INTERACTIONS OF VIOLOGENS WITH CONDUCTING POLYMERS, METAL SALT SOLUTIONS AND GLUCOSE OXIDASE ZHAO LUPING NATIONAL UNIVERSITY OF SINGAPORE 2004 INTERACTIONS OF VIOLOGENS WITH CONDUCTING POLYMERS, METAL SALT SOLUTIONS AND GLUCOSE OXIDASE ZHAO LUPING (B. Eng, Qingdao Institute of Chemical Technology) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMICAL & ENVIRONMENTAL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2004 Acknowledgement ACKNOWLEDGEMENT First and foremost, I would like to express my deepest gratitude to my supervisors, Professor Neoh Koon Gee and Professor Kang En-Tang for their inspired guidance, invaluable advice, and constant supervision throughout the length of my candidature. I gratefully acknowledge the research scholarship offered to me by the National University of Singapore (NUS), which enabled me to pursue my Ph.D. program. Special thanks are due to Dr. Zhang Yan and Dr. Li Sheng. They have been most helpful to me, both technically and personally. I enjoyed and benefited tremendously from the discussion on my project and their invaluable suggestions and advices. I would like to thank our group members like Dr. Lin Qidan, Mr. Ying Lei, Miss Cen Lian for sharing the research experience with me. Particular acknowledgements go to Madam Chow Pek and other lab technologists of Department of Chemical and Environmental Engineering for their assistance and help. Last but not least, I must express my deepest love and gratefulness to my family for their long-term concern and support. In addition, special thanks to my wife, Huang Yuehong, for her persistent love and encouragement. Zhao Luping i Table of Contents TABLE OF CONTENTS ACKNOWLEDGEMENT i TABLE OF CONTENTS ii SUMMARY vi NOMENCLATURE ix LIST OF FIGURES xi LIST OF TABLES xvi CHAPTER INTRODUCTION CHAPTER LITERATURE SURVEY 2.1 Viologens 2.1.1 Synthesis of Viologens 2.1.2 Physical Properties of Viologens 2.1.2.1 Dimerization of Viologen Radical Cations 2.1.2.2 Association and Charge Transfer 2.1.2.3 Solid State Conductivity 2.1.2.4 Radical Solubility 2.1.3 Photochromism of Viologens 2.1.4 Applications of Viologen Systems 2.1.4.1 Electrochromism and Electrochromic Devices (ECD) 2.1.4.2 Electron Mediation 2.1.4.3 Other Miscellaneous Applications 2.2 Conducting Polymers 2.2.1 Structure and Synthesis 2.2.1.1 Polyaniline ii Table of Contents 2.2.1.2 Polypyrrole 2.2.2 Doping of Conducting Polymers 2.2.3 Degradation and Stability 2.2.4 Applications of Conducting Polymers 2.2.4.1 Antistatic Coatings 2.2.4.2 Electromagnetic Shielding 2.2.4.3 Organic Conducting Patterns 2.2.4.4 Optoelectronic Devices 2.2.4.5 Batteries and Solid Electrolytes 2.2.4.6 Sensors 2.2.4.7 ‘Smart’ Structures 2.3 Polymer Surface Modification and Characterization 2.3.1 Surface Grafting 2.3.2 Plasma Modification 2.3.2.1 Plasma Treatment 2.3.2.2 Plasma Polymerization 2.3.3 Surface Characterization CHAPTER PHOTO-INDUCED REACTION OF POLYANILINE WITH VIOLOGEN IN THE SOLID STATE 45 3.1 Introduction 3.2 Experimental 3.3 Results and Discussion 3.3.1 LDPE Graft-modified with VBC and Viologen 3.3.2 Photo-induced Doping of PANI Films in EB State 3.3.3 Photo-induced Doping of PANI Films in Other Oxidation States 3.3.4 Stability of Films iii Table of Contents 3.3.4.1 Adhesion Tests 3.3.4.2 Stability of Irradiated Films in Air and Water 3.3.4.3 Dedoping Characteristics of EB-viologen Film after Irradiation 3.4 Conclusion CHAPTER FLUORINATED ETHYLENE PROPYLENE COPOLYMER COATING FOR THE STABILITY ENHANCEMENT OF ELECTROACTIVE AND PHOTOACTIVE SYSTEMS 87 4.1 Introduction 4.2 Experimental 4.2.1 Preparation of Substrates 4.2.2 Radio Frequency (RF) Sputtering of FEP 4.2.3 Stability Tests 4.2.4 Sample Characterization 4.3 Results and Discussion 4.3.1 PANI-LDPE Film 4.3.2 PANI-viologen Film 4.3.3 Viologen Grafted Film 4.4 Conclusion CHAPTER NANOSCALED METAL COATINGS AND 110 DISPERSIONS PREPARED USING VIOLOGEN SYSTEMS 5.1 Introduction 5.2 Experimental 5.3 Results and Discussion 5.3.1 Metal Reduction by VBV-LDPE Film 5.3.2 Colloid/Nanosized Metal Particles in PVA-BV Matrix 5.4 Conclusion iv Table of Contents CHAPTER FORMATION OF CONDUCTING PATTERNS USING PANI-VIOLOGEN COMPOSITE FILM AND METALLIZED VIOLOGEN FILM 137 6.1 Introduction 6.2 Experimental 6.3 Results and Discussion 6.3.1 Photo-irradiated PANI-viologen System 6.3.2 Reaction of VBV-LDPE Patterned Films with Metal Salt Solutions 6.4 Conclusion CHAPTER CO-IMMOBILIZATION OF ENZYME AND ELECTRON MEDIATOR ON CONDUCTING POLYMER FILM FOR GLUCOSE SENSING 155 7.1 Introduction 7.2 Experimental 7.3 Results and Discussion 7.3.1 Co-immobilization of GOD and MAV 7.3.2 Effect of Viologen on Enzyme Activity 7.3.3 Electrochemical Characterization of the GOD-MAV-PPY Film 7.4 Conclusion CHAPTER CONCLUSIONS AND RECOMMENDATIONS 177 8.1 Conclusions 8.2 Recommendations REFERENCES 184 APPENDIX PATENT AND PUBLICATIONS 205 v Summary SUMMARY Studies on viologens have led to enormous advances and potential applications which capitalize on the viologens’ reversible redox properties. In this thesis, the interactions of viologens with conducting polymers, metal salt solutions and an enzyme were investigated. The potential applications of viologens resulting from these interactions were also demonstrated. The conversion of polyaniline (PANI) from the insulating state to the doped and conductive state was accomplished through the photo-induced reaction with viologen in the solid state. Photo-sensitive films consisting of PANI coatings in different oxidative states on viologen-grafted low density polyethylene (LDPE) substrates were employed. The effects of the ultraviolet (UV) irradiation time, grafted vinylbenzyl chloride (VBC) and viologen density, and UV irradiation intensity were discussed. The density of the grafted VBC and viologen does not play an important role in the doping of PANI under UV irradiation since the reactions are confined to the interfacial region between PANI and the grafted moieties. However, the photo-induced doping of PANI shows a strong dependence on the UV intensity. The photo-irradiated films show good electrical stability in air up to 75°C, but undope rapidly in water. The conductivity of the irradiated films decreases sharply after the films were immersed in water due to the loss of the HCl dopants. To enhance the electrical stability of conducting polymers and prolong the photochromic effect of photoactive materials, a radio frequency sputtering technique to deposit fluorinated ethylene propylene copolymer (FEP) coatings of controllable thickness on these materials was employed. This technique can be applied to both vi Summary conventional acid protonated PANI film and PANI doped via photo-induced reaction with viologen. Both systems with the FEP coating remain conductive even after 3h in water. With a thicker FEP coating, the stability enhancement can also be achieved in basic solutions of pH up to 12. The photochromic effect of viologen grafted films with the sputtered FEP coating was also prolonged since the sputtered FEP coating retards the diffusion of O2 to the photo-generated viologen radical cations. Nanoscaled metal coatings on the surface of 1,1’-bis(4-vinylbenzyl)-4,4’-bipyridilium dichloride (VBV) grafted LDPE films were successfully achieved via the photoinduced reactions between the viologen and noble metal salt solutions. The distribution of gold or platinum in the elemental and ionic state on the VBV-LDPE films is dependent on the UV irradiation time and the concentration of the metal salt solutions used. Well-dispersed gold and platinum particles ranging from 10 nm can also be readily obtained via the reduction of the corresponding salt solution in a poly(vinyl alcohol) (PVA) matrix containing benzyl viologen (BV). 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Filed on 13 Feb 2003. Application No., 10/367,180. Zhao, L.P., K.G. Neoh and E.T. Kang. Photo-induced and Thermal-activated Doping of Polyaniline. Chem. Mater., 14, pp.1098-1106. 2002. Zhao, L.P., K.G. Neoh, S.W. Ng and E.T. Kang. Photo-induced Reaction of Polyaniline with Viologen in the Solid State. SPIE International Conference of Photonics Fabrication Europe, Belgium, Proceedings of SPIE Vol.4946, pp.215-223. 2002. Zhao, L.P., K.G. Neoh and E.T. Kang. Nanoscaled Metal Coatings and Dispersions Prepared Using Viologen Systems. Langmuir, 19, pp.5137-5144. 2003. Zhao, L.P., K.G. Neoh, Yan Zhang and E.T. Kang. Fluorinated Ethylene Propylene Copolymer Coating for the Stability Enhancement of Electroactive and Photoactive Systems. J. Vac. Sci. Technol. A, 21, pp.1865-1872. 2003. Zhao, L.P., J. G. Wang, K.G. Neoh and E.T. Kang. “Electroactive Polymer Patterns with Metal Incorporation on a Polymeric Substrate”, Polymer Engineering and Science, 44, pp.2061-2069, 2004. Liu, X., K.G. Neoh, L.P. Zhao and E.T. Kang. Surface Functionalization of Glass and Polymeric Substrates via Graft Copolymerization of Viologen in an Aqueous Medium. Langmuir, 18, pp.2914 -2921. 2002. Wang, J.G., K.G. Neoh, L.P. Zhao and E.T. Kang. Plasma Polymerization of Polyaniline on Different Surface Functionalized Substrates. J. Colloid. Interf. Sci., 251, pp.214-224. 2002. 205 [...]... treated with metal salt solutions for the incorporation of metal or metal ions The second patterning approach takes advantage 5 Chapter 1 of the redox property of viologens VBV patterns were formed on LDPE surfaces via graft copolymerization Through the reduction of metal salt solutions under UV irradiation, the metal can be successfully deposited on the patterned VBV-LDPE film to form the conducting. .. Figure 5.3 XPS N 1s and Cl 2p core-level spectra of the VBV-LDPE film before ((a) and (d)) and after treatment with 1000 ppm gold chloride solutions under UV irradiation for 5 min ((b) and (e)) and 15 min ((c) and (f)) Figure 5.4 XPS Cl 2p core-level spectra of the VBV-LDPE film after reaction with gold chloride solutions of concentration of (a) 100 ppm, (b) 200 ppm, (c) 500 ppm, and (d) 1000 ppm under... Structure of 1,1’-bis(4-vinylbenzyl)-4,4’-bipyridilium dichloride(VBV) Figure 4.2 XPS C 1s and N 1s core-level spectra of doped PANI-LDPE film before sputtering with FEP ((a) and (b)), after sputtering with FEP for 10s ((c) and (d)), and for 100s ((e) and (f)), and the FEP sputtered (100s) film after treatment in water for 3h ((g) and (h)) xii List of Figures Figure 4.3 SEM and AFM images of (a) and (d)... co-immobilization of glucose oxidase (GOD) and viologen mediator on the surface of conducting PPY film, and the effects of the viologen and enzyme acting in tandem for glucose detection The as-synthesized Nmethyl-N’-(3-aminopropyl)-4,4’-bipyridilium (MAV) serves as an effective mediator for electron transfer from the active sites of GOD to the surface of PPY electrode in the absence of oxygen and under UV... concentration of the metal salt solution used The existence of these metals primarily in the elemental state on the VBV-LDPE film surface can be achieved with metal salt solutions of a low concentration and long irradiation time The results indicate that platinum ions are more readily reduced than gold ions by the VBV-LDPE film The reduction of palladium salt solution is much more difficult with the resultant... doping and oxidative doping of different forms of polyaniline to the same conducting material Figure 3.1 Schematic diagram illustrating the process of Ar plasma treatment, grafting of VBC and viologen, and deposition of the PANI coating on LDPE films Figure 3.2 XPS (a) C 1s and (b) Cl 2p core-level spectra of VBC-graft copolymerized LDPE film(Sample VBC-2), (c) N 1s and (d) Cl 2p core-level spectra of. .. (4mg/ml GOD and 9mM MAV in co-immobilization step) grafted with different AAc concentrations after reaction with glucose solution (a) under UV irradiation for 30min in the absence of O2 (b) with O2 for 30 min and without UV irradiation (c) for 30 min without UV irradiation and O2 Figure 7.6 (a) Cyclic voltammograms of GOD-MAV-PPY film in glucose solution containing 0, 0.2, 0.4, 0.6, 0.8, 1.0mM glucose. .. solution with 0.1M NaCl was used as supporting electrolyte (b) Peak currents at 0.435V as a function of glucose concentration xv List of Tables LIST OF TABLES Table 3.1 Table 3.2 Surface composition of VBC-graft copolymerized and viologen-graft modified LDPE film Surface composition and Rs of PANI-VBC and PANI-viologen films Table 3.3 Surface composition of NA and LM-coated films before irradiation and. .. of work has been done on viologens, ranging from the chemical fundamentals to the applications It includes studies on the structures and preparation of different viologen species, the investigation of the redox states, electrochemistry and electron-transfer reactions, electrochromism, photochemistry, and so on 2.1.1 Synthesis of viologens Due to the stability of the dication salt, the majority of viologens. .. practical applications of the viologens in the preparation of nanoscaled metal coatings and dispersions, and (4) to study the involvement of the viologens in the electron mediation between the immobilized enzyme and the analyte for glucose sensing This dissertation comprised eight chapters and one appendix Chapter One provides a brief introduction to the dissertation The research objectives of this dissertation . INTERACTIONS OF VIOLOGENS WITH CONDUCTING POLYMERS, METAL SALT SOLUTIONS AND GLUCOSE OXIDASE ZHAO LUPING NATIONAL UNIVERSITY OF SINGAPORE 2004 INTERACTIONS. SINGAPORE 2004 INTERACTIONS OF VIOLOGENS WITH CONDUCTING POLYMERS, METAL SALT SOLUTIONS AND GLUCOSE OXIDASE ZHAO LUPING (B. Eng, Qingdao Institute of Chemical Technology) . advances and potential applications which capitalize on the viologens reversible redox properties. In this thesis, the interactions of viologens with conducting polymers, metal salt solutions and