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Coordination Chemistry-Based Strateg...

McGuirk, Christopher Michael.

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Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity./
Author:	McGuirk, Christopher Michael.
Description:	293 p.
Notes:	Source: Dissertation Abstracts International, Volume: 77-10(E), Section: B.
Contained By:	Dissertation Abstracts International77-10B(E).
Subject:	Organic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10117188
ISBN:	9781339785912

Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity.
McGuirk, Christopher Michael.

Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity. - 293 p.

Source: Dissertation Abstracts International, Volume: 77-10(E), Section: B.

Thesis (Ph.D.)--Northwestern University, 2016.

Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity C. Michael McGuirk Through control of the local environment at their active sites, enzymes are able to catalyze a wide variety of organic transformations with impressive rates and selectivity. Additionally, by reversibly changing the local architecture of the active site in response to environmental signals, many enzymes are able to control catalytic properties in situ via a process termed allosteric regulation. While transition metals often behave as the catalytically active motifs of active sites, many enzymes employ highly organized and cooperative hydrogen-bonding interactions between the organic side chains of amino acid residues and the desired substrates to effect catalytic turnover. Inspired by hydrogen-bond-donating (HBD) enzymatic catalysis, chemists have recently designed and studied a series of synthetic small molecules similarly capable of facilitating catalytic behavior through these HBD interactions. Although these catalysts have rapidly become a key tool in synthetic chemistry, they have not yet been explored as motifs in supramolecular systems, where their environments can be finely and dynamically controlled in such a way that their chemistries can be regulated in a context analogous to allosteric biological systems. Therefore, the studies discussed herein are focused on exploring how the supramolecular environment of HBD catalysts can be controlled with small molecule or elemental anion cues, elucidating the effects of this control on functional behavior, and then using this knowledge to develop strategies to both enhance and allosterically regulate catalytic activity. In particular, this is achieved using coordination chemistry as a modular and convergent tool for the realization of higher-order synthetic architectures. Chapter 2 details the use of the weak-link approach (WLA) to supramolecular coordination chemistry to improve the activity of a HBD urea-based catalyst by controlling deleterious hydrogen-bond-driven self-association. Additionally, due to the configurational addressability of WLA-based complexes, catalyst self-association and catalytic activity can be controlled in situ. With the observation that controlling catalyst self-association improves activity, Chapter 3 focuses on the incorporation of a HBD catalyst into a three-dimensional coordination framework, termed a metal-organic framework (MOF). By introducing the HBD motif into the rigid, porous environment of a MOF, catalytic activity is dramatically improved. While, Chapters 2 and 3 focus on using coordination chemistry to control the deleterious self-association of HBD catalysts, Chapters 4 and 5 detail efforts to use coordination-based architectures for the in situ regulation of interactions of HBD catalysts and regulatory hydrogen-bond-accepting (HBA) groups. Specifically, Chapter 4 is concerned with the allosteric regulation of the catalytic activity of a HBD catalyst by its incorporation into a heteroligated WLA construct containing a HBA ligand. Regulation is achieved by controlling intermolecular ligand-ligand hydrogen-bonding interactions based on the configuration of the coordination site. Chapter 5 elaborates on the work of Chapter 4 by describing a novel strategy for the allosteric regulation of HBD-Lewis base co-catalysis. Using a concerted two-prong hydrogen-bonding-acid/base approach, the catalytic activity of a co-catalytic system can be controlled in situ in an on-off fashion. Finally, Chapter 6 details future directions for the potential application of the novel catalyst structures described herein.

ISBN: 9781339785912Subjects--Topical Terms:

523952
Organic chemistry.

Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity.
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245 1 0 $a Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity.
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500 $a Source: Dissertation Abstracts International, Volume: 77-10(E), Section: B.
500 $a Adviser: Chad A. Mirkin.
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520 $a Coordination Chemistry-Based Strategies for the Regulation and Enhancement of Hydrogen-Bond-Donating Catalyst Activity C. Michael McGuirk Through control of the local environment at their active sites, enzymes are able to catalyze a wide variety of organic transformations with impressive rates and selectivity. Additionally, by reversibly changing the local architecture of the active site in response to environmental signals, many enzymes are able to control catalytic properties in situ via a process termed allosteric regulation. While transition metals often behave as the catalytically active motifs of active sites, many enzymes employ highly organized and cooperative hydrogen-bonding interactions between the organic side chains of amino acid residues and the desired substrates to effect catalytic turnover. Inspired by hydrogen-bond-donating (HBD) enzymatic catalysis, chemists have recently designed and studied a series of synthetic small molecules similarly capable of facilitating catalytic behavior through these HBD interactions. Although these catalysts have rapidly become a key tool in synthetic chemistry, they have not yet been explored as motifs in supramolecular systems, where their environments can be finely and dynamically controlled in such a way that their chemistries can be regulated in a context analogous to allosteric biological systems. Therefore, the studies discussed herein are focused on exploring how the supramolecular environment of HBD catalysts can be controlled with small molecule or elemental anion cues, elucidating the effects of this control on functional behavior, and then using this knowledge to develop strategies to both enhance and allosterically regulate catalytic activity. In particular, this is achieved using coordination chemistry as a modular and convergent tool for the realization of higher-order synthetic architectures. Chapter 2 details the use of the weak-link approach (WLA) to supramolecular coordination chemistry to improve the activity of a HBD urea-based catalyst by controlling deleterious hydrogen-bond-driven self-association. Additionally, due to the configurational addressability of WLA-based complexes, catalyst self-association and catalytic activity can be controlled in situ. With the observation that controlling catalyst self-association improves activity, Chapter 3 focuses on the incorporation of a HBD catalyst into a three-dimensional coordination framework, termed a metal-organic framework (MOF). By introducing the HBD motif into the rigid, porous environment of a MOF, catalytic activity is dramatically improved. While, Chapters 2 and 3 focus on using coordination chemistry to control the deleterious self-association of HBD catalysts, Chapters 4 and 5 detail efforts to use coordination-based architectures for the in situ regulation of interactions of HBD catalysts and regulatory hydrogen-bond-accepting (HBA) groups. Specifically, Chapter 4 is concerned with the allosteric regulation of the catalytic activity of a HBD catalyst by its incorporation into a heteroligated WLA construct containing a HBA ligand. Regulation is achieved by controlling intermolecular ligand-ligand hydrogen-bonding interactions based on the configuration of the coordination site. Chapter 5 elaborates on the work of Chapter 4 by describing a novel strategy for the allosteric regulation of HBD-Lewis base co-catalysis. Using a concerted two-prong hydrogen-bonding-acid/base approach, the catalytic activity of a co-catalytic system can be controlled in situ in an on-off fashion. Finally, Chapter 6 details future directions for the potential application of the novel catalyst structures described herein.
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