Molecular tweezers: Synthetic receptors for the DNA base adenine
Zeng, Zijian
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Permalink
https://hdl.handle.net/2142/23618
Description
Title
Molecular tweezers: Synthetic receptors for the DNA base adenine
Author(s)
Zeng, Zijian
Issue Date
1991
Doctoral Committee Chair(s)
Zimmerman, Steven C.
Department of Study
Chemistry, Organic
Discipline
Chemistry, Organic
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
The design and syntheses of a series of molecular tweezers containing functional groups in the bay area of the spacers are discussed. Molecular tweezers 98, 99, 120, and 128 were designed to complex the DNA base adenine through a combination of hydrogen bonding and $\pi$-stacking interactions. They were synthesized in a convergent fashion that was fast and efficient. A new methodology for 9-substituted acridines was developed to facilitate the syntheses of molecular tweezers containing acridine chromophores. A novel rearrangement in 9-arylacridines is described. An aryl-aryl coupling reaction was applied to form the molecular tweezers containing anthracene chromophores.
The X-ray analysis of tweezer ester 96 confirmed the predicted 3-dimensional structure of molecular tweezers. The PC Model program was used to perform molecular mechanics calculations in order to determine the structure of tweezer esters 96, 97, 119, and 127.
The strength and the properties of the complexes formed between molecular tweezer 128 and control compounds and 9-propyladenine were studied. The strength of the complexes is strongly influenced by the $\pi$-$\pi$ overlap between the host and the guest. The acid strength of the carboxylic acid was found to have a small effect on the strength of the complexation. Tweezer acid 128 exhibited a high pKa in dioxane-water mixture, suggesting an unusual cavity effect.
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