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

Abstract

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.