University of Connecticut OpenCommons@UConn Doctoral Dissertations University of Connecticut Graduate School 5-15-2014 Principles of Structure-Function Relationships Applicable To Sensing Materials ─ Explosives and Bio-Diagnosis Hyun-Sook Jang University of Connecticut - Storrs, [email protected] Follow this and additional works at: https://opencommons.uconn.edu/dissertations Recommended Citation Jang, Hyun-Sook, "Principles of Structure-Function Relationships Applicable To Sensing Materials ─ Explosives and Bio-Diagnosis" (2014). Doctoral Dissertations. 399. https://opencommons.uconn.edu/dissertations/399 Principles of Structure-Function Relationships Applicable To Sensing Materials -Explosives and Bio-Diagnosis Hyun-Sook Jang, Ph. D University of Connecticut, 2014 Functions of nanomaterials can be strongly dependent on their structures. Therefore, the knowledge of structure-function relationship can provide important information for designing functional materials. This dissertation aims to gain fundamental knowledge through structural analysis of nano-sensing materials for explosives and bio-diagnosis in order to enhance the sensitivity. The main project of my research involved the investigation into the fluorescence and quenching mechanisms of pyrene with a series of organic salts and/or polystyrene of a variety of architectures as well as the function of explosive detection. The major findings of this dissertation includes: (1) the formation of pyrene excimers can be enhanced by high solvent vapor pressure annealing with the polystyrene (2) tetrabutylammonium cation + - (TBA ) can effectively suppress the fluorescence but hexafluorophosphate anion (PF6 ) with TBA+ can counteract this effect at high solvent vapor pressure driven by temperature. This process is reasoned by dynamic quenching, (3) Polystyrene can effectively lower LUMO (lowest unoccupied molecular orbit) level of pyrene, thus facilitating the detection of the nitro-aromatic explosives. This process is presumably accomplished through radiationless energy transfer from polystyrene emission to pyrene absorption resulting in Hyun-Sook Jang – University of Connecticut, 2014 the efficient photoinduced electron transfer (PET) to explosives, (4) the diffusion coefficients of 2,4-DNT (dinitrotoluene) through pyrene/polystyrene films was evaluated and film thickness is found to be a key parameter affecting the diffusion of 2,4-DNT. The second project mainly focused on constructing potential nanotemplates for biocompatible sensing and diagnosis by using the complexes made of phospholipid/gold nanoparticles and phospholipid/polymer. The 2-nm surface-modified gold nanoparticles can be incorporated in the phospholipid bilayers. Such template can be further developed into theranostic carriers for medical imaging or hyperthermia treatment. In addition, I have shown that lipid vesicles can interact with a triblock copolymer forming clusters of vesicles – this template can also be used as sensitive biosensors. Principles of Structure-Function Relationships Applicable To Sensing Materials -Explosives and Bio-Diagnosis Hyun-Sook Jang B.E., Sogang University, 2006 A Dissertation Submitted in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy at the University of Connecticut 2014 i © Copyright by Hyun-Sook Jang 2014 ii Approval Page Doctorof PhilosophyDissertation Principlesof Structure-FunctionRelationships ApplicableTo SensingMaterials -Explosivesand Bio-Diagnosis Presentedby Hyun-SookJang, Ph.D. ts- MajorAdvisor V Mu-PingNie\ r t. t/ | AssociateAdvisor U2)" Yt4 AssociateAdvisor Df AssociateAdvisor AssociateAdvisor StevenL. Suib Universityof Connecticut 2014 iii DEDICATON To my beloved mom (Sun-hee Jun), brother (Jae-hyuk Jang) and papa (Dong-wee Jang) whom I will see for sometime in the heaven for their dedication, encouragement and endless love. iv ACKNOWLEDGEMENT The years of pursuing my PhD in UCONN have been the most memorable time for me. There are many great people that I got to know during this period deserve my heartfelt gratitude. First and foremost, I would like to express my sincere gratitude to Prof. Mu-Ping Nieh for his patience, insightful advice, and endless support for the research. Without him, my Ph.D. journey could have not been possible. He was a remarkably active adviser to initiate my potentials and support me with positive views. His door was always widely opened for students and ready for the discussion regardless of topics. I want to thank him that he has given a number of opportunities to expand my network outside of school by attending many national meetings, national lab experiment and National X-ray/Neutron school. I truly respect his educational philosophy and I am grateful that you were with me to get through many things together along my up and down Ph.D. life. I also would like to thank Prof. Yu Lei for his inspiration and creative suggestions, Prof. Douglas Adamson for his support, three classes that I have taken and advice, Prof. Jing Zhao for the guidance about lifetime experiment and warm words for the encouragement and Prof. Steven Suib for his insightful suggestions and experiences about research topic. Because of their profound knowledge, I was exposed to a tremendous amount of learning opportunities. Before coming to USA, I did not have any background about this research topic, but I learned a lot from you. I truly v want to thank each of you for your valuable time to guide me, review my dissertation and to attend my final defense. I appreciate many people for their supports and assistances with various aspects of this project: Dr. Flavio Maran (Univ. of Padova, Italy) for providing gold nanoparticles, Dr. David Uhrig (Oak Ridge National Lab) for synthesizing different architectures of polystyrenes, Dr. Hyun-Seok Cho (Univ. of Alabama) for conducting the cyclic voltammetry experiment for me, and Dr. Boualem Hammouda (NIST) for helping the neutron scattering experiment in NIST. Indeed, I should thank to all the IMS staffs (Jack Gromek for XRD, Marcurs Giotto for NMR, Lichun Zhang and Rogers Ristau for SEM/(HR)- TEM, Gary Lavigne for fluorescence, Raman/IR spectrocopy) who not only trained me to run the instruments but also gave many great suggestions to solve my experimental challenges. I would like to thank everyone in my group members and undergraduate students as well for working and dealing with me for all these years, especially for Ming-Li who was a great batch and lab mate (Hope you get well soon.) and Ying Liu who shared many of those experiences together. It was enjoyable to interact with Andrew Hu, Yan Xia, Wafa Aresh and Chenlu Yu as well. Also, I learned a lot from my undergraduate students (Joshua Lemkin, Rose Cersonsky, Nicholas Fleming and Naomi Tennakoon). Thanks for all the failures and results from your hands. All the best for you guys! vi It was a great pleasure to be friends with the amazing people. I was lucky to meet Dr. Ying Wang who taught me about the initial experiment setup of explosives detection and Dr. Ching-Chang Chung who helped many of my experiments (XRD/SEM) initially. A special thanks goes to Aaron Baldwin for proof reading some of this dissertation. After I arrived in Storrs alone, many Korean seniors or friends in IMS/UCONN helped me to adjust my life safely. I appreciate their support and friendship of Dr. Suk- kyun Ahn, Dr. Ki-Ryong Lee and Joon-Sung Kim. I also thank all my friends and mentors from previous company and KIST in Korea and/or USA for their encouragement and just being there. I deeply appreciate Younghee and Bob Chudy for their warmest care and thoughtful encouragement in my Storrs life. Thanks you for giving me a memorable chapter in my life with you and your family. Finally, I wish to express my deepest gratitude to my lovely family, my mom and brother. They always trusted me undoubtedly and encouraged me with endless love during the most stressful time. I have no adequate words that can express my love to them. Their unconditional love gave me unbelievable motivation and power to accomplish my dissertation research. Thank you being my family and always love you. vii TABLE OF CONTENTS Dedication ………………………………………………………………. iv Acknowledgements …………………………………………………….....v List of Tables…………………………………………………………… xii List of Figures …………………………………………………………..xiii List of Schemes …………………………………………………..........xxiv List of Symbols ……………………………………………………….. xxv List of Abbreviations………………………………………………....xxviii CHAPTER 1. INTRODUCTION.……………………………….......... 1 1.1 Explosives detection…………………………………………………1 1.2. Pyrene as a Fluorophore…………………………………………… 4 1.2.1. Pyrene Monomers (IM) and Excimers (IE)………..……….. 4 1.2.2. Ground-associate dimers…………………………………. 11 1.3. Fluorescence Quenching Mechanism………………………........ 14 1.3.1. Static and Dynamic quenching………………...…….….. 14 1.3.2. Quenching mechanisms………………………………… 16 1.4. Bio-diagnosis ……………………………………………………. 19 1.5. Dissertation objectives …………………………………………… 20 1.6. References ………………………………………………………. 22 CHAPTER 2. INSTRUMENTAL METHODS OF FUNCTIONAL AND STRUCTURAL CHARACTERIZATION…………………. 30 2.1. Fluorescence ………………………………………………….…… 30 viii 2.1.1 Theory………………………………………………….………. 30 2.1.2 Instrumentation ………………………………………………... 32 2.2. Scattering …………………………………………………….…… 34 2.2.1. Small Angle X-ray Scattering (SAXS) ……………….…..…... 40 2.3. Electron microscopy ……………………………………….…. ...... 41 2.3.1. Transmission Electron Microscopy (TEM)…………………... 41 2.4. References …………………………………………….………..…..44 CHAPTER 3. CONTROLLABLE FORMATION OF PYRENE (C16H10)