Green Processes, Volume 9 Designing Safer Chemicals

by Anastas, Paul T.; Boethling, Robert; Voutchkova-Kostal, Adelina

• ISBN13: 9783527326396
• ISBN10: 3527326391
• Edition: 1st
• Format: Hardcover
• Copyright: 2013-09-23
• Publisher: Wiley-VCH

Summary

The shift towards being as environmentally-friendly as possible has resulted in the need for this important reference on the topic of designing safer chemicals. Edited by the leading international experts in the field, this volume covers such topics as toxicity, reducing hazards and biochemical pesticides.
An essential resource for anyone wishing to gain an understanding of the world of green chemistry, as well as for chemists, environmental agencies and chemical engineers.

Author Biography

Paul T. Anastas joined Yale University as Professor and iserves 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. In 1991, he established the industry-government-university partnership Green Chemistry Program, which was expanded to include basic research, and the Presidential Green Chemistry Challenge Awards. He has published and edited several books in the field of Green Chemistry and developed the 12 principles of Green Chemistry.

Table of Contents

About the Editors XVII

List of Contributors XIX

Preface XXIII

1 The Design of Safer Chemicals: Past, Present, and Future Perspectives 1
Stephen C. DeVito

1.1 Evolution of the Concept 1

1.2 Characteristics of a ‘‘Safer Chemical’’ 9

1.3 The Future of the Concept 16

1.4 Disclaimer 18

References 18

2 Differential Toxicity Characterization of Green Alternative Chemicals 21
Richard Judson

2.1 Introduction 21

2.2 Chemical Properties Related to Differential Toxicity 23

2.3 Modeling Chemical Clearance – Metabolism and Excretion 25

2.4 Predicting Differential Inherent Molecular Toxicity 28

2.5 Integrating In Vitro Data to Model Toxicity Potential 31

2.6 Databases Relevant for Toxicity Characterization 33

2.7 Example of Differential Toxicity Analysis 34

2.8 Conclusion 39

2.9 Disclaimer 40

References 40

3 Understanding Mechanisms of Metabolic Transformations as a Tool for Designing Safer Chemicals 47
Thomas G. Osimitz and John L. Nelson

3.1 Introduction 47

3.2 The Role of Metabolism in Producing Toxic Metabolites 47

3.3 Mechanisms by Which Chemicals Produce Toxicity 59

3.4 Conclusion 69

References 72

4 Structural and Toxic Mechanism-Based Approaches to Designing Safer Chemicals 77
Stephen C. DeVito

4.1 Toxicophores 77

4.2 Designing Safer Electrophilic Substances 82

4.3 Structure–Activity Relationships 86

4.4 Quantitative Structure–Activity Relationships (QSARs) 92

4.5 Isosteric Substitution as a Strategy for the Design of Safer Chemicals 95

4.6 Conclusion 100

4.7 Disclaimer 102

References 102

5 Informing Substitution to Safer Alternatives 107
Emma Lavoie, David DiFiore, Meghan Marshall, Chuantung Lin, Kelly Grant, Katherine Hart, Fred Arnold, Laura Morlacci, Kathleen Vokes, Carol Hetfield, Elizabeth Sommer, Melanie Vrabel, Mary Cushmac, Charles Auer, and Clive Davies

5.1 Design for Environment Approaches to Risk Reduction: Identifying and Encouraging the Use of Safer Chemistry 107

5.2 Assessment of Safer Chemical Alternatives: Enabling Scientific, Technological, and Commercial Development 108

5.3 Informed Substitution 111

5.4 Examples that Illustrate Informed Substitution 116

5.5 Conclusion 132

5.6 Disclaimer 133

References 133

6 Design of Safer Chemicals – Ionic Liquids 137
Ian Beadham, Monika Gurbisz and Nicholas Gathergood

6.1 Introduction 137

6.2 Environmental Considerations 137

6.3 Ionic Liquids – a Historical Perspective 138

6.4 From Ionic Liquid Stability to Biodegradability 141

6.5 Conclusion 152

References 155

7 Designing Safer Organocatalysts – What Lessons Can Be Learned When the Rebirth of an Old Research Area Coincides with the Advent of Green Chemistry? 159
Ian Beadham, Monika Gurbisz and Nicholas Gathergood

7.1 Introduction 159

7.2 A Brief History of Organocatalysis 159

7.3 Catalysts from the Chiral Pool 163

7.4 ‘‘Rules of Thumb’’ for Small Molecule Biodegradability Applied to Organocatalysts 167

7.5 Cinchona Alkaloids – Natural Products as a Source of Organocatalysts: Appendix 7.A 174

7.6 Proline, the Most Extensively Studied Organocatalyst: Appendix 7.B 175

7.7 Process of Catalyst Development 177

7.8 Analogs of Nornicotine – an Aldol Catalyst Exemplifying ‘‘Natural’’ Toxicity 179

7.9 Pharmaceutically Derived Organocatalysts and the Role of Cocatalysts 180

7.10 Conclusion 185

7.11 Summary 185

References 221

8 Life-Cycle Concepts for Sustainable Use of Engineered Nanomaterials in Nanoproducts 227
Bernd Nowack, Fadri Gottschalk, Nicole C. Mueller and Claudia Som

8.1 Introduction 227

8.2 Life-Cycle Perspectives in Green Nanotechnologies 228

8.3 Release of Nanomaterials from Products 230

8.4 Exposure Modeling of Nanomaterials in the Environment 237

8.5 Designing Safe Nanomaterials 243

8.6 Conclusion 245

References 245

9 Drugs 251
Klaus Kümmerer

9.1 Introduction 251

9.2 Pharmaceuticals – What They Are 251

9.3 Pharmaceuticals in the Environment – Sources, Fate, and Effects 252

9.4 Risk Management 257

9.5 Designing Environmentally Safe Drugs 259

9.6 Conclusion 271

References 272

10 Greener Chelating Agents 281
Nicholas J. Dixon

10.1 Introduction 281

10.2 Chelants 282

10.3 Common Chelants 284

10.4 Issues with Current Chelants 285

10.5 Green Design Part 1 – Search for Biodegradable Chelants 290

10.6 Comparing Chelating Agents 293

10.7 Six Steps to Greener Design 299

10.8 Case Study – Six Steps to Greener Chelants for Laundry 302

10.9 Conclusion 305

10.10 Abbreviations 305

References 306

11 Improvements to the Environmental Performance of Synthetic-Based Drilling Muds 309
Sajida Bakhtyar and Marthe Monique Gagnon

11.1 Introduction 309

11.2 Drilling Mud Composition 310

11.3 Characteristics and Biodegradability of SBFs 312

11.4 Case Study: Improvements in the Environmental Performance of Synthetic-Based Drilling Muds 314

11.5 Conclusion 323

References 323

12 Biochemical Pesticides: Green Chemistry Designs by Nature 329
Russell S. Jones

12.1 Introduction 329

12.2 The Historical Path to Safer Pesticides 329

12.3 Reduced-Risk Conventional Pesticides 331

12.4 The Biopesticide Alternative: an Overview 331

12.5 Biochemical Pesticides 333

12.6 Are Biochemical Pesticides the Wave of the Future? 340

12.7 Conclusion 343

12.8 Disclaimer 343

References 344

13 Property-Based Approaches to Design Rules for Reduced Toxicity 349
Adelina Voutchkova, Jakub Kostal, and Paul Anastas

13.1 Possible Approaches to Systematic Design Guidelines for Reduced Toxicity 349

13.2 Analogy with Medicinal Chemistry 354

13.3 Do Chemicals with Similar Toxicity Profiles Have Similar Physical/Chemical Properties? 356

13.4 Proposed Design Guidelines for Reduced Human Toxicity 358

13.5 Using Property Guidelines to Design for Reducing Acute Aquatic Toxicity 362

13.6 Predicting the Physicochemical Properties and Attributes Needed for Developing Design Rules 365

13.7 Conclusion 371

References 371

14 Reducing Carcinogenicity and Mutagenicity Through Mechanism-Based Molecular Design of Chemicals 375
David Y. Lai and Yin-tak Woo

14.1 Introduction 375

14.2 Mechanisms of Chemical Carcinogenesis and Structure–Activity Relationship (SAR) 376

14.3 General Molecular Parameters Affecting the Carcinogenic and Mutagenic Potential of Chemicals 378

14.4 Specific Structural Criteria of Different Classes of Chemical Carcinogens and Mutagens 382

14.5 Molecular Design of Chemicals of Low Carcinogenic and Mutagenic Potential 398

14.6 Conclusion 403

14.7 Disclaimer 404

References 404

15 Reducing Ecotoxicity 407
Keith R Solomon and Mark Hanson

15.1 Introduction to Key Aspects of Ecotoxicology 407

15.2 Environmental Fate and Pathways of Exposure to Chemicals in the Environment 413

15.3 Mechanisms of Toxic Action 419

15.4 Examples of Methods That Can Be Used in Designing Chemicals with Reduced Ecological Risks 424

15.5 Overview, Conclusions, and the Path Forward 437

References 440

16 Designing for Non-Persistence 453
Philip H. Howard and Robert S. Boethling

16.1 Introduction 453

16.2 Finding Experimental Data 454

16.3 Predicting Biodegradation from Chemical Structure 461

16.4 Predicting Chemical Hydrolysis 467

16.5 Predicting Atmospheric Degradation by Oxidation and Photolysis 469

16.6 Designing for Biodegradation I: Musk Fragrances Case Study 470

16.7 Designing for Biodegradation II: Biocides Case Study 472

16.8 Designing for Abiotic Degradation: Case Studies for Hydrolysis and Atmospheric Degradation 477

16.9 Conclusion 479

16.10 Disclaimer 479

Abbreviations 480

References 480

17 Reducing Physical Hazards: Encouraging Inherently Safer Production 485
Nicholas A. Ashford

17.1 Introduction 485

17.2 Factors Affecting the Safety of a Production System [1] 485

17.3 Chemical Safety and Accident Prevention: Inherent Safety and Inherently Safer Production 488

17.4 Incentives, Barriers, and Opportunities for the Adoption of Inherently Safer Technology 491

17.5 Elements of an Inherently Safer Production Approach [2, 3] 493

17.6 A Methodology for Inherently Safer Production 495

References 499

18 Interaction of Chemicals with the Endocrine System 501
Thomas G. Osimitz

18.1 Interaction with the Endocrine System 501

18.2 Estrogens 504

18.3 Androgens 515

18.4 Hypothalamic-Pituitary-Thyroid (HPT) Axis 516

18.5 Endocrine Disruptor Data Development Efforts 519

18.6 Research Needs and Future 521

References 522

Index 525