Model ices related to Titan’s surface show that polycyclic aromatic hydrocarbons are not solely formed in Titan’s atmosphere.

As one of the simplest molecules containing a peptide bond, N-methyl formamide (HCONHCH 3) represents a potential key molecule involved in the peptide bond polymerization in extraterrestrial ices. Detected tentatively toward the star-forming region Sgr B2(N2), the synthetic pathways have previously been elusive. By exploiting isomer-selective detection of the reaction products via photoionization, coupled with reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), we present compelling evidence for the formation of N-methyl formamide (HCONHCH 3) in astrochemically relevant ice mixtures of methylamine (CH 3 NH 2) and carbon monoxide (CO), upon irradiation with energetic electrons as generated in the track of galactic cosmic ray particles (GCRs) penetrating interstellar ices. As one of the simplest molecules containing a peptide bond (-CO-NH-), N-methyl formamide could represent a benchmark involved in radiation-induced peptide bond polymerization in extraterrestrial ices, and thus bring us closer to revealing where in the Universe the molecular precursors linked to the origins of life might have been synthesized.

Methoxymethanol (CH3OCH2OH) was recently detected toward the MM1 core in the high-mass star-forming region NGC 6334I. However, the underlying formation mechanisms of this complex organic molecule (COM) as well as its structural isomers ethylene glycol (HOCH2CH2OH) and the hitherto unobserved dimethyl peroxide (CH3OOCH3) are still elusive. Here, we report the very first confirmed synthesis of dimethyl peroxide—at various deuteration levels within interstellar analogous ices of D3-methanol (CD3OH) exposed to ionizing radiation at ultralow temperatures of 5 K. The discrimination of specific isomers is achieved by exploiting reflectron time-of-flight mass spectrometry coupled with isomer-selective photoionization of the subliming molecules in the temperature programmed desorption phase of the experiment. Based on the distribution of the identified species at distinct mass-to-charge ratios, we reveal primary and secondary reaction pathways to methoxymethanol, ethylene glycol, and dimethyl peroxide involving radical–radical recombination of methoxy (CH3O) and hydroxymethyl (CH2OH). Our findings help to constrain the formation mechanism of COMs detected within star-forming regions (methoxymethanol, ethylene glycol) and propose that the hitherto elusive dimethyl peroxide isomer represents an excellent candidate for future astronomical searches.

Intermolecular reactions in and on icy films on silicate and carbonaceous grains constitute a major route for the formation of new molecular constituents in interstellar molecular clouds. In more diff use regions and in protoplanetary discs, energetic radiation can trigger reaction routes far from thermal equilibrium. As an analog of interstellar ice-covered dust grains, highly-oriented pyrolytic graphite (HOPG) covered with D2O, NO, and H atoms is irradiated by ultrashort XUV pulses and the desorbing ionic and neutral products are analysed. The yields of several products show a nonlinear intensity dependence and thus enable the elucidation of reaction dynamics by two-pulse correlated desorption.

The hitherto elusive phosphino formic acid molecule (H2PCOOH) was detected for the first time in the gas phase. Theoretical calculations revealed an unexpected kinetic stability of H2PCOOH compared to the isovalent carbamic acid (H2NCOOH) although the replacement of a single nitrogen atom by phosphorus decreases the bond order from a partial double (-C[double bond, length as m-dash]N-) to a single (-C-P-) bond. This work provides a fundamental framework to explore the synthesis and stability of derivatives of carbonic acid (H2CO3), in which one or both hydroxyl groups (OH) are replaced by hydride moieties involving third row atoms.