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Investigations of cation-pi binding by cyclophane receptors in aqueous media

Citation

Mizoue, Laura S. (1995) Investigations of cation-pi binding by cyclophane receptors in aqueous media. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-10172007-133747

Abstract

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The binding properties of two new cyclophane receptors in aqueous media were explored. Replacement of two benzene rings of the host P with furans or thiophenes was expected to enhance cation-[pi] interactions, but significant improvements in the binding of positively-charged guests were not observed. Ab initio calculations provided a rationalization for the experimental findings and a better understanding of the cation-[pi] interaction.

The binding in water of various guanidinium compounds to host P was also investigated. These molecules represented a new type of cationic guest for the receptor. Arginine was not measureably bound by P, but several alkylated guanidiniums were well bound, especially considering their high water solubility. Hexamethylguanidinium, a nonplanar molecule with [...] symmetry, was a particularly interesting guest which displayed enantioselective binding to P. In addition, some progess was achieved towards the synthesis of receptors that have either an amide or a carboxylate group attached to the rim of the cavity. The appended group is positioned such that it can form hydrogen bonds or electrostatic interactions with a bound guanidiniumn guest.

Finally, exploratory work was carried out towards the synthesis of a cyclophane host that possesses a disulfide near the binding cavity. This receptor was designed to mimic the acetylcholine binding site of the nicotinic acetylcholine receptor. Although various disulfide containing macrocycles were synthesized, they were not sufficiently water soluble to permit studies of their binding properties.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Restricted to Caltech community only
Research Advisor(s):
  • Dougherty, Dennis A.
Thesis Committee:
  • Unknown, Unknown
Defense Date:12 October 1994
Record Number:CaltechETD:etd-10172007-133747
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-10172007-133747
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4143
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:30 Oct 2007
Last Modified:26 Dec 2012 03:05

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