The influence of crystallinity degree on the glycine decomposition induced by 1 MeV proton bombardment in space analog conditions

Abstract

Glycine is the simplest proteinaceous amino acid and is present in all life-forms on Earth. In aqueous solutions, it appears mainly as zwitterion glycine (+NH3CH2COO−); however, in solid phase, it may be found in amorphous or crystalline (α, β, and γ) forms. The crystalline forms differ from each other by the packing of zwitterions in the unitary cells and by the number of intermolecular hydrogen bonds. This molecular species has been extensively detected in carbonaceous meteorites and was recently observed in the cometary samples returned to Earth by NASA's Stardust spacecraft. In space, glycine is exposed to several radiation fields at different temperatures. We present an experimental study on the destruction of zwitterionic glycine crystals at room temperature by 1 MeV protons, in which the dependence of the destruction rates of the α-glycine and β-glycine crystals on bombardment fluence is investigated. The samples were analyzed in situ by Fourier transform infrared spectrometry at different proton fluences. The experiments occurred under ultrahigh vacuum conditions at the Van de Graaff accelerator lab at the Pontifical Catholic University at Rio de Janeiro (PUC-Rio), Brazil. For low fluences, the dissociation cross section of α-glycine was observed to be 2.5×10−14 cm2, a value roughly 5 times higher than the dissociation cross section found for β-glycine. The estimated half-lives of α-glycine and β-glycine zwitterionic forms extrapolated to the Earth orbit environment are 9×105 and 4×106 years, respectively. In the diffuse interstellar medium the estimated values are 1 order of magnitude lower. These results suggest that pristine interstellar β-glycine is the one most likely to survive the hostile environments of space radiation. A small feature around 1650–1700 cm−1, tentatively attributed to an amide functional group, was observed in the IR spectra of irradiated samples, suggesting that cosmic rays may induce peptide bond synthesis in glycine crystals. Combining this finding with the fact that this form has the highest solubility among the other glycine polymorphs, we suggest that β-glycine is the one most likely to have produced the first peptides on primitive Earth.