Full metadata
Title
Reactivity of metal (Co, Ni, Cu) bound peptides with organometallic fragments and small molecules
Description
Understanding the mechanisms of metalloproteins at the level necessary to engineer new functionalities is complicated by the need to parse the complex overlapping functions played by each amino acid without negatively impacting the host organism. Artificial or designed metallopeptides offer a convenient and simpler platform to explore metal-ligand interactions in an aqueous, biologically relevant coordination context. In this dissertation, the peptide SODA (ACDLPCG), a synthetic derivative of the nickel-binding pocket of nickel superoxide dismutase, is used as a scaffold to construct a variety of novel metallopeptides and explore their reactivity. In Chapter 2, I show that SODA binds Co(II) and the resulting peptide, CoSODA, reacts with oxygen in an unexpected two step process that models the biosynthesis of Co nitrile hydratase. First, the thiolate sulfur is oxidized and then the metallocenter is oxidized to Co(III). In Chapter 3, I show that both CoSODA and CuSODA form CN- adducts. Spectroscopic investigations of these metallopeptides are compared with data from NiSODA and Ni(CN)SODA to show the remarkable geometric versatility of SODA with respect to interactions with metallocenters. In Chapter 4, exploiting the propensity of sulfur ligands to form bridging structures, NiSODA is used as a metallosynthon to direct synthesis of hetero bi- and tri-metallic peptides as models for [NiFe]-hydrogenases and the A cluster of acetyl-CoA synthase carbon monoxide dehydrogenase. Building on this synthetic strategy, in Chapter 5, I demonstrate synthesis of NiRu complexes including a Ru(bipyridine)2 moiety and characterize their photochemistry.
Date Created
2012
Contributors
- Dutta, Arnab (Author)
- Jones, Anne K (Thesis advisor)
- Moore, Ana L (Committee member)
- Vermass, Willem (Committee member)
- Arizona State University (Publisher)
Topical Subject
Resource Type
Extent
xv, 207 p. : ill. (some col.)
Language
eng
Copyright Statement
In Copyright
Primary Member of
Peer-reviewed
No
Open Access
No
Handle
https://hdl.handle.net/2286/R.I.15798
Statement of Responsibility
by Arnab Dutta
Description Source
Retrieved on Sept. 12, 2013
Level of coding
full
Note
thesis
Partial requirement for: Ph.D., Arizona State University, 2012
bibliography
Includes bibliographical references
Field of study: Chemistry
System Created
- 2013-01-17 06:33:32
System Modified
- 2021-08-30 01:44:51
- 3 years 2 months ago
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