Title page for ETD etd-09202010-214945


Type of Document Dissertation
Author Han, Sangil
Author's Email Address sangil.hahn@gmail.com
URN etd-09202010-214945
Title Transport of Liquid Phase Organic Solutes in Liquid Crystalline Membranes
Degree PhD
Department Chemical Engineering
Advisory Committee
Advisor Name Title
Martin, Stephen M. Committee Chair
Davis, Richey M. Committee Member
Madsen, Louis A. Committee Member
Marand, Eva Committee Member
Keywords
  • enantiomers
  • circular dichroism
  • chirality
  • Liquid crystals
  • membrane
  • isomers
Date of Defense 2010-09-08
Availability restricted
Abstract
Porous cellulose nitrate membranes were impregnated with 8CB and PCH5 LCs (liquid crystals) and separations of solutes dissolved in aqueous phases were performed while monitoring solute concentration via UV-VIS spectrometry. The diffusing organic solutes, which consist of one aromatic ring and various functional groups, were selected to exclude molecular size effects on the diffusion and sorption.

We studied the effects on solute transport of solute intra-molecular hydrogen bonding and solute/LC intermolecular hydrogen bonding. Hydrogen-bonding effects are a significant factor in the permeation selectivity of positional isomers. The reduction of available hydrogen-bond donors in aromatic ortho-isomers due to intramolecular H-bonding resulted in significant differences in the diffusion relative to the para-isomers which possessed more available H-bond donors. Solutes possessing multiple H-bonding interactions experienced a higher barrier to diffusion and, consequently, lower diffusivities. Diffusing solutes with a single available H-bond donor exhibited faster diffusion than solutes without H-bond donors.

PCH5 embedded membranes showed higher solubility and diffusivity than the 8CB embedded membranes due to less dense molecular packing in PCH5 resulting from the bent cyclohexyl ring. The PCH5 LC membranes demonstrated enhanced permeation selectivity for hydroxybenzoic acid and aminophenol isomers primarily due to increased sorption selectivity. Shape selective absorption of rod-like para-isomers in the nematic phase was observed in both 8CB and PCH5 LCs.

A nonchiral based HPLC-CD (High Performance Liquid Chromatography-CD) system was developed for the characterization of enantioselective separations. An enantioselective cholesteric liquid crystal membrane was fabricated and evaluated using the nonchiral HPLC-CD system. The cholesteric LC membrane showed enantioselectivity in the cholesteric phase where activation energies of permeation for 1-phenylethanol enantiomers were significantly increased due to the increased interactions between enantiomer and LC phase. The enantioselectivity increased with decreasing pore size of the membrane and increasing chiral dopant compositions. The selectivity decreases when there are no hydrogen bonding interactions between enantiomer and chiral dopant.

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