Part I. Molecular tweezers: Role of preorganization and synthetic progress toward a water soluble tweezer. Part II. Progress towards an empirical approach to carbohydrate recognition

Part I. Three molecular tweezers have been synthesized to determine the role of preorganization in the host-guest complexation of these systems. The synthesis of these tweezers was accomplished by the reaction of their respective dibromo-pyrylium salts with an absolute ethanol/aqueous ammonium hydroxide solution followed by a lithium/halogen exchange and addition of dimethoxyacridone chromophores. Tweezers 11-13 have zero, one, and two additional degrees of free rotation, respectively, which lessens the enforced syn cofacial orientation of the diacridine chromophores and the overall rigidity of the system. $\sp1$H NMR binding studies indicate an increase in the association constant (K$\sb{a}$) with the increase in rigidity. The effects of increasing rigidity are additive with $\rm\Delta\Delta G\sp\circ\sb{13\to11}=2\Delta\Delta G\sp\circ\sb{13\to12}$ = 1.8 kcal$\cdot$mol$\sp{-1}$. Thus, the enforced syn orientation of 11 provides no special benefit other than its role in preorganizing the host.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Baloga, Monica Helaine

Contributors dc:contributor

• Zimmerman, Steven C.

• Chemistry, Organic

Statement dc:rights

• Copyright 1995 Baloga, Monica Helaine

Language dc:language

eng

Identifier

AAI9543524
(UMI)AAI9543524

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/21404