MALDI in-source decay mass spectrometry of polyamidoamine dendrimers.

We report using MALDI-ISD (in-source decay) mass spectrometry (MS) to characterize highly branched synthetic polymers of polyamidoamine (PAMAM) dendrimer. This inherently monodisperse polymer possesses dendritic branches networked by tertiary amines and an amide functionality in each repeating unit. Among various ISD matrices examined, 2,5-DHB was the most efficient, yielding 33 fragments produced by single- or multiple-bond cleavages. Detailed analysis revealed that cleavages at tertiary amine sites (S- and E-type fragments) were the most pronounced, with various other cleavages around amide groups. The fragmentation mechanism appeared to follow the radical-induced dissociation pathway. In addition, the matrix dependence of PAMAM MALDI-ISD differed from that of peptides/proteins. The observed fragments provided rich structural information, which was suitable to characterize dendritic polymers.