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Optical Resonance Sensors Based on Whispering-Gallery-Mode Technique

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Optical Resonance Sensors Based on Whispering-Gallery-Mode Technique Optical Resonance Sensors Based on Whispering-Gallery-Mode Technique Sirirat Panich A thesis submitted in partial fulfilment of the requirement for the degree of doctor of Philosophy Department of Chemistry, Imperial College London May 2016 1 | P a g e Declaration of Originality I hereby declare that this thesis is entirely my own original work. All other sources of information presented which are not part of my own work have been properly cited in the bibliography. No part of this thesis has been submitted for any degree at any other university or academic institution. Sirirat Panich 2 | P a g e Copyright Declaration The copyright of this thesis rests with the author and is made available under a Creative Commons Attribution Non-Commercial No Derivatives licence. Researchers are free to copy, distribute or transmit the thesis on the condition that they attribute it, that they do not use it for commercial purposes and that they do not alter, transform or build upon it. For any reuse or redistribution, researchers must make clear to others the licence terms of this work. 3 | P a g e Abstract In recent years, the whispering gallery mode (WGM) technique has received considerable attention as a novel and extremely sensitive technique for use in sensors. The technique is able to detect target molecules at very low levels and in real time, a capability which cannot be matched by any other detection technique currently in use. With this potential rarely found in common sensors, WGM is becoming one of the most widely used. The WGM set-up is simple and inexpensive. Light generated by a tunable laser, circumnavigates the surface of a resonator through a tapered waveguide. This light is strongly confined inside the microresonator by total internal reflection (TIR). Energy is extracted from the fibre, resulting in a negative peak. The surface of the resonator needs to be functionalised for reacting with the target molecule. If a chemical or biological analyte is to be bound on the surface of the resonator, the negative peak must be shifted. This shift can be used for measuring the amount of the analyte. In view of its exciting potential, it is not surprising that WGM is establishing itself as the detection method of choice, especially in chemical and biomedical applications. The work reported in this thesis is in two sections. In the first part, the use of the WGM technique integrated self-assembled glutathione (GSH) modified gold nanoparticles (Au NPs) on an optical microsphere resonator in an ultrasensitive chemical detection assay for Pb(II) (down to 10 ppt or 0.05 nM) is described. This satisfies the demanding sensitivity required for monitoring the maximum Pb(II) exposure limits set by both International Agency for Research on Cancer (IARC) and the United States Environmental Protection Agency (EPA). The second section presents an example of the use of WGM in a biosensor to study the interactions between small molecules and G-quadruplex DNA which is well known to be active targets for anticancer treatments. Currently methods typically used to study such systems have proven to be valuable; however, they have limitations, such as low sensitivity, time-consuming monitoring and lack of real time analysis. To circumvent these problems, a novel platform based around WGM is developed. The sensor offers a real time, fast and sensitive analysis. In addition, kinetic data such as dissociation equilibrium constant (KD) as well as association and dissociation constant (kon and koff, respectively) can be easily obtained. 4 | P a g e Acknowledgement I would like to express my gratitude to the following people, without whose help this thesis could not have been complete. Dr. Joshua B Edel, my supervisor, whose constant guidance and sympathetic encouragements has been indispensable. Dr. Sylvain Ladame, my co-supervior, who made valuable suggestions during my work on G-quadruplex. Dr. Kerry Wilson, my mentor in Edel group, whose patient explanation of the WGM technique was vital at the start of my project. Dr. Mazen Sleiman, who helped me to set up the G-quadruplex DNA experiment. Dr. Jame Redman and Dr. Ramon Vilar for their valuable comments during my viva. Isobel Steer, Jame Million, Dr. Binoy Nadappuram and Dr. Collin Click, for their help with proof-reading. Faculty of Science and Technology, Rajamangala University of Technology Phanakorn (RMUTP), my work place in Thailand, for the opportunity to do my Ph.D. aboard. The Royal Thai Government for my Ph.D. scholarship. My colleagues in the Edel group especially Dr. Aleksandar Ivanov, Dr. Kristelle Bougot-Robin, Dr. Agnieszka Rutkowska for their advices and helping me during my experiment in the lab. My sincere thanks also go to Yuwadee Sundarasaradula, Chaipat Lapinee and Nuchutha Thamsumet for their supporting me during living in London. Thanks are also due to many personal friends I have made while working at Imperial College. I would like to mention especially the kindness and support I have received from Christopher Wood, Jasmine Sze and Cadinu Paolo. Finally, I want to acknowledge my indebtedness to my family, whose understanding and love have sustained me at times when living in foreign country far from home has proven difficult. Sirirat Panich 5 | P a g e Table of Contents Declaration of Originality...................................................................................2 Copyright Declaration.........................................................................................3 Abstract.................................................................................................................4 Acknowledgements................................................................................................ 5 List of Abbreviations.........................................................................................10 List of Symbols...................................................................................................13 Chapter 1 Introduction…………………………………………………………………….......15 1.1 Sensors.................................................................................................................... 16 1.1.1 Advantages and disadvantages of WGM sensing compared with other sensing techniques...........................................................................................................................................19 1.2 Theories of optical WGM ...................................................................................... 22 1.2.1 Gallery of whispers .....................................................................................................................22 1.2.2 From the whispering gallery to a chemical and a biological sensor ......................................22 1.2.3 Resonant mode and total internal reflection effect .................................................................23 1.2.4 The operating principles of WGM ...........................................................................................24 1.2.5 WGM microresonators ..............................................................................................................30 1.2.6 Microresonator surface modification ........................................................................................30 1.2.7 Light coupling into a microresonator .......................................................................................31 1.2.8 Cavity Q-factor ............................................................................................................................32 1.3 WGM based sensing and applications ................................................................... 34 1.3.1 Chemical WGM based sensing .................................................................................................34 1.3.2 Biological WGM based sensing ................................................................................................34 1.3.3 Other sensing ..............................................................................................................................36 1.4 Project aims and objectives .................................................................................... 38 1.4.1 Chapter 3: Pb(II) sensor experiment ........................................................................................38 1.4.2 Chapter 4: G-quadruplex experiment.......................................................................................38 1.4.3 Chapter 5: thrombin experiment ..............................................................................................38 1.4.4 Chapter 6: conclusion ................................................................................................................38 1.5 References ............................................................................................................... 39 6 | P a g e Chapter 2 Instrumentation and Methodology ........................................................... 49 2.1 WGM experiment set-up ....................................................................................... 50 2.1.1 Instrumentations and devices ................................................................................... 50 2.1.1.1. Devices ..........................................................................................................................51 2.1.1.2 Consumable fibre cables ..............................................................................................52 2.1.1.3. Instruments ..................................................................................................................53
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