It has been observed that the use of the salts of transition metals other t
han silver, copper or palladium as the cationizing agent, often fails to ca
tionize polystyrenes in matrix-assisted laser/desorption ionization (MALDI)
. This work shows that the ability of MALDI to reduce metals to the oxidati
on state +1 is critically important to polystyrene cationization, Without t
his reduction, MALDI tends to fail to form polystyrene-metal cations, In ad
dition, this work demonstrates the importance of the use of a good combinat
ion of metal salts and matrix in polystyrene cationization. Finally, the im
plications of this work in the MALDI time-of-flight analysis of polystyrene
s are discussed.