Molecular Design and Self-Assembly of Polydiacetylene for Biosensors and Sensor Arrays

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Molecular Design and Self-Assembly of Polydiacetylene for Biosensors and Sensor Arrays Molecular Design and Self-assembly of Polydiacetylene for Biosensors and Sensor Arrays by Ji Seok Lee A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Macromolecular Science and Engineering) in The University of Michigan 2011 Doctoral Committee: Professor Jinsang Kim, Chair Professor L. Jay Guo Professor Kenichi Kuroda Professor David C. Martin Jiseok Lee © 2011 All Rights Reserved ACKNOWLEDGMENTS I would like to thank my advisor, Professor Jinsang Kim. He guided me with a great patience for my experimental kowledge as well as my presentation skill improvement. He has always encouraged me even when I made mistakes. I would like to give my sincere respect to Prof Kim for his generous concern. I could not have published good journals, enjoyed the research and successfully finished the doctoral program without his advice. I also would like to thank my committee members, Prof Martin, Prof Kuroda and Prof Guo. Under their guidance, I could draw a big picture of my research and train myself as a scientist not a technician. It was a great honor for me to do my research under their thoughtful guidance. I also thanks to Prof Laine and Nonna. I could finish my degree as a Macro student by his permission. Also Nonna helped me a lot for every student business. She saved me a lot of times from troubles. I would like to thank all of my lab members. It was good experience for me to work with them. The past members of the Kim’s group, Dr Kim and Dr Jo gave me a lot of advice. Kangwon Lee gave me a chance to enhance my knowledge for biomaterials. Myung-su Kim has always cheered me up with his kind compliment. I could improve my English a lot from Onas, Rob, Laura, and David. Bonggi and Doc Jeong gave me a lot of information for the organic synthesis. I specially thanks to Doc Jeong for her contribution for melamine sensor work. My small lab mate, Sungbaek helped me a lot for the PDA work and I had a really enjoyed the time with him in the small lab. He made the small lab very active and cozy. I wish he might show much more performance than me. I also appreciate many Korean friends, Seungwhan, Seokhun Brother, Jason and all of my Hanyang University friends. They made my Ann Arbor life much more ii enjoyable. Lastly, but most importantly, I thank my family. Seongsoo Jung, my precious wife, made my life as a real one. I could not have accomplished all of my works without her sacrifice. Also I thanks to my lovely son. He encouraged me and we are expecting to meet him on August 2011. Kyungrae Shin, my mother, and Myunggoon Lee, my farther, have always supported and prayed for me with great care. Their great support helped me to focus on my research. I thank God that I could have such a great opportunity to live with my precious people. iii TABLE OF CONTENTS ACKNOWLEDGMENTS ................................................................................................ ii LIST OF SCHEMES ....................................................................................................... ix LIST OF FIGURES ...........................................................................................................x LIST OF TABLES ...........................................................................................................xv CHAPTER 1: Introduction ...............................................................................................1 1.1 Motivation of biosensor development ...............................................................1 1.2 Conjugated Polymer...........................................................................................3 1.3 Polydiacetylene Polymer ...................................................................................4 1.4 Self-assembly of Diacetylene Molecules ...........................................................5 1.4.1 Langmuir-blodgett (LB)/ Lnagmuir-Schaefer (LS) Method .......................................................................................6 1.4.2 Layer-by-Layer Thin Film ......................................................8 1.4.3 Colloidal Dispersion .............................................................10 1.4.4 Conclusion of Self-assembled Structure ...............................13 1.5 Topochemical Polymerization .........................................................................14 1.6 Optical Property of Polydiacetylene ................................................................15 1.6.1 Colorimetric Property ...........................................................15 1.6.2 Mechanism of Color Change ................................................16 1.6.3 Emissive Property .................................................................18 1.6.4 Conclusion for Optical Property of Polydiacetylene ............19 1.7 PDA Sensors in the Literature .........................................................................19 1.8 References ........................................................................................................22 CHAPTER 2: Polydiacetylene–Liposome Arrays for Selective Potassium Detection ...........................................................................................................................29 iv 2.1 Introduction ......................................................................................................29 2.2 Results and Discussion ....................................................................................30 2.3 Conclusions. .....................................................................................................34 2.4 Experimental section. .......................................................................................35 2.4.1 Preparation of the Liposome Microarray ..............................35 2.4.2 Potassium Detection of the Liposome Microarray ...............35 2.4.3 Quantitative Data of Fluorescence Intensity with Various Concentrations of Potassium ......................................35 2.4.4 Potassium Detection of G-rich ssDNA Modified Liposome Solution ...................................................................36 2.4.5 Circular Dichroism................................................................36 2.4.6 Synthesis and characterization ..............................................36 2.5 References ........................................................................................................38 CHAPTER 3: Polydiacetylene–Liposome Microarrays for Selective and Sensitive Mercury(II) Detection .....................................................................................41 3.1 Introduction ......................................................................................................41 3.2 Results and Discussion ....................................................................................43 3.3 Conclusions. .....................................................................................................49 3.4 Experimental section. .......................................................................................50 3.4.1 Preparation of the Liposomes ...............................................50 3.4.2 Preparation of the Diacetylene Liposome having the Thymine-rich ssDNA Aptamer Immobilization of the Liposomes ................................................................................50 3.4.3 Immobilization of the Liposomes .........................................51 3.4.4 Fabrication of the PDA Microarray ......................................51 3.4.5 Fluorescent Microscope Images ...........................................51 3.4.6 Mercury Detection with the PDA Liposome in Solution......52 3.4.7 Synthesis and characterization ..............................................52 3.5 References ........................................................................................................54 CHAPTER 4: Selective and sensitive detection of melamine by intra/inter liposomal interaction of polydiacetylene liposomes ......................................................57 4.1 Introduction ......................................................................................................57 v 4.2 Results and Discussion ....................................................................................58 4.3 Conclusions ......................................................................................................66 4.4 Experimental section ........................................................................................66 4.4.1 Materials and Method ...........................................................66 4.4.2 Melamine Detection with the PDA Liposome in Solution .................................................................................67 4.4.3 Fluorescent Microscope Images ...........................................67 4.4.4 Preparation of the Diacetylene Liposome .............................68 4.4.5 Immobilization of the Liposomes .........................................68 4.4.6 Synthesis of PCDA Derivatives ............................................68 4.5 References ........................................................................................................71 CHAPTER 5: Colorimetric Detection of Warfare Gases by Polydiacetylenes toward Equipment-free detection ...................................................................................73 5.1 Introduction ......................................................................................................73 5.2 Results and
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