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Synthesis and Characterization of Biomimetic Model Systems for the Study of Diiron Hydrogenase and Porphyrin Enzymes

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Synthesis and Characterization of Biomimetic Model Systems for the Study of Diiron Hydrogenase and Porphyrin Enzymes University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 2020 Synthesis and Characterization of Biomimetic Model Systems for the Study of Diiron Hydrogenase and Porphyrin Enzymes Brian Francis Patenaude University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Patenaude, Brian Francis, "Synthesis and Characterization of Biomimetic Model Systems for the Study of Diiron Hydrogenase and Porphyrin Enzymes" (2020). Doctoral Dissertations. 2514. https://scholars.unh.edu/dissertation/2514 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. SYNTHESIS AND CHARACTERIZATION OF BIOMIMETIC MODEL SYSTEMS FOR THE STUDY OF DIIRON HYDROGENASE AND PORPHYRIN ENZYMES BY BRIAN F PATENAUDE B.S. Physics & B.S. Mathematics, University of New Hampshire, 2009 DISSERTATION Submitted to the University of New Hampshire In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy In Chemistry May 2020 This dissertation has been examined and approved in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry by: Dissertation Director, Samuel Pazicni, Assistant Professor of Chemistry, University of Wisconsin - Madison Roy P. Planalp, Associate Professor of Chemistry Christopher F. Bauer, Professor of Chemistry Glen P. Miller, Professor of Chemistry and Materials Science, Chair of Chemistry Department Karsten Pohl, Professor of Physics and Material Science, Chair of Physics & Astronomy Department On April 1st, 2020 ii DEDICATION To my wife, Adina, who is my pillar of strength and to my daughter, Ariana, who has fought through a difficult start in life and makes me prouder every day. iii ACKNOWLEDGEMENTS I would like to thank my advisor, Samuel Pazicni, for his continued support and understanding as I grew as a chemist. You made my graduate career exciting and enjoyable as you allowed me a great degree of independence in my research which made the research projects feel much more personal. In addition, you were an excellent and patient mentor with a wealth of knowledge to share. I would like to thank Prof. Rudi Seitz for his supportive advice as I transitioned from a continuing education student without an actual degree in chemistry to a full graduate student. Without meeting with you I may not have started my path as a graduate student in chemistry. I would like to thank Prof. Erik Berda for his continued support during the porphyrin project. Whether discussing polymer synthesis and characterization, martial arts, or life in general, conversations with you tended to refocus me and send me in the right direction. I would like to thank my past and current committee members, Profs. Marc Boudreau, Christine Caputo, Gonghu Li, Christopher Bauer, Glen Miller, Roy Planalp, and Karsten Pohl for your guidance and continued support. It was greatly helpful to have a group of professors in which I felt comfortable consulting with, without fear of judgement due to my own lack of knowledge or perspective. You all helped hone my approach to problem solving and aided my growth as a scientist. I would like to thank Dr. Pat Wilkinson for her continual help with spectroscopy and instrumentation. Your mentoring and hard work are greatly appreciated. Without your guidance and training I would not have been able to finish my projects. ii I would like to thank everyone in the chemistry office and stockroom; Cindi, Peg, Laura, and Kristin thank you for keeping the department running smoothly and advocating for the students. You were always there when the graduate students were in need. Thank you to all my friends in the department; Carter, Charlie, Ethan, Hannah, Jon, Liz, M.J., Stacie, and Zane your support and camaraderie made graduate school a great and fulfilling experience. And to the previous Pazicni group members; Christian, David, Kyle, Matt, Sarah, Drew, Madison, Cole, and Graham thank you for being great coworkers. May you all have success in all your future endeavors. Lastly, if it wasn’t for the support of my friends and family, I would not have the chance to pursue my love of science. To my wife, thank your continued patience through this time and for keeping me sane. To my daughter Ariana thank you for giving me a new perspective on life. To my parents thank you for imbuing me with a love for science and logic and the work ethic to never give up. iii TABLE OF CONTENTS DEDICATION ................................................................................................................................................. iii ACKNOWLEDGEMENTS ................................................................................................................................. ii LIST OF SCHEMES .......................................................................................................................................... v LIST OF FIGURES ........................................................................................................................................... vi LIST OF TABLES ............................................................................................................................................xiii ABSTRACT .................................................................................................................................................... xv Chapter I. Introduction to Artificial Enzymes ................................................................................................ 1 A Brief History of Artificial Enzymes ...................................................................................................... 1 Introduction Biotin-Avidin Artificial Enzymes ........................................................................................ 5 Introduction to Polymeric Enzyme Models .............................................................................................. 8 Chapter II. Artificial Diiron Hydrogenase Enzyme ....................................................................................... 11 Introduction ............................................................................................................................................. 11 Results and Discussion ........................................................................................................................... 16 Conclusions ............................................................................................................................................. 44 Experimental ........................................................................................................................................... 46 Materials ............................................................................................................................................. 46 Instrumentation ................................................................................................................................... 47 Experimental Procedures .................................................................................................................... 48 Chapter III. Secondary Sphere Interactions Studied within Porphyrin-Cored Nanoparticles ..................... 77 Introduction ............................................................................................................................................. 77 Results and Discussion ........................................................................................................................... 81 Conclusions ............................................................................................................................................. 90 Experimental ........................................................................................................................................... 91 Materials ............................................................................................................................................. 91 Instrumentation ................................................................................................................................... 91 Experimental Procedures .................................................................................................................... 93 LIST OF REFERENCES ................................................................................................................................. 117 APPENDICES .................................................................................................................................................. 1 APPENDIX A: 1H NMR Spectra .............................................................................................................. 1 APPENDIX B: 13C NMR Spectra ........................................................................................................... 54 APPENDIX C: 19F NMR spectra ............................................................................................................ 65 APPENDIX D: 1H DOSY NMR Spectra ................................................................................................ 72 iv APPENDIX F: IR Spectra
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