Investigation of porphyrins and metalloporphyrins using two-step laser mass spectrometry.

Laser desorption time-of-flight mass spectrometry with laser postionization at 193 nm has been used to study a series of selected porphyrins and metalloporphyrins. Molecular ions are predominantly formed under soft ionization conditions, with extensive fragmentation of the peripheral substituents being observed under hard ionization conditions. Cu-octaethylporphyrin is found to exhibit anomalous demetallation at this ionization wavelength. At high ionization laser fluences it is also possible to observe extensive fragmentation of the porphyrin macrocycle. Much of the observed fragmentation can be understood with reference to previous studies using electron impact (EI) ionization. The stability of the porphyrin nucleus allows the fragmentation of the side chains to be examined. As in earlier EI studies dehydration products are observed in the mass spectra of hematoporphyrin IX. These products are shown to be thermally induced during infrared laser desorption, rather than fragments arising from photoionisation. The flexibility of this two-step laser mass spectrometric approach has allowed the analysis of chlorophyll a directly from an organic matrix. The data obtained suggest that information concerning the interaction between adsorbate and substrate can be extracted.