Biocatalysis for Green Chemistry and Chemical Process Development E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 789

Veröffentlichungsjahr: 2011

Beschreibung

This book describes recent progress in enzyme-driven green syntheses of industrially important molecules. The first three introductory chapters overview recent technological advances in enzymes and cell-based transformations, and green chemistry metrics for synthetic efficiency. The remaining chapters are directed to case studies in biotechnological production of pharmaceuticals (small molecules, natural products and biologics), flavors, fragrance and cosmetics, fine chemicals, value-added chemicals from glucose and biomass, and polymeric materials. The book is aimed to facilitate the industrial applications of this powerful and emerging green technology, and catalyze the advancement of the technology itself.

Leseprobe

Table of Contents

Title Page

Copyright

Preface

Contributors

Part I: Introduction Chapters

Chapter 1: Biotechnology Tools for Green Synthesis: Enzymes, Metabolic Pathways, and their Improvement by Engineering

1.1 Introduction

1.2 The Natural Fit of Biocatalysis with Green Chemistry

1.3 Why Biocatalysts Need to be Engineered

1.4 Strategies to Engineer Enzymes

1.5 Engineering of Metabolic Pathways

1.6 Outlook

1.7 Acknowledgment

Chapter 2: How Green Can The Industry Become With Biotechnology?

2.1 Introduction

2.2 How Green (Sustainable) Can The Industry Become?

2.3 Fine Chemicals and Small-Molecule Pharmaceuticals

2.4 Oligopeptides

2.5 Oligonucleotides

2.6 Oligosaccharides

2.7 Summary and Outlook

2.8 Acknowledgments

Chapter 3: Emerging Enzymes and Their Synthetic Applications

3.1 Emerging Enzymes

3.2 Strategic Synthetic Applications

3.3 Case Studies: “Green” Synthesis of Pregabalin, API of Lyrica

3.4 Conclusion

Chapter 4: Reaction Efficiencies and Green Chemistry Metrics of Biotransformations

4.1 Introduction to Reaction Efficiency and Selectivity in Organic Synthesis

4.2 Green Chemistry and Sustainability

4.3 The Metrics of Green Chemistry: Atom Economy and The Environmental Factor

4.4 The Nature of the Waste

4.5 The Role of Catalysis and Alternative Reaction Media in Waste Minimization

4.6 Biocatalysis and Green Chemistry

4.7 Green Metrics of Biotransformations

4.8 Case Studies of Enzymatic Versus Classical Chemical Processes

4.9 Conclusions and Prospects

Part II.: Application and Case Studies—Pharmaceuticals and Fine Chemicals

Chapter 5: Biocatalytic Routes to Chiral Intermediates for Development of Drugs

5.1 Introduction

5.2 Enzymatic Preparation of Chiral Unnatural Amino Acids

5.3 Enzymatic Desymmetrization Process

5.4 Enzymatic Hydroxylation

5.5 Enzymatic Reduction Process

5.6 Microbial Baeyer–Villiger Oxidations

5.7 Enzymatic Condensation Reactions

5.8 Enantioselective Enzymatic Acylation

5.9 Dynamic Kinetic Resolution (DKR)

5.10 Conclusions

Chapter 6: Transglutaminase for Protein Drug Modification: Pegylation and Beyond

6.1 Introduction

6.2 Chemical Conjugation of PEG

6.3 Tailor-Made TG for Site-Specific Modification of Protein Drugs

6.4 Conclusion

Chapter 7: Microbial Production of Plant-Derived Pharmaceutical Natural Products Through Metabolic Engineering: Artemisinin and Beyond

7.1 The Case for Microbial Production of Plant-Derived Pharmaceuticals

7.2 Using Artemisinin to Establish an Isoprenoid Biosynthesis Platform

7.3 Terpene Indole Alkaloids: Expanding Upon the Mevalonate Pathway

7.4 Benzylisoquinoline Alkaloids (BIAs): Revisiting Plant-Derived Enzyme Overexpression

7.5 Conclusions

Chapter 8: Toward Greener Therapeutic Proteins

8.1 Introduction

8.2 Characteristics of Therapeutic Proteins

8.3 General Features of Therapeutic Protein Manufacture

8.4 Environmental Assessment Considerations

8.5 Therapeutic Protein Manufacturing Process Assessment

8.6 Single-Use Manufacturing

8.7 Alternative Production Platforms

8.8 Summary

8.9 Acknowledgments

Part III.: Application and Case Studies—Flavor & Fragrance, Agrochemicals and Fine Chemicals

Chapter 9: Opportunities for Biocatalysis in the Flavor, Fragrance, and Cosmetic Industry

9.1 Introduction

9.2 Natural Flavor

9.3 Nature-Identical Flavors, Artificial Flavors, and Fragrances

9.4 Biocatalysis for the Production of Cosmetic Ingredients, Functional Perfumery

9.5 Summary and Outlook

Chapter 10: Application of Biocatalysis in the Agrochemical Industry

10.1 Introduction

10.2 Natural Product Production by Fermentation

10.3 Preparation of Building Blocks by Biotransformations

10.4 Emamectin Case—Can Biocatalysis Play a Role?

10.5 Conclusions and Outlook

10.6 Acknowledgments

Chapter 11: Green Production of Fine Chemicals by Isolated Enzymes

11.1 Introduction

11.2 Enzymatic Oxidations and Reductions for the Green Production of Fine Chemicals

11.3 Enzymatic Group Transfer Reactions for the Green Production of Fine Chemicals

11.4 Hydrolases in the Green Production of Fine Chemicals: The Workhorses

11.5 Lyases in Green Production of Fine Chemicals

11.6 Isomerases in the Green Production Fine Chemicals

11.7 Ligases in the Green Production of Fine Chemicals

11.8 Enzyme Reaction Engineering

11.9 Summary and Outlook

Chapter 12: Whole Cell Production of Fine Chemicals and Intermediates

12.1 Introduction

12.2 l-Carnitine

12.3 Nicotinamide

12.4 (S)-(−)-2,2-Dimethylcyclopropane Carboxamide

12.5 Regiospecific Hydroxylation of Heterocyclic Carboxylic Acids

12.6 Methyl and Ethyl Group Oxidation of Aromatic Heterocycles

12.7 Ethyl (R)-4-Cyano-3-Hydroxybutyrate

12.8 Conclusion

12.9 Acknowledgment

Part IV.: Application and Case Studies—polymers and renewable chemicals

Chapter 13: Green Chemistry for the Production of Biodegradable, Biorenewable, Biocompatible, and Polymers

13.1 Introduction

13.2 Polyhydroxyalkanoates

13.3 Engineering Polymer Properties

13.4 PHA Copolymers

13.5 Metabolic Pathways to Polymer Precursors in Native PHA Producing Organisms

13.6 Metabolic Pathways in Recombinant EscherichiaColi

13.7 PHA Production in Eukaryotic Cells

13.8 Raw Material Sources for PHA Production

13.9 PHA Production Using Mixed Microbial Cultures

13.10 Polylactic Acid

13.11 In Vitro Synthesis of PHAs

13.12 Applications of PHAs

13.13 Recovery and Purification of PHAs from Microbial Culture

13.14 Summary

Chapter 14: Enzymatic Degradation of Lignocellulosic Biomass

14.1 Introduction

14.2 Composition and Structure of Lignocellulosic Materials

14.3 Degradation, Modification, or Conversion of Lignocellulose

14.4 Lignocellulose-Degrading Enzymes: An Overview

14.5 Cellulases and Cellulose Degradation

14.6 Hemicellulases and Hemicellulose Degradation

14.7 Oxidoreductases and Lignin Degradation

14.8 Biological and Synthetic Enhancers for Enzymatic Degradation of Lignocellulose

14.9 Recent and Future Developments of Enzymatic Lignocellulose Hydrolysis

14.10 Acknowledgments

Chapter 15: Bioconversion of Renewables—Plant Oils

15.1 Introduction

15.2 Lipases—Tools for the Bioconversion of Plant Oils

15.3 Surface-Active Compounds

15.4 Lipase-Catalyzed Syntheses of Lipids for Dietary Applications

15.5 Surface-Active Compounds II

15.6 Oxidative Functionalizations of Unsaturated Fatty Acids

15.7 Biodiesel—Enzymatic

15.8 Summary and Conclusions

Chapter 16: Microbial Bioprocesses for Industrial-Scale Chemical Production

16.1 General Introduction

16.2 Mature Market and Established Technology (Citric Acid)

16.3 Chemicals Obtained from Citric Acid Coproduct Stream Conversion

16.4 Chemicals Currently Produced on a Commercial Scale with Markets that Still Need Development

16.5 Emerging Technology for Sustainable Production of Chemicals that can Feed Into Existing Markets

16.6 Conclusions

Index

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Library of Congress Cataloging-in-Publication Data:

Biocatalysis for green chemistry and chemical process development / edited by

Junhua (Alex) Tao, Romas Kazlauskas.

p. cm.

Includes index.

ISBN 978-0-470-43778-0 (cloth)

1. Environmental chemistry-Industrial applications. 2. Enzymes Biotechnology. 3. Green technology. I. Tao, Junhua. II. Kazlauskas, R. J. (Romas J.), 1956-

TP155.2.E58B56 2011

660.6′3–dc22

2010046369

Preface

Green chemistry is a goal and an approach to design safer, more efficient, and less expensive chemical processes. Many disciplines can contribute to green chemistry: organometallic chemists design new catalytic reactions and invent better ligands; others discover organocatalysts or safer solvents derived from biomass. Process chemists and engineers scale up reactions and find ways to carry out several steps in the same solvent, often water. Although this wide-ranging and multidisciplinary approach is essential for progress in green chemistry, it makes it hard for green chemists to exchange ideas and the tips and tricks that lead to progress in the field.

This book focuses on one important tool of green chemistry—biocatalysis. Though the focus is only on this one tool, this book explores more of the details, and exchanges some of these tips and tricks with others to spur further progress in this area. It shows how biocatalysis contributes to a wide range of industrial applications.

Biocatalysis is one of the most important tools for green chemistry. Biocatalysis is environmentally benign (often even edible!), and, because it can catalyze otherwise difficult transformations it can eliminate multiple steps involved in complex chemical syntheses. Eliminating the steps reduces waste and hazards, improves yields, and cuts costs.

This book describes recent progress in biocatalysis-driven green syntheses of industrially important molecules. The first three chapters introduce recent technological advances in enzymes and cell-based transformations, and green chemistry metrics for synthetic efficiency. The remaining chapters are case studies of biotechnological production of pharmaceuticals, including small molecules, natural products and biologics, flavor, fragrance and cosmetics, fine chemicals, value-added chemicals from glucose and biomass, and polymeric materials.

Currently, there are no books specifically devoted to a comprehensive overview of green chemistry applications of enzyme-driven transformations for a wide range of industries. There are a number of books that discuss green chemistry or biocatalysis, which mention these applications, but not in a comprehensive manner.

Saint Paul, Minnesota Romas Kazlauskas

Hangzhou, China Junhua (Alex) Tao

Contributors

Banner, Todd (Ph.D.) Cargill Biotechnology Development Center (BioTDC), Minneapolis, MN

Barrett, John S. F. (Graduate Research Assistant) Department of Chemical Engineering and Material Science, University of Minnesota, Minneapolis, MN

Chen Zhenming (Ph.D.) Institute of Sustainability, Hangzhou Normal University, Hangzhou, China

De Souza, Mervyn (Ph.D.) Cargill Specialty Canola Oils, Fort Collins, CO

Dietrich, Jeffrey A. (Ph.D.) UCB-UCSF Joint Graduate Group in Bioengineering, UC-Berkeley, UC-San Francisco, Berkeley, CA

Farid, Suzanne S. (Professor) Advanced Centre for Biochemical Engineering, Dept. of Biochemical Engineering, University College London, Torrington Place, London, UK

Fortman, J.L. (Ph.D.) Fuels Synthesis Division, Joint BioEnergy Institute, Lawrence Berkeley, National Lab, Berkeley, CA

Fosmer, Arlene (Ph.D.) Cargill Biotechnology Development Center (BioTDC), Minneapolis, MN

Gordon, John (D.Phil.) LES R&D Evaluations and Business Process Excellence, Lonza AG, Visp., Switzerland

Ho, Sa (Ph.D.) Pfizer Biotherapeutics Pharmaceutical Sciences, Chesterfield, MO

Hu, Sean (Ph.D.) Novozymes, Davis, CA

Jackson, David A. (Ph.D.) Syngenta Crop Protection Muenchwilen AG., Muenchwilen, Switzerland

Jessen, Holly (Ph.D.) Cargill Biotechnology Development Center (BioTDC), Minneapolis, MN

Juminaga, Darmawi (Ph.D.) California Institute of Quantitative Biomedical Research (QB3), University of California-Berkeley, Berkeley, CA

Kazlauskas, Romas (Professor) Department of Biochemistry, Molecular Biology and Biophysics and The Biotechnology Institute, University of Minnesota, Saint Paul, MN

Keasling, Jay D. (Professor) Fuels Synthesis Division, Joint BioEnergy Institute, Lawrence Berkeley National Laboratory, Berkeley, CA

Kim, Byung Gee (Professor) Department of Chemical and Biological Engineering, Seoul National University, Seoul, South Korea

Marasco, Erin (Ph.D.) Cargill Biotechnology Development Center (BioTDC), Minneapolis, MN

McLaughlin, Joseph M. (Ph.D.) Pfizer Biotherapeutics Pharmaceutical Sciences, Chesterfield, MO

Meyer, Hans-Peter (Ph.D.) Lonza Innovation for Future Technologies (LIFT), Lonza AG, Visp, Switzerland

Patel, Ramesh (Ph.D.) SLRP Associates, Biotechnology Consultation, Bridgewater, NJ

Pollock, James (Professor) Department of Biochemical Engineering, University College London, London, UK

Robins, Karen (MSc. Applied Science) Senior Research Associate, Lonza AG, Switzerland

Rush, Brian (Ph.D.) Cargill Biotechnology Development Center (BioTDC), Minneapolis, MN

Schneider, Manfred P. (Professor) FB C–Organische Chemie, Bergische Universitaet Wuppertal, Wuppertal, Germany

Serra, Stefano (Professor) C.N.R., Istituto di Chimica del Riconoscimento Molecolare, Milano, Italy

Sheldon, Roger A. (Professor) Department of Biotechnology, Delft University of Technology, The Netherlands

Srienc, Friedrich (Professor) Department of Chemical Engineering and Material Science, University of Minnesota, Minneapolis, MN

Tao, Junhua (Alex) (Ph.D.) Institute of Sustainability, Hangzhou Normal University, Hangzhou, China

Veldhouse, Jon (Ph.D.) Cargill Biotechnology Development Center (BioTDC), Minneapolis, MN

Werbitzky, Oleg (Ph.D.) Lonza Innovation for Future Technologies (LIFT), Lonza AG, Visp, Switzerland

Wohlgemuth, Roland (Ph.D.) Sigma-Aldrich, Buchs, Switzerland

Xu, Feng (Ph.D.) Novozymes, Davis, CA

Yin, Yifeng (Ph.D.) Trinity Biosystems, Inc., Menlo Park, CA

Part I

INTRODUCTION CHAPTERS

Chapter 1

Biotechnology Tools for Green Synthesis: Enzymes, Metabolic Pathways, and their Improvement by Engineering

Romas J. Kazlauskas

Department of Biochemistry, Molecular Biology and Biophysics and The Biotechnology Institute, University of Minnesota , Saint Paul, Minnesota

Byung-Gee Kim

Department of Chemical and Biological Engineering, Seoul National University, Seoul, Korea

1.1 Introduction

Green chemistry is the design of products and processes that eliminate or reduce waste, toxic, and hazardous materials. Green chemistry is not a cleanup approach, but a prevention approach. Preventing problems is inevitably easier and less expensive than contending with difficulties after they occur.

The risk associated with a chemical depends both on how dangerous it is (hazard) and on one's contact with it (exposure) (Figure 1.1). In the past, governments and industry focused on reducing risk by minimizing exposure. Rules limit the exposure of workers to hazardous chemicals and the release of these chemicals into the environment. This approach is expensive; it is difficult to establish a safe level of hazardous chemicals, and currently, only a small fraction of the chemicals manufactured are regulated.

Figure 1.1 The risk associated with a chemical depends on both how dangerous it is (hazard) and one's contact with it (exposure). In the past, the focus was on minimizing exposure by rules that limit the amounts of hazardous chemicals in air and water. The green chemistry approach is to eliminate or reduce hazardous materials. This change requires redesigning of synthetic approaches.

The green chemistry approach focuses on reducing risk by reducing or eliminating the hazard. Hazardous materials are eliminated by, for example, replacing them with nonhazardous ones. Hazardous materials are eliminated also by increasing the yield of a reaction, as higher yield eliminates some of the waste from that reaction. In addition, higher yield allows any preceding reactions to be carried out on a smaller scale, thus eliminating some of the waste from these steps as well. This prevention approach saves money, as fewer raw materials are needed and the cost of treatment of waste is reduced.

Reducing costs and being environmentally friendly are goals that everyone agrees on. Why has this not been done before? One reason is that environmental costs were ignored in the early days of the chemical industry. Now that more of the cleanup cost falls on the manufacturer, there is a big financial incentive to be greener. Another reason is that chemists in research and design laboratories did not view environmental hazards as their problems. It was something to be fixed later in the scale-up stage. The green chemistry approach changes this thinking. By thinking about hazards and environmental consequences at the research and design stage, many problems are prevented and do not need a fix later. The principles of green chemistry outlined by Anastas and Warner [1] provide specific guidelines for what to look for at the research and design stage to make a greener process. These principles are discussed below in the context of biocatalysis.

The first use of biochemical reactions for organic synthesis was probably in 1858, when Louis Pasteur resolved tartaric acid by using a microorganism to destroy one enantiomer [2]. In spite of this early demonstration, chemists have used biocatalysis only sporadically. Chemists gradually recognized the potential of biochemical reactions, but there were both practical and conceptual hurdles. Practical problems were how to get the enzymes and how to stabilize them. The conceptual problems were beliefs that enzymes accept only a narrow range of biochemical intermediates as substrates, and that enzymes are too complex to consider engineering them for key properties like stability, stereoselectivity, substrate range, and even reaction type. The recent advances in biotechnology have solved many of the practical problems, and the increased understanding of biochemical structures and mechanisms has made biocatalysts more understandable to chemists. This chapter surveys the state of the art for engineering biocatalysts for chemistry applications. If you find an enzyme that catalyzes your desired reaction, regardless of how poor the enzyme is, it is highly likely that it can be engineered into an enzyme suitable for industrial and large-scale use.

1.2 The Natural Fit of Biocatalysis with Green Chemistry

Biotechnology methods fit naturally to the goals and principles of green chemistry. Green chemistry, or sustainable chemistry, seeks to integrate industrial manufacturing practice with the natural world. This natural world is the biological world, where sustainability and recycling are integral parts. Use of the biological methods for industrial manufacturing is an excellent starting point to create a green process. In some cases, biotechnology tools, unlike chemical tools, are even edible. Baker's yeast, used to make bread, also catalyzes the reduction of various carbonyl compounds. Lipases are the most commonly used enzymes for biocatalysis. These enzymes are also eaten in multigram amounts by patients with pancreatic insufficiency and in smaller amounts when food-grade lipases are used in the manufacture of cheese.