Synthesis and evaluation of quadruple hydrogen-bonding modules for smart materials applications

Anderson, Cyrus A.

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https://hdl.handle.net/2142/26098 Copy

Description

Title

Synthesis and evaluation of quadruple hydrogen-bonding modules for smart materials applications

Author(s)

Anderson, Cyrus A.

Issue Date

2011-08-25T22:12:52Z

Director of Research (if dissertation) or Advisor (if thesis)

Zimmerman, Steven C.

Doctoral Committee Chair(s)

Zimmerman, Steven C.

Committee Member(s)

• Moore, Jeffrey S.
• Burke, Martin D.
• Braun, Paul V.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

• Hydrogen-Bonding
• Supramolecular Chemistry
• Self-assembly
• Molecular recognition
• Adhesion
• Polymer functionalization
• Coupling agents

Abstract

The research described herein pertains to the design, synthesis and evaluation of DNA base pair mimics for supramolecular and materials chemistry applications. Recently, the ureido-7-deazaguanine (DeUG) and 2,7-diamidonaphthyridine (DAN) H-bonding modules have been shown to form a highly stable complex (Kassoc = 10^8 M^–1) in chloroform solution. Use of these units in applications requires derivatives that can be incorporated into polymers and onto surfaces. A method for the synthesis of non-symmetric diamidonaphthyridines from bromonaphthyridines using copper catalysis with aqueous ammonia at ambient temperature and pressure is detailed in chapter two. Chapter three relates several general strategies for the preparation of functional DeUG derivatives. The chemistry described in the first two chapters allows the synthesis of DAN and DeUG units featuring vinyl monomers, azide, alkyne, and other reactive groups for various coupling chemistries. Evaluation of the DAN and DeUG pair as a coupling agent for improving the interfacial adhesion between styrene and glass is explored in chapter four. Potential applications include advanced adhesives and coatings. Incorporation of the DAN unit into polystyrene via C–H activation and Suzuki-Miyaura coupling and functionalization of glass substrates with organosilanes are reported. Materials characterization and mechanical test results are consistent with the recognition units playing a role in the improved adhesive response as compared to an unmodified system. Progress toward a photoresponsive bisureidonaphthyridine H-bonding unit is disclosed in chapter 5. The photoresponsive naphthyridine is designed to allow reversible, light-driven modulation of the binding between the naphthyridine and DeUG. Synthetic results are discussed and binding data for bisureidonaphthyridine and DeUG are reported. The conformational change required of bisureidonaphthyridine prior to complexation with DeUG results in a smaller association constant as compared to the DAN·DeUG system, which does not require reorganization prior to binding. The binding properties of the DAN·DeUG and bisuredionaphthyridine-DeUG units allow complexation induced control over the conformational preference of bisureidonaphthyridine.

Graduation Semester

2011-08

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http://hdl.handle.net/2142/26098

Copyright and License Information

Copyright 2011 Cyrus Anderson

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