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
2.2.1 Open-Circuit Measurements, 5
2.2.2 Cyclic Voltammetry, 5
2.2.3 Electron Transfer, 6
2.2.4 Polarization Curves, 6
2.2.5 Power Curves, 8
2.2.6 Electrochemical Impedance Spectroscopy, 8
2.2.7 Multienzyme Cascades, 8
2.2.8 Rotating Disk Electrode Voltammetry, 9
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
3.2.1 Determining the Redox Potential of MCO, 13
3.2.2 Effect ofpHand Inhibitors on the Electrochemistry ofMCO, 17
3.3 Achieving DET of MCO by Rational Design, 18
3.3.1 Surface Analysis of Enzyme-Modified Electrodes, 20
3.3.2 Design of MCO-Modified Biocathodes Based on Direct Bioelectrocatalysis, 21
3.3.3 Design of MCO-Modified Air-Breathing Biocathodes, 22
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
4.2.1 Electron Transfer Mechanisms of Glucose Oxidase, 34
4.3 Dehydrogenases, 35
4.3.1 The NADH Reoxidation Issue, 35
4.3.2 Mediators for Electrochemical Oxidation of NADH, 37
4.3.3 Electropolymerization of Azines, 38
4.3.4 Alcohol Dehydrogenase as a Model System, 41
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
5.3.1 Promiscuous Enzymes, 55
5.3.2 Multienzyme Cascades, 56
5.3.3 Metabolons, 56
5.4 Direct and Mediated Electron Transfer, 57
5.5 Fuels, 58
5.5.1 Hydrogen, 58
5.5.2 Ethanol, 58
5.5.3 Methanol, 60
5.5.4 Methane, 61
5.5.5 Glucose, 61
5.5.6 Sucrose, 65
5.5.7 Trehalose, 65
5.5.8 Fructose, 67
5.5.9 Lactose, 68
5.5.10 Lactate, 68
5.5.11 Pyruvate, 69
5.5.12 Glycerol, 70
5.5.13 Fatty Acids, 70
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
6.4.1 [FeFe]-Hydrogenase Models, 92
6.4.2 [NiFe]-Hydrogenase Models, 95
6.4.3 Incorporation of Outer Coordination Sphere Features, 97
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
7.2.1 Stability, 112
7.2.2 Size, 113
7.2.3 Cofactor Specificity, 113
7.3 Enzyme Immobilization and Self-Assembly, 115
7.3.1 Engineering for Supermolecular Assembly, 116
7.4 Artificial Metabolons, 117
7.4.1 DNA-Templated 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
9.2.1 Electron Transfer Overpotentials, 147
9.2.2 Electron Transfer Rate, 151
9.2.3 Enzyme Kinetics, 151
9.3 Types of Mediation, 152
9.3.1 Freely Diffusing Mediator in Solution, 152
9.3.2 Mediation in Cross-Linked Redox Polymers, 154
9.3.3 Further Redox Polymer Mediation, 156
9.3.4 Mediation in Other Immobilized Layers, 160
9.4 Aspects of Mediator Design I: Mediator Overpotentials, 162
9.4.1 Considering Species Potentials in a Methanol Oxygen BFC, 162
9.4.2 The Earliest Methanol-Oxidizing BFC Anodes, 162
9.4.3 A Four-Enzyme Methanol-Oxidizing Anode, 164
9.5 Aspects of Mediator Design II: Saturated Mediator Kinetics, 165
9.5.1 An Immobilized Laccase Cathode, 166
9.5.2 Potential of the Osmium Redox Polymer, 167
9.5.3 Concentration of Redox Sites in the Mediator Film, 170
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
10.2.1 Carbon Black Nanomaterials, 184
10.2.2 Carbon Nanotubes, 185
10.2.3 Graphene, 187
10.2.4 CNT-Decorated Porous Carbon Architectures, 188
10.2.5 Buckypaper, 188
10.3 Biotemplating: The Assembly of Nanostructured Biological Inorganic Materials, 191
10.3.1 Protein-Mediated 3D Biotemplating, 192
10.4 Fabrication of Hierarchically Ordered 3D Materials for Enzyme and Microbial Electrodes, 194
10.4.1 Chitosan CNT Conductive Porous Scaffolds, 195
10.4.2 Polymer/Carbon Architectures Fabricated Using Solid Templates, 196
10.5 Incorporating Conductive Polymers into Bioelectrodes for Fuel Cell Applications, 198
10.5.1 Conductive Polymer-Facilitated DET Between Laccase and a Conductive Surface, 198
10.5.2 Materials Design for MFC, 200
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
11.2.1 Adsorption, 209
11.3 Entrapment as a Pre- and Post-Immobilization Strategy, 211
11.3.1 Stabilization via Encapsulation, 212
11.3.2 Redox Hydrogels, 212
11.4 Enzyme Immobilization via Chemical Methods, 213
11.4.1 Covalent Immobilization, 213
11.4.2 Molecular Tethering, 213
11.4.3 Self-Assembly, 215
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
12.2.1 Modeling the Performance of Immobilized Redox Enzymes in Flow-Through Mode to Estimate the Concentration of Substrate at the Enzyme Surface, 229
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
13.2.1 Scanning Electron Microscopy, 243
13.2.2 Transmission Electron Microscopy, 248
13.3 Characterizing the Bio Nano Interface, 248
13.3.1 X-Ray Photoelectron Spectroscopy, 248
13.3.2 Surface Plasmon Resonance, 256
13.4 Interrogating the Bio Nano Interface, 256
13.4.1 Atomic Force Microscopy, 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
14.3.1 Approach Curve Method of Analysis, 276
14.4 Modes of SECM Operation, 278
14.4.1 Negative Feedback Mode, 278
14.4.2 Positive Feedback Mode, 279
14.4.3 Generation Collection Mode, 279
14.4.4 Induced Transfer Mode, 280
14.5 SECM for BFC Anodes, 281
14.5.1 Enzyme-Mediated Feedback Imaging, 281
14.5.2 Generation Collection Mode Imaging, 284
14.6 SECM for BFC Cathodes, 285
14.6.1 Tip Generation Substrate Collection Mode, 286
14.6.2 Redox Competition Mode, 289
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
14.10.1 Atomic Force Microscopy, 294
14.10.2 Confocal Laser Scanning Microscopy, 295
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
15.3.1 Mediated Electron Transfer, 307
15.4 The Blue Copper Oxidases, 308
15.4.1 Laccase, 309
15.5 In Situ XAS, 310
15.5.1 Os L3-Edge, 314
15.5.2 uMET, 317
15.5.3 Mediated Electron Transfer, 319
15.5.4 FEFF8.0 Analysis, 323
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
16.3.1 Anodes, 339
16.3.2 Cathodes, 340
16.3.3 Separator and Membrane, 341
16.3.4 Reference Electrode, 342
16.3.5 Fuel and Electrolyte, 342
16.4 Single-Cell Design, 345
16.4.1 Design of Single-Cell EFC Compartment, 345
16.5 Microfluidic EFC Design, 348
16.6 Stacked Cell Design, 348
16.6.1 Series-Connected EFC Stack, 348
16.6.2 Parallel-Connected EFC Stack, 349
16.7 Bipolar Electrodes, 350
16.8 Air/Oxygen Supply, 351
16.9 Fuel Supply, 351
16.9.1 Fuel Flow-Through, 352
16.9.2 Fuel Flow-Through System, 354
16.9.3 Fuel Flow-Through Operation and Fuel Waste Management, 355
16.10 Storage and Shelf Life, 356
16.11 EFC Operation, Control, and Integration with Other Power Sources, 356
16.11.1 Activation, 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
17.2.1 Insertion MEFC with Needle Anode and Gas Diffusion Cathode, 363
17.2.2 Windable, Replaceable Enzyme Electrode Films, 364
17.3 Microfluidic MEFC, 366
17.3.1 Effects of Structural Design on Cell Performances, 366
17.3.2 Automatic Air Valve System, 367
17.3.3 SPG System, 369
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
18.8.1 Switchable/Tunable BFCs Controlled by Electrical Signals, 397
18.8.2 Switchable/Tunable BFCs Controlled by Magnetic Signals, 399
18.8.3 BFCs Controlled by Logically Processed Biochemical Signals, 402
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
19.2.1 Cell- and Organelle-Based Fuel Cells, 425
19.2.2 Enzymatic Fuel Cells, 426
19.3 Design Aspects of EFCs, 427
19.3.1 Electron Transfer, 427
19.3.2 Enzymes, 428
19.3.3 Electrodes and Electrode Materials, 430
19.3.4 Biodevice Design, 431
19.4 In Vitro and In Vivo BFC Studies, 433
19.4.1 In Vitro BFCs, 433
19.4.2 In Vivo Operating BFCs, 435
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
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