Bioelectrocatalysis

Shelley D. Minteer, PhD, is the Dr. Ken Robertson Memorial Professor of Chemistry and the Director of the Kummer Institute Center for Resource Sustainability at Missouri University of Science and Technology. She’s also the Director of the NSF Center for Synthetic Organic Electrochemistry. Matteo Grattieri, PhD, is an Assistant Professor of (Bio)Electrochemistry at the Chemistry Department of the Università degli Studi di Bari Aldo Moro. His research is focused on microbial electrochemical systems, semi-artificial photosynthesis, biomaterials, and biosensors development.

• Preface ixList of Contributors xi1 Fundamentals of Bioelectrocatalysis 1Matteo Grattieri and Shelley D. Minteer1.1 Introduction 11.2 Bioelectrocatalysts and Electron Transfer 21.2.1 Enzymatic Bioelectrocatalysis 41.2.2 Microbial Bioelectrocatalysis 61.3 Conclusions and Outlook 8Acknowledgments 9References 92 Electron Transfer in Enzymatic Catalysis 17Fred Lisdat and Daniel Schäfer2.1 Introduction 172.2 Overview of Approaches 192.3 Mediated Electron Transfer 212.3.1 Concept 212.3.2 Reaction of the Mediator with the Electrode 222.3.2.1 Mediator in Solution 222.3.2.2 Mediator Immobilized 242.3.2.3 Mediators Operating in a Volume in Front of the Electrode 262.3.3 Reaction of the Mediator with the Enzyme 282.4 Direct Electron Transfer 302.5 Conducting Polymers 342.6 Application of Nanoparticles 372.7 Mass Transport Limited Systems 392.8 Protein Engineering 402.8.1 Truncation 432.8.2 Fusion Proteins 432.8.3 Point Mutations 442.8.4 Unnatural Amino Acids 452.9 Conclusions and Outlook 45References 453 Extracellular Electron Transfer in Microbial Bioelectrocatalysis 59César I. Torres, Christine Lewis, Juan F. Ortiz Medina, and Jesús A. Pérez García3.1 Introduction 593.1.1 Electrons Through Insulating Cell Bodies 593.2 Electrochemical Responses of Electroactive Bacteria 623.2.1 Extracellular Electron Shuttle Transport Under Substrate Excess Conditions 623.2.2 Effects of Substrate Depletion, Redox Mediators, and Catalyst Wear on EES-Mediated Eet 653.2.3 Extracellular Electron Transfer Through a Solid Conductive Matrix 673.3 Shewanella sp. and its Extracellular Electron Shuttles 683.4 Phenazine-Mediated Extracellular Transfer in Pseudomonas aeruginosa 703.5 Aiding the Movement of Electrons with the Addition of Extracellular Electron Shuttles (EESs) 723.5.1 Characterization of EES Candidates 723.5.2 What Makes a Good EES Candidate? 733.5.2.1 An EES Must Reduce/Oxidize at the Correct Cellular Target Potential Within Its Given Chemical Environment 743.5.2.2 An EES Should be Both Electrochemically Reversible and Stable 743.5.2.3 An EES Must be Soluble and Diffusible with Limited Kinetic Loss to “Shuttle” 753.5.2.4 Ensure that an EES Addition is Nontoxic and Does Not Influence Other Cellular Processes 753.5.2.5 EES Must Function in Dynamic Systems 753.5.3 Examples of Exogenous Electron Shuttles Used in METs 753.5.3.1 Humic Acid [Eo′ ∼−200 to +300 mV vs. Standard Hydrogen Electrode (SHE)] 753.5.3.2 Quinones (Eo′ ∼−300 to +200 mV vs. SHE) 763.5.3.3 Phenazines, Flavins, and Dyes (Eo′ Range Approximately Between −100 and +500 mV) 793.5.3.4 Ferrocene Analogs (Eo′ ∼−200 to +500 mV vs. SHE) 813.5.3.5 EES-MET Systems, EES with Genetic Modifications, and EES Effects on Biofilms 823.5.4 Closing Perspective on Exogenous EES 823.6 Geobacter sulfurreducens and Nanowires 833.6.1 Components of Extracellular Conductive Matrix of G. sulfurreducens 843.6.1.1 Protein Filaments (pili) 843.6.1.2 Outer Membrane Cytochromes 843.6.1.3 Other Conductive Matrix Components in Anodic G. sulfurreducens Biofilms 863.6.2 Importance of Nanowire Conductivity in Establishing High-Current Biofilm Matrix 863.6.3 Current Efforts to Understand Nanowire Utilization 873.7 Final Perspective on EET Approaches in Microbial Electrochemistry 92References 924 Glucometers and Continuous Glucose Monitors 107Nunzio Giorgio G. Carducci and David P. Hickey4.1 Introduction 1074.1.1 Evolution of Modern Glucometers 1084.2 Glucose Oxidation Catalysts in Glucometers 1104.2.1 Glucose Oxidase 1114.2.2 Glucose Dehydrogenase 1114.2.3 Engineering Enzymes for Improved Glucometers 1124.3 Operating Principles of Glucometers 1134.3.1 Detection of H2 O2 from GOx/O2 Glucose Oxidation 1134.3.2 Mediated Bioelectrocatalysis for Glucose Sensing 1154.3.3 Electrical “Wiring” of GOx or GDH in Redox Hydrogels 1164.3.4 DET Bioelectrocatalysis for Glucose Sensing 1174.3.5 Glucose Concentrations and Forms in Clinically Relevant Conditions 1174.3.6 Error Analysis and Sampling of Glucometers 1194.4 From Single-Point Testing to Continuous Monitoring 1204.4.1 POC Glucometers 1204.4.2 Single-Point Test Glucometers 1214.4.3 Continuous Glucose Monitoring 1224.4.4 Interstitial Fluid 1234.4.5 Tears, Saliva, and Sweat 1244.5 Ongoing Challenges 125References 1255 Ex Situ Biosensors 135Jacquelyn E. McBride and Michelle Rasmussen5.1 Introduction 1355.1.1 Background 1355.2 Organic Carbon Load 1365.2.1 BOD Determination by Oxygen Monitoring 1375.2.2 Mediator-Based BOD Sensors 1385.2.3 Microbial Fuel Cell BOD Sensors 1395.3 Toxic Compounds 1395.3.1 Pesticides 1405.3.2 Phenolic Compounds 1405.3.3 Heavy Metals 1425.3.4 Explosives 1425.4 Emerging Trends for Enhanced Performances 1435.5 Conclusions and Future Outlook 143References 1446 Biofuel Cells and Biosolar Cells 149Matteo Grattieri and Shelley D. Minteer6.1 Introduction 1496.2 Enzymatic Fuel Cells 1506.2.1 Historical Overview: From Early Studies to Current Days 1506.2.2 Deep Oxidation of Fuel 1536.2.3 Substrate Channeling 1536.2.4 Nanostructured Electrodes for High-Performance EFC 1566.3 Microbial Fuel Cells 1566.3.1 Complex Substrates and Microbial Species for Power Production 1586.3.2 Current Approaches for Improving Power Density Production 1596.4 Biosolar Cells 1606.4.1 Biosolar Cells with Isolated Photosynthetic Apparatuses 1626.4.2 Biosolar Cells with Intact Organisms and Organelles 1636.4.3 Engineered Biosolar Cell Setups for Improved Power Production 1646.5 Conclusions: Future Perspective and Emerging Approaches 166Acknowledgments 166References 1667 Microbial Electrochemical Technologies for Used Water Treatment 175Ruggero Rossi7.1 Introduction 1757.2 Integrating Microbial Electrochemical Technologies in Wastewater Treatment Plants 1787.3 Large-Scale MFCs for Wastewater Treatment – Material Selection 1797.4 Large-Scale MFCs for Wastewater Treatment – Architecture 1847.5 Internal Resistance in Large-Scale MFCs 1857.6 Large-Scale MFCs for Wastewater Treatment – Substrate 1877.7 Treatment Efficiency 1887.8 Energy Recovery 1907.9 Comparison of MFCs with Conventional Wastewater Treatment Technologies 1907.10 Treatment Technologies Other than MFCs: Microbial Electrolysis Cells 1917.11 Outlook and Future Directions 194References 1958 Electrosynthesis 203Marcos Pita, Gabriel García-Molina, Kavita Jayakumar, Jose María Abad, and AntonioL.DeLacey8.1 Introduction 2038.2 Bioelectrosynthesis for CO2 Reduction 2048.2.1 Bioelectrocatalysts for CO2 Reduction 2068.2.2 CO2 Bioelectrocatalytic Pathways 2068.2.3 CO2 Reduction Products and Recent Advances 2078.2.4 Formic Acid Production: Enzymatic Approach 2078.2.5 Acetate and Butyrate Production: MES 2088.2.6 Alcohol Production 2098.2.7 Olefin and Methane Production: MES and Nitrogenases 2098.2.8 Bioelectrochemical CO2 Reduction to Complex Carbon-Based Products 2098.3 Bioelectrocatalytic Production of H 2 2118.3.1 Introduction 2118.3.2 Electroenzymatic Production of H 2 2118.3.3 Microbial Production of H 2 2138.4 Bioelectrosynthesis of Ammonia 2148.5 Bioelectrocatalysis for Organic Synthesis 2228.6 Conclusions 225References 2259 Wearable and Implantable Devices 237Edmond Magner9.1 Introduction 2379.2 Skin-Based Systems 2389.2.1 Electrode Material 2429.3 Ocular Systems 2449.4 Textile Material-Based Systems 2469.5 Conclusions 248References 248Index 251