Interactions of viologens with conducting polymers, metal salt solutions and glucose oxidase

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). Conducting patterns can be generated from the UV irradiation of the PANI-viologen composite film through a mask, and via gold deposition on VBV patterns grafted on LDPE film. In this work, it was also demonstrated that viologen can serve as an effective mediator for electron transfer from the active sites of glucose oxidase (GOD) to the surface of a polypyrrole (PPY) electrode under UV irradiation and in the absence of oxygen. The amounts of GOD and N-methyl-N’-(3-aminopropyl)-4,4’-bipyridilium (MAV) immobilized on the PPY film could be controlled by changing the graft concentration of the linkage group, acrylic acid (AAc), on the PPY film and the ratio of GOD to MAV in the co-immobilization step. The electrochemical response of the as- vii Summary functionalized enzyme electrode changes linearly in the range of to 1.0 mM of glucose in solution. viii References Genies, E.M., J.M. Pernaut, C. Santier, A.A. Syed and C. Tsintavis. Electrochemical and Spectroelectrochemical Studies of Polypyrrole and Polyaniline, Springer Ser. Solid-State Sci., 63, pp.211-217. 1985b. Genies, E.M. and C. Tsintavis. Electrochemistry Behavior, Chronocoulometric and Kinetic Study of the Redox Mechanism of Polyaniline Deposits. J. Electroanal. Chem. Interfacial Electrochem., 200, pp.127-145. 1986. Genies, E.M., A. Boyle, M. Lapkowski and C. Tsintavis. Polyaniline: a Historical Survey. Synth. Met., 36, pp.139-182. 1990. Ginder, J.M. and A.J. Epstein. Role of Ring Torsion Angle in Polyaniline - ElectronicStructure and Defect States. Phys Rev B., 41, pp.10674-10685. 1990. Goddard, N.J., A.C. Jackson and M.G. Thomas. Spectroelectrochemical Studies of Some Viologens Used in Electrochromic Display Applications. J. Electroanal. Chem., 159, pp.325-335. 1983. Goldner, R.B. Proceedings of the International Seminar on Solid State Ionic Devices. p.379. Singapore: World Publishing Co. 1988a. Goldner, R.B., T.E. Haas, G. Seward, K.K. Wong, P. Norton, G. Foley, G. Berera, G. Wei, S. Schulz and R. Chapman. Thin Film Solid State Ionic Materials for Electrochromic Smart WindowTM Glass. Solid State Ionics, 28-30, pp.1715-1721. 1988b. Good, R.J. A Thermodynamic Derivation of Wenzel's Modification of Young's Equation for Contact Angles; Together with a Theory of Hysteresis. J. Am. Chem. Soc., 74, pp.5041-5042. 1952. Granqvist, C.G., A. Azens, A. Hjelm, L. Kullman, G.A. Niklasson, D. Ronnow, M.S. Mattsson, M. Veszelei and G. Vaivars. Recent Advances in Electrochromics for Smart Windows Applications. Sol. Energy., 63, pp.199-216. 1998. Green, A.G. and A.E. Woodhead. Aniline Black and Allied Compounds. J. Chem. Soc., 97, pp.2388-2403. 1910. Green, A.G. and A.E. Woodhead. Aniline Black and Allied Compounds. J. Chem. Soc. Trans., 101, pp.1117-1123. 1912. Gregory, R.V., W.C. Kimbrell and H.H. Kuhn. Conductive textiles. Synth. Met., 28, pp.823-835. 1989. Gustafsson, G., Y. Cao, G.M. Treacy, F. Klavetter, N. Colaneri and A.J. Heeger. Flexible Light-Emitting-Diodes Made from Soluble Conducting Polymers. Nature, 357, pp.477-479. 1992. Hagiwara, T., M. Yamaura and K. Iwata. Thermal Stability of Polyaniline. Synth. Met., 25, pp.243-252. 1988. 190 References Hagiwara, T., M. Hirasaka, K. Sato and M. Yamaura. Enhancement of the Electrical Conductivity of Polypyrrole Film by Stretching: Influence of the Polymerization Conditions. Synth. Met., 36, pp.241-252. 1990. Haladjian, J., R. Pilard and P. Bianco. Effect of Methyl Viologen on the Electrochemical Behavior of Denatured Cytochrome-c at Mercury and Solid Electrodes. J. Electroanal. Chem., 184, pp.391-400. 1985. Hale, P.D., L.I. Boguslavsky, H.I. Karan, H.L. Lan, H.S. Lee, Y. Okamoto and T.A. Skotheim. Investigation of Viologen Derivatives as Electron-Transfer Mediators in Amperometric Glucose Sensors. Anal. Chim. Acta., 248, pp.155-161. 1991. Hatchett, D.W., M. Josowicz, J. Janata and D.R. Baer. Electrochemical Formation of Au Clusters in Polyaniline. Chem. Mater., 11, pp.2989-2994. 1999. Heeger, A.J., S. Kivelson, J.R. Schrieffer and W.P. Su. Solitons in Conducting Polymers. Rev Mod Phys., 60, pp.781-850. 1988. Ho, C.P. and H. Yasuda. Ultrathin Coating of Plasma Polymer of Methane Applied on the Surface of Silicone Contact-Lenses. J. Biomed. Mater. Res., 22, pp.919-937. 1988. Hoebergen, A, Uyama Y, Okada T, Ikada Y. Graft-Polymerization of Fluorinated Monomer onto Corona-Treated PVA and Cellulose Films. J. Appl. Polym. Sci., 48, pp.1825-1829. 1993. Hsing, C.F., P. Kovacic and I.A. Khoury. Oligomers from Biphenyl, Biphenyl-d10, or p-Terphenyl with Aluminum Chloride-Cupric Chloride: Mechanism, ESR, and Conductivity. J. Polym. Sci. Polym. Chem. Ed., 21, pp.457-466. 1983. Hsu, S.L., A.J. Signorelli, G.P. Pez, and R.H. Baughman. Highly Conducting Iodine Derivatives of Polyacetylene: Raman, XPS and X-Ray Diffraction Studies. J. Chem. Phys., 69, pp.106-111. 1978. Huang, S.W., K.G. Neoh, C.W. Shih, D.S. Lim, E.T. Kang, H.S. Han and K.L. Tan. Synthesis, Characterization and Catalytic Properties of Palladium-Containing Electroactive Polymers. Synth. Met., 96, pp.117-122. 1998. Huang, W.S., B.D. Humphrey and A.G. MacDiarmid. Polyaniline: a Novel Conducting Polymer. J. Chem. Soc., Faraday Trans I, 82, pp.2385-2387. 1986. Ikada, Y. and Y. Uyama. Lubricating Polymer Surfaces. pp.76, Lancaster, PA: Technomic Pub. Co. Inc. 1993. Ikada, Y. Surface Modification of Polymers for Medical Applications. Biomaterials, 15, pp.725-736. 1994. Inagaki, N. Plasma Surface Modification and Plasma Polymerization. pp.32. Lancaster, PA: Technomic Publishing Company, Inc. 1996. 191 References Inagaki, N., Y. Ohnishi and K.S. Chen. Glow Discharge Polymerization of Tetramethylsilane by Capacitive Coupling of 20 kHz Frequency and Surface Hardening of Polyethylene Sheet. J. Appl. Polym. Sci., 28, pp.3629-3640. 1983. Ito, S., K. Murata, S. Teshima, R. Aizawa, Y. Asako, K. Takahashi and B.M. Hoffman. Simple Synthesis of Water-soluble Conducting Polyaniline. Synth. Met., 96, pp.161-163. 1998. Jaeger, R.C. Introduction to Microelectronic Fabrication. G.W. Neudeck and R.F. Pierret (Ed), pp.66-70, Reading, Massachusetts: Addison-Wesley Publishing Company. 1993. Jiang, H., Y.H. Geng, J. Li, X.B. Jing and F.S. Wang. Organic Acid Doped Polyaniline Derivatives, Synth. Met., 84, pp.125-126. 1997. Johnston, E.E. and B.D. Ratner. Surface Characterization of Plasma Deposited Organic Thin Films. J. Electron. Spectrosc., 81, pp.303-317. 1996. Kajiya, Y., T. Okamoto and H. Yoneyama. Glucose Sensitivity of Thiol Modified Gold Electrodes Having Immobilized Glucose-Oxidase and 2-Aminoethylferrocene. Chem. Lett., 12, pp.2107-2110. 1993. Kamogawa, H., T. Masui and S. Amemiya. Organic Solid Photochromism by Photoreduction Mechanism: Viologen Embedded in Solid Polar Aprotic Polymer Matrix. J. Polym. Sci., Polym. Chem. Ed., 22, pp.383-390. 1984. Kamogawa, H. and M. Nanasawa. Effect of Temperature on the Color Developed by Near-Ultraviolet Light for 4,4'-Bipyridinium Salts (Viologens) Embedded in Poly(1Vinyl-2-Pyrrolidone) Matrix. Bull. Chem. Soc. Jpn., 66, pp.2443-2445. 1993. Kang, E.T., K.G. Neoh, T.C. Tan, S.H. Khor and K.L. Tan. Structural Studies of Poly(Para-phenyleneamine) and Its Oxidation. Macromolecules, 23, pp.2918-2926. 1990. Kang, E.T., K.G. Neoh, Y.K. Ong, K.L. Tan and B.T.G. Tan. X-Ray Photoelectron Spectroscopy Studies of Polypyrrole Synthesized with Oxidative Fe(III) Salts. Macromolecules, 24, pp.2822-2828. 1991. Kang, E.T., K.G. Neoh, K.L. Tan, Y. Uyama, N. Morikawa and Y. Ikada. Surface Modification of Polyaniline Films by Graft-copolymerization. Macromolecules, 25, pp.1959-1965. 1992. Kang, E.T., K.G. Neoh, M.Y. Pun and K.L. Tan. Charge-transfer Interactions between Polyaniline and Surface Functionalized Polymer Substrates. Synth. Met., 69, pp.105108. 1995. Kang, E.T., K.G. Neoh and K.L. Tan. In Handbook of Organic Conductive Molecules and Polymers: Vol.3. Conductive Polymers: Spectroscopy and Physical Properties, ed by H. S. Nalwa, New York: John Wiley & Sons Ltd. 1997. 192 References Kang, I.K., B.K. Kwon, J.H. Lee and H.B. Lee. Immobilization of Proteins on Poly(Methyl Methacrylate) Films. Biomaterials., 14, pp.787-792. 1993. Kaneko, M. and K. Kaneto. Electrochemomechanical Deformation of Polyaniline Films Doped with Self-existent and Giant Anions. React. Funct. Polym., 37, pp.155161. 1998. Katz, E., A.L. Delacey, J.L.G. Fierro, J.M. Palacios and V.M. Fernandez. Covalent Binding of Viologen to Electrode Surfaces Coated with Poly(Acrylic Acid) Formed by Electropolymerization of Acrylate Ions .1. Electrode Preparation and Characterization. J. Electroanal. Chem. 358, pp. 247-259. 1993. Keller, P. and A. Moradpour. Is There a Particle-Size Dependence for the Mediation by Colloidal Redox Catalysts of the Light-Induced Hydrogen Evolution from Water? J. Am. Chem. Soc., 102, pp.7193-7196. 1980a. Keller, P., A. Moradpour, E. Amouyal and H. Kagan. Visible-Light Photoreduction of Water. Hydrogen Formation Yields as A Function of the Structure of the ViologenDye Relays. J. Mol. Catal., 7, pp.539-542. 1980b. Kim, E.Y., M.H. Lee, B.S. Moon, C.J. Lee and S.B. Rhee. Redox Cyclability of A Self-doped Polyaniline, J. Electrochem. Soc., 141, pp.L26-L28. 1994. Kim, H.K., M.S. Kim, K. Song, Y.H. Park, S.H. Kim, J. Joo and J.Y. Lee. EMI Shielding Intrinsically Conducting Polymer/PET Textile Composites. Synth. Met. 135, pp.105-106. 2003. Kosower, E.M. and J.L. Cotter. Stable Free Radicals. II. The Reduction of 1-Methyl-4cyanopyridinium Ion to Methylviologen Cation Radical. J. Am. Chem. Soc., 86, pp.5524-5527. 1964. Koul, S., R. Chandra and S.K. Dhawan. Conducting Polyaniline Composite for ESD and EMI at 101 GHz. Polymer, 41, pp.9305-9310. 2000. Kuczynski, J.P., B.H. Milosavljevic, A.G. Lappin and J.K. Thomas. Ion-Pair Complexes of Methyl Viologen and Anionic Solutes. Chem. Phys. Lett., 104, pp.149152. 1984. Kulik, E.A., K. Kato, M.I. Ivanchenko and Y. Ikada. Trypsin Immobilization on to Polymer Surface Through Grafted Layer and Its Reaction with Inhibitors. Biomaterials., 14, pp.763-769. 1993. Kulkarni, V.G., L.D. Campbell and W.R. Mathew. Thermal Stability of Polyaniline. Synth. Met., 30, pp.321-325. 1989. Kuzmany, H., N.S. Sariciftci, H. Neugebauer and A. Neckel. Evidence for Two Separate Doping Mechanisms in the Polyaniline System. Phys. Rev. Lett., 60, pp.212215. 1988. 193 References Levey, G. and T.W. Ebbesen. Methyl Viologen Radical Reactions with Several Oxidizing Agents. J. Phys. Chem., 87, pp.829-832. 1983. Libert, J., J.L. Bredas and A.J. Epstein. Theoretical-Study of P-Type and N-Type Doping of the Leucoemeraldine Base Form of Polyaniline - Evolution of the Geometric and Electronic-Structure. Phys Rev B., 51, pp.5711-5724. 1995. Liu, F.T., B.L. He, L.J. Liang and L.B. Feng. Studies on the Selective Reduction of Nitroarenes Mediated by Insoluble Resins with Viologen Structure as ElectronTransfer Catalysts. Eur. Poly. J., 33, pp.311-315. 1997. 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. Liu, X., K.G. Neoh, Lian Cen and E.T. Kang. Enzymatic Activity of Glucose Oxidase Covalently Wired via Viologen to Electrically Conductive Polypyrrole Films. Biosensors & Bioelectronics, 19, pp.823-834. 2004. Lonergan, M.C., E.J. Severin, B.J. Doleman, S.A. Beaber, R.H. Grubb and N.S. Lewis. Array-Based Vapor Sensing Using Chemically Sensitive, Carbon Black-Polymer Resistors. Chem. Mater., 8, pp.2298-2312. 1996. Lub, J., F.C.B.M. Van Vroonhoven, E. Brunix and A. Benninghoven. Interaction of Nitrogen and Ammonia Plasmas with Polystyrene and Polycarbonate Studied by X-ray Photoelectron Spectroscopy, Neutron Activation Analysis and Static Secondary Ion Mass Spectroscopy. Polymer, 30, pp.40-44. 1989. Ma, Y.M., H.Q. Xie, S.L. Wang and D.S. Feng. Preparation of Polyaniline Doped with Different Organic Acids from Precipitation Polymerization. Chem. J. Chinese Univ., 19, pp.1171-1174. 1998. MacDiarmid, A.G., J.C. Chiang, M. Halpern, W.S. Huang, S.L. Mu, N.L.D. Somasiri and A.J. Epstein. Polyaniline –Interconversion of Metallic and Insulating Form. Mol. Cryst. Liq. Cryst. 121, pp.173-180. 1985. MacDiarmid, A.G., J.C. Chiang, A.F. Richter and A.J. Epstein. Polyaniline: A New Concept in Conducting Polymers. Synth. Met., 18, pp.285-290. 1987. MacDiarmid, A.G. and A.J. Epstein. Polyanilines –A Novel Class of Conducting Polymers. Faraday Discuss., 88, pp.317. 1989. MacDiarmid, A.G., S.K. Manohar, J.G. Masters, Y. Sun, H. Weiss and A.J. Epstein. Polyaniline: Synthesis and Properties of Pernigraniline Base. Synth. Met., 41, pp.621626. 1991. MacDiarmid, A.G. The Polyanilines: A Novel Class of Conducting Polymers. In Conjugated Polymers and Related Materials, Salaneck, W. R., Lundström, I. and Ranby, B. (Ed.), pp.73-98. Oxford Science Publications. 1993. 194 References Machida, S., S. Miyata and A. Techagumpuch. Chemical Synthesis of Highly Electrically Conductive Polypyrrole. Synth. Met., 31, pp.311-318. 1989. Makela, T., S. Pienimaa, S. Jussila and H. Isotalo. Lithographic Patterning of Conductive Polyaniline. Synth. Met., 101, pp.705-706. 1999. Malitesta, C., F. Palmisano, L. Torsi and P. G. Zambonin. Glucose Fast-Response Amperometric Sensor Based on Glucose Oxidase Immobilized in an Electropolymerized Poly(O-Pheylenediamine) Film. Anal. Chem., 62, pp.2735-2740. 1990. Mammone, R.J. and A.G. MacDiarmid. The Aqueous Chemistry and Electrochemistry of Polyacetylene, (CH)X. Synth. Met., 9, pp.143-154. 1984. Mandal, T.K. and B.M. Mandal. Interpenetrating Polymer Network Composites of Polypyrrole and Poly(methyl acrylate) or Poly(styrene-co-butyl acrylate) with Low Percolation Thresholds. Synth. Met., 80, pp.83-89. 1996. Mark, S., C. Stewart, S.L. Christopher and A.K. Gary. Surface Modification of Polypropylene with CF4, CF3H, CF3Cl, and CF3Br Plasmas. J. Poly. Sci. Polym. Chem. Ed., 23, pp.1125-1135. 1985. Marvell, E.N., G. Caple and I. Shahidi. Formation of Phenylpyridinium Chloride from 5-Anilino-N-Phenyl-2,4-Pentadienylideniminium Chloride. Kinetics in Basic Media. J. Am. Chem. Soc., 92, pp. 5641-5645, 1970. Mathieson, I. and R.H. Bradley. Improved Adhesion to Polymers by UV/Ozone Surface Oxidation. Int. J. Adhes. Adhes., 16, pp.29–31. 1996. Matveenva, E.S., R.D. Calleja, E.S. Martinez. AC Conductivity of Thermally Dedoped Polyaniline. Synth. Met., 67, pp.207-210. 1994. May, P. Polymer Electronics - Fact or Fantasy. Phys. World., 8, pp.52-57. 1995. McArdle, C.B. (ed). Applied Photochromic Polymer Systems. Glasgow: Blackie. 1992. McCall, R.P., J.M. Ginder, J.M. Leng, H.J. Ye, S.K. Manohar, J.G. Masters, A.G. MacDiarmid and A.J. Epstein. Spectroscopy and Defect States in Polyaniline. Phys, Rev. B, 41, pp.5202-5213. 1990. Mell, L.D. and J.T. Maloy. Amperometric Response Enhancement of the Immobilized Glucose Oxidase Enzyme Electrode. Anal. Chem., 48, pp.1597-1601. 1976. Mercier, R., O. Bohnke, C. Bohnke and G.R.B. CarquilleMarie-France Mercier. Etude in situ par spectrometrie vibrationnelle de couches minces electrochromes d'oxyde de tungstène WO3 et d'oxyde de molybdene MoO3. Mater. Res. Bull., 18, pp.1-7. 1983. 195 References Massey, L.K. Permeability Properties of Plastics and Elastomers: A Guide to Packaging and Barrier Materials. pp. 85-90. William Andrew Publishing. 2003. Michaelis, L. and E.S. Hill. The Viologen Indicators. J. Gen. Physiol., 16, pp.859-862. 1933. Mirrezaei, S.R., H.S. Munro, and D. Parker. The Influence of Applied Potential on the Surface-compositions of Electrochemically Synthesized Polyanilines. Synth. Met., 26, pp.169-175. 1988. Mittal, K.L. Polymer Surface Modification: Relevance to Adhesion. Zeist, the Netherlands: VSP. 1995. Monk, P.M.S., R.D. Fairweather, M.D. Ingram and J.A. Duffy. Evidence for the Product of the Viologen Comproportionation Reaction Being a Spin-Paired Radical Cation Dimmer. Chem. Soc. Perkin Trans., 2, pp.2039-2042. 1992. Monk, P.M.S., R.J. Mortimer, and D.R. Rosseinsky. Electrochromism: Fundamentals and Applications. Weinheim: VCH. 1995. Monk, P.M.S. The Effect of Ferrocyanide on the Performance of Heptyl ViologenBased Electrochromic Display Devices. J. Electroanal. Chem., 432, pp.175-179. 1997. Monk, P.M.S. The Viologens: Physicochemical Properties, Synthesis and Applications of the Salts of 4, 4’-Bipyridine. Chichester: John Wiley & Sons Ltd. 1998. Monkman, A.P. and P. Adams. Observed Anisotropies in Stretch Oriented Polyaniline. Synth. Met., 41, pp.627-633. 1991. Morra, M., E. Occhiello and F. Garbassi. Contact Angle Hysteresis on Oxygen Plasma Treated Polypropylene Surfaces. J. Coll. Interf. Sci., 132, pp.504-508. 1989. Moshonov, A. and Y. Avny. The Use of Acetylene Glow Discharge for Improving Adhesive Bonding of Polymeric Films. J. Appl. Polym. Sci., 25, pp.771-781. 1980. Moulder, J.F., W.F. Stickle, P.E. Sobol and K.D. Bomben. Handbook of X-ray Photoelectron Spectroscopy, J. Chastain (ed). Minnesota: Perkin-Elmer Corporation. 1992. Münstedt, H., G. Köhler, H. Möhwald, D. Naegele, R. Bitthin, G. Ely and E. Meissner, Rechargeable polypyrrole/lithium cells. Synth. Met., 18, pp.259-264. 1987. Naarmann, H., K. Penzien, D. Naegele and J. Schlag. Electrically conductive polymer materials. Eur. Pat. Appl. EP 54683. 1982. Nakajima, T. and T. Kawagoe. Polyaniline - Structural-Analysis and Application for Battery. Synth. Met., 28, pp.C269-C638. 1989a. 196 References Nakajima, T., M. Harada, R. Osawa, T. Kawagoe, Y. Furukawa, and I. Hurada. Study on the Interconversion of Unit Structures in Polyaniline by X-Ray PhotoelectronSpectroscopy. Macromolecule, 22, pp.2644-2648. 1989b. Nakayama, Y., T. Takahagi, F. Soeda, K. Hatada, S. Nagaoka, J. Suzuki and A. Ishitani. XPS Analysis of NH3 Plasma-treated Polystyrene Films Utilizing Gas-phase Chemical Modification. J. Polym. Sci., A26, pp.559-572. 1988. Nalwa, H.S. Evaluation of Electrical-Conduction in Iodine-Doped Polypyrrole. J. Mater. Sci., 27, pp.210-214. 1992. Naoi, K., M.M. Lien and W.H. Smyrl. Quarts Crystal Microbalance Analysis, 1. Evidence of Anion or Cation Insertion into Electropolymerized Conducting Polymers. J. Electroanal. Chem., 272, pp.273-275. 1989. Neoh, K.G., E.T. Kang, S.H. Khor and T.C. Tan. Stability Studies of Polyaniline. Polym. Degrad. Stabil., 27, pp.107-117. 1990a. Neoh, K.G., E.T. Kang and K.L. Tan. Thermal Degradation of Leucoemeraldine, Emeraldine Base and Their Complexes. Thermochim Acta, 171, pp.279-291. 1990b. Neoh, K.G., T.C. Tan, K.L. Tan and E.T. Kang. Effects of Protonic Acids on Polyaniline Structure and Characteristics. J. Macromol. Sci. Chem. A27, pp.347-360. 1990c. Neoh, K.G., E.T. Kang and K.L. Tan. A Comparative Study on the Structural Changes in Leucoemeraldine and Emeraldine Base upon Doping by Perchlorate. J. Polym. Sci. Polym. Chem., 29, pp.759-766. 1991. Neoh, K.G., E.T. Kang and K.L Tan. Physicochemical Properties of Polyaniline Base and Salt Films. J. M. S. -Pure Appl. Chem., A29, pp.401-404. 1992. Neoh, K.G., E.T. Kang and K.L. Tan. Coexistence of External Protonation and Selfdoping in Polyaniline. Synth. Met., 60, pp.13-21. 1993a. Neoh, K.G., E.T. Kang and K.L. Tan. Protonation and Deprotonation Behavior of Amine Units in Polyaniline. Polymer, 34, pp.1630-1636. 1993b. Neoh, K.G., E.T. Kang and K.L. Tan. Degradation Behavior of Polyanilines with Different Modes of Doping. Polym. Degrad. Stabil., 43, pp.141-147. 1994. Neoh, K.G., M.Y. Pun, E.T. Kang and K.L. Tan. Polyaniline Treated with Organic Acids- Doping Characteristics and Stability. Synth. Met., 73, pp.209-215. 1995. Ng, S.W., K.G. Neoh, J.T. Sampanthar, E.T. Kang and K.L. Tan. Conversion of Polyaniline from Insulating to Conducting State In Aqueous Viologen Solutions. J. Phys. Chem. B, 105, pp.5618-5625. 2001a. 197 References Ng, S.W., K.G. Neoh, Y. T. Wong, J.T. Sampanthar, and E.T. Kang. Surface Graft Copolymerization of viologens on Polymeric Substrates. Langmuir, 17, pp.1766-1772. 2001b. Nigrey, P.J., D.F. MacInnes, Jr., D.P. Nairns, A.J. Heeger, and A.G. MacDiarmid, Lightweight Rechargeable Storage Batteries Using Polyacetylene, (CH)X as the Cathode-Active Material. J. Electrochem. Soc., 128, pp.1651-1654. 1981. Ogiwara, Y., M. Kanda, M. Takumi and H. Kubota. Photosensitized Grafting on Polyolefin Films in Vapor and Liquid Phases. J. Polym. Sci., Polym. Lett. Ed., 19, pp.457–462. 1981. Ohtani, B., M. Ye, H. Miyadzu, S. Nishimoto and T. Kagiya. Visible-Light Induced Reduction of Methyl Viologen in Poly(Vinyl Alcohol) Film Containing N-Methyl-2Pyrrolidone. J. Photoch. Photobio. A, 56, pp. 359-364. 1991. Ohtani, B., M. Ye, S. Nishimoto and T. Kagiya. Effect of Iron(III) Sulfate on Radiation-Induced Reduction of Methyl Viologen Incorporated in Poly(Vinyl Alcohol) Film. Radiat. Phys. Chem., 40, pp.49-53. 1992. Omastova, M., S. Kosina, J. Pionteck, A. Janke and J. Pavlinec. Electrical Properties and Stability of Polypyrrole Containing Conducting Polymer Composites. Synth. Met., 81, pp.49-57. 1996. Parente, A.H., E.T.A. Marques, W.M. Azevedo, F.B. Diniz, E.H.M. Melo and J.L.L. Filho. Glucose Biosensor Using Glucose-Oxidase Immobilized in Polyaniline. Appl. Biochem. Biotech., 37, pp.267-273. 1992. Park, J.Y., S.B. Lee, Y.S. Park, Y.W. Park, C.H. Lee, J.I. Lee and H.K. Shim. Doping Effect of Viologen on Photoconductive Device Made of Poly (P-Phenylenevinylene). Appl. Phys. Lett., 72, pp.2871-2873. 1998. Park, K.K., C.H. Oh and W.K. Joung. Sodium Dithionite Reduction of Nitroarenes Using Viologen as An Electron Phase-Transfer Catalyst. Tetrahedron. Lett., 34, pp.7445-7446. 1993. Park, K.K., C.H. Oh and W.J. Sim. Chemoselective Reduction of Nitroarenes and Nitroalkanes by Sodium Dithionite Using Octylviologen as an Electron-Transfer Catalyst. J. Org. Chem., 60, pp.6202-6204. 1995. Park, K.K. and S.Y. Han. Convenient Reduction of Azobenzenes and Azoxybenzenes to Hydrazobenzenes by Sodium Dithionite Using Dioctylviologen as An Electron Transfer Catalyst. Tetrahedron. Lett., 37, pp.6721-6724. 1996. Partridge, A.C., P. Harris and M.K. Andrews. High Sensitivity Conducting Polymer Sensors. Analyst, 121, pp.1349-1353. 1996. Petrat, F.M., D. Wolany, B.C. Schwede, L. Wiedmann and A. Benninghoven. In-situ TOF-SIMS XPS Investigation of Nitrogen Plasma Modified Polystyrene Surfaces. Surf. Interf. Sci., 21, pp.274-282. 1994. 198 References Pitchuman, S. and F. Willig. Photochemically Doped Polypyrrole. J. Chem. Soc. Chem. Commun., 15, pp.809-810. 1983. Price, W.E. and G.G. Wallace. Effect of Thermal Treatment on the Electroactivity of Polyaniline. Polymer, 37, pp.917-923. 1996. Pun, M.Y., K.G. Neoh, E.T. Kang and K.L. Tan. Protonation of Polyaniline by Surface-functionalized Polymer Substrates. J. Appl. Polym. Sci., 56, pp.355-364. 1995. Qi, Z.G. and P.G. Pickup. High Performance Conducting Polymer Supported Oxygen Reduction Catalysts. Chem. Commun., 21, pp.2299-2300. 1998. Qian, J.M., X.X. Li and A.L. Suo. Study on Immobilization of Glucose Oxidase on Aminated Silica Gel. Prog. Biochem. Biophys., 29, pp.394-397. 2002. Racicot, R., R. Brown and S.C. Yang. Corrosion Protection of Aluminum Alloys by Double-Strand Polyaniline. Synth. Met., 85, pp.1263-1264. 1997. Rammelt, U., P.T. Nguyen and W. Plieth. Corrosion Protection by Ultrathin Films of Conducting Polymers. Electrochim. Acta., 48, pp.1257-1262. 2003. Rannou, P. and M. Nechtschein. Aging Studies on Polyaniline: Conductivity and Thermal Stability. Synth. Met., 84, pp.755-756. 1997. Rapi, S., V. Bocchi and G.P. Gardini. Conducting Polypyrrole by Chemical Synthesis in Water. Synth. Met., 24, pp.217-221. 1988. Rauwel, F. and D. Thévenot. Use of Ring-Disc Electrodes and Viologens for the Titration of Cytochrome-c and Oxygen and for the Study of Their Reduction Kinetics. J. Electroanal. Chem., 75, pp.579-593. 1977. Ray, A., G.E. Asturias, D.L. Kershener, A.F. Richter, A.G. MacDiarmid and A.J. Epstein. Polyaniline: Doping, Structure and Derivatives. Synth. Met., 29, pp.E141-150. 1989a. Ray, A., A.F. Richter, A.G. MacDiarmid and A.J. Epstein. Polyaniline: Protonation/Deprotonation of Amine and Imine Sites. Synth. Met., 29, pp. E151-E156. 1989b. Reddy, S.M. and P. Vadgama. Entrapment of Glucose Oxidase in Non-Porous Poly(Vinyl Chloride). Anal. Chim. Acta., 461, pp.57-64. 2002. Reuss, R.H. and L.J. Winters. Cyanide-Induced Dimerization of (4-Pyridyl)Pyridinium Chloride. Synthesis of 4,4'-Bipyridine and (4-Pyridyl)Viologen Salts. J. Org. Chem., 38, pp. 3993-3995. 1973. Richard, J.P. The Chemistry of Gold. pp.6. Amsterdam, the Netherlands: Elsevier Scientific Publishing Company. 1978. 199 References Romand, M., M. Charbonnier, M. Alami and J. Baborowski. Electroless Metallization of Polymers: Simplification of the Process by Using Plasma or UV-laser Pretreatment. In Metallized Plastics & 6: Functional and Applied Aspects, Part 1, ed by K. L. Mittal. pp.3-23. Utrecht: VSP. 1998. Rossnagel, S. In Opportunities for Innovation: Advanced Surface Engineering, ed by W.D. Sproul, and K.O. Legg, pp.7. Switzerland: Technomic Publishing Co. 1995. Rozsnyai, L.F. and M.S. Wrighton. Selective Electrochemical Deposition of Polyaniline via Photopatterning of a Monolayer-Modified Substrate. J. Am. Chem. Soc., 116, pp.5993-5994. 1994. Salamone, J.C. (ed). Polymeric Materials Encyclopedia. pp.8606-8613. Boca Raton: CRC Press. 1996. Salaneck, W.R., H.R. Thomas, R.W. Bigelow, C.B. Duke, E.W. Plummer, A.J. Heeger, and A.G. MacDiarmid. Photoelectron Spectroscopy of Iodine-Doped Polyacetylene. J. Chem. Phys., 72, pp.3674-3678. 1980. Salaneck, W.R., D.T. Clark, E. Samuelsen. Science and Application of Conducting Polymers. Bristol: Adam Hilger. 1991. Salmon, M., K.K. Kanazawa, A.F. Diaz and M. Krounbi. A Chemical Route to Pyrrole Polymer Films. J. Polym. Sci. Polym. Lett. Ed., 20, pp.187-193. 1982. Sano, S., K. Kato and Y. Ikada. Introduction of Functional-Groups onto the Surface of Polyethylene for Protein Immobilization. Biomaterials., 14, pp.817-822. 1993. Satoh, H., K. Tokuda and T. Ohsaka. Observation of Intermolecular Charge-Transfer Spectra for Propyl Viologen Dihalides in a Series of Polyether Media. Chem. Lett., pp.51-52. 1996. Schanze, K.S., T.S. Bergstedt, B.T. Hauser and C.S.P. Cavalaheiro. Photolithographically-Patterned Electroactive Films and Electrochemically Modulated Diffraction Gratings. Langmuir, 16, pp.795-810. 2000. Scharifker, B. and C. Wehrmann. Phase Formation Phenomena During Electrodeposition of Benzyl and Heptyl Viologen Bromides. J. Electroanal. Chem., 185, pp.93-108. 1985. Scheirs, J. Modern Fluoropolymers: High Performance Polymers for Diverse Applications. pp.63. Chichester, England: John Wiley & Sons Ltd. 1997. Schoot, C.J., J.J. Ponjeé, H.T. van Dam, R.A. van Doorn and P.T. Bolwijn. New Electrochromic Memory Display. Appl. Phys. Lett., 23, pp.64-65. 1973. Sei, U., T. Kenjiro, T. Satoru, K. Norihisa and H. Ryo. Photopolymerized Conducting Polyaniline Micropattern and Its Application. Synth. Met., 101, pp.701-702, 1999. 200 References Sei, U., S. Teppei, K. Kazuhiko, N. Takayuki and K. Norihisa. Template Photopolymerization of Dimeric Aniline by Photocatalytic Reaction with Ru(bpy)32+ in the presence of DNA. J. Mater. Chem., 11, pp.267-268, 2001a. Sei, U., N. Takayuki and K. Norihisa. Photopolymerization of Aniline Derivatives by Photoinduced Electron Transfer for Application to Image Formation. J. Mater. Chem., 11, pp. 1585-1589, 2001b. Sevil U.A., O. Guven and S. Suzer. Spectroscopic Investigation of Onset and Enhancement of Electrical Conductivity in PVC/PANI Composites and Blends by Gamma-Ray or UV Irradiation. J. Phys. Chem. B., 102, pp. 3902-3905. 1998. Sertova, N.; B. Geffroy, J.M. Nunzi and I. Petkov. PVC as Photodonor of HCl for Protonation of Polyaniline. J. Photochem. & Photobio. A, 113, pp.99-101. 1998. Shirakawa, H., E.J. Louis, A.G. MacDiarmid, C.H. Chiang and A.J. Heeger. Synthesis of Electrically Conducting Organic Polymers: Halogen Derivatives of Polyacetylene (CH)x. J. Chem. Soc.: Chem. Commun., C16, pp.578-580. 1977. Shu, C.F. and M.S. Wrighton. Synthesis and Charge-Transport Properties of Polymers Derived from the Oxidation of 1-Hydro-1'-(6-(Pyrrol-1-yl)Hexyl)-4,4'-Bipyridinium Bis(Hexafluorophosphate) and Demonstration of a pH-Sensitive Microelectrochemical Transistor Derived from the Redox Properties of A Conventional Redox Center. J. Phys. Chem., 92, pp.5221-5229. 1988. Shacham-Diamand, Y. and S. Lopatin, High Aspect Ratio Quarter-Micron Electroless Copper Integrated Technology. Microelectron. Eng., 37-8, pp.77-88. 1997. Skotheim, T.A. (ed). Handbook of Conducting Polymers. New York: Marcel-Dekker. 1986. Stargardt, J.F., F.M. Hawkridge and H.L. Landrum. Reversible Heterogeneous Reduction and Oxidation of Sperm Whale Myoglobin at A Surface Modified Gold Minigrid Electrode. Anal. Chem., 50, pp.930-932. 1978. Suzuki, M., A. Kishida, H. Iwata and Y. Ikada. Graft-copolymerization of Acrylamide onto a Polyethylene Surface Pretreated with a Glow-discharge. Macromolecules, 19, pp.1804-1808. 1986. Tan, C.K. and D.J. Blackwood. Corrosion Protection by Multilayered Conducting Polymer Coatings. Corros. Sci., 45, pp.545-557. 2003. Tan, K.L., B.T.G. Tan, E.T. Kang and K.G. Neoh. X-Ray Photoelectron Spectroscopy Studies of the Chemical Structure of Polyaniline. Phys, Rev. B, 39, pp.8070-8073. 1989. Tan, K.L., B.T.G. Tan, E.T. Kang and K.G. Neoh. The Chemical Nature of the Nitrogens in Polypyrrole and Polyaniline- a Comparative Study by X-ray Photoelectron Spectroscopy. J. Chem. Phys., 94, pp.5382-5388. 1991. 201 References Tan, K.L., L.L. Woon, H.K. Wong, E.T. Kang and K.G. Neoh. Surface Modification of Plasma-Pretreated Poly(Tetrafluoroethylene) Films by Graft Copolymerization. Macromolecules, 26, pp.2832-2836. 1993. Tanaka, T. and H.J. Doi. Chemical Sensor Element and Element for Biochemical Analysis, JP 2221851. 1990. Tazuke, S. and H. Kimura. Modification of Polypropylene Film Surface by Graft Polymerization of Acrylamide. Makromol. Chem., 179, pp.2603–2612. 1978. Tokito, S., P. Smith and A.J. Heeger. Highly Conductive And Stiff Fibers of Poly(2,5Dimethoxy-para-Phenylenevinylene) Prepared from Soluble Precursor Polymer. Polymer, 32, pp.464-470. 1991. Tol, A.J.W. The Instability of A Bipolaron Versus Polarons - Charge Localization in Cyclo-Dodecathiophene. Synth. Met., 74, pp.95-98. 1995. Traore, M.K., W.T.K. Stevenson, R.J. McCormick, R.C. Dorey, S. Wen and D. Meyers. Thermal Analysis of Polyaniline, Part I. Thermal Degradation of HCl-doped Emeraldine Base. Synth. Met., 40, pp.137-153. 1991. Venugopal G., X. Quan, G.E. Johnson, F.M. Houlihan, E. Chin and O. Nalamasu, Photoinduced Doping and Photolithography of Methyl-Substituted Polyaniline. Chem. Mater., 7, pp.271-276. 1995. Walzak, M.J., S. Flynn, R. Foerch, J.M. Hill, E. Karbashewski, A. Lin and M. Strobel. UV and Ozone Treatment of Polypropylene and Poly(Ethylene Terephthalate). J. Adhes. Sci. Technol., 9, pp.1229–1248. 1995. Wang, J.G., K.G. Neoh, E.T. Kang, and K.L. Tan. Chemical Deposition of Palladium on Leucoemeraldine from Solutions: State and Distribution of Palladium Species. J. Mater. Chem., 10, pp.1933-1938. 2000. Wang, J.G., K.G. Neoh and E.T. Kang. Preparation of Nanosized Metallic Particles In Polyaniline. J. Colloid. Interf. Sci., 239, pp.78-86. 2001. Warrant, L.F., J.A. Walker, D.P. Anderson, C.G. Rhodes and L.J. Buckley. A Study of Conducting Polymer Morphology –The Effect of Dopant Anions upon Order. J. Electrochem. Soc., 136, pp.2286-2295. 1989. Weast, R.C. and M.J., Astle. Handbook of Chemistry and Physics, 63rd ed. pp.D162163, E153. Boca Raton, FL: CRC Press. 1982. Wertheimer, M.R. and H.P. Schreibe. Surface Property Modification of Aromatic Polyamides by Microwave Plasmas. J. Appl. Polym. Sci., 26, pp.2087-2096. 1981. Witucki, D., F. Edward, F. Warren, Jr., F. Leslie, W. Newman and R. Paul. Method of Stabilizing Conductive Polymers. US Patent 4692225. 1987. 202 References Wright, A.N. Surface Photopolymerization of Vinyl and Diene Monomers. Nature, 215, pp.953–955. 1967. Yamaura, M., T. Hagiwara, M. Hirasaka, T. Demura and K. Iwata. Structure and Properties of Biaxially Stretched Polypyrrole Films. Synth. Met., 28, pp.C157-C164. 1989. Yang, H., T.D. Chung, Y.T. Kim, C.A. Choi, C.H. Jun and H.C. Kim. Glucose Sensor Using a Microfabricated Electrode and Electropolymerized Bilayer Films. Biosens. Bioelectron., 17, pp.251-259. 2002. Ying, L., E.T. Kang and K.G. Neoh. Covalent Immobilization of Glucose Oxidase on Microporous Membranes Prepared from Poly(Vinylidene Fluoride) with Grafted Poly(Acrylic Acid) Side Chains. J. Membr. Sci., 208, pp.361-374. 2002. Yoon, K.B. and J.K. Kochi. Shape-Selective Access to Zeolite Supercages. Arene Charge-Transfer Complexes with Viologens as Visible Probes. J. Am. Chem. Soc., 111, pp.1128-1130. 1989. Yue, J., A.J. Epstein, Z. Zhong, P.K. Gallagher and A.G. MacDiarmid. Thermal Stability of Polyanilines. Synth. Met., 41, pp.765-768. 1991. Yutaka, O. Electroless plating of gold and gold alloys. In Electroless Plating: Fundamentals and Applications, ed by O.M. Glenn and B.H. Juan. pp.401. Orlando: American Electroplaters and Surface Finishers Society. 1990. Zen, J.M. and C.W. Lo. A Glucose Sensor Made of an Enzymic Clay-Modified Electrode and Methyl Viologen Mediator. Anal. Chem., 68, pp.2635-2640. 1996. Zeng, X.R. and T.M. Ko. Structure-conductivity Relationships of Iodine-doped Polyaniline. J. Polym. Sci., Polym. Phys., 35, pp.1993-2001. 1997. Zhang, P.Y. and B. Ranby. Surface Modification by Continuous Graft Copolymerization. III. Photoinitiated Graft Copolymerization onto Poly(Ethylene Terephthalate) Fiber Surface. J. Appl. Polym. Sci., 41, pp.1469–1478. 1990. Zhang, P.Y. and B. Ranby. Surface Modification by Continuous Graft Copolymerization. II. Photoinitiated Graft Copolymerization onto Polypropylene Film Surface. J. Appl. Polym. Sci., 43, pp.621–636. 1991. Zhang, Y., K.L. Tan, G.H. Yang, E.T. Kang and K.G. Neoh. Electroless Plating of Copper and Nickel via a Sn-Free Process on Polyimide Films Modified by Surface Graft Copolymerization with 1-Vinylimidazole. J.Electrochem. Soc., 148, pp.C574C582. 2001. Zhang, Y., G.H. Yang, E.T. Kang, K.G. Neoh, Wei Huang, A.C.H. Huan, and S.Y. Wu. Deposition of Fluoropolymer Films on Si(100) Surfaces by Rf Magnetron Sputtering of Poly(tetrafluoroethylene). Langmuir, 18, pp.6373-6380. 2002. 203 References Zhao, B.Z., K.G. Neoh, F.T. Liu, E.T. Kang and K.L. Tan. Enhancement of Electrical Stability of Polyaniline Films in Aqueous Media by Surface Graft Copolymerization with Hydrophobic Monomers. Langmuir, 15, pp.8259-8264. 1999. Zhao, B.Z., K.G. Neoh, E.T. Kang and K.L. Tan. Concurrent N-alkylation and Doping of Polyaniline by Alkyl Halides. Chem. Mater., 12, pp.1800-1806. 2000a. Zhao, B.Z., K.G. Neoh, F.T. Liu, E.T. Kang and K.L. Tan. N-alkylation of Polyaniline with Simultaneous Surface Graft Copolymerization for Inducing and Maintaining a Conductive State. Langmuir, 16, pp.10540-10546. 2000b. 204 Appendix PATENT AND PUBLICATIONS Zhao, L.P., K.G. Neoh and E.T. Kang. Method of Enhancing the Stability of an Electroactive Polymer and a Redox Active Material. US Patent Application. 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