Tools for Green Chemistry, Volume 10

Evan Beach received his PhD under the mentorship of Terry Collins at Carnegie Mellon University (2007) and was a Postdoctoral Associate at Yale University (2007-2009) in the research groups of Paul Anastas and Julie Zimmerman. He was an Associate Research Scientist (2009-2014) in the Center for Green Chemistry and Green Engineering at Yale, serving as Program Manager and contributing to the Center?s course offerings. He served on the editorial board of Green Chemistry Letters and Reviews from 2010-2014. Since 2015 he has been working as a research scientist in the chemical industry. Soumen Kundu obtained his Bachelor of Science and Master of Science degrees in chemistry at the University of Calcutta and the Indian Institute of Technology at Kanpur, respectively. He received his PhD in Inorganic Chemistry at Carnegie Mellon University in 2012 under the supervision of Professor Terrence J. Collins, during which he worked on the development and application of Fe-TAML (Tetra Amido Macrocyclic Ligand) catalysts for the remediation of organic pollutants in water. After completing his graduate studies, Dr. Kundu worked with Professor Chao-Jun Li at McGill University (2013-2015) as a postdoctoral fellow, where his research endeavors included methodology development and mechanistic understanding of ruthenium-catalyzed coupling reactions of carbonyls and alkynes to form olefins. In 2015, Dr. Kundu joined Phillips 66 as a research scientist, where his research is focused on heterogeneous catalyst development and application towards transportation fuel production. Paul T. Anastas joined Yale University as Professor and serves as the Director of the Center for Green Chemistry and Green Engineering at Yale. From 2004-2006, Paul Anastas has been the Director of the Green Chemistry Institute in Washington, D.C. Until June of 2004 he served as Assistant Director for Environment at e White House Office of Science and Technology Policy where his responsibilities included a wide range of environmental science issues including furthering international public-private cooperation in areas of Science for Sustainability such as Green Chemistry.

• ContentsAbout the Editors XIIIList of Contributors XVPreface XIX1 Application of Life Cycle Assessment to Green Chemistry Objectives 1Thomas E. Swarr, Daniele Cespi, James Fava, and Philip Nuss1.1 Introduction 11.2 Substitution of Safer Chemicals 41.2.1 Missing Inventory Data and Characterization Factors 41.2.2 Linking LCA and Chemical Risk 51.3 Design Material and Energy-Efficient Processes 71.3.1 Introduction 71.3.2 System Boundaries and Design Guidance 81.3.3 Impact Categories and Green Metrics 101.3.4 Policy Implications 121.4 Promote Renewable Materials and Energy 131.4.1 Introduction 131.4.1.1 Glycerol Case Study 131.4.2 Biochemicals Production 161.4.2.1 Life Cycle Stages of Biochemical Production 161.4.2.2 Environmental Implications of Biomass Production 161.4.2.3 Carbon Accounting and Land Use Change 181.4.2.4 Global Availability of Arable Land 201.5 Conclusion and Recommendations 20References 212 Shortcut Models Based on Molecular Structure for Life Cycle Impact Assessment: The Case of the FineChem Tool and Beyond 29Stavros Papadokonstantakis, Pantelis Baxevanidis, Effie Marcoulaki, Sara Badr, and Antonis Kokossis2.1 Introduction 292.2 Concept and Development of the FineChem Tool 312.3 Illustrative Applications of the FineChem Tool 352.3.1 LCA Aspects of Solvent Selection for Postcombustion CO2 Capture (PCC) 352.3.2 Bio-Based Production of Platform Chemicals 362.4 Toward A New Group Contribution-Based Version of the FineChem Tool 372.4.1 Introduction to GC models 372.4.2 Development of GC-Based LCA Models 382.4.3 Screening for Substances with Desirable Properties 402.4.4 Illustrative Example of Screening Molecules 442.5 Conclusions and Outlook 46References 463 Models to Estimate Fate, Exposure, and Effects of Chemicals 49Rosalie Van Zelm, Rik Oldenkamp, Mark A.J. Huijbregts, and A. Jan Hendriks3.1 Introduction 493.2 Fate 503.3 Ecological Exposure 523.4 Ecosystem Effects 543.4.1 Intraspecies Variability in Populations 543.4.2 Interspecies Variability in Assemblages 553.5 Human Exposure and Effect 553.6 Environmental Impact Evaluation 583.6.1 Life Cycle Assessment 583.6.2 Risk Assessment 613.7 Recent Developments 623.7.1 New Chemicals 623.7.2 Nontoxic Stressors 633.7.3 Uncertainty and Variability 64References 654 Collaborative Approaches to Advance Chemical Safety 71Philip Judson4.1 Introduction 714.2 Incentives for Collaboration and Constraints 724.3 Options for Sharing 744.3.1 Sharing Research 744.3.2 Sharing Knowledge 754.3.3 Sharing Data 764.3.4 Sharing Software Development 774.4 The Implementation of Collaborative Organizations 784.5 Collaborative Projects 814.5.1 British Industrial Biological Research Association (BIBRA) 814.5.2 The Chemical Bioactivity Information Centre (CBIC) 844.5.3 The Distributed Structure-Searchable Toxicity Database Network – DSSTox 844.5.4 ICH 854.5.5 Innovative Medicines Initiative (IMI) 854.5.5.1 CHEM21 864.5.5.2 Electronic Health Record for Clinical Research (EHR4CR) 874.5.5.3 eTOX 874.5.5.4 GETREAL 874.5.5.5 iPiE 884.5.5.6 MARCAR 884.5.5.7 MIP-DILI 884.5.6 International Life Sciences Institute (ILSI) and ILSI Health and Environmental Sciences Institute (HESI) 894.5.7 Lhasa Limited 904.5.8 OECD (Q)SAR Toolbox 914.5.9 OpenTox 924.5.10 PhUSE 934.5.11 The Pistoia Alliance 934.5.12 REACH Substance Information Exchange Forums (SIEF) 934.5.13 SEURAT-1 (Safety Evaluation Ultimately Replacing Animal Testing) 944.5.13.1 COSMOS 944.5.13.2 DETECTIVE 944.5.13.3 HeMiBio 954.5.13.4 NOTOX 954.5.13.5 SCR&Tox 954.5.13.6 ToxBank 954.5.14 ToxML 954.5.15 The Traditional Chinese Medicine Database 964.5.16 United Nations – the European Agreement Concerning the International Carriage of Dangerous Goods by Road (ADR) and the Globally Harmonized System of Classification and Labeling of Chemicals (GHS) 964.5.17 US Government–Industry Collaborations 974.5.18 VEGA 984.5.19 Yale University Open Data Access (YODA) 984.6 Conclusions 99References 995 Introduction to Green Analytical Chemistry 103Marek Tobiszewski5.1 Introduction 1035.1.1 Defining Green Analytical Chemistry 1035.1.2 Dualistic Role of Analytical Chemistry in Relation to Green Chemistry 1055.1.3 Brief History of Green Analytical Chemistry 1055.2 Greener Analytical Separations 1075.2.1 Green Gas Chromatography 1075.2.2 Greener Liquid Chromatography 1075.2.3 Supercritical Fluid Chromatography 1085.3 Green Sample Preparation Techniques and Direct Techniques 1085.3.1 Direct Analytical Methods 1085.3.2 Microextraction Sample Preparation Techniques 1095.3.2.1 Solid-Phase Microextraction 1105.3.2.2 Liquid-Phase Microextraction 1105.3.2.3 Dispersive Liquid–Liquid Microextraction 1115.3.3 Stir Bar Sorptive Extraction 1125.3.4 Supercritical Fluid Analytical Extraction 1125.3.5 Microwave- and Ultrasound-Assisted Extraction 1125.3.6 Ionic Liquids in Extraction 1135.4 Chemometrics for Signals Processing 1145.5 Conclusions 114References 1156 Cosmo-RS-Assisted Solvent Screening for Green Extraction of Natural Products 117Anne-Gaëlle Sicaire, Aurore Filly, Maryline Vian, Anne-Sylvie Fabiano-Tixier, and Farid Chemat6.1 Introduction 1176.2 Solvents for Green Extraction 1196.2.1 Definition 1196.2.2 Solute–Solvent Interaction 1196.2.3 Substitution Concept 1206.2.4 Panorama of Alternative Solvents for Extraction 1216.2.4.1 Water: Solvent with Variable Polarity 1216.2.4.2 Bio-Based Solvents 1216.2.4.3 Solvent Obtained from Chemical Synthesis 1236.2.4.4 Vegetable Oils 1236.2.4.5 Eutectic Solvents 1236.2.4.6 Supercritical CO2 1246.3 Prediction of Solvent Extraction of Natural Product 1246.3.1 COSMO-RS Approach 1246.3.2 Applications of COSMO-RS-Assisted Substitution of Solvent 1286.3.2.1 Example 1: COSMO-RS Assisted Selection of Solvent for Extraction of Seed Oils 1296.3.2.2 Example 2: Cosmo-Rs-assisted Selection of Solvent for Extraction of Aromas 1316.4 Conclusion 135References 1367 Supramolecular Catalysis as a Tool for Green Chemistry 139Courtney J. Hastings7.1 Introduction 1397.2 Control of Selectivity through Supramolecular Interactions 1407.2.1 Catalysis with Supramolecular Directing Groups 1417.2.2 Scaffolding Ligands 1457.2.3 Selectivity through Confinement and Binding Effects 1467.3 Reactions in Water 1507.3.1 Water-Soluble Nanoreactors 1507.3.2 Dehydration Reactions 1567.4 Catalyst/Reagent Protection 1587.4.1 Catalyst Protection 1597.4.2 Protection of Water-Sensitive Reagents 1597.5 Tandem Reactions 1607.5.1 Synthetic Tandem Reactions 1617.5.2 Chemoenzymatic Tandem Reactions 1627.6 Conclusion 164References 1648 A Tutorial of the Inverse Molecular Design Theory in Tight-Binding Frameworks and Its Applications 169Dequan Xiao and Rui Hu8.1 Introduction 1698.2 Inverse Molecular Design Theory in Tight-Binding Frameworks 1708.2.1 LCAP Principle in Density Functional Theory 1718.2.2 LCAP Principle in Tight-Binding Frameworks 1728.2.2.1 One-Orbital Tight-Binding Framework 1728.2.2.2 Extended Hückel Tight-Binding Framework 1738.2.3 Gradient for Optimization 1758.3 How to Prepare a Molecular Framework for TB-LCAP Inverse Design? 1758.4 How to Choose Optional Atom Types or Functional Groups? 1778.5 Optimizing Molecular Properties Using the TB-LACP Methods 1828.6 Conclusion 186References 1879 Green Chemistry Molecular Recognition Processes Applied to Metal Separations in Ore Beneficiation, Element Recycling, Metal Remediation, and Elemental Analysis 189Reed M. Izatt, Steven R. Izatt, Neil E. Izatt, Ronald L. Bruening, and Krzysztof E. Krakowiak9.1 Introduction 1899.2 Molecular Recognition Technology as a Green Chemistry Process 1909.3 Metal Separations Using Molecular Recognition Technology 1949.3.1 Separation and Recovery of Individual Rare Earth Elements 1949.3.2 Platinum Group Metals 1969.3.2.1 General 1969.3.2.2 Palladium Recovery from Native Ore 1979.3.2.3 Rhodium Recovery from Spent Catalyst and Other Wastes 1979.3.2.4 Platinum Recovery from Alloy Scrap 1989.3.2.5 Ruthenium Recovery from Alloy Scrap 1999.3.2.6 Iridium Separation from Rhodium and Base Metals 2009.3.2.7 Purification of 103Palladium for Use in Brachytherapy 2029.3.3 Gold Separation and Recovery from Process Streams 2029.3.3.1 General 2029.3.3.2 Gold Recovery from Plating Solutions 2039.3.4 Nickel Separations and Recovery 2049.3.4.1 Nickel Separations from Laterite Ores 2049.3.4.2 Nickel, Aluminum, and Molybdenum Recovery from Acid Leachate of Spent Hydrodesulfurization Catalyst 2059.3.4.3 Nickel Removal from Cadmium- and Zinc-Rich Sulfate Electrolyte 2069.3.5 Cadmium Removal from a Cobalt Electrolyte Solution Containing a Complex Matrix 2079.3.6 Bismuth and Antimony Removal from Copper Electrolyte in Production of High-Purity Copper 2089.3.7 Cobalt Recovery from Zinc Streams using Iron(III) as a Pseudo-Catalyst 2099.3.8 Molybdenum and Rhenium Separations 2109.3.9 Indium Recovery from Etching Wastes 2119.3.10 Separation of Indium and Germanium from Zinc Electrolyte Solutions 2129.3.10.1 Indium Separation and Recovery 2129.3.10.2 Germanium Separation and Recovery 2139.3.11 Mercury Recovery from Sulfuric Acid Streams 2139.3.12 Metal Recovery from Acid Mine Drainage Streams, Industrial Waste Streams, Mine Leach Streams, and Fly Ash 2149.3.12.1 Metal Remediation from Berkeley Pit Acid Mine Drainage Site 2149.3.12.2 Removal, Separation, and Recovery of Heavy Metals from Industrial Waste Streams using MRT 2169.3.12.3 Uranium Separation and Recovery from Mine Leach Streams 2179.3.12.4 Lead Separation from Fly Ash Generated by Ash Melting 2189.3.13 Lithium Separation and Recovery from Brine and End-of-Life Rechargeable Batteries 2199.3.14 Radionuclide Remediation 2209.3.14.1 General 2209.3.14.2 Cesium Separation and Recovery from Savannah River Nuclear Wastes 2209.3.14.3 Cesium and Technetium Separation and Recovery from Nuclear Wastes at Hanford, Washington 2219.3.14.4 Cesium Separation and Recovery from Fly Ash 2229.3.14.5 Separation and Recovery of Radioactive Cesium and Strontium from Fukishima, Dai’ichi, Japan Harbor 2259.4 Analytical Applications of Molecular Recognition Technology 2279.4.1 General 2279.4.2 Radionuclides 2299.4.2.1 Strontium Separation and Analysis using EmporeTM Strontium Rad Disks 2299.4.2.2 Radium Separation and Analysis Using EmporeTM Radium Rad Disks 2299.4.2.3 Other Radionuclide and Mixed Waste Separations 2309.4.3 Precious Metals 2309.4.4 Toxic Metals 2319.4.4.1 Arsenic Separation and Analysis 2319.4.4.2 Lead Separation and Analysis 2319.4.4.3 Mercury Separation and Analysis 2319.4.5 Rare Earth Metal Separation and Analysis from Rainfall 2329.4.6 Multimetal Separations and Recovery 2339.5 Conclusion 233References 23410 Shaping the Future of Additive Manufacturing: Twelve Themes from Bio-Inspired Design and Green Chemistry 241Thomas A. McKeag10.1 Introduction 24110.1.1 Disruptive Revolution of Additive Manufacturing 24110.1.1.1 Basic Types 24110.1.1.2 Historical Trend of the Industry 24310.1.1.3 Impacts and Implications 24510.1.2 Bio-inspired Design 24910.1.2.1 Definition 24910.1.2.2 Applications/State of the Industry 24910.1.3 Green Chemistry 25010.1.3.1 Definition 25010.1.3.2 Applications/State of the Industry 25010.1.4 Where These Three Realms Converge 25010.1.5 Twelve Themes That Could Change the Way AM is Developed 25110.1.5.1 Unity Within Diversity: Minimum Parts for Maximum Diversity 25110.1.5.2 Systems Approach: Relationships Matter 25210.1.5.3 The Optimal Activator: the Environment is the Catalyst 25310.1.5.4 Taking Advantage of Gradients: Making Delta Do Work 25410.1.5.5 Shape is Strength 25410.1.5.6 Self Organization 25510.1.5.7 Bottom-Up Construction 25610.1.5.8 Hierarchy Across Linear Scales 25610.1.5.9 Functionally Graded Material 25710.1.5.10 Composite Construction 25710.1.5.11 Controlled Sacrifice 25810.1.5.12 Water is the Universal Medium 25910.2 Conclusion 260References 26011 The IFF Green Chemistry Assessment Tool 263Geatesh Tampy11.1 Introduction 26311.2 Sustainability: An IFF Commitment 26411.3 The IFF Green Chemistry Assessment Tool: Requirements 26511.4 The 12 Principles of Green Chemistry 26611.5 The IFF Green Chemistry Assessment Tool: Scoring and Analysis 26711.6 Illustrative Example: Veridian 26811.6.1 Veridian: Description of the Technology 26911.6.2 Step 1: Development of a Practical Continuous Flow Technology for Grignard Addition 27011.6.2.1 Original Process 27011.6.2.2 Assessment 27011.6.2.3 Improved Process 27011.6.3 Step 2: Development of Air Oxidation Technology for Conversion of Alcohol to Ketone 27411.7 Summary 275References 276Index 277