Date of Award

2000

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Isiah M. Warner

Abstract

This research involves the synthesis and characterization of charged chiral polymeric surfactants for their use as pseudostationary phases in electrokinetic chromatography (EKC). Poly sodium N-undecanoyl L-valinate (poly L-SUV), poly sodium N-undecanoyl L-threoninate (poly L-SUT), and poly sodium N-undecanoyl L-isoleucinate (poly L-SUIL) were synthesized in this study. The partial specific volumes of these polymers, determined using a densitometer, were 0.81, 0.77, and 0.83 mL/g, respectively. Molecular weights of 9,984, 11,252 and 10,563 were obtained for poly L-SUV, poly L-SUT and poly L-SUIL, respectively by using sedimentation equilibrium. In addition, sedimentation coefficients of 0.67 and 1.03 S were found for poly L-SUV and poly L-SUT, respectively. Selectivity factors of 5 PTH-amino acids were in good agreement with their differences in free energy. In addition, one and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, as well as luminescence spectroscopy were used to determine the binding interactions of these polymers with binaphthyl derivatives. The second component of this research involved an application of cyclodextrins for improved separation of free bile acids along with their taurine and glycine derivatives in capillary zone electrophoresis (CZE). The effects of various parameters such as pH and type of chromophore are investigated in order to optimize the electrophoretic separation and to maximize the peak capacity. The separation of bile acids is significantly improved by incorporating gamma-cyclodextrin (gamma-CD) in the run buffer solution. This improvement in resolution is accompanied by a decrease in migration time, suggestive of an increase in association of gamma-CD with the bile acids. In addition, the complexation of gamma-CD with the guest molecule 2,5-bis-(4-methylphenyl)oxazole (MPPO) was investigated using fluorescence and high-field proton nuclear magnetic resonance (NMR) spectroscopies.

ISBN

9780599906358

Pages

173

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