The influence of electrospray deposition in matrix-assisted laser desorption/ionization mass spectrometry sample preparation for synthetic polymers

Although electrospray sample deposition in matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry (MS) sample preparation increases the repeatability of both the MALDI signal intensity and the measured molecular mass distribution (MMD), the electrospray sample deposition method may influence the apparent MMD of a synthetic polymer. The MMDs of three polymers of differing thermal stability, polystyrene (PS), poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG), were studied by MALDI time‐of‐flight (TOF) MS as the electrospray deposition voltage was varied. The MMDs obtained using the electrospray deposition method were compared with those obtained for hand‐spotted samples. No change was observed in the measured polymer MMD when the electrospray deposition voltage was varied in the analysis of PS, but those of PEG and PPG changed at higher electrospray voltages due to increased ion fragmentation. It was also shown that the fragmentation in the hand‐spotted samples is dependent on the matrix used in sample preparation. Copyright © 2004 John Wiley & Sons, Ltd.