Electrospray Ionization-Mass Spectrometry of Synthetic Polymers Functionalized with Carboxylic Acid End-Groups

Electrospray ionization-mass spectrometry (ESI-MS) of low-charging synthetic polymers typically produces mass spectra exhibiting a bias toward the low-mass region of the polymer mass distribution. To examine the origin(s) of this ionization bias, narrow dispersity polystyrene polymers (Đ < 1.10) were prepared with ionizable carboxylic acid end-groups at one or both chain termini. The mixture complexity was further reduced through preparative size-exclusion chromatography (SEC), and these well-defined polymers were subjected to negative ion ESI-MS on a high-resolution instrument with a mass-to-charge (m/z) range up to 8000. Incorporation of one carboxylic acid end-group facilitated the generation of singly charged [M - H]^- ions across the entire range of the mass analyzer. The comparison of mass spectra with size-exclusion chromatograms of the same polymer revealed an ionization bias toward lower masses, which was partially overcome through fractionation, modification of electrospray solvent, and increased declustering potentials. Incorporation of a second ionizable moiety within polymers of equivalent size facilitated multiply charged [M - 2H]^2- ion formation with significantly improved ionization efficiency, spectral coverage of the molar mass distribution, and minimal cluster ion formation. These findings indicate that increased charging of polymers through multiple, well-defined sites of ionization can enhance volatilization and ionization of higher-mass polymers. Generation of higher-molecular-weight polymers in low-charge states-while possible under ideal conditions-competes ineffectively with either nonspecific, multiple-charging of similar sized polymers or ionization of the smaller polymers in the distribution.