Biomolecule Analogues 2‑Hydroxypyridine and 2‑Pyridone Base Pairing on Ice Nanoparticles

Ice nanoparticles (H₂O)_<i>N</i>, <i>N</i> ≈ 450 generated in a molecular beam experiment pick up individual gas phase molecules of 2-hydroxypyridine and 2-pyridone (HP) evaporated in a pickup cell at temperatures between 298 and 343 K. The mass spectra of the doped nanoparticles show evidence for generation of clusters of adsorbed molecules (HP)_<i>n</i> up to <i>n</i> = 8. The clusters are ionized either by 70 eV electrons or by two photons at 315 nm (3.94 eV). The two ionization methods yield different spectra, and their comparison provides an insight into the neutral cluster composition, ionization and intracluster ion–molecule reactions, and cluster fragmentation. Quite a few molecules were reported <i>not to coagulate</i> on ice nanoparticles previously. The (HP)_<i>n</i> cluster generation on ice nanoparticles represents the first evidence for coagulating of molecules and cluster formation on free ice nanoparticles. For comparison, we investigate the coagulation of HP molecules picked up on large clusters Ar_<i>N</i>, <i>N</i> ≈ 205, and also (HP)_<i>n</i> clusters generated in supersonic expansions with Ar buffer gas. This comparison points to a propensity for the (HP)₂ dimer generation on ice nanoparticles. This shows the feasibility of base pairing for model of biological molecules on free ice nanoparticles. This result is important for hypotheses of the biomolecule synthesis on ice grains in the space. We support our findings by theoretical calculations that show, among others, the HP dimer structures on water clusters