Abstract
In matrix-assisted laser desorption/ionization (MALDI), the true molecular structures of some analytes are not represented by the observed ions due to a redox reaction. In earlier reports, electron transfer from analyte to chemical matrix has been proposed for the oxidation of ferrocene derivatives in MALDI. To address such a redox phenomenon in laser desorption/ionization processes, two ferrocene derivatives, FcCH2CH2Fc and FcCH2NMe2 [Fc:(CsHs)Fe(CsH4)], were analyzed by a matrix-free method, desorption/ionization on porous silicon (DIOS). The oxidized species, Fc+CH2NMe2 and FcCH2CH2Fc+, were detected in the DIOS mass spectra. The results suggested that electron transfer from the analytes to the sample target occurs during the ionization process.
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