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University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations Dissertations and Theses November 2017 NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS Gulen Yesilbag Tonga University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_2 Part of the Materials Chemistry Commons, Medicinal-Pharmaceutical Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Yesilbag Tonga, Gulen, "NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS" (2017). Doctoral Dissertations. 1141. https://doi.org/10.7275/10521708.0 https://scholarworks.umass.edu/dissertations_2/1141 This Open Access Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS A Dissertation Presented by GULEN YESILBAG TONGA Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY September 2017 Department of Chemistry i © Copyright by Gulen Yesilbag Tonga 2017 All Rights Reserved ii NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS A Dissertation Presented by GULEN YESILBAG TONGA Approved as to style and content by: __________________________________ Vincent M. Rotello, Chair __________________________________ Richard W. Vachet, Member __________________________________ James J. Chambers, Member __________________________________ Barbara A. Osborne, Member __________________________________ Richard W. Vachet, Department Head Department of Chemistry iii DEDICATION To my husband Murat and my son Ali Eray, and to my family. iv ACKNOWLEDGEMENTS First, I would like to thank to my research advisor, Professor Vincent M. Rotello for his support and guidance during my PhD studies. As a mentor and advisor, he contributed a lot to my scientific skills and understanding. I have learned how to approach and solve scientific problems, perform multiple projects, and be multitasking and independent researcher. Under his guidance, I did not only improve my scientific skills but also my social skills such as managing my time as well as managing relationships with my colleagues and collaborators. I always admired him for how well he manages such a big group and endless number of projects. I appreciate the opportunity he gave me to work in his group. When I looked behind, I think I achieved a lot during my PhD and I truly believe this is because I was in Rotello group. I am so proud of being a member of Rotello group and I believe wherever I go I will carry the excellent impacts of Rotello group for my future career and I will never forget Professor Vincent`s precious advices. I would like to thank my committee, Professor Richard W. Vachet, Professor Barbara A. Osborne and Dr. James J. Chambers for their valuable comments on my research. I appreciate their time and effort advising and helping me. I also would like to thank all the past and present research group members including all the visiting students and scholars for sharing their thoughts, cultures, and scientific advice. They were all my friends and colleagues. Especially, I would like to mention some of them here, Chaekyu, Youngdo, Riddha, Roberto, Mine, Ying, Ngoc Le, Moumita, Rubul, and Ryan. Lastly, I would like to express my gratitude to my family and friends. I always felt their support and love during my PhD. Also, I would like to thank my husband Murat and our son Ali Eray for their unconditional support and love. They are the best thing that ever happened to me. v ABSTRACT NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS SEPTEMBER 2017 GULEN YESILBAG TONGA, B.S., BOGAZICI UNIVERSITY M.S., BOGAZICI UNIVERSITY Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Vincent M. Rotello Nanoparticles (NPs) are being investigated widely for many applications including imaging, drug delivery, therapeutics, materials, and catalysis due to their unique and tunable physical and chemical properties. Among NPs, gold nanoparticles (AuNPs) have attracted great attention due to ease of synthesis and surface functionalization, inertness of the core, biocompatibility, and functional versatility. Introducing supramolecular chemistry into the nanoparticle-based platforms brings out controllable properties, dynamic self assembly processes, and adjustable performance. My research has focused on the synthesis of AuNPs bearing different surface functionalities and their host-guest interactions with synthetic small molecules or commercially available hydrophobic catalysts for delivery and therapeutic applications. My research is consisted of two main sections. First part is the regulation of the exocytosis of AuNPs using host-guest interactions and characterization of these interactions in solution using isothermal titration calorimetry and inside cells using laser desorption/ionization/matrix assisted laser desorption/ionization mass spectrometry. Second part is about encapsulating various hydrophobic transition metal catalysts into the monolayer of AuNPs. These catalyst-embedded vi AuNPs were used to catalyze industrially important reactions in aqueous environment. For biological applications, this system was called as ‘nanozyme’ because it was used as an enzyme mimic to perform bioorthogonal activation of profluorophores and prodrugs for imaging and therapeutic applications, respectively. Using the host-guest chemistry, intracellular catalysis was supramolecularly regulated. Lastly, different monolayer designs were engineered to increase the catalyst loading and improve catalytic efficiency. vii TABLE OF CONTENTS Page ACKNOWLEDGEMENTS ............................................................................................................. v ABSTRACT .................................................................................................................................... vi LIST OF TABLES ......................................................................................................................... xii LIST OF FIGURES ...................................................................................................................... xiii LIST OF SCHEMES................................................................................................................... xxiii CHAPTER 1. GOLD NANOPARTICLES IN DELIVERY AND THERAPEUTICS ...................................... 1 1.1 Introduction ............................................................................................................................ 1 1.2 Application of Gold Nanoparticles in Drug Delivery and Therapeutics ................................ 3 1.3 Supramolecular Chemistry ..................................................................................................... 5 1.3.1 Supramolecular Chemistry in Drug Delivery ................................................................. 5 1.3.2 Supramolecular Platforms Using Gold Nanoparticles .................................................... 7 1.3.3. Characterization and Monitoring of Host-Guest Interactions in Solution and Living Cells ............................................................................................................. 9 1.4 Bioorthogonal Catalysis ....................................................................................................... 11 1.4.1 Bioorthogonal Catalysis Using Transition Metal Catalysts .......................................... 13 1.4.2 Non-Covalent Incorporation of Hydrophobic Transition Metal Catalysts into AuNP Monolayers ................................................................................................ 16 1.5. Dissertation Overview......................................................................................................... 17 1.6. References ........................................................................................................................... 21 2. REGULATING EXOCYTOSIS OF NANOPARTICLES VIA HOST-GUEST CHEMISTRY ........................................................................................................................... 32 2.1 Introduction .......................................................................................................................... 32 2.2 Results and Discussion......................................................................................................... 34 2.2.1 Complexation between AuNP-TBen and CB[7] ........................................................... 34 2.2.2 Inducing Assemblies of AuNP-TBen-CB[7] ................................................................ 35 2.2.3 Controlling Exocytosis of AuNP-TBen-CB[7] Inside Cells ......................................... 38 2.2.4 Tracking Exocytosis of CB[7]-complexed Nanoparticles Inside Cells Using Inductively Coupled Plasma Mass Spectrometry ........................................................ 39 2.2.5 Cellular Viability of the Induced Assemblies ............................................................... 41 2.3 Summary and Future Outlook .............................................................................................
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