Polymer-Immobilized Catalysts for Protection Against Harmful Agents Público

Abstract

Heterogeneous (solid) catalysts are ubiquitous in both industrial processes and academic research. The benefits of using a heterogeneous catalyst include ease of product separation, catalyst recovery and reuse, and catalyst stability. Homogenous catalysts, which are typically dissolved in the solution phase, can be immobilized into or onto a number of substrates (polymers, silica, ceramic, etc.). The components of the solid support material can confer various physical properties to the heterogenized catalyst. This is especially true for polymer systems which have an extensive range of physical forms - including fibers, films, hard plastics, porous membranes, and malleable foams among many others. Because of this, polymer-immobilized catalysts present an extensive research space of potential applications compared to homogeneous catalysts alone. Growing interest has turned to the development of reactive personal protective equipment (PPE) utilizing functionalized polymer systems. This work details the development of two seemingly unrelated polymer-based protective materials: 1) chemically reactive solid systems for the protection from chemical warfare agents (CWAs), and 2) polymeric thin films containing polyoxometalates (POMs) that exhibit potent antiviral activity. The materials differ in the catalyst, target decontaminate, and mode of action. Yet, the theme of the dissertation stands: the formulation of functionalized polymers for protective purposes.

Table of Contents

Table of Contents

Chapter 1: Introduction................................................................................................................... 1

Solid Catalysts and Their Activity Against Harmful Agents ............................................................ 1

1.1 Abstract ................................................................................................................................... 2

1.2 Overview on Solid Catalysts ..................................................................................................... 2

1.3 Introduction to the Tribromide/Nitrate Aerobic Oxidation Catalyst for the Destruction of Sulfur Mustard and Its Simulants .............................................................................................................. 4

1.4 Polymeric Systems for the Protection from CWAs...................................................................... 7

1.5 Solid Materials with Antiviral Activity .................................................................................... 10

1.6 Introduction to Polyoxometalates ............................................................................................ 13

1.7 Overview of the Next Chapters................................................................................................ 14

1.8 References ............................................................................................................................. 15

Chapter 2: Functionalized Reactive Polymers for the Removal of Chemical Warfare Agents: A Review ........................................................................................................................................... 22

2.1 Abstract ................................................................................................................................. 23

2.2 Introduction ........................................................................................................................... 23

2.3. Degradation by Reactive Polymer Units .................................................................................. 27

2.4 Degradation via Metal-Containing Catalysts ............................................................................ 38

2.5 Degradation by Biocatalysts .................................................................................................... 65

2.6 Conclusions ........................................................................................................................... 69

2.7 References ............................................................................................................................. 70

Chapter 3: Materials for the Simultaneous Entrapment and Catalytic Aerobic Oxidative Removal of Sulfur Mustard Simulants ......................................................................................................... 78

3.1 Abstract ................................................................................................................................. 79

3.2 Introduction ........................................................................................................................... 79

3.3 Experimental Section.............................................................................................................. 81

3.3.1 Materials and Methods ..................................................................................................... 81

3.3.2 Synthesis of HCPs............................................................................................................ 82

3.3.3 Experimental Setup .......................................................................................................... 83

3.4 Results and Discussion ........................................................................................................... 84

3.5 Conclusions ........................................................................................................................... 89

3.6 References ............................................................................................................................. 90

Appendix A: ................................................................................................................................ 93

viii

Chapter 4: A Solvent-Free System for the Dual-Decontamination of Chemical Warfare Agent Simulants ..................................................................................................................................... 100

4.1 Abstract ............................................................................................................................... 101

4.2 Introduction ......................................................................................................................... 101

4.3 Experimental........................................................................................................................ 103

4.3.1 Materials and Methods ................................................................................................... 103

4.3.2 Fabrication of Polymer Microcapsules ............................................................................. 104

4.3.3. CWA-Simulant Decontamination Studies ....................................................................... 105

4.4 Results and Discussion ......................................................................................................... 106

4.5 Conclusion........................................................................................................................... 119

4.6 References ........................................................................................................................... 120

Appendix B ............................................................................................................................... 124 Chapter 5: Design of Polyoxometalate-Based Solid Materials with Anti-SARS-CoV-2 Activity ... 133 5.1 Abstract ............................................................................................................................... 134

5.2 Introduction ......................................................................................................................... 134

5.3 Experimental........................................................................................................................ 139

5.3.1 Materials and Methods ................................................................................................... 139

5.3.2 Fabrication of POM-Containing Films. ............................................................................ 139

5.3.3 Experimental Setup. ....................................................................................................... 140

5.4 Results and Discussion ......................................................................................................... 142

5.5 Conclusions ......................................................................................................................... 150

5.6 References ........................................................................................................................... 151

Appendix C: .............................................................................................................................. 156

About this Dissertation

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School	Laney Graduate School
Department	Chemistry
Degree	Ph.D.
Submission	Dissertation
Language	English
Research Field	Chemistry, Inorganic Chemistry, Polymer
Palabra Clave	Materials Science Antiviral Surface Chemical Warfare Agent
Committee Chair / Thesis Advisor	Craig L. Hill, Emory University Brian Dyer, Emory University Cora MacBeth, Emory University

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