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Durham E-Theses Durham E-Theses The surface chemistry of polymeric bioseparation materials Tasker, Simon How to cite: Tasker, Simon (1996) The surface chemistry of polymeric bioseparation materials, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/5333/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk A Thesis Entitled THE SURFACE CHEMISTRY OF POLYMERIC BIOSEPARATION MATERIALS Submitted for the Degree of Doctor of Philosophy by Simon Tasker, BSc. (Dunelm) November 1996 The copyright of this thesis rests with the author. No quotation from it should be pubhshed without his prior written consent and information derived from it should be acknowledged. University of Durham 4 JAN 1997 ACKNOWLEDGEMENTS Firstly, I would like to thank my parents and my sister who have always enouraged me to do my best, I couldn't have achieved this without their love and support. I acknowledge the help and guidance of Professor Jas Pal Badyal both during the course of this research and the subsequent writing up period. In addition, thanks must go to the many technical and support staff that have enabled my ideas to be put in to practice, and the DTI and SERC for fimding this research. I would like to thank all of my friends in Lab 98, particularly Campbell, Pete, Phil, Rachel, Janet, Oily and Martin, for the fim and beers that we had along the way. I must also mention Gary, Karen, Ahce and Don who have all done a great deal to keep me sane over the last few years and hopefiiUy will continue to do so. Finally I must thank Linda for her love and friendship which has meant a great deal to me during the last nine months. I dedicate this thesis to the memory of my grandparents, Ashley and Kathleen Nicolson. ABSTRACT The aim of this thesis was to test existing theories concerning biocompatibility of polymeric materials, and in the process to try and identify the major factors which pertain to their use as bioseparation matrices. The surface chemistry of cellulose and poly(tetrafluoroethylene) based bioseparation materials have been examined. We have been able to demonstrate a direct link in the case of the cellulose materials between tlie crystallinity and the accessibihty of the hydroxyl groups which are the primary sites of fimctionaUzation. In addition, the effect of processing conditions on the pore structure of an amorphous cellulose matrix was demonstrated and this has been shown to have a direct consequence for the protein binding characteristics of the material. The fimctionalisation of PTFE has been achieved by reaction with sodium naphthalenide, which lead to the defluorination of the PTFE surface and the formation of a imsaturated carbonised layer containing oxygenated fimctionaUties. The reaction has also been shown to alter the morphology of PTFE membranes as evidenced by AFM analysis. In the case of powdered PTFE we observed the formation of a microporous layer, however this was found to revert back to a fluorinated layer with gentle heating. A novel insight in to the defluorination reaction was obtained using the bombardment of PTFE and PVDF with a Na atom beam under ultra-high vacuum conditions. This demonstrated the single valence electron mechanism of the reaction and also showed the formation of NaF at the surface of the polymer. The formation of CF3 groups was attributed to the nucleophilic attack of fluoride ions from molecxilar NaF species formed at the initial stages of the reaction. iii DECLARATION The work described in this thesis was undertaken in the Department of Chemistry at the University of Durham between October 1991 and September 1994. It is the original work of the author except where indicated or where specific reference is made to the source material. No part of this thesis has been previously submitted for a degree, however the following articles which are based on work contained in this thesis have been published as indicated: 'Hydroxyl Accessibility in Celluloses' S. Tasker. J. P. S. Badyal, Polymer, 35, 4717 (1994). 'Influence of CrossUnking upon the Pore Structure of Cellulose' S. Tasker, J. P. S. Badyal, J. Phys. Chem., 98, 7599 (1994). 'Surface Defluorination of PTFE by Sodium Atoms' S. Tasker. J. P. S. BadyalJ. Phys. Chem., 98, 12442 (1994). rv CONTENTS 1. INTRODUCTION l.l.BIOMATERIALS 1.1.1. Polymeric Biomaterials 1.2. INTERFACIAL BIOCOMPATIBLITY OF POLYMERS 3 1.2.1. Protein/Polymer Interactions .4 1.2.2. The Polymeric Biosurface 1.2.2.1. Surface Dynamics ^ 1.2.2.2. Electrical Properties ^ 1.2.2.3. Interfacial Energetics ^ 1.3. SURFACE MODIFICATION OF POLYMERS FOR ENHANCED BIOCOMPATIBILITY ^ 1 1.3.1. Polymer Blends ^1 1.3.2. Co-polymerization 13 1.3.3. Chemical Modification of Surfaces^ . 14 1.3.4. Chemical Grafting 16 1.3.5. Glow-discharge Modification 17 1.3.6. Bioactive Polymer Systems 17 1.4. BIOSEPARATION 18 1.4.1. Introduction 1^ 1.4.2. Chromatographic Considerations 19 1.4.3. Factors Affecting the Performance of a Chromatography System 21 1.5. STATIONARY PHASES FOR HIGH PERFORMANCE BIOSEPARATION 23 1.5.1. Introduction 23 1.5.2. Polymeric Bioseparation Materials 24 1 6. OUTLINE OF THESIS ^ 25 1.7. REFERENCES 26 2. EXPERIMENTAL TECHNIQUES 35 2.1. INTRODUCTION 35 2.2. X-RAY PHOTOELECTRON SPECTROSCOPY (XPS) 36 2.2.1. The Photoexcitation Process 36 2.2.2. Spectral Features 37 2.2.3. Spectral Deconvolution ^ ^—^39 2.2.4. Surface Sensitivity ^ 41 2.2.5. X-Ray Monochromatization ^ 42 2.2.6. Sample Charging Phenomena 43 2.2.7. Angular Dependant Studies ^43 2.2. 8. Electron Spectroscopy of Polymers ] ; 44 2.2.9. Instrumentation ^ 47 2.3. ATTENUATED TOTAL REFLECTANCE FOURIER TRANSFORM INFRA-RED SPECTROSCOPY (ATR-FTIR) ^ 49 2.3.1. Background . 49 2.3.2. Fourier Transform Infra-red Spectroscopy 50 2.3.3. Attenuated Total Reflection Spectroscopy ^ .51 2.3.4. Vibrational Spectroscopy of Polymers 52 2.4. SURFACE AREA AND PORE SIZE DISTRIBUTION BY GAS SORPTION vi EXPERIMENTS 55 2.4.1. Introduction 55 2.4.2. The Adsorption Isotherm . 2.4.3. Classification of adsorption isotherms_ _56 2.4.4. Classification of Pore Sizes ^ ^ ^7 2.4.5. Adsorption Forces —^9 2.4.6. Surface Area Measurement _59 2.4.7. Determination of Micropore Size 60 2.4.8. Determination of Meso and Macropore size distribution 61 2.4.9. Experimental ^ 2.5. ATOMIC FORCE MICROSCOPY 66 2.5.1. Introduction 66 2.5.2. AFM Analysis of Polymers —68 2.6. SCANNING ELECTRON MICROSCOPY^ 70 2.6.1. Introduction ^ _70 2.6.2. Experimental 70 2.7. X-RAY DIFFRACTION 71 2.7.1. Introduction : '. 71 2.7.2. Experimental 72 2.8. REFERENCES 74 3. HYDROXYL ACCESSIBILITY IN CELLULOSES 79 3 .1. INTRODUCTION 79 3.1.1. The Chemical Modification of Cellulose ^ 79 vu 3.1.2. The Chemical and Physical Structure of Cellulose, _80 3.1.2.1. Hydroxyl Group Reactivity _81 3.1.2.2. The Crystalline and Amorphous Microenvironment. _8l 3.1.2.3. The Cellulose Lattice. " '_ _82 3.1.2.4. The Fibrillar Structure. _85 3.1.3. Accessibility and the Microstructural Nature of Cellulose _85 3.1.3.1. Methods to Determine Cellulose Microstructure _85 3.1.3.2. Chemical Labelling and XPS Analysis as a Probe for Hydroxyl Accessibility. 86 3.2. EXPERIMENTAL 89 3 .3. RESULTS 92 3.3.1. XPS and TFAA Labelling, _92 3.3.2. ATR-FTER. of Cellulose Materials, 93 3.4. X-RAY DIFFRACTION 102 3 .5. DISCUSSION 104 3.5.1. Chemical Accessibility and Crystallinity 104 3.5.2. XRD vs Infra-red Crystallinity Indices 105 3.5.3. TFAA Labelling. 105 3 .6. CONCLUSIONS 106 3.7. REFERENCES 106 4. AN INVESTIGATION OF THE EFFECTS OF SWELLING AND CROSSLINKING ON THE SURFACE AREA PORE STRUCTURE AND PROTEIN CAPACITY OF A CELLULOSE BASED BIOSEPARATION MEDIUM. 111 4.1. INTRODUCTION 111 vm 4.1.1. Porosity and Specific Surface Area ' ' 2 4.1.2. The Pore Structure of Cellulose 1 13 4.1.3. Matrix Processing ' '4 4.1.3.1. Swelling '14 4.1.3.2. Crosslinking 115 4.1.3.3. Drying 115 4.2. EXPERIMENTAL ' 116 4.2.1. Sample Preparation 116 4.2.1.1. Swelling with NaOH 116 4.2.1.2. Crosslinking 117 4.2.2. Specific Surface Area and Pore Structure Analysis 117 4.2.3. Scanning Electron Microscopy (SEM) study of the Cellulose Matrix 119 4.2.4. Protein Uptake Measurements 119 4.3. RESULTS 120 4.3.1. The Cellulose Nitrogen Adsorption Isotherm •. 120 4.3.2. Specific Surface Area 121 4.3.3. Pore Structure ^ 124 4.3.3.1. Untreated Cellulose 124 4.3.3.2. Swelling with NaOH 124 4.3.3.3. Cross-linked Cellulose 125 4.3.4. Protein Uptake Experiments 130 4.4. DISCUSSION , , 132 4.4.1. Swelling with NaOH ' 13 2 4.4.2.
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