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Soft Materials at Interfaces for Controlling and Studying Marine Biofouling, Cellular Growth, and Phonon Polaritons

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Soft Materials at Interfaces for Controlling and Studying Marine Biofouling, Cellular Growth, and Phonon Polaritons Soft Materials at Interfaces for Controlling and Studying Marine Biofouling, Cellular Growth, and Phonon Polaritons by Kris Sanghyun Kim A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Chemistry University of Toronto © Copyright by Kris Sanghyun Kim 2017 Soft Materials at Interfaces for Controlling and Studying Marine Biofouling, Cellular Growth, and Phonon Polaritons Kris Sanghyun Kim Doctor of Philosophy Department of Chemistry University of Toronto 2017 Abstract Several “soft” material systems are investigated at the nanoscale through the application of surface sensitive techniques. The first family of projects focus on providing environmentally- friendly solutions to challenges faced in aquaculture, including marine biofouling and sea lice infestations. To address fouling, an aqueous-based method was developed for fabricating nanostructured block copolymer films. Specifically, a water-insoluble triblock copolymer, Poly(styrene-block-2 vinyl pyridine-block-ethylene oxide), was phase transferred from a water- immiscible phase into an aqueous environment, where it was found to self-assemble into core- shell-corona type micelles. These micelles were then coated onto surfaces to form thin films and adhesion studies using atomic force microscopy (AFM), zoospore settlement assays, and field tests reveal its ability to serve as a potential marine antifouling coating. Conventional drugs used to control sea lice infestations are becoming less effective as parasites grow tolerant and have been found to harm non-target local species. Here, I present the efficacy of biologically extracted ingredients to serve as potential biopesticides. Liquid chromatography and mass spectrometry techniques are developed and optimized to monitor the fate of azadirachtin (extracted from neem oil) when orally administered to Atlantic salmon and exposed to aqueous environments. Field trial results reveal that azadirachtin levels as low as 0.01 ppm ii accumulated in the tissue of salmon results in over 85% efficacy against sea lice, relative to controls. The next group of projects investigates properties of synthetic materials at the nanoscale. We show that by supporting hexagonal boron nitride (hBN) on materials with varying dielectric responses in the infrared results in control of surface momenta of hyperbolic phonon polaritons (HPhPs). Our results show that by supporting hBN on materials with higher dielectric responses leads to a higher surface momenta of HPhPs. Furthermore, propagating waves in hBN were found to be highly sensitive to the reflections at the upper and lower interfaces, which provides opportunities for energy to dissipate. The damping behavior of HPhPs was shown to be sensitive to adjacent layers and a method of applying HPhPs in hBN as a sensor is demonstrated. iii Acknowledgments Pursuing a PhD has been a truly rewarding endeavour. To be the first to test, observe, and explain new scientific phenomena is an experience unlike any other, and I’ve been fortunate to have been able to share these moments with amazing people through various projects in the past few years. I’d first like to acknowledge my supervisor, Professor Gilbert Walker. I want to thank him for believing in and supporting all my endeavours. He’s a brilliant scientist and has provided me with insight that I could never have imagined myself. His enthusiasm for science has always been contagious and I’m incredibly fortunate to have shared unique moments with him, such as grinding and processing fish, which I’ll certainly never forget. It was during these experiences that his style of leading by example really showed and is something that I hope to adopt one day. Not only has he provided me with motivation and direction as a researcher, but I want to thank him for being an invested and caring mentor throughout the years and I’ll always be grateful for the advice, support, and opportunities that he has provided me. I want to acknowledge my PhD supervisory committee members, Professor Cynthia Goh and Professor Shirley Wu. Thank you both for your insightful research suggestions, approachability, and overall guidance and motivation through my research and extracurricular endeavours. I also want to thank Professor Aaron Wheeler for providing me with an experiential collaboration, providing me opportunities to learn about digital microfluidics, and for actively engaging and participating on my comprehensive and defense committee. And I want to thank Professor Mark Fast for serving as my external committee member and taking the time to fly out to Toronto. I could not have asked for a better group of friends and colleagues to share the last few years with. I would like to first acknowledge those who have gone on to do bigger and better things. I want to express my gratitude to Dr. Nikhil Gunari, who helped me immensely during my first year of graduate school and provided me with the confidence and training necessary to succeed. As someone completely new to the field, I’m grateful for all your patience and guidance inside and outside of the lab. I also want to thank Professor Sissi de Beer. Not only have you been an amazing collaborator, but your excitement for science has been incredibly contagious. I want to thank Mandy Koroniak- your help and support made my experience as a researcher, teacher, and student incredibly smooth. Thanks for your patience and willingness to deal with such urgent and immediate requests over the years. To Dr. Christina MacLaughlin- I want to thank you for iv all your suggestions and advice when I was a junior graduate student, and thank you for your continued support and friendship. To Dr. Alex Stewart- thanks for all the pedagogical discussions over the years. And finally, I want to thank Brandon Gagnon- your upbeat personality and openness to tackle new projects and other endeavours has and still motivates me today. I would also like to acknowledge friends and colleagues currently in graduate school or finishing up. I want to first acknowledge Leonid Gilburd. Aside from all the corny jokes about physicists and chemists, thank you for all the insightful scientific discussions, motivation to go to Hart House, and most importantly, for being a supportive friend. To Duncan Smith-Halverson- thanks for all the deep and insightful discussions and, this is way overdue, thank you for inviting me to grab a desk in the office with all the other graduate students when I first joined the lab and making me feel welcomed. Daniel and Kevin, thanks for all your hard work and enthusiasm on the AFM and other projects the past couple years. Cass, Sam, Caroline, and Alex- although I was a senior student I feel like you’ve helped me more than I’ve helped you. Thank you all for all the laughs and memories over the years and I’ll always treasure “Our Treasures”. 엄마 (정영의) and 아빠 (김시형), thank you for all the sacrifices you’ve made and continue to make for me. 스트레쓰 받을때, 몸 아플때, 건강할때, 언제나 항상 나 몰래 도와주고 항상 사랑해줘서 너무 고맙고 마음이따뜻하네요. 엄마 아빠 덕분에 캐나다에서 박사 까지 경험해보네요. 할머니 할아버지, 직접 얼굴 못봐도 항상 응원 해줘서 고맙습니다. To my little sister, 수겅, thanks for putting up with me and being patient over the past couple years. Thanks for dealing with my stubbornness and helping me feel confident as an older brother. Thanks for being a great 동생. Bonnie- while my time in the lab has had many ups and downs, you’ve always been there to provide comfort, support, and positivity in my life. Thank you for hearing out all my struggles and celebrating any successes with me throughout the years, none of this work would have been possible without someone so supportive and motivating always by my side. v Table of Contents Acknowledgments .......................................................................................................................... iv Table of Contents ........................................................................................................................... vi List of Tables ............................................................................................................................... xiii List of Figures ............................................................................................................................... xv 1 Background and Motivation ....................................................................................................... 1 1.1 Challenges Faced in Aquaculture ....................................................................................... 1 1.1.1 Marine Biofouling ................................................................................................... 1 1.1.2 Infestation of Sea Lice ............................................................................................ 8 1.2 Hexagonal Boron Nitride .................................................................................................. 10 1.2.1 Properties of Hexagonal Boron Nitride ................................................................ 10 1.2.2 Hyperbolic Phonon Polaritons .............................................................................. 12 1.3 Summary of Thesis ........................................................................................................... 13 1.4 References ......................................................................................................................... 14 2 Instrumental Techniques .......................................................................................................... 27 2.1 Atomic Force
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