| The theoretical and experimental approach to the determination of the thermochemistry of small biological systems in the gas phase is addressed and advanced. Chapters 1 and 2 examine the detailed binding of glycine to Na+ and K+, respectively. These chapters explore the complicated nature of this interaction despite glycine being the simplest amino acid. Chapter 3 examines the unique binding of the amino acid proline and its four and six membered ring analogs to Li+, Na +, and K+. The computational section of this chapter introduces a new and powerful simulated annealing methodology. This annealing process allows for the conformational space of small biological systems to be explored in a highly intelligent and efficient manner. An instruction manual for the core program in the annealing suite, crd check, is included in the appendix. Finally, in Chapter 4 the development of a new electrospray source with the ability to deliver a vast array of ionic species to the gas phase is described. Both the source intensity and energetic definition of the ion beam produced by this source far exceed previous attempts to develop an electrospray source suitable for rigorous thermochemical measurement. |
