Rational Design and Green Fabrication of Antimicrobial Metal Nanoparticle/ Cellulose Nanocrystal Composites
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Rational Design and Green Fabrication of Antimicrobial Metal Nanoparticle/ Cellulose Nanocrystal Composites by Christopher Deutschman A thesis presented to the University of Waterloo in fulfillment of the thesis requirement for the degree of Master of Applied Science in Chemical Engineering (Nanotechnology) Waterloo, Ontario, Canada, 2020 © Christopher Deutschman 2020 Author’s Declaration This thesis consists of material all of which I authored or co-authored: see Statement of Contributions included in the thesis. This is a true copy of the thesis, including any required final revisions, as accepted by my examiners. I understand that my thesis may be made electronically available to the public. ii Statement of Contributions Christopher Deutschman was the sole author of Chapters 1, 2, 4, and 5, which were not written for publication. This thesis contains work in Chapter 3 which was written as part of a manuscript pending submission. The contributions for Chapter 3 are as follows: Christopher Deutschman and Joanna Jardin jointly conceptualized this project under the supervision of Dr. Michael Tam and Dr. Michael Pope. Christopher Deutschman performed all of the data mining, data cleaning, and data analysis. Christopher Deutschman and Joanna Jardin contributed to the writing of the manuscript. Christopher Deutschman generated the figures and tables for the manuscript. Christopher Deutschman contributed to the final editing. All co- authors participated in the intellectual development of the content in the final manuscript. As the lead author of the manuscript, I piloted the majority of the experimental design, set-up, and execution, with valued guidance and input from my co-authors. iii Abstract The primary goals of the work presented in this thesis were to better understand how metal nanoparticles (MNPs) affect antimicrobial activity, and to develop green synthesis protocols for the fabrication of nanocomposites designed specifically for antimicrobial applications. This work utilized a meta-analytical framework to mine data from recent literature and determine which MNP physiochemical properties dictate their antibacterial activity. Linear regression models revealed a size dependence for the antibacterial activity of silver MNPs, where smaller nanoparticles are more effective at combating Gram-negative E. coli (R2 = 40.3%, p < 0.001). In contrast, surface charge was determined to be the dominate physiochemical parameter in predicting the efficacy of silver MNPs against Gram-positive S. aureus, with potential secondary dependency on MNP size (R2 < 44%, p < 0.001 and < 0.05 for charge and size respectively). Better standardization in antimicrobial testing and reporting protocols will be critical in allowing for more powerful analyses in the future. Building off of the meta-analytical work, ecofriendly and cost effective synthesis protocols were developed to generate copper nanoparticles using cellulose nanocrystals and tannic acid. Cellulose nanocrystals provided an effective and environmentally benign base for silver and copper MNPs to be deposited using simple one-pot reduction. The developed one-pot synthesis method was also shown to be effective for the generation of silver/cellulose and copper/silver/cellulose nanomaterials. The final morphology of the copper/cellulose MNPs was found to be heavily dependent on the order of reagents during one-pot reduction, where coating of tannic acid on cellulose nanocrystals was a necessary first step to generate small and well- dispersed copper nanoparticles. The copper/cellulose composite was highly effective at suppressing the growth of S. cerevisiae microbes at a concentration of 25 µg/mL of copper. iv Acknowledgements I would like to thank my supervisors, Dr. Michael Tam and Dr. Mike Pope, for their guidance and support during the course of my degree at the University of Waterloo. This work would not have been possible without their insight and counsel. I would also like to thank my committee members, Dr. Bill Anderson and Dr. Boxin Zhao, for their time and effort throughout the thesis defense process. Thank you to Dr. Juewen Liu for allowing me the use of his lab’s time, expertise, and equipment, as zeta potential analysis would not have been possible without it. Thank you also to Mishi Groh for training and assistance with the transmission electron microscope, which enabled a complete characterization for my experimental work. To my colleagues in the Tam and Pope groups, thank you for an enjoyable and memorable two years! v Table of Contents List of Figures.............................................................................................................................viii List of Tables..................................................................................................................................x Chapter 1: Introduction ............................................................................................................... 1 1.1 Project Motivation .................................................................................................................... 2 1.2 Project Outcomes ...................................................................................................................... 3 1.3 Thesis Outline ........................................................................................................................... 4 Chapter 2: Literature Review ...................................................................................................... 5 2.2 Mechanisms of Antimicrobial Activity of Metal Nanoparticles............................................... 7 2.2.1 Physical Adsorption Dependent Pathways ......................................................................... 8 2.2.2 Redox Dependent Pathways ............................................................................................. 11 2.2.3 Metal Ion Dependent Pathways........................................................................................ 13 2.2.4 Influence of Surface Coatings on Antimicrobial Activity ............................................... 14 2.3 Metal Nanoparticle Synthesis ................................................................................................. 16 2.3.1 Single Metal Nanoparticle Synthesis ............................................................................... 16 2.3.2 Bimetallic Nanoparticle Synthesis ................................................................................... 19 2.3.3 Green Nanoparticle Synthesis .......................................................................................... 21 2.3.4 Green Synthesis Using Biopolymers................................................................................ 24 2.4 Conclusions ............................................................................................................................. 26 Chapter 3: Determining Critical Physiochemical Properties Affecting Antibacterial Activity of Metal Nanoparticles: A Meta-Analytical Approach ............................................. 27 3.2. Experimental Procedure ......................................................................................................... 31 3.2.1 Initial article collection..................................................................................................... 31 3.2.2 Dataset refinement and inclusion criteria ......................................................................... 32 3.2.3 Statistical analysis ............................................................................................................ 34 3.3 Results and Discussion ........................................................................................................... 34 3.3.1 Literature search & data extraction. ................................................................................. 34 3.3.2 Trends in antimicrobial nanoparticle evaluation and reporting. ...................................... 35 3.3.3 Cross-comparative analysis of silver, copper, gold, and zinc antimicrobial MNPs......... 37 3.3.4 Determining influential physiochemical characteristics of silver MNPs. ........................ 38 vi 3.4 Conclusions ............................................................................................................................. 42 Chapter 4: Synthesis and Characterization of Copper-, Silver-, and Copper/Silver- Cellulose Nanocrystal Composites with Antimicrobial Activity ............................................ 44 4.1 Introduction ............................................................................................................................. 45 4.2. Experimental Procedure ......................................................................................................... 46 4.2.1 Materials ........................................................................................................................... 46 4.2.2 One Pot Preparation of Metal/CNC/Tannic Acid Composites......................................... 47 4.2.3 Composite Characterization ............................................................................................. 47 4.3 Results and Discussion ........................................................................................................... 49 4.3.1 Characterization of Copper/CNC Nanoparticles .............................................................. 49 4.3.2 Effects of Fabrication Parameters on Copper/CNC Morphology ...................................