Examination of “Primary”, “Secondary”, and “Tertiary” Structural Elements of Bis-Amino Acids: Progress toward “Fauxteins”

Parker, Matthew (2015) Examination of “Primary”, “Secondary”, and “Tertiary” Structural Elements of Bis-Amino Acids: Progress toward “Fauxteins”. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

Proteins are in a category all their own as supramolecular entities enriched with both chirality and functionality. Inspired by them, we have created a new class of building blocks, called Bis-Amino Acids, for making molecules several kilodaltons in size that possess high degrees of both functionality and chirality. Bis-amino acids can assemble into shape-programmable macromolecules, called Spiroligomers that connect through pairs of amide bonds. They serve as water-soluble, rigid scaffolds capable of presenting collections of functional groups in different spatial orientations by virtue of their sequence, shape and stereochemistry of each chiral building block.
This dissertation utilizes these unique building block as scaffolding for the presentation of functional groups in localized domains. A short spiroligomer sequence is used to presents a donor and acceptor pair facially for measuring electron-transfer in water. The same cleft motif is used to present a pair of hydrogen bonding donors to catalyze an aromatic Claisen rearrangement. Methods are developed to improve and expand the chemistry to make the bis-amino acids as well as their assembly into spiroligomers. Lastly, spiroligomers are utilized as intermediate building materials forming sequences of two and three connected by short, flexible linkers and cross-linked them into assemblies. We envision the use of these macromolecules, called “Fauxteins” to position multiple functional groups over large surface areas for mimicry of protein-protein interactions, recreation of complex active sites of enzymes, and form unique, chiral pockets for host-guest molecular recognition.

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Details

Item Type:	University of Pittsburgh ETD
Status:	Unpublished
Creators/Authors:	Creators Email Pitt Username ORCID Parker, Matthew mfp1@pitt.edu MFP1
ETD Committee:	Title Member Email Address Pitt Username ORCID Committee Chair Waldeck, David H. dave@pitt.edu DAVE Committee Member Horne, Seth horne@pitt.edu HORNE Committee Member Liu, Peng pengliu@pitt.edu PENGLIU Committee Member Schafmeister, Christian E. meister@temple.edu
Date:	27 September 2015
Date Type:	Publication
Defense Date:	20 July 2015
Approval Date:	27 September 2015
Submission Date:	27 August 2015
Access Restriction:	No restriction; Release the ETD for access worldwide immediately.
Number of Pages:	182
Institution:	University of Pittsburgh
Schools and Programs:	Dietrich School of Arts and Sciences > Chemistry
Degree:	PhD - Doctor of Philosophy
Thesis Type:	Doctoral Dissertation
Refereed:	Yes
Uncontrolled Keywords:	Bis-amino acid, Diketopiperazine, Spiroligomer, Fauxtein
Date Deposited:	27 Sep 2015 23:55
Last Modified:	15 Nov 2016 14:30
URI:	http://d-scholarship.pitt.edu/id/eprint/26065

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