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Applications of Chemical Methodology in Environmental Science, Systems Biology, and Interdisciplinary Chemical Education

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Applications of Chemical Methodology in Environmental Science, Systems Biology, and Interdisciplinary Chemical Education University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 5-2019 Applications of Chemical Methodology in Environmental Science, Systems Biology, and Interdisciplinary Chemical Education Caleb Michael Gibson University of Tennessee, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Recommended Citation Gibson, Caleb Michael, "Applications of Chemical Methodology in Environmental Science, Systems Biology, and Interdisciplinary Chemical Education. " PhD diss., University of Tennessee, 2019. https://trace.tennessee.edu/utk_graddiss/5400 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Caleb Michael Gibson entitled "Applications of Chemical Methodology in Environmental Science, Systems Biology, and Interdisciplinary Chemical Education." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Shawn Campagna, Major Professor We have read this dissertation and recommend its acceptance: Elizabeth Fozo, MIchael Sepaniak, Ampofo Darko Accepted for the Council: Dixie L. Thompson Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) APPLICATIONS OF CHEMICAL METHODOLOGY IN ENVIRONMENTAL SCIENCE, SYSTEMS BIOLOGY, AND INTERDISCIPLINARY CHEMICAL EDUCATION A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Caleb Michael Gibson May 2019 Copyright © 2019 by Caleb Michael Gibson All rights reserved. ii DEDICATION To Ellie, my beautiful daughter. Though you are very small, your curiosity is already evident. I hope that you grow more inquisitive as you grow bigger, leading you in the pursuit of knowledge and truth. iii ACKNOWLEDGEMENTS There are many people to whom I wish to express gratitude. Initially, I must extend many thanks to my advisor, Dr. Shawn Campagna. Without his investment in me, his continued direction, and his reassurance during the distresses of research, I would never have realized my goals. Likewise, I wish to thank my committee of Drs. Ampofo Darko, Elizabeth Fozo, and Michael Sepaniak who have helped me grow as a scientist through their collective input and constructive scrutiny of my ideas. My greatest opportunities in science were made possible through collaborations with excellent researchers. Most prominent among these are Drs. Brynn Voy and Elizabeth Fozo who have introduced me to intriguing systems and inspired me to apply myself to pursuit of answers. Moreover, they patiently aided me in developing from a strict chemist into an interdisciplinary scientist. Other collaborators including Dr. Maria Campa have allowed me to expand my horizons and gain experience in environmental science. In addition, there are a few individuals to whom I owe gratitude for their input in the implementation of my curriculum. These are Dr. Elizabeth Fozo, April Armes, Dr. Lauren Anderson, Matt Gleason, and Megan Qualls. My history as an academic did not begin with my graduate studies. I would be remiss if I did not reflect further into the past and acknowledge those that instilled me with curiosity and encouraged me to pursue knowledge. Foremost among these are Drs. Marc Strand, Christine Dalton, and Paul Martino. Through their mentorship, these individuals helped me find my niche in science. Others, such as Drs. John McClellan and Brian Austin, reinforced the critical thinking skills that are foundational to the pursuit of any knowledge, regardless of the field. During my studies, I have worked alongside several group members who have aided me by providing scientific input and camaraderie. These are: Dr. Hector Castro, Dr. Stephen Dearth, Dr. Carson Prevatte, Dr. Abigail Farmer, Dr. Allen Bourdon, Brandon Kennedy, Eric Tague, Alexander Fisch, Joshua Powers, Jordan Rogerson, Maggie Lookadoo, Ashley Lato, Katarina Jones, and Katharina Hölland. In addition, I have had the iv opportunity to work with some excellent undergraduate researchers including Sheev Zaver, Hannah Holst, and Brittni Woodall, who have each contributed to my projects. This document will not fully communicate the arduous ventures of my graduate studies. This journey has, at times, been both exciting and demoralizing and I must express my appreciation towards those close friends and family who have provided constant moral support along the way. My close friend and fellow chemist Joshua Hinkle has afforded fresh perspectives and astute insights when I need them. My parents, Bruce and Diane, have always lovingly supported me with sincerity and without undue pressure. My siblings and in-laws are close friends whose confidence in me has been encouraging. My daughter Ellie has introduced a joyful motivation these past few months. Most of all, my wife Maggie has stubbornly believed in me more than I believe in myself. Her love and companionship have been prime and enduring motivators. She has been my quintessential “better half”, and I am ever grateful. It may seem inconsequential, but I must offer earnest gratitude to the serene beauty of the Blue Ridge Mountains and the vibrant fish populations of local rivers and streams. They have provided a welcome respite for an overactive mind, allowing me to rest and refocus. My final and most humble thanks are expressed to the Bringer of the Good News, who has extended gracious gifts of which I am far less worthy than I ever feared but far more grateful than I ever imagined. v I am wiser than this human being. For probably neither of us knows anything noble and good, but he supposes he knows something when he does not know, while I, just as I do not know, do not even suppose that I do. I am likely to be a little bit wiser than he in this very thing: that whatever I do not know, I do not even suppose I know. -Socrates, from Plato’s Apology vi TABLE OF CONTENTS Chapter One : Introduction ........................................................................................... 1 The bridges between fields: chemical techniques applied to biological systems ......... 2 A chemical toolbox ....................................................................................................... 2 Ecotoxicology of small molecules in the environment .................................................. 3 Chemical biology: the interdisciplinary science ............................................................ 4 Central metabolism and ancillary networks ................................................................. 5 Small-molecule mitochondrial uncouplers and obesity management .......................... 7 Membrane disruptors in the intermediate molecular space ......................................... 9 Addressing the need for interdisciplinarity in science education ................................ 10 Chapter Two: Impact of hydraulic fracturing on degradation potential of the biocide glutaraldehyde ............................................................................................... 11 Abstract ..................................................................................................................... 12 Preface ...................................................................................................................... 12 Introduction ................................................................................................................ 14 Materials and methods .............................................................................................. 15 Results and discussion .............................................................................................. 22 Chapter Three: Exploring endogenous expression of N-Acyl amino acids ........... 40 Abstract ..................................................................................................................... 41 Preface ...................................................................................................................... 42 Chapter 3A: A single UPLC-HRMS method for the profiling of bile acids and N-acyl amino acids, two classes of obesity-mediating metabolites ....................................... 44 Chapter 3B: Expression of N-acyl amino acids is influenced by fasting-induced lipolysis and dietary supplementation with exogenous fatty acids ............................. 60 Chapter Four: Investigation of the toxic ZorO peptide ............................................ 75 Abstract ..................................................................................................................... 76 Preface ...................................................................................................................... 76 Introduction ................................................................................................................ 77 Methods ..................................................................................................................... 85 Results and discussion .............................................................................................
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