Syntheses, Separations, and Applications of Water-Soluble Chiral Calixarenes.

This dissertation focuses on the study of water-soluble calixarene derivatives as receptors for fluorescence probes and as chiral selectors. The synthesis of sulfonated calixarenes was first pursued and a method for the separation of sulfonated calixarenes (4), (6), (8) and the 4-hydroxylbenzene sulfonate monomer by capillary zone electrophoresis with direct UV absorbance detection is described. Fluorescence and absorption studies of water-soluble sulfonated calix(6)arene (SCX6) are reported. A red shift in the absorption spectrum and a change in the fluorescence spectrum of the calixarenes are observed upon an increase in pH from 2.0 to 13.0. The spectroscopic changes are attributed to intramolecular hydrogen bonding between adjacent hydroxyl groups of SCX6. Auramine O dye was used to study the complexation properties of the host molecules, calix(6)arene sulfonates. The fluorescence of Auramine O is enhanced as a result of its association with calixarenes. The formation constants for these 1:1 complexes are estimated to be about $\rm1.5\times10\sp4\ M\sp{-1}.$. Novel synthesis and characterization of chiral aminocalixarene derivatives with amino acid groups attached to the lower-rim of p-tert-butyl calix(4)arene are presented. The new chiral water-soluble calix(4)arenes have been used in the resolution of three racemic $(\pm)1,1\sp\prime$-binaphthyl derivatives using capillary electrophoresis (CE). Moreover, p-pentoxylsulfonated calix(6)arene was synthesized and used as an additive in CE for chiral separations. (R, S)-Propranolol and(R, S)-1-naphthylethyl isocyanate have been successfully baseline separated by addition of the chiral calixarene to the electrolyte. These water-soluble chiral calixarenes act as a pseudostationary phase to provide enantiomeric recognition, resulting in chiral separations. In addition to calixarene studies, $\rm H\sb3O\sp+$ has been quantitatively detected by use of creatinine as a UV absorbance reagent. The limit of quantification is about 0.03 nanomoles. The late appearance of $\rm H\sb3O\sp+$ at pH = 4.4 is attributed to the weak acid-base equilibria of HIBA and HAc in the buffers as $\rm H\sb3O\sp+$ migrates through the capillary