University of New Mexico UNM Digital Repository Nanoscience and Microsystems ETDs Engineering ETDs 1-28-2015 Structural Influences on the Photochemistry and Photophysical Properties of p-Phenylene Ethynylenes: Aggregation Effects and Solvent Interactions Eric Harris Hill Follow this and additional works at: https://digitalrepository.unm.edu/nsms_etds Recommended Citation Hill, Eric Harris. "Structural Influences on the Photochemistry and Photophysical Properties of p-Phenylene Ethynylenes: Aggregation Effects and Solvent Interactions." (2015). https://digitalrepository.unm.edu/nsms_etds/14 This Dissertation is brought to you for free and open access by the Engineering ETDs at UNM Digital Repository. It has been accepted for inclusion in Nanoscience and Microsystems ETDs by an authorized administrator of UNM Digital Repository. For more information, please contact [email protected]. i Structural Influences on the Photochemistry and Photophysical Properties of p-Phenylene Ethynylenes: Aggregation Effects and Solvent Interactions by Eric Harris Hill B.S. Chemistry, Southern Oregon University, 2009 Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Nanoscience and Microsystems Engineering The University of New Mexico Albuquerque, New Mexico December 2014 ii Acknowledgements I consider the path my life has taken to reach this point to be a combination of serendipity and an intense interest in science and technology spurred by the influential people in my life. By this measure, my pursuit of a doctorate would not have been possible without the contributions of many others. My heartfelt thanks go to my advisors David Whitten and Debi Evans for all that they have taught me in my time as a graduate student. When I arrived at UNM, I had not selected a graduate advisor, but after a brief period of frustration after several unproductive interviews I was taken on by Professors Evans and Whitten for a collaborative project involving computational work with the OPEs. After five years since arriving in Albuquerque, NM in August 2009, I feel lucky to have been graced with the opportunity to work under Debi and David. They have different styles of mentoring, and work in completely separate areas, but their combined mentorship has given a really well-rounded experience. I truly appreciate all that they have done for me, both as a student and as a friend. I also sincerely appreciate the great conversations and support of their respective spouses, Mark Ondrias and Jo Whitten. There are several people who must be acknowledged for their particular advice and tutelage during my time at UNM. Ken Sherrell and Professor Charlotte Mobarak took me on as an intern at the UNM Mass Spectrometry Facility for two years and taught me a great deal about the different types of mass spectrometry instrumentation and methods. This was an awesome experience, and gave me the knowledge and experience using the mass spectrometers needed for elucidating photochemical products and mechanisms. Professor Kirk Schanze has been a collaborator of the group since I have joined and has been a great mentor, friend, and is always a pleasure to see at a conference. Professor Andrew Shreve began advising me a few years into my work, and our discussions about potential experiments and spectral deconvolution were very useful. I would like to also thank Professor John Grey for providing advice and training on his instrumentation for potential experiments, though I was not able to complete any experiments with him. I am also grateful to Professor Ying-Bing Jiang for training me to use the transmission electron microscope in the Earth and Planetary Sciences department at UNM, and providing assistance with his easygoing nature as needed. Finally, Heather Armstrong, the former Nanoscience and microsystems program coordinator, deserves heaping praise for all her help with everything related to the PhD program since before I even arrived in Albuquerque. She truly iii cares about her students, and is always keen to have an interesting conversation. Much of the work that I have done relies heavily on the previous work of the members of the Whitten and Schanze group, to whom I am extremely grateful for their mentorship and camaraderie. Dr. Yanli Tang, Dr. Ying Wang, Dr. Anand Parthasarathy, Dr. Tom Corbitt, Dr. Zhijun Zhou, and Dr. Eunkyung Ji provided a great deal of help with settling into the lab when I first arrived to UNM. Yanli Tang and Zhijun Zhou introduced me to the synthesis of the OPEs, which I did not pursue for research but still found interesting. Tom Corbitt was also a great coworker and mentor, training me to do bactericidal testing, open-minded enough to humor me in a few pilot experiments, and always great to discuss Sci-fi novels with. Though Anand Parthasarathy was a postdoc in Professor Kirk Schanzes group at the University of Florida, we have had many meetings through our groups’ collaborations, and his friendly manner and advice are always welcome. Ying Wang, being the graduate student a year ahead of me, deserves special praise for his unending friendliness and mentorship up until he was awarded his PhD in Fall 2013. I thank the entire Whitten and Schanze and Evans groups, past and present, students and coworkers, for their participation in my experience at UNM. Subhadip Goswami, Linnea Ista, Jeremiah Anderson, Jasper Thompson, Tye Martin, Yue (Phoeby) Zhang, Patrick Donabedian, Harry Pappas, and Taylor Canady. In addition, several students from other research groups deserve thanks: Gregory Soliz, Lance Edens, Melissa Hernandez, Alex Leonard, Mark Fleharty, Dr. Christina Salas, Dr. Adam Wise, and Dr. Arjun Thapa. I thank my Chinese collaborators at Tsinghua University, particularly Prof. Xu Huaping, Prof. Zhang Xi, Kai Liu, Han Peng, Ma Ning, Ren Huifeng, Pengbo Wan, and Wu Guanglu. Of course, the office staff of the Center for Biomedical Engineering at UNM receive huge thanks for all of their help; Thank you Stephanie Sanchez, Isela Roeder, Fernando Santillanes, and Travis Woods for everything. I have to acknowledge the UNM Nanoscience and Microsystems REU program for bringing me into contact with some of my best students during my time at UNM. Dominic Sanchez (California Polytechnic University) and Kelly Stratton (currently in the Biomedical Engineering PhD program at University of Connecticut) were a thrill to have as students, and their dedication and energy led to great interactions which made for an excellent teaching experience. iv I have to thank former teachers throughout my education for their guidance. The Chemistry professors at Southern Oregon University are amazing teachers, and they directly prepared me for graduate school. I would like to give particular thanks to Professors Doug Chapman, Hala Schepmann, and Steven Petrovic at SOU for their guidance throughout my undergraduate education. Stepping further back in time, I owe profound thanks to Michael J. McDonough, the current Principal of Bellaire High School in Bellaire, TX. At the time when I was in highschool at Bellaire (2000-2004), he was the one assistant principal who kept me on the path to staying on track in school, despite my best friend at that time dropping out. He was able to give me personal counseling that I needed and was a strong role-model for my future development. I should thank the funding agencies which supported me and my work during my time at UNM. U.S. Defense Threat Reduction Agency for support through Grants W911NF07-1-0079 and HDTRA1-08-1-0053. The U.S. National Science Foundation for support through grant DMR-1207362. The U.S. Department of Education for support through the Graduate Assistance in Areas of National Need (GAANN) grant P200A090028. The University of New Mexico Office of Graduate Studies for multiple Research Project and Travel Grants and support through an Excellence Fellowship. The Chemistry Department at UNM for funds to design and build two high-performance computing clusters. Special thanks to all the software developers who provide free or open-source software. Last in the list but far from last in importance, I thank my family and friends for their unending support. My Dad’s enthusiasm for cars, video games, and computers has from an early age contributed to my ongoing interest in computers and technology, while my Mom’s career as a Physicians Assistant led to frequent discussions about medicine and anatomy, leading to my interest in biochemistry. While thanking my parents, I should probably also thank the LEGO corporation, as those blocks were a toy of choice which undoubtedly helped foster my interest in science and engineering. Thanks to my sister Leah and brother-in-law Jody for their support. Special thanks to all my Cousins, Uncles, Aunts, Nieces, Nephews, In-laws, and of course my Great-uncle Wiley. Thanks to my friends both here and abroad for all the great times, with special thanks to W.P. for getting me through the last few years. v Structural Influences on the Photochemistry and Photophysical Properties of p-Phenylene Ethynylenes: Aggregation Effects and Solvent Interactions by Eric Harris Hill B.S. Chemistry, Southern Oregon University, 2009 Ph.D. Nanoscience and Microsystems Engineering, University of New Mexico, 2014 Compounds based on the p-phenylene ethynylene backbone with pendant charged groups, known as conjugated polyelectrolytes, have been of particular interest in recent years due to their solubility in water, sensing properties, and biocidal activity against bacteria, viruses,