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Thesis of a Hollow Fibre Boronic Acid Fixed Carrier Membrane System for Saccharide Separation University of Bath PHD Chemical modification of polysulfone Cox, Owen Award date: 2013 Awarding institution: University of Bath Link to publication Alternative formats If you require this document in an alternative format, please contact: [email protected] General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Download date: 07. Oct. 2021 Acknowledgements First and foremost I would like to thank my supervisors, Dr Semali Perera and Professor Tony James for their guidance and funding throughout my project. A big thanks to all the past and present members of the James group for generally being a friendly helpful bunch of lads. Special thanks goes to those who helped me out in my first year; Kit, Francois, Axe, Kelly, Maggy, Wenbo, Sabrina etc. for making me feel at home and welcome. An extra special thanks to Flower for constantly listening to my never ending stream of questions and not once seeming annoyed by it. Thanks to all the undergraduate students I’ve helped look after over the years, it was one of the most enjoyable aspects of my PhD. Thanks to my family for their extreme patience with me. Most of all I’d like to thank Hannah, for just generally putting up with me and in spite of all my faults still supporting me one hundred percent. ii Abstract The research presented herein is concerned with the chemical modification of polysulfone towards the synthesis of a hollow fibre boronic acid fixed carrier membrane system for saccharide separation. Chapter 1 firstly introduces the area of boronic acids as chemosensors, in particular for detecting saccharides. Secondly, membrane separation techniques are discussed focussing on hollow fibre membranes and their synthesis. Chapter 2 discusses the potential of boronic acid fixed carrier hollow fibre membranes for saccharide separation. Three general routes are highlighted to achieve the desired boronic acid appended polymers: electrophilic aromatic substitution, lithiation and functional monomer polymerisation. Chapter 3 describes the various attempts at achieving the target polymer via electrophilic aromatic substitution methodology. Chapter 4 describes the various attempts at achieving the target polymer via lithiation methodology. Chapter 5 investigates the ability to create functional monomers with which functional polymers can be polymerised from. Chapter 6 describes the synthesis and characterisation of the compounds discussed in chapters 3, 4 and 5. iii Table of Contents Acknowledgements ...............................................................................................................ii Abstract ............................................................................................................................... iii Table of Contents ................................................................................................................ iv Abbreviations ................................................................................................................... viii Chapter 1: Introduction ...................................................................................................... 1 1.1 General Introduction ..................................................................................................... 1 1.2 Chemosensors ............................................................................................................... 1 1.2.1 Cyanide Detection ................................................................................................. 2 1.2.2 Carbon Dioxide Detection ..................................................................................... 3 1.2.3 Saccharide Recognition ......................................................................................... 4 1.3 Boronic Acid Chemosensors ........................................................................................ 6 1.4 Boronic Acid Oligosaccharide Sensors ...................................................................... 16 1.5 Membranes ................................................................................................................. 18 1.5.1 Traditional Membranes ........................................................................................ 18 1.5.2 Types of Membrane Separation ........................................................................... 23 1.5.3 Types of Module .................................................................................................. 26 1.5.3.1 Plate and Frame Module .............................................................................. 26 1.5.3.2 Membrane Cartridge Module ....................................................................... 26 1.5.3.3 Spiral Wound Module .................................................................................. 27 1.5.3.4 Tubular Membranes ..................................................................................... 28 1.5.3.5 Capillary Membranes ................................................................................... 28 1.6 Hollow Fibre Membranes ........................................................................................... 29 1.6.1 Hollow Fibre Synthesis ....................................................................................... 29 1.6.1.1 Melt Spinning ............................................................................................... 30 1.6.1.2 Dry-Wet Spinning ........................................................................................ 32 1.6.2 Hollow Fibre Applications .................................................................................. 34 1.6.3 Membrane Contactors .......................................................................................... 34 1.6.3.1 Liquid-Liquid Extraction ............................................................................. 36 1.6.3.2 Gas-Liquid Extraction .................................................................................. 38 iv 1.6.3.3 Chiral Resolution ......................................................................................... 38 1.6.4 Supported Liquid Membranes ............................................................................ 38 1.6.5 Hollow Fibres in Sugar Separation ...................................................................... 42 1.7 Conclusion .................................................................................................................. 43 1.8 References .................................................................................................................. 44 Chapter 2: Boronic Acid Appended Polymers for Sensing and Separation ................. 46 2.1 Introduction ................................................................................................................ 46 2.1.1 Diabetes Blood Monitors ..................................................................................... 46 2.1.2 Oligosaccharide Disease Biomarkers .................................................................. 46 2.1.3 Natural Sugar Separation ..................................................................................... 47 2.2 Research Rationale and Aims ..................................................................................... 47 2.2.1 Fructose Selectivity of Boronic Acids ................................................................. 48 2.2.2 Fructose Selective SLM ....................................................................................... 51 2.2.3 Problems and Possible Solutions ......................................................................... 52 2.2.4 Fixed Carrier Membranes .................................................................................... 53 2.2.4.1 Carrier Diffusion .......................................................................................... 53 2.2.4.2 Fixed-Site Jumping ...................................................................................... 54 2.2.5 Boronic Acid Fixed Carrier Membrane ............................................................... 57 2.3 Design ......................................................................................................................... 61 2.3.1 Previous Work ..................................................................................................... 61 2.3.2 Types of Fibre ...................................................................................................... 62 2.3.3 Boronic Acid FCM Hollow Fibre Implementation ............................................. 64 2.3.3.1 Homogenous Modification........................................................................... 66 2.3.3.2 Heterogenous Modification .......................................................................... 66 2.3.3.3 Functional Monomer
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