Analogous fragmentation of the M+. of E2 under EI conditions and the radical E2 cation in the MS3 spectrum of the PS deriviatve of E2. Structural assignments for the ions of m/z 146, 213, 172, 186, and 244 are those proposed in previous studies [38–41] based on the MS of steroidal estrogens under EI conditions. When the PS derivative of E2 was analyzed by LC-ESI-MS3 with the scan function m/z 414 → 272 → scan 50–300, ions of m/z 146, 213, 172, 186, and 244 were also produced (Fig. 3), suggesting that common fragmentation mechanisms are occurring in the two techniques.