NATURAL AND ARTIFICIAL PHOTOSYNTHESIS -- Contents -- Preface -- Contributors -- Acronyms -- 1 Physics Overview of Solar Energy -- 1.1 Introduction -- 1.2 The Sun -- 1.2 The Sun -- 1.3 Light -- 1.4 Thermodynamics -- 1.5 Photovoltaics -- 1.6 Photosynthesis -- References -- 2 Oxygenic Photosynthesis -- 2.1 Introduction -- 2.1.1 Importance of Photosynthesis: Why Study Photosynthesis? -- 2.1.2 Oxygenic Versus Anoxygenic Photosynthesis -- 2.1.3 What Can We Learn from Natural Photosynthesis to Achieve Artificial Photosynthesis? -- 2.1.4 Atomic Level Structures of Photosynthetic Systems -- 2.1.5 Scope of the Chapter -- 2.2 Path of Energy: From Photons to Charge Separation -- 2.2.1 Overview: Harvesting Sunlight for Redox Chemistry -- 2.2.2 Light absorption and Light-Harvesting Antennas -- 2.2.3 Excitation Energy Transfer: Coherent Versus Incoherent or Wavelike Versus Hopping -- 2.2.4 Concluding Remarks and Future Perspectives for Artificial Photosynthesis -- 2.3 Electron Transfer Pathways -- 2.3.1 Overview of the Primary Photochemistry and the Electron Transfer Chain -- 2.3.2 Components Associated with P680 and P700 and the Entry into the Electron Transfer Chain -- 2.3.3 Photosystem II: Function and Electron Transfer Pathway -- 2.3.4 Photosystem I: Function and the Electron Transfer Pathways -- 2.3.5 Intersystem Electron Transfer -- 2.3.6 Water as a Source of Electrons for the Photosynthetic Electron Transfer Chain -- 2.3.7 Can the Rate Limitation of O2 Production by Photosystem II Be Improved in Future Artificial Water-Splitting Systems? -- 2.4 Photophosphorylation -- 2.4.1 Overview -- 2.4.2 Mechanism of ATP Synthesis -- 2.4.3 Concluding Remarks -- 2.5 Carbon Dioxide to Organic Compounds -- 2.5.1 Overview of Carbon Dioxide Assimilation Systems in Oxygenic Organisms -- 2.5.2 C3 Pathway Versus C4 Pathway.

2.5.3 C3 versus C4 Plants During Glacial/Interglacial Periods -- 2.5.4 Concluding Remarks: Can the Natural Assimilation Pathways Be Improved to Help Solve the Energy Crisis? -- 2.6 Evolution of Oxygenic Photosynthesis -- 2.6.1 Overview -- 2.6.2 Two Photosystems for Oxygenic Photosynthesis -- 2.6.3 Evolutionary Acclimation to Decreasing CO2 Availability -- 2.7 Some Interesting Questions about Whole Plants -- 2.7.1 Overview -- 2.7.2 Why Are There Grana in Land Plants but Not in Algae? -- 2.7.3 Why Are Leaves Darker on the Upper Side than on the Lower Side? -- 2.7.4 How Much Do Different Layers in the Leaf Contribute to Photosynthesis? -- 2.7.5 How Does Photosynthesis Interact with Climate-Atmosphere? -- 2.7.6 Is There Photosynthesis Without CO2 Assimilation (N2 Fixation in Cyanobacteria, Light-Dependent N3_ Assimilation in Land Plants)? -- 2.7.7 How Can Animals Carry Out Photosynthesis? -- 2.8 Perspectives for the Future -- 2.9 Summary -- Acknowledgments -- References -- 3 Apparatus and Mechanism of Photosynthetic Water Splitting as Nature's Blueprint for Efficient Solar Energy Exploitation -- 3.1 Introduction -- 3.2 Overall Reaction Pattern of Photosynthesis and Respiration -- 3.3 Bioenergetic Limit of Solar Energy Exploitation: Water Splitting -- 3.4 Humankind's Dream of Using Water and Solar Radiation as "Clean Fuel" -- 3.5 Nature's Blueprint of Light-Induced Water Splitting -- 3.6 Types of Approaches in Performing Light-Driven H2 and O2 Formation from Water -- 3.6.1 Use of Photosynthetic Organisms -- 3.6.2 Hybrid Systems -- 3.6.3 Synthetic Systems -- 3.6.4 Oxidative Water Splitting into O2 and 4H+ -- 3.6.5 Synthetic WOCs -- 3.6.6 Light-Induced Water Splitting in Photosystem II -- 3.7 Light-Induced "Stable" Charge Separation -- 3.8 Energetics of Light-Induced Charge Separation -- 3.9 Oxidative Water Splitting: The Kok Cycle.

3.10 YZ Oxidation by P680+ -- 3.11 Structure and Function of the WOC -- 3.11.1 Structure of the Catalytic Mn-Ca Cluster and its Coordination Sphere -- 3.11.2 Electronic Configuration and Nuclear Geometry in the Si States of the Catalytic Site -- 3.11.3 Kinetics of Oxidative Water Splitting in the WOC -- 3.11.4 Substrate/Product Pathways -- 3.11.5 Mechanism of Oxidative Water Splitting -- 3.12 Concluding Remarks -- Acknowledgments -- References -- 4 Artificial Photosynthesis -- 4.1 Introduction -- 4.2 Organic Pigment Assemblies on Electrodes -- 4.3 Photosystem Assemblies on Electrodes -- 4.4 Hydrogen Production by Photosystem I Hybrid Systems -- 4.5 Mimicking Water Oxidation with Manganese Complexes -- 4.6 Protein Design for Introducing Manganese Chemistry in Proteins -- 4.7 Protein Design and Photoactive Proteins with Chl Derivatives -- 4.8 Conclusion -- Acknowledgment -- References -- 5 Artificial Photosynthesis: Ruthenium Complexes -- 5.1 Ruthenium(II) -- 5.2 Ligand Influence on the Photochemistry of Ru(II) -- 5.3 Importance of Polypyridyl Ligands and Metal Ion for Tuning of MLCT Transitions -- 5.4 Electron Transfer of Ru(II) Complexes -- 5.5 Light-Harvesting Complexes Using Ru(II) Complexes -- 5.6 Ru(II) Artificial Photosystem Models for Photosystem II -- 5.7 Ru (II) Artificial Photosystem Models for Hydrogenase -- 5.8 Conclusion -- References -- 6 CO2 Sequestration and Hydrogen Production Using Cyanobacteria and Green Algae -- 6.1 Introduction -- 6.2 Microbiology -- 6.3 Biochemistry of CO2 Fixation -- 6.3.1 CO2 Assimilation and Concentrating Mechanisms in Algae -- 6.3.2 Carbon-Concentrating Mechanisms (CCMs) -- 6.4 Parameters Affecting the CO2 Sequestration Process -- 6.4.1 Selection of Algal Species -- 6.4.2 Effect of Flue Gas Component -- 6.4.3 Effect of Physiochemical Parameters -- 6.4.4 Issues of Product Inhibition.

6.5 Hydrogen Production by Cyanobacteria -- 6.5.1 Mechanism of Hydrogen Production -- 6.5.2 Mode of Hydrogen Production -- 6.5.3 Hydrogenase Versus Nitrogenase-Based Hydrogen Production -- 6.5.4 Factors Affecting Hydrogen Production in Cyanobacteria -- 6.5.5 Recent Advances in the Field of Hydrogen Production Using Cyanobacteria -- 6.6 Mechanisms of H2 Production in Green Algae -- 6.6.1 Light Fermentation -- 6.6.2 Dark Fermentation -- 6.6.3 Use of Chemicals -- 6.6.4 Sulfur Deprivation -- 6.6.5 Control of Sulfur Quantity -- 6.6.6 Immobilization -- 6.6.7 Molecular Approach -- 6.6.8 Recent Trends in the Field of Hydrogen Production by Green Algae -- 6.7 Photobioreactors -- 6.7.1 Vertical Tubular Photobioreactor -- 6.7.2 Horizontal Tubular Photobioreactor -- 6.7.3 Helical Tubular Photobioreactor -- 6.7.4 Flat Panel Photobioreactor -- 6.7.5 Stirred Tank Photobioreactor -- 6.7.6 Hybrid Photobioreactor -- 6.8 Conclusion -- Acknowledgments -- References -- 7 Cyanobacterial Biofuel and Chemical Production for CO2 Sequestration -- 7.1 Carbon Sequestration by Biomass -- 7.2 Introduction to Cyanobacteria -- 7.3 CO2 Uptake Efficiency of Cyanobacteria -- 7.4 Mitigation of Costs Through Captured-Carbon Products -- 7.5 Captured-Carbon Products from Engineered Cyanobacteria -- 7.5.1 Isobutyraldehyde -- 7.5.2 Isobutanol -- 7.5.3 Fatty Acids -- 7.5.4 Hydrocarbons -- 7.5.5 1-Butanol -- 7.5.6 Isoprene -- 7.5.7 Hydrogen -- 7.5.8 Poly-3-hydroxybutyrate -- 7.5.9 Indirect Production Technology -- 7.6 Conclusion -- References -- 8 Hydrogen Production by Microalgae -- 8.1 Introduction -- 8.2 Hydrogenase Engineering -- 8.3 Metabolic Reprograming -- 8.4 Light Capture Improvement -- Acknowledgments -- References -- 9 Algal Biofuels -- 9.1 Introduction -- 9.2 Advantages of Algae -- 9.3 Algal Strains and Biofuel Production -- 9.4 Algal Biofuels -- 9.4.1 Complete Cell Biomass.

9.4.2 Lipids -- 9.4.3 Biodiesel -- 9.4.4 Advantages of Biodiesel from Algae Oil -- 9.4.5 Hydrocarbons -- 9.4.6 Hydrogen -- 9.4.7 Ethanol -- 9.4.8 Unique Products -- 9.5 Algal Cultivation for Biofuel Production -- 9.5.1 Carbon Dioxide Capture -- 9.5.2 Light -- 9.5.3 Nutrient Removal -- 9.5.4 Temperature -- 9.5.5 Biomass Harvesting -- 9.6 Photobioreactors Employed for Algal Biofuels -- 9.6.1 Tubular Photobioreactors -- 9.6.2 Flat Panel Photobioreactors -- 9.6.3 Offshore Membrane Enclosure for Growing Algae (OMEGA) -- 9.7 Recent Achievements in Algal Biofuels -- 9.8 Strategies for Enhancement of Algal Biofuel Production -- 9.8.1 Biorefinery: The High-Value Coproduct Strategy -- 9.8.2 Exploration of Growth Conditions and Nutrients -- 9.8.3 Design of Advanced Photobioreactors -- 9.8.4 Biotechnological Tools -- 9.8.5 Cost-Effective Technologies for Biomass Harvesting and Drying -- 9.9 Conclusion -- References -- 10 Green Hydrogen: Algal Biohydrogen Production -- 10.1 Introduction -- 10.2 Hydrogen Production by Algae -- 10.3 Hydrogenase Enzyme -- 10.4 Diversity of Hydrogen-Producing Algae -- 10.5 Model Microalgae for H2 Production Studies: Chlamydomonas Reinhardtii -- 10.6 Approaches for Enhancing Hydrogen Production -- 10.6.1 Immobilization Processes -- 10.6.2 Increasing the Resistance of Algal Cells to Stress Conditions -- 10.6.3 Optimization of Bioreactor Conditions -- 10.6.4 Integrated Photosynthetic Systems -- 10.6.5 Genetic Engineering Approaches to Improve Photosynthetic Efficiency -- 10.6.6 Metabolic Pathways of H2 Production -- 10.7 Conclusion -- References -- 11 Growth in Photobioreactors -- 11.1 Introduction -- 11.2 Design of Photobioreactors -- 11.3 Limitations to Productivity of Microalgal Cultures -- 11.4 Actual Productivities of Microalgal Cultures -- 11.5 Distribution of Light in Photobioreactors -- 11.6 Gas Exchange in Photobioreactors.

11.7 Shear Stress in Photobioreactors.