Electrospray Fourier transform ion cyclotron resonance mass spectrometry (FTMS) of synthetic oligomers

Fourier transform mass spectrometry (FTMS) provides high mass resolving power (RP) and the facility for tandem MS experiments. Electrospray ionization (ESI) is a soft ionization technique that allows transfer of intact molecular ions from solution to the gas-phase. Thus, the combination of ESI-FTMS has the potential to precisely and readily provide detailed information about oligomer distributions including statistical molecular weight, repeat unit and end group sequence, degree of oligomerization, and evidence for co-oligomers, impurities or various modifications. Despite the analytical merits associated with ESI-FTMS, until recently virtually no attention has been given to the analysis of synthetic oligomers by this method. This thesis demonstrates the unique potential ESI-FTMS offers toward synthetic oligomer analysis by highlighting its performance in applications of tandem MS and high resolution (accurate mass measurement). As is frequently the case in analytical chemistry, method validation for a particular technique is generally limited by an incomplete understanding of the underlying principles of operation. In this regard other portions of this dissertation are dedicated to the study of measurement discriminations and the development of new hardware which offers increased versatility in the application of oligomer analysis by ESI-FTMS.