Tandem Mass Spectrometry Reflects Architectural Differences in Analogous, Bis-MPA-Based Linear Polymers, Hyperbranched Polymers, and Dendrimers.

The growing use of branched polymers in various industrial and technological applications has prompted significant interest in understanding their properties, for which accurate structure determination is vital. This work is the first instance where the macromolecular structures of dendrimers, linear polymers, and hyperbranched polymers with analogous 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) backbone groups were synthesized and analyzed via tandem mass spectrometry (MS/MS). When comparing the fragmentation pathways of these polymers, some unique and interesting patterns emerge that provide insight into the primary structures and architectures of each of these materials. As expected, the linear polymer undergoes multiple random backbone cleavages resulting in several fragment ion distributions that vary in size and end group composition. The hyperbranched polymer dissociates preferentially at branching sites; however, differently branched isomers exist for each oligomer size, thus giving rise again to several fragment distributions. In contrast, the dendrimer presents a unique fragmentation pattern comprising key fragment ions of high molecular weight; this unique characteristic stands out as a signature for identifying dendrimer structures. Overall, dendrimers, hyperbranched polymers, and linear polymers display individualized fragmentation behaviors, which are caused by differences in primary structure. As a result, tandem mass spectrometry fragmentation is a particularly useful analytical tool for distinguishing such macromolecular architectures.