Applications of mass spectrometry to poly(electrolytes) and kinetics

The only prerequisite for studying an analyte molecule using mass spectrometry is that the sample must be ionizable. For this reason, mass spectrometry can be utilized to study many types of molecules with a wide mass range. This dissertation utilizes that characteristic to examine the metal ion thermochemistry of small biomolecules and the structures of larger synthetic polymers.;This work aims at determining the sodium binding affinity of adenine experimentally based on the metal binding location. By using derivatives of adenine to sequentially block potential binding sites of the sodium ion, mass spectrometry can measure experimentally the sodium binding affinity of adenine as a function of the binding site. Specifically, adenine, 3-methyladenine and N6-methylaminopurine were found to have different sodium binding affinities due to their different metal binding sites.;The second part of this work describes the study of larger molecules, namely polymers. The first study involving polymers determined the monomer composition of a copolymer containing styrene and allyl alcohol monomers. Using mass spectrometry, monomer composition differed from the value reported when using other methods. Tandem mass spectrometry experiments reveal internal fragments due to polystyrene and water loss from the allyl alcohol monomer.;The mass spectrum of poly(acrylic acid) revealed water loss in addition to sodium exchange with the acidic proton on the side chain of the polymer. In the positive mode mass spectrum of poly(styrene sulfonate sodium salt), Na+/H+ exchange was not observed, but occurred readily in negative mode.;The tandem mass spectrum of poly(acrylic acid) showed that H2O loss is more abundant than previously thought. Further, the new data support that CO2 loss does not lead to a four membered ring as previously proposed, but most likely causes a six-membered ring to form.;For poly(styrene sulfonate sodium salt), the tandem mass spectra of the tetramer in positive and negative mode showed very similar fragmentation patterns. Monomer evaporation and nominal monomer + CH2 loss were the most abundant fragments observed. This fragmentation depends on the number of Na +/H+ exchanges that have taken place. Each SO 3Na → SO3H exchange enables the loss of a SO3 group from the side chain of the polymer.