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Full Description
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
Contents
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
