Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric and semi-empirical calculations study of five isoflavone aglycones

Five isoflavones, daidzein, genistein, formononetin, prunetin and biochanin A, known for their biological properties, are investigated by electrospray ionization mass spectrometry in the positive ion mode. The most probable protonation sites are determined taking into account semi-empirical calculations using the PM6 Hamiltonian. Fragmentation mechanisms are proposed based on accurate mass measurements, MS3 experiments and supported by the semi-empirical calculations. Some of the fragmentation pathways were found to be dependent on the substitution pattern of the B-ring and the ions afforded by these fragmentations can be considered as diagnostic. It was possible to distinguish between prunetin and biochanin A, two isobaric isoflavone aglycones included in this study. Furthermore, a comparison of the fragmentation patterns of genistein and biochanin A, two isoflavones, with those of their flavone counterparts, apigenin and acacetin, enabled us to identify some key ions mainly due to structural features, allowing distinction to be made between these two classes of compounds. Copyright (C) 2010 John Wiley & Sons, Ltd.