Ionic Liquids in Biotransformations and Organocatalysis: Solvents and Beyond

A one–stop reference on the state of the art of biocatalysis inionic liquids

Owing to their remarkable properties, ionic liquids (ILs) haveemerged as a promising solution for biotransformations andorganocatalysis. This book provides a much–needed multidisciplinaryreview of this field, highlighting current and potentialapplications in organic chemistry, electrochemistry, catalysis,physical chemistry, and engineering.

Written by world–class authorities on ILs, Ionic Liquids inBiotransformations and Organocatalysis covers both fundamentals andpractical applications. Contributed chapters examine ILs′interactions with proteins and enzymes as well as current uses inbiotransformations, then go on to explore state–of–the–art ILapplications.

A key feature of this book is its emphasis on non–solventapplications. In addition to addressing ILs as solvents andco–catalysts, it covers a wide range of non–solvent uses, such asperformance additives, a tool for process engineering, whole–cellprocesses, organocatalyst immobilization, and many more. Up–to–dateinformation on the toxicity of ILs for microorganisms is alsoincluded. Several chapters discuss their promising uses for greentechnology and emerging deep–eutectic solvents, and numerousexamples further illustrate the tremendous potential of thistechnology.

Chemists, materials scientists, chemical engineers,biotechnologists, crystallographers, and electrochemists will findIonic Liquids in Biotransformations and Organocatalysis anindispensable reference work for this rapidly evolving field.

Foreword by Prof. Dr. Roger Sheldon xiii

Preface xv

Contributors xvii

PART I FUNDAMENTALS 1

1 IONIC LIQUIDS: DEFINITION, APPLICATIONS, AND CONTEXT FORBIOTRANSFORMATIONS AND ORGANOCATALYSIS 3
Pablo Domínguez de María

1.1 Ionic Liquids: Definition, Development, and Overview ofCurrent Main Applications 3

1.2 On the Greenness of ILs: Toward the Third Generation of ILsand DES 6

1.3 Context of ILs in Biotransformations and Organocatalysis12

References 13

2 IONIC LIQUIDS AND PROTEINS: ACADEMIC AND SOME PRACTICALINTERACTIONS 15
Zhen Yang

2.1 Introduction 17

2.2 Ionic Liquids, Water, and Proteins 18

2.3 Hofmeister Effects on Biocatalysis 26

2.4 Impact of Ionic Liquids on Enzymes and Proteins 41

2.5 Protein Extraction by Means of Ionic Liquids 52

2.6 Proper Selection of Ionic Liquids for Biocatalysis 57

2.7 Concluding Remarks 65

PART II IONIC LIQUIDS IN BIOTRANSFORMATIONS 73

3 IONIC LIQUIDS IN BIOTRANSFORMATIONS: MOTIVATION ANDDEVELOPMENT 75
Christina Kohlmann and Lasse Greiner

3.1 First Uses of Ionic Liquids in Biotransformations 75

3.2 Motivation to Use IL in Biotransformations 80

3.3 Challenges for the Use of IL in Biotransformations 91

4 IONIC LIQUIDS AND OTHER NONCONVENTIONAL SOLVENTS INBIOTRANSFORMATIONS: MEDIUM ENGINEERING AND PROCESS DEVELOPMENT103
Pedro Lozano and Eduardo García–Verdugo

4.1 Introduction: Toward Greener Catalytic Processes 103

4.2 The Importance of the Medium Engineering inBiotransformations 106

4.3 Biocatalysis in Monophasic ILs Systems 110

4.4 (Bio)catalytic Processes in SCFs 118

4.5 Multiphase Biotransformations 124

4.6 Prospects 140

5 IONIC LIQUIDS AS (CO–)SOLVENTS FOR HYDROLYTIC ENZYMES151
Hua Zhao

5.1 Introduction 152

5.2 State–of–the–art: Lipases, Esterases, Proteases in ILs as(co–)Solvents 155

5.3 Use of ILs for (dynamic) Kinetic Resolutions ((D)KRs)183

5.4 Hydrolase–Catalyzed Esterifi cations of Saccharides andCellulose Derivatives in ILs 205

5.5 ILs for Glycosidases 210

5.6 Prospects 212

6 IONIC LIQUIDS AS (CO–)SOLVENTS FOR NONHYDROLYTIC ENZYMES229
Daniela Gamenara, Patricia Saenz Méndez, GustavoSeoane, and Pablo Domínguez de María

6.1 Ionic Liquids and Nonhydrolytic Enzymes 231

6.2 Use of ILs in Oxidoreductase–Catalyzed Enzymatic Reactions232

6.3 ILs in Lyase–Catalyzed Reactions 253

6.4 Prospects 256

7 IONIC LIQUIDS AND WHOLE–CELL CATALYZED PROCESSES261
Danielle Dennewald and Dirk Weuster–Botz

7.1 Ionic Liquids Compatible with Whole–Cell Biocatalysis:Fundamentals and Design 263

7.2 Biocompatibility, Tolerance, and Accumulation in the Cell272

7.3 State of the Art 281

7.4 Prospects 308

8 NONSOLVENT APPLICATIONS OF IONIC LIQUIDS INBIOTRANSFORMATIONS 315
Pablo Domínguez de María and ChristinaKohlmann

8.1 Introduction 315

8.2 Ionic Liquids as Additives in Biotransformations 316

8.3 Ionic Liquids for Coating Enzymes: The ILCE Concept 318

8.4 Ionic Liquids Combined with Membranes and Biotransformations321

8.5 Ionic Liquids Anchoring Substrates 321

8.6 Ionic Liquids and Bioelectrochemistry 324

PART III IONIC LIQUIDS IN ORGANOCATALYSIS 331

9 IONIC LIQUIDS AS (CO–)SOLVENTS AND CO–CATALYSTS FORORGANOCATALYTIC REACTIONS 333
tefan Toma and Radovan ebesta

9.1 Nontraditional Media in Organocatalysis 333

9.2 Early Organocatalytic Reactions in Ionic Liquids 334

9.3 Ionic Liquids as Solvents for Organocatalytic Reactions335

9.4 Ionic Liquids as Co–catalysts for Organocatalytic Reactions:Toward New Reactivities and Selectivities 353

9.5 Key Factors in Choosing Ionic Liquids for Organocatalysisand Prospects 355

10 "NONSOLVENT" APPLICATIONS OF IONIC LIQUIDS INORGANOCATALYSIS 361
Michelangelo Gruttadauria, Francesco Giacalone, Paola Agrigento,and Renato Noto

10.1 Introduction 361

10.2 Immobilizing Ionic Liquids and Organocatalysts 363

10.3 Anchoring of Organocatalyst to Ionic Liquids 378

10.4 Ionic Liquids as Organocatalysts 409

10.5 Conclusions 414

References 414

Index 419

Pablo Dominguez De Maria is Group Leader at the Institute of Technical and Macromolecular Chemistry (ITMC), RWTH Aachen University in Germany. He was previously affiliated with AkzoNobel NV in the Netherlands and Degussa AG in Germany. Dr. Dominguez de Maria has also worked as a technical freelance advisor on emerging technologies (e.g., catalysis) applied to sustainable chemistry (www.sustainable–momentum.net). He was awarded the Young Scientist Prize by the Iberoamerican Academy of Pharmacy.