Preface ix
List of Contributors xi
1 Fundamentals of Bioelectrocatalysis 1
Matteo Grattieri and Shelley D. Minteer
1.1 Introduction 1
1.2 Bioelectrocatalysts and Electron Transfer 2
1.2.1 Enzymatic Bioelectrocatalysis 4
1.2.2 Microbial Bioelectrocatalysis 6
1.3 Conclusions and Outlook 8
Acknowledgments 9
References 9
2 Electron Transfer in Enzymatic Catalysis 17
Fred Lisdat and Daniel Sch¤fer
2.1 Introduction 17
2.2 Overview of Approaches 19
2.3 Mediated Electron Transfer 21
2.3.1 Concept 21
2.3.2 Reaction of the Mediator with the Electrode 22
2.3.2.1 Mediator in Solution 22
2.3.2.2 Mediator Immobilized 24
2.3.2.3 Mediators Operating in a Volume in Front of the Electrode 26
2.3.3 Reaction of the Mediator with the Enzyme 28
2.4 Direct Electron Transfer 30
2.5 Conducting Polymers 34
2.6 Application of Nanoparticles 37
2.7 Mass Transport Limited Systems 39
2.8 Protein Engineering 40
2.8.1 Truncation 43
2.8.2 Fusion Proteins 43
2.8.3 Point Mutations 44
2.8.4 Unnatural Amino Acids 45
2.9 Conclusions and Outlook 45
References 45
3 Extracellular Electron Transfer in Microbial Bioelectrocatalysis 59
C©sar I. Torres, Christine Lewis, Juan F. Ortiz Medina, and Jesºs A. P©rez Garca
3.1 Introduction 59
3.1.1 Electrons Through Insulating Cell Bodies 59
3.2 Electrochemical Responses of Electroactive Bacteria 62
3.2.1 Extracellular Electron Shuttle Transport Under Substrate Excess Conditions 62
3.2.2 Effects of Substrate Depletion, Redox Mediators, and Catalyst Wear on EES-Mediated Eet 65
3.2.3 Extracellular Electron Transfer Through a Solid Conductive Matrix 67
3.3 Shewanella sp. and its Extracellular Electron Shuttles 68
3.4 Phenazine-Mediated Extracellular Transfer in Pseudomonas aeruginosa 70
3.5 Aiding the Movement of Electrons with the Addition of Extracellular Electron Shuttles (EESs) 72
3.5.1 Characterization of EES Candidates 72
3.5.2 What Makes a Good EES Candidate? 73
3.5.2.1 An EES Must Reduce/Oxidize at the Correct Cellular Target Potential Within Its Given Chemical Environment 74
3.5.2.2 An EES Should be Both Electrochemically Reversible and Stable 74
3.5.2.3 An EES Must be Soluble and Diffusible with Limited Kinetic Loss to âShuttleâ 75
3.5.2.4 Ensure that an EES Addition is Nontoxic and Does Not Influence Other Cellular Processes 75
3.5.2.5 EES Must Function in Dynamic Systems 75
3.5.3 Examples of Exogenous Electron Shuttles Used in METs 75
3.5.3.1 Humic Acid [Eoâ² â¼â'200 to +300 mV vs. Standard Hydrogen Electrode (SHE)] 75
3.5.3.2 Quinones (Eoâ² â¼â'300 to +200 mV vs. SHE) 76
3.5.3.3 Phenazines, Flavins, and Dyes (Eoâ² Range Approximately Between â'100 and +500 mV) 79
3.5.3.4 Ferrocene Analogs (Eoâ² â¼â'200 to +500 mV vs. SHE) 81
3.5.3.5 EES-MET Systems, EES with Genetic Modifications, and EES Effects on Biofilms 82
3.5.4 Closing Perspective on Exogenous EES 82
3.6 Geobacter sulfurreducens and Nanowires 83
3.6.1 Components of Extracellular Conductive Matrix of G. sulfurreducens 84
3.6.1.1 Protein Filaments (pili) 84
3.6.1.2 Outer Membrane Cytochromes 84
3.6.1.3 Other Conductive Matrix Components in Anodic G. sulfurreducens Biofilms 86
3.6.2 Importance of Nanowire Conductivity in Establishing High-Current Biofilm Matrix 86
3.6.3 Current Efforts to Understand Nanowire Utilization 87
3.7 Final Perspective on EET Approaches in Microbial Electrochemistry 92
References 92
4 Glucometers and Continuous Glucose Monitors 107
Nunzio Giorgio G. Carducci and David P. Hickey
4.1 Introduction 107
4.1.1 Evolution of Modern Glucometers 108
4.2 Glucose Oxidation Catalysts in Glucometers 110
4.2.1 Glucose Oxidase 111
4.2.2 Glucose Dehydrogenase 111
4.2.3 Engineering Enzymes for Improved Glucometers 112
4.3 Operating Principles of Glucometers 113
4.3.1 Detection of H2 O2 from GOx/O2 Glucose Oxidation 113
4.3.2 Mediated Bioelectrocatalysis for Glucose Sensing 115
4.3.3 Electrical âWiringâ of GOx or GDH in Redox Hydrogels 116
4.3.4 DET Bioelectrocatalysis for Glucose Sensing 117
4.3.5 Glucose Concentrations and Forms in Clinically Relevant Conditions 117
4.3.6 Error Analysis and Sampling of Glucometers 119
4.4 From Single-Point Testing to Continuous Monitoring 120
4.4.1 POC Glucometers 120
4.4.2 Single-Point Test Glucometers 121
4.4.3 Continuous Glucose Monitoring 122
4.4.4 Interstitial Fluid 123
4.4.5 Tears, Saliva, and Sweat 124
4.5 Ongoing Challenges 125
References 125
5 Ex Situ Biosensors 135
Jacquelyn E. McBride and Michelle Rasmussen
5.1 Introduction 135
5.1.1 Background 135
5.2 Organic Carbon Load 136
5.2.1 BOD Determination by Oxygen Monitoring 137
5.2.2 Mediator-Based BOD Sensors 138
5.2.3 Microbial Fuel Cell BOD Sensors 139
5.3 Toxic Compounds 139
5.3.1 Pesticides 140
5.3.2 Phenolic Compounds 140
5.3.3 Heavy Metals 142
5.3.4 Explosives 142
5.4 Emerging Trends for Enhanced Performances 143
5.5 Conclusions and Future Outlook 143
References 144
6 Biofuel Cells and Biosolar Cells 149
Matteo Grattieri and Shelley D. Minteer
6.1 Introduction 149
6.2 Enzymatic Fuel Cells 150
6.2.1 Historical Overview: From Early Studies to Current Days 150
6.2.2 Deep Oxidation of Fuel 153
6.2.3 Substrate Channeling 153
6.2.4 Nanostructured Electrodes for High-Performance EFC 156
6.3 Microbial Fuel Cells 156
6.3.1 Complex Substrates and Microbial Species for Power Production 158
6.3.2 Current Approaches for Improving Power Density Production 159
6.4 Biosolar Cells 160
6.4.1 Biosolar Cells with Isolated Photosynthetic Apparatuses 162
6.4.2 Biosolar Cells with Intact Organisms and Organelles 163
6.4.3 Engineered Biosolar Cell Setups for Improved Power Production 164
6.5 Conclusions: Future Perspective and Emerging Approaches 166
Acknowledgments 166
References 166
7 Microbial Electrochemical Technologies for Used Water Treatment 175
Ruggero Rossi
7.1 Introduction 175
7.2 Integrating Microbial Electrochemical Technologies in Wastewater Treatment Plants 178
7.3 Large-Scale MFCs for Wastewater Treatment â" Material Selection 179
7.4 Large-Scale MFCs for Wastewater Treatment â" Architecture 184
7.5 Internal Resistance in Large-Scale MFCs 185
7.6 Large-Scale MFCs for Wastewater Treatment â" Substrate 187
7.7 Treatment Efficiency 188
7.8 Energy Recovery 190
7.9 Comparison of MFCs with Conventional Wastewater Treatment Technologies 190
7.10 Treatment Technologies Other than MFCs: Microbial Electrolysis Cells 191
7.11 Outlook and Future Directions 194
References 195
8 Electrosynthesis 203
Marcos Pita, Gabriel Garca-Molina, Kavita Jayakumar, Jose Mara Abad, and AntonioL.DeLacey
8.1 Introduction 203
8.2 Bioelectrosynthesis for CO2 Reduction 204
8.2.1 Bioelectrocatalysts for CO2 Reduction 206
8.2.2 CO2 Bioelectrocatalytic Pathways 206
8.2.3 CO2 Reduction Products and Recent Advances 207
8.2.4 Formic Acid Production: Enzymatic Approach 207
8.2.5 Acetate and Butyrate Production: MES 208
8.2.6 Alcohol Production 209
8.2.7 Olefin and Methane Production: MES and Nitrogenases 209
8.2.8 Bioelectrochemical CO2 Reduction to Complex Carbon-Based Products 209
8.3 Bioelectrocatalytic Production of H 2 211
8.3.1 Introduction 211
8.3.2 Electroenzymatic Production of H 2 211
8.3.3 Microbial Production of H 2 213
8.4 Bioelectrosynthesis of Ammonia 214
8.5 Bioelectrocatalysis for Organic Synthesis 222
8.6 Conclusions 225
References 225
9 Wearable and Implantable Devices 237
Edmond Magner
9.1 Introduction 237
9.2 Skin-Based Systems 238
9.2.1 Electrode Material 242
9.3 Ocular Systems 244
9.4 Textile Material-Based Systems 246
9.5 Conclusions 248
References 248
Index 251
