420 K) is measured with the best-fit pre-exponential factor A=10 12 s −1 . A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (E des = 4930 K), which is calculated with the same preexponential factor A=10 12 s −1 . The best wetting ability of methylamine compared to H 2 O molecules makes CH 3 NH 2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

Interstellar Complex Organic Molecules are thought to be the building blocks of more complex pre-biotic compounds. In particular, formamide (or methanimide, NH 2 CHO), is presented as a multifunctional pre-biotic precursor, the starting point of both pregenetic and pre-metabolic species. NH 2 CHO is widely observed in different astrophysical media, as well as in comets that may have had a crucial role in the delivery of exogenous material to Earth. In star forming regions, gas phase synthesis of formamide is possible, even if it is still debated. In this paper, we present laboratory experiments demonstrating formamide formation in interstellar ice analogues at astronomically relevant temperatures via simultaneous hydrogenation of NO and H 2 CO, two abundant molecules in star-forming regions. Inclusion of the experimental results in an astrochemical gas-grain model confirms the importance of the investigated solidstate reaction channel leading a high yield of formamide in dark interstellar clouds, and adds a valuable perspective about the way this refractory molecule may have been part of the pre-biotic molecular building blocks delivered to the young Earth.