A. F. Lago

Mass spectrometry study of the fragmentation of valence and core-shell (Cl 2p) excited CHCl3 and CDCl3 molecules

The dissociative photoionization of the chloroform and chloroform-d molecules has been studied in the valence region and around the chlorine 2p edge. Time-of-flight mass spectrometry in the coincidence mode-namely, photoelectron-photoion coincidence (PEPICO)-was employed. He I lamp and tunable synchrotron radiation were used as light sources. Total and partial ion yields have been recorded as a function of the photon energy. Singly, doubly, and triply ionized species have been observed below (195 eV), on (201 eV), and above (230 eV) the Cl 2p resonances. A definite degree of site-selective fragmentation was observed at the Cl 2p resonance as the relative contributions of several ionic species were seen to go through a maximum at 201 eV. At the same time all stable doubly charged ions were also observed at 198 eV (below the 2p resonances), resulting from direct ionization processes. Isotopic substitution is shown to provide a very efficient means of improving the mass resolution and assignment of unresolved peaks in spectra of CHCl(3), particularly for those fragments differing by a hydrogen atom. It is suggested that ultrafast fragmentation of the system following 2p excitation to a strongly antibonding state contributes to the large amount of Cl(+) observed in the PEPICO spectrum measured at 201 eV. Kinetic energy distributions were determined for the H(+), D(+), and Cl(+) fragments.

Photoabsorption and photoionization studies of the amino acid proline in the VUV region

Ionic fragmentation of the sublimated amino acid DL-proline has been studied using time-of-flight mass spectrometry and synchrotron radiation. Total ion yield and mass spectra were recorded in the 13 to 21.6 eV energy range. Partial ion yields have been calculated for the produced fragments and the results analyzed in a comparative way. Mass spectrum of proline previously obtained at 21.21 eV using photons from a discharge lamp (He I), was used as reference in the comparison to the synchrotron radiation based spectra. The loss of the COOH fragment represents the most probable dissociation pathway following the photoionization of DLproline in the valence region. These are the first results of total and partial ion yields spectra for this molecule in its gas phase in the valence region using time-of-flight spectrometry.

Survival of gas phase amino acids and nucleobases in space radiation conditions

We present experimental studies on the photoionization and photodissociation processes (photodestruction) of gaseous amino acids and nucleobases in interstellar and interpla-netary radiation analogs conditions. The measurements have been undertaken at the Brazilian Synchrotron Light Laboratory (LNLS), employing vacuum ultraviolet (VUV) and soft X-ray photons. The experimental set up basically consists of a time-of-flight mass spectrometer kept under high vacuum conditions. Mass spectra were obtained using a photoelectron photoion coincidence technique. We have shown that the amino acids are effectively more destroyed (up to 70–80%) by the stellar radiation than the nucleobases, mainly in the VUV. Since polycyclic aromatic hydrocarbons have the same survival capability and seem to be ubiquitous in the ISM, it is not unreasonable to predict that nucleobases could survive in the interstellar medium and/or in comets, even as a stable cation.

Excitation and ionic fragmentation of gas-phase biomolecules using electrons and synchrotron radiation

An experimental study of the electronic excitation and ionic dissociation of two important classes of biomolecules–natural products (biogenic volatile organic compounds, VOCs, and volatile components of essential oils) and DNA and RNA constituents (aminoacids and bases) is here exemplified with recent results on the fragmentation of thymine and isoprene as induced by synchrotron radiation and fast electrons. Fragmentation of the thymine molecule was seen to dramatically increase as the photon energy increased from 21 to 300 eV and 450 eV. At the highest photon energy, simply and doubly charged N and O atoms were observed. The parent ion (m/z = 126) could be observed at all photon energies. The fragmentation pattern observed in the 1.0 keV electron impact mass spectrum of thymine resembled more closely the fragmentation observed with 21 eV photons. In isoprene, the dominant fragments observed at 21 eV and 310 eV photon energy as well as in the 1.0 keV electron impact mass spectrum were C5H7+(m/z = 67), C4H5+(m/z = 53), C3H3+(m/z = 39) and C2H3+(m/z = 27). Previously unreported fragments, namely H+, C+, CH+, CH2+, and CH3+ were observed at the high photon energies and at the electron impact mass spectrum.