Nanomaterials Based Fluorescent Sensors for Sensitive and Selective Nitro-Explosives Detection Xiangcheng Sun [email protected]
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University of Connecticut OpenCommons@UConn Doctoral Dissertations University of Connecticut Graduate School 8-10-2015 Nanomaterials Based Fluorescent Sensors for Sensitive and Selective Nitro-explosives Detection Xiangcheng Sun [email protected] Follow this and additional works at: https://opencommons.uconn.edu/dissertations Recommended Citation Sun, Xiangcheng, "Nanomaterials Based Fluorescent Sensors for Sensitive and Selective Nitro-explosives Detection" (2015). Doctoral Dissertations. 815. https://opencommons.uconn.edu/dissertations/815 Nanomaterials Based Fluorescent Sensors for Sensitive and Selective Nitro-explosives Detection Xiangcheng Sun, Ph.D. University of Connecticut, 2015 The reliable detection of explosives is one of the pressing concerns in anti-terrorism efforts and environmental pollution controls. Up to date, fluorescence-based sensing technology represents one of the most promising approaches for trace explosives detection due to the advantages such as short response time, excellent sensitivity, and instrumental simplicity. The Ph.D. project aims at developing novel fluorescent nanomaterials for fast, sensitive, selective, reliable and cost- effective detection of nitro-explosives. Early research focused on the pyrene-doped polymer systems. Firstly, pyrene-polystyrene fluorescent nanoporous films have been prepared through a simple dip-coating process, and used for explosives vapour detection with ultra-sensitivity and selectivity. Morphology investigations revealed that the fluorescent polymer films consisted of a large-surface, three-dimensional nanoporous array of holes and the possible molecular origin of fluorescence quenching was investigated through structural XRD studies and the electronic structure of the polymer film. Later super-hydrophobic sand was prepared and applied for buried explosives detection. In order to detect nitro-explosives in aqueous phase, pyrene-polyethersulfone electrospun nanofibers were synthesized through electrospinning. The effects of mixed solvent ratio and polymer/fluorophore concentrations on nanofiber’s morphology as well as its sensing performance were systematically investigated and optimized. The current sensor demonstrated excellent sensitivity, selectivity and reusability to nitro-explosives detection. Further fluorescence lifetime studies have revealed a dominant static quenching mechanism. Xiangcheng Sun – University of Connecticut, 2015 An ultrafast and facile method for the preparation of fluorescent nitrogen-doped carbon nanoparticles (CNPs) has also been developed from a single precursor (ammonium citrate dibasic) under microwave conditions. The obtained CNPs showed strong blue fluorescence, which could be quenched by picric acid sensitively and selectively. Furthermore, fluorescent carbon dots co-doped with nitrogen and phosphorus were synthesized with high quantum yield and dual (blue and green) fluorescence emission, and applied as ratiometric sensors for explosives detection. Finally, a fully biodegradable and environmental-friendly biopolymer (protein) showed sensitive, selective and rapid detection of picric acid, and its excellent sensing performance was attributed to the synergistic effect of the low molecular orbital, presence of fluorescent resonance energy transfer as well as acid-base interactions. This dissertation opens an avenue in the design and synthesis of fluorescent nanomaterials for wide applications beyond nitro-explosives detection. Nanomaterials Based Fluorescent Sensors for Sensitive and Selective Nitro-explosives Detection Xiangcheng Sun B.E., Harbin Institute of Technology, 2008 M.E., Graduate University of Chinese Academy of Sciences, 2011 A Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Connecticut 2015 Copyright by Xiangcheng Sun 2015 APPROVAL PAGE Doctor of Philosophy Dissertation Nanomaterials Based Fluorescent Sensors for Sensitive and Selective Nitro-explosives Detection Presented by Xiangcheng Sun, M.E. Major Advisor ___________________________________________________________________ Dr. Yu Lei Associate Advisor ___________________________________________________________________ Dr. Christian Brückner Associate Advisor ___________________________________________________________________ Dr. Mu-Ping Nieh Associate Advisor ___________________________________________________________________ Dr. Steven L. Suib Associate Advisor ___________________________________________________________________ Dr. Jing Zhao University of Connecticut 2015 ii This work is dedicated to my beloved parents, for the pride and hope they always hold on their son, for the love and life they devote to their son. 2015 iii Acknowledgements First of all, I’d like to express my sincere gratitude to my major advisor Prof. Yu Lei for his guidance throughout my graduate study. This work is impossible without his encouragement and support. During the recent four years, he has offered me the opportunity to be a Ph.D. student, provided me with comfortable environment for research, given me the freedom to explore, and when necessary, guided me back on the right track. Furthermore, he cared about the students’ growth outside scientific areas. I am grateful to him as a great mentor in both scientific and extracurricular aspects. In addition, I wish to thank my advisory committee for their valuable guidance, support, and feedback during my Ph.D. research. Prof. Christian Brückner helped me on fluorescence knowledge, experimental design, manuscript composition, and he also encouraged me to explore the mechanisms behind the data. Furthermore, his enthusiasm, cautiousness and kindness greatly impressed me. Prof. Mu-Ping Nieh helped me a lot on the polymer background, English improvement, career development, etc. Prof. Steven L. Suib gave me great convenience in using various equipments in his lab, and Prof. Jing Zhao helped me through the “Optical Analysis” class, valuable discussion and lab equipment. I also appreciate many collaborators such as Prof. Pu-Xian Gao and Dr. Haiyong Gao for high temperature gas sensing, Prof. Hanchen Huang and Dr. Stephen Stagon for surface enhanced Raman scattering based glucose detection, and Prof. Challa Kumar for protein based sensors. I need to thank staff, Dr. Gary Lavinge, Dr. Lichun Zhang, Dr. Heng Zhang, Dr. Jack Gromek in IMS for materials characterization and Ms. Susan Soucy and Ms. Leah Winterberger in Department of Chemical and Biomolecular Engineering for their help in my Ph.D. studies. iv Furthermore, for the excellent group, efficient cooperation and harmonious atmosphere, I acknowledge my labmates such as Ying Wang, Liang Su, Yixin Liu, Xiaoyu Ma, Jun Chen, George Shaw, Andrew Carrier, Jorge Paz Soldan, Qiuchen Dong, Sichen Zhang, Jing Bao, etc. I would also like to thank Yongtao Meng and Junkai He in Prof. Suib’s lab, Swayandipta Dey in Prof. Zhao’s lab for their help and suggestions in my research. Kan Fu and Wenxiao Huang are greatly appreciated for the amazing experience in BASF Science Competition. I also thank my roommates and all good friends for their support in the past four years, in which I had a wonderful, colorful and unforgettable life. Most of all, I would like to express my never ending love to my parents and my family for their unconditional support and care. v Table of Contents Chapter 1 Introduction ............................................................................................................................... 1 1.1 The Background of Explosives Detection ........................................................................................... 1 1.2 Methods and Mechanisms for Fluorescence Based Explosives Detection ......................................... 5 1.2.1 Interactions Caused Fluorescence Detection ............................................................................... 6 1.2.2 Fluorescence Quenching Theory................................................................................................ 13 1.3 Sensory Materials for Fluorescence Based Explosives Detection .................................................... 15 1.3.1 Fluorescent Conjugated Polymers ............................................................................................. 16 1.3.2 Small Molecule Fluorophores .................................................................................................... 17 1.3.3 Supramolecular Systems ............................................................................................................ 19 1.3.4 Bio-inspired Fluorescent Materials ............................................................................................ 20 1.4 Nanomaterials for Fluorescence Based Explosives Detection ......................................................... 21 1.5 Motivation, Objectives and Organization ......................................................................................... 22 Chapter 2 A Fluorescent Polymer Film with Three-Dimensionally Ordered Nanopores for Explosives Vapor Detection ..................................................................................................................... 26 Abstract ................................................................................................................................................... 27 2.1 Experimental ..................................................................................................................................... 27 2.1.1 Materials ...................................................................................................................................