Charge reversal Fourier transform ion cyclotron resonance mass spectrometry.

We report the first charge reversal experiments performed by tandem-in-time rather than tandem-in-space MS/MS. Precursor odd-electron anions from fullerene C(60), and even-electron ions from 2,7-di-tert-butylfluorene-9-carboxylic acid and 3,3'-bicarbazole were converted into positive product ions ((-)CR(+)) inside the magnet of a Fourier transform ion cyclotron resonance mass spectrometer. Charge reversal was activated by irradiating precursor ions with high energy electrons or UV photons: the first reported use of those activation methods for charge reversal. We suggest that high energy electrons achieve charge reversal in one step as double electron transfer, whereas UV-activated (-)CR(+) takes place stepwise through two single electron transfers and formally corresponds to a neutralization-reionization ((-)NR(+)) experiment.