Radiolysis of Amino Acids by Heavy and Energetic Cosmic Ray Analogs in Simulated Space Environments: $alpha$-Glycine Zwitterion Form

In this work, we studied the stability of the glycine molecule in the crystalline zwitterion form, known as {alpha}-glycine ($^{+}$NH$_{3}$CH$_{2}$COO$^{-}$) under action of heavy cosmic ray analogs. The experiments were conducted in a high vacuum chamber at heavy ions accelerator GANIL, in Caen, France. The samples were bombarded at two temperatures (14 K and 300 K) by $^{58}$Ni$^{11+}$ ions of 46 MeV until the final fluence of $10^{13}$ ions cm$^{-2}$. The chemical evolution of the sample was evaluated in-situ using Fourrier Transformed Infrared (FTIR) spectrometer. The bombardment at 14 K produced several daughter species such as OCN$^-$, CO, CO$_2$, and CN$^-$. The results also suggest the appearing of peptide bonds during irradiation but this must be confirmed by further experiments. The halflives of glycine in Interstellar Medium were estimated to be 7.8 $times 10^3$ years (300 K) and 2.8 $times 10^3$ years (14 K). In the Solar System the values were 8.4 $times 10^2$ years (300 K) and 3.6 $times 10^3$ years (14 K). It is believed that glycine could be present in space environments that suffered aqueous changes such as the interior of comets, meteorites and planetesimals. This molecule is present in proteins of all alive beings. So, studying its stability in these environments provides further understanding about the role of this specie in the prebiotic chemistry on Earth.

The Influence of Crystallinity Degree on the Glycine Decomposition Induced by 1 MeV Proton Bombardment in Space Analog Conditions

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 (alpha, beta, and gamma) forms. This molecular species has been extensively detected in carbonaceous meteorites and was recently observed in the cometary samples returned to Earth by NASAs Stardust spacecraft. 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 alpha-glycine and beta-glycine crystals on bombardment fluence is investigated. The samples were analyzed in situ by FTIR spectrometry at different proton fluences at under ultrahigh vacuum conditions at the Van de Graaff accelerator lab at PUC-Rio, Brazil. The dissociation cross section of alpha-glycine was observed to be 2.5E-14 cm^-2, a value roughly 5 times higher than the dissociation cross section found for beta-glycine. The estimated half-lives of alpha-glycine and beta-glycine forms extrapolated to the Earth orbit environment are 9E5 and 4E6 years, respectively. In the diffuse interstellar medium the estimated values are 1 order of magnitude lower. These results suggest that pristine interstellar beta-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 beta-glycine is the one most likely to have produced the first peptides on primitive Earth.

Formation of unsaturated hydrocarbons in interstellar ice analogs by cosmic rays

The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National dIons Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometry at different ion fluences. Dissociation cross section of cyclohexane and its half-life in astrophysical environments were determined. A comparison between spectra of bombarded ices and young stellar sources indicates that the initial composition of grains in theses environments should contain a mixture of H2O, NH3, CO (or CO2), simple alkanes, and CH3OH. Several species containing double or triple bounds were identified in the radiochemical products, such as hexene, cyclohexene, benzene, OCN-, CO, CO2, as well as several aliphatic and aromatic alkenes and alkynes. The results suggest an alternative scenario for the production of unsaturated hydrocarbons and possibly aromatic rings (via dehydrogenation processes) in interstellar ices induced by cosmic ray bombardment.

Radiolysis of ammonia-containing ices by energetic, heavy and highly charged ions inside dense astrophysical environments

Deeply inside dense molecular clouds and protostellar disks, the interstellar ices are protected from stellar energetic UV photons. However, X-rays and energetic cosmic rays can penetrate inside these regions triggering chemical reactions, molecular dissociation and evaporation processes. We present experimental studies on the interaction of heavy, highly charged and energetic ions (46 MeV Ni^13+) with ammonia-containing ices in an attempt to simulate the physical chemistry induced by heavy ion cosmic rays inside dense astrophysical environments. The measurements were performed inside a high vacuum chamber coupled to the heavy ion accelerator GANIL (Grand Accelerateur National dIons Lourds) in Caen, France.textit{In-situ} analysis is performed by a Fourier transform infrared spectrometer (FTIR) at different fluences. The averaged values for the dissociation cross section of water, ammonia and carbon monoxide due to heavy cosmic ray ion analogs are ~2x10^{-13}, 1.4x10^{-13} and 1.9x10^{-13} cm$^2$, respectively. In the presence of a typical heavy cosmic ray field, the estimated half life for the studied species is 2-3x10^6 years. The ice compaction (micropore collapse) due to heavy cosmic rays seems to be at least 3 orders of magnitude higher than the one promoted by (0.8 MeV) protons . In the case of the irradiated H2O:NH3:CO ice, the infrared spectrum at room temperature reveals five bands that were tentatively assigned to vibration modes of the zwitterionic glycine (+NH3CH2COO-).