Enzymatic Fuel Cells

Summarizes research encompassing all of the aspects required to understand, fabricate and integrate enzymatic fuel cells Contributions span the fields of bio-electrochemistry and biological fuel cell research Teaches the reader to optimize fuel cell performance to achieve long-term operation and realize commercial applicability Introduces the reader  to the scientific aspects of bioelectrochemistry including electrical wiring of enzymes and charge transfer in enzyme fuel cell electrodes Covers unique engineering problems of enzyme fuel cells such as design and optimization

Preface xv Contributors xvii 1 Introduction 1 Heather R. Luckarift, Plamen Atanassov, and Glenn R. Johnson List of Abbreviations 3 2 Electrochemical Evaluation of Enzymatic Fuel Cells and Figures of Merit 4 Shelley D. Minteer, Heather R. Luckarift, and Plamen Atanassov 2.1 Introduction 4 2.2 Electrochemical Characterization 5 2.3 Outlook 9 Acknowledgment 10 List of Abbreviations 10 References 10 3 Direct Bioelectrocatalysis: Oxygen Reduction for Biological Fuel Cells 12 Dmitri M. Ivnitski, Plamen Atanassov, and Heather R. Luckarift 3.1 Introduction 12 3.2 Mechanistic Studies of Intramolecular Electron Transfer 13 3.3 Achieving DET of MCO by Rational Design 18 3.4 Outlook 25 Acknowledgments 26 List of Abbreviations 26 References 27 4 Anodic Catalysts for Oxidation of Carbon-Containing Fuels 33 Rosalba A. Rincón, Carolin Lau, Plamen Atanassov, and Heather R. Luckarift 4.1 Introduction 33 4.2 Oxidases 34 4.3 Dehydrogenases 35 4.4 PQQ-Dependent Enzymes 42 4.5 Outlook 44 Acknowledgment 45 List of Abbreviations 45 References 45 5 Anodic Bioelectrocatalysis: From Metabolic Pathways to Metabolons 53 Shuai Xu, Lindsey N. Pelster, Michelle Rasmussen, and Shelley D. Minteer 5.1 Introduction 53 5.2 Biological Fuels 53 5.3 Promiscuous Enzymes Versus Multienzyme Cascades Versus Metabolons 55 5.4 Direct and Mediated Electron Transfer 57 5.5 Fuels 58 5.6 Outlook 72 Acknowledgment 72 List of Abbreviations 73 References 73 6 Bioelectrocatalysis of Hydrogen Oxidation/Reduction by Hydrogenases 80 Anne K. Jones, Arnab Dutta, Patrick Kwan, Chelsea L. McIntosh, Souvik Roy, and Sijie Yang 6.1 Introduction 80 6.2 Hydrogenases 81 6.3 Biological Fuel Cells Using Hydrogenases: Electrocatalysis 85 6.4 Electrocatalysis by Functional Mimics of Hydrogenases 92 6.5 Outlook 97 Acknowledgments 98 List of Abbreviations 98 References 99 7 Protein Engineering for Enzymatic Fuel Cells 109 Elliot Campbell and Scott Banta 7.1 Engineering Enzymes for Catalysis 109 7.2 Engineering Other Properties of Enzymes 112 7.3 Enzyme Immobilization and Self-Assembly 115 7.4 Artificial Metabolons 117 7.5 Outlook 118 List of Abbreviations 118 References 118 8 Purification and Characterization of Multicopper Oxidases for Enzyme Electrodes 123 D. Matthew Eby and Glenn R. Johnson 8.1 Introduction 123 8.2 General Considerations for MCO Expression and Purification 124 8.3 MCO Production and Expression Systems 125 8.4 MCO Purification 128 8.5 Copper Stability and Specific Considerations for MCO Production 133 8.6 Spectroscopic Monitoring and Characterization of Copper Centers 136 8.7 Outlook 139 Acknowledgment 140 List of Abbreviations 140 References 140 9 Mediated Enzyme Electrodes 146 Joshua W. Gallaway 9.1 Introduction 146 9.2 Fundamentals 147 9.3 Types of Mediation 152 9.4 Aspects of Mediator Design I: Mediator Overpotentials 162 9.5 Aspects of Mediator Design II: Saturated Mediator Kinetics 165 9.6 Outlook 172 List of Abbreviations 172 References 172 10 Hierarchical Materials Architectures for Enzymatic Fuel Cells 181 Guinevere Strack and Glenn R. Johnson 10.1 Introduction 181 10.2 Carbon Nanomaterials and the Construction of the Bio–Nano Interface 184 10.3 Biotemplating: The Assembly of Nanostructured Biological–Inorganic Materials 191 10.4 Fabrication of Hierarchically Ordered 3D Materials for Enzyme and Microbial Electrodes 194 10.5 Incorporating Conductive Polymers into Bioelectrodes for Fuel Cell Applications 198 10.6 Outlook 201 Acknowledgment 201 List of Abbreviations 201 References 202 11 Enzyme Immobilization for Biological Fuel Cell Applications 208 Lorena Betancor and Heather R. Luckarift 11.1 Introduction 208 11.2 Immobilization by Physical Methods 209 11.3 Entrapment as a Pre- and Post-Immobilization Strategy 211 11.4 Enzyme Immobilization via Chemical Methods 213 11.5 Orientation Matters 216 11.6 Outlook 218 Acknowledgment 219 List of Abbreviations 219 References 219 12 Interrogating Immobilized Enzymes in Hierarchical Structures 225 Michael J. Cooney and Heather R. Luckarift 12.1 Introduction 225 12.2 Estimating the Bound Active (Redox) Enzyme 227 12.3 Probing the Distribution of Immobilized Enzyme Within Hierarchical Structures 232 12.4 Probing the Immediate Chemical Microenvironments of Enzymes in Hierarchical Structures 235 12.5 Enzyme Aggregation in a Hierarchical Structure 236 12.6 Outlook 238 Acknowledgment 239 List of Abbreviations 239 References 239 13 Imaging and Characterization of the Bio–Nano Interface 242 Karen E. Farrington, Heather R. Luckarift, D. Matthew Eby, and Kateryna Artyushkova 13.1 Introduction 242 13.2 Imaging the Bio–Nano Interface 243 13.3 Characterizing the Bio–Nano Interface 248 13.4 Interrogating the Bio–Nano Interface 256 13.5 Outlook 267 Acknowledgment 267 List of Abbreviations 267 References 268 14 Scanning Electrochemical Microscopy for Biological Fuel Cell Characterization 273 Ramaraja P. Ramasamy 14.1 Introduction 273 14.2 Theory and Operation 274 14.3 Ultramicroelectrodes 275 14.4 Modes of SECM Operation 278 14.5 SECM for BFC Anodes 281 14.6 SECM for BFC Cathodes 285 14.7 Catalyst Screening Using SECM 290 14.8 SECM for Membranes 291 14.9 Probing Single Enzyme Molecules Using SECM 293 14.10 Combining SECM with Other Techniques 293 14.11 Outlook 297 List of Abbreviations 297 References 298 15 In Situ X-Ray Spectroscopy of Enzymatic Catalysis: Laccase-Catalyzed Oxygen Reduction 304 Sanjeev Mukerjee, Joseph Ziegelbauer, Thomas M. Arruda, Kateryna Artyushkova, and Plamen Atanassov 15.1 Introduction 304 15.2 Defining the Enzyme/Electrode Interface 305 15.3 Direct Electron Transfer Versus Mediated Electron Transfer 306 15.4 The Blue Copper Oxidases 308 15.5 In Situ XAS 310 15.6 Proposed ORR Mechanism 327 15.7 Outlook 331 Acknowledgments 331 List of Abbreviations 331 References 332 16 Enzymatic Fuel Cell Design, Operation, and Application 337 Vojtech Svoboda and Plamen Atanassov 16.1 Introduction 337 16.2 Biobatteries and EFCs 338 16.3 Components 339 16.4 Single-Cell Design 345 16.5 Microfluidic EFC Design 348 16.6 Stacked Cell Design 348 16.7 Bipolar Electrodes 350 16.8 Air/Oxygen Supply 351 16.9 Fuel Supply 351 16.10 Storage and Shelf Life 356 16.11 EFC Operation, Control, and Integration with Other Power Sources 356 16.12 EFC Control 357 16.13 Power Conditioning 357 16.14 Outlook 358 List of Abbreviations 359 References 359 17 Miniature Enzymatic Fuel Cells 361 Takeo Miyake and Matsuhiko Nishizawa 17.1 Introduction 361 17.2 Insertion MEFC 362 17.3 Microfluidic MEFC 366 17.4 Flexible Sheet MEFC 370 17.5 Outlook 371 List of Abbreviations 372 References 372 18 Switchable Electrodes and Biological Fuel Cells 374 Evgeny Katz, Vera Bocharova, and Jan Halámek 18.1 Introduction 374 18.2 Switchable Electrodes for Bioelectronic Applications 375 18.3 Light-Switchable Modified Electrodes Based on Photoisomerizable Materials 376 18.4 Magnetoswitchable Electrochemical Reactions Controlled by Magnetic Species Associated with Electrode Interfaces 378 18.5 Modified Electrodes Switchable by Applied Potentials Resulting in Electrochemical Transformations at Functional Interfaces 381 18.6 Chemically/Biochemically Switchable Electrodes 383 18.7 Coupling of Switchable Electrodes with Biomolecular Computing Systems 389 18.8 BFCs with Switchable/Tunable Power Output 396 18.9 Outlook 412 Acknowledgments 413 List of Abbreviations 413 References 414 19 Biological Fuel Cells for Biomedical Applications 422 Magnus Falk, Sergey Shleev, Claudia W. Narváez Villarrubia, Sofia Babanova, and Plamen Atanassov 19.1 Introduction 422 19.2 Definition and Classification of BFCs 424 19.3 Design Aspects of EFCs 427 19.4 In Vitro and In Vivo BFC Studies 433 19.5 Outlook 440 List of Abbreviations 442 References 443 20 Concluding Remarks and Outlook 451 Glenn R. Johnson, Heather R. Luckarift, and Plamen Atanassov 20.1 Introduction 451 20.2 Primary System Engineering: Design Determinants 453 20.3 Fundamental Advances in Bioelectrocatalysis 454 20.4 Design Opportunities from EFC Operation 454 20.5 Fundamental Drivers for EFC Miniaturization 455 20.6 Commercialization of EFCs: Strategies and Opportunities 455 Acknowledgment 457 List of Abbreviations 457 References 457 Index 459