IONIC LIQUIDS INBIOTRANSFORMATIONS AND ORGANOCATALYSIS -- CONTENTS -- FOREWORD -- PREFACE -- CONTRIBUTORS -- PART I: FUNDAMENTALS -- 1: IONIC LIQUIDS: DEFINITION, APPLICATIONS, AND CONTEXT FOR BIOTRANSFORMATIONS AND ORGANOCATALYSIS -- 1.1 IONIC LIQUIDS: DEFINITION, DEVELOPMENT, AND OVERVIEW OF CURRENT MAIN APPLICATIONS -- 1.2 ON THE GREENNESS OF ILs: TOWARD THE THIRD GENERATION OF ILs AND DES -- 1.3 CONTEXT OF ILs IN BIOTRANSFORMATIONS AND ORGANOCATALYSIS -- REFERENCES -- 2: IONIC LIQUIDS AND PROTEINS: ACADEMIC AND SOME PRACTICAL INTERACTIONS -- ABBREVIATIONS FOR IONIC LIQUID CATIONS -- ABBREVIATIONS FOR IONIC LIQUID ANIONS -- ABBREVIATIONS FOR AMMONIUM IONIC LIQUIDS -- OTHER ABBREVIATIONS -- 2.1 INTRODUCTION -- 2.2 IONIC LIQUIDS, WATER, AND PROTEINS -- 2.2.1 Ionic Nature of Ionic Liquids -- 2.2.2 Protic and Aprotic Ionic Liquids -- 2.2.3 Water Present in the Ionic Liquids -- 2.2.4 Interactions of Water and Ionic Liquids with Proteins -- 2.2.4.1 Effect of Water and Water Activity -- 2.2.4.2 Effect of Ionic Liquids -- 2.3 HOFMEISTER EFFECTS ON BIOCATALYSIS -- 2.3.1 Hofmeister Effects of Inorganic Salts -- 2.3.1.1 Quantification of Hofmeister Series -- 2.3.1.2 Effect of Ions on Protein Stability -- 2.3.1.3 Effect of Ions on Enzyme Activity -- 2.3.2 Hofmeister Effects of Ionic Liquids -- 2.3.2.1 Effect of Ionic Liquid Ions on Enzyme Performance in Aqueous Solution -- 2.3.2.2 Kinetic Studies of Enzymes in Ionic Liquid-Containing Aqueous Solution -- 2.3.2.3 Enzyme Performance in Ionic Liquid-Dominating Reaction Systems -- 2.4 IMPACT OF IONIC LIQUIDS ON ENZYMES AND PROTEINS -- 2.4.1 Effect of Ionic Liquids on Enzyme Activity and Stability -- 2.4.1.1 Hydrophobicity and Log P -- 2.4.1.2 Nucleophilicity and H-bond Basicity -- 2.4.1.3 Viscosity -- 2.4.2 Effect of Ionic Liquids on Protein Structure and Dynamics.

2.4.3 Effect of Ionic Liquids on Protein Refolding and Renaturation -- 2.4.4 Effect of Ionic Liquids on Protein Crystallization and Fibrilization -- 2.5 PROTEIN EXTRACTION BY MEANS OF IONIC LIQUIDS -- 2.5.1 Aqueous/Ionic Liquid-Liquid Extraction Systems -- 2.5.2 Ionic Liquid-Based Aqueous Biphasic Systems -- 2.5.3 Water-in-Ionic Liquid Microemulsion Systems -- 2.6 PROPER SELECTION OF IONIC LIQUIDS FOR BIOCATALYSIS -- 2.6.1 Amino Acid Ionic Liquids -- 2.6.2 Ammonium and Phosphonium Ionic Liquids -- 2.6.3 Design of Ionic Liquids for Biocatalysis -- 2.6.4 Proposed Guidelines for Selecting/Designing Biocompatible Ionic Liquids -- 2.7 CONCLUDING REMARKS -- REFERENCES -- PART II: IONIC LIQUIDS IN BIOTRANSFORMATIONS -- 3: IONIC LIQUIDS IN BIOTRANSFORMATIONS: MOTIVATION AND DEVELOPMENT -- 3.1 FIRST USES OF IONIC LIQUIDS IN BIOTRANSFORMATIONS -- 3.2 MOTIVATION TO USE IL IN BIOTRANSFORMATIONS -- 3.3 CHALLENGES FOR THE USE OF IL IN BIOTRANSFORMATIONS -- REFERENCES -- 4: IONIC LIQUIDS AND OTHER NONCONVENTIONAL SOLVENTS IN BIOTRANSFORMATIONS: MEDIUM ENGINEERING AND PROCESS DEVELOPMENT -- 4.1 INTRODUCTION: TOWARD GREENER CATALYTIC PROCESSES -- 4.2 THE IMPORTANCE OF THE MEDIUM ENGINEERING IN BIOTRANSFORMATIONS -- 4.2.1 Enzymes in Nonaqueous Environments -- 4.3 BIOCATALYSIS IN MONOPHASIC ILs SYSTEMS -- 4.3.1 Medium Engineering in Monophasic ILs System -- 4.3.2 Isolation and Recyclability Issues in Monophasic ILs System -- 4.4 (BIO)CATALYTIC PROCESSES IN SCFs -- 4.4.1 Properties of SFCs -- 4.4.2 Medium Engineering in Supercritical Biocatalysis -- 4.4.3 Processes Design for SCF Biocatalysis -- 4.5 MULTIPHASE BIOTRANSFORMATIONS -- 4.5.1 Biocatalytic Processes in Biphasic Fluorous Solvents -- 4.5.2 Bioprocesses in Water/scCO2 Systems -- 4.5.3 Bioprocesses in Biphasic ILs System -- 4.5.3.1 Biphasic ILs/Water System -- 4.5.3.2 Phase Behavior of IL/scCO2 Biphasic Systems.

4.5.3.3 Bioprocesses in IL/scCO2 Biphasic Systems -- 4.6 PROSPECTS -- ACKNOWLEDGMENTS -- REFERENCES -- 5: IONIC LIQUIDS AS (CO-)SOLVENTS FOR HYDROLYTIC ENZYMES -- NOMENCLATURE OF ILs -- Cations -- Anions -- 5.1 INTRODUCTION -- 5.1.1 Type of Hydrolases -- 5.1.2 Properties and Applications of ILs -- 5.2 STATE-OF-THE-ART: LIPASES, ESTERASES, PROTEASES IN ILs AS (CO-)SOLVENTS -- 5.2.1 Effect of Physical Properties of ILs on Hydrolase Activity and Stability -- 5.2.1.1 IL Polarity -- 5.2.1.2 Hydrogen-bond (H-bond) Basicity and Nucleophilicity of Anions -- 5.2.1.3 IL Network -- 5.2.1.4 Ion Kosmotropicity -- 5.2.1.5 Viscosity -- 5.2.1.6 Hydrophobicity -- 5.2.1.7 Enzyme Dissolution -- 5.2.2 Other Factors Influencing Hydrolase Activity and Stability -- 5.2.2.1 Halide Impurities in ILs -- 5.2.2.2 Water Activity -- 5.2.3 Methods to Improve Hydrolase Activity and Stability -- 5.2.3.1 Enzyme Immobilization -- 5.2.3.2 PEG-Modification -- 5.2.3.3 EPRP -- 5.2.3.4 Water-in-IL Microemulsions -- 5.2.3.5 Coating Enzymes with ILs -- 5.2.3.6 Designing Hydrolase-Compatible ILs -- 5.3 USE OF ILs FOR (DYNAMIC) KINETIC RESOLUTIONS ((D)KRs) -- 5.3.1 Kinetic Resolutions via Hydrolysis in Aqueous Solutions of ILs -- 5.3.1.1 Enantioselective Hydrolysis of Amino Acid Esters -- 5.3.1.2 Enantioselective Hydrolysis of Other Esters -- 5.3.2 Kinetic Resolution via Synthesis in Nonaqueous Solutions of ILs -- 5.3.2.1 Evaluating Hydrolase's Enantioselectivity via the Kinetic Resolution of 1-phenylethanol -- 5.3.2.2 Kinetic Resolutions of Other Alcohols -- 5.3.2.3 Kinetic Resolutions of Amines -- 5.3.2.4 Kinetic Resolutions Integrated with Supported IL Membranes (SILMs) or Microfluidic Separation -- 5.3.2.5 Kinetic Resolution Using IL/scCO2 Biphasic Systems -- 5.4 HYDROLASE-CATALYZED ESTERIFICATIONS OF SACCHARIDES AND CELLULOSE DERIVATIVES IN ILs -- 5.5 ILs FOR GLYCOSIDASES.

5.5.1 Glycosidase-Catalyzed Synthesis in ILs -- 5.5.2 Cellulase-catalyzed Hydrolysis in ILs -- 5.6 PROSPECTS -- ACKNOWLEDGMENTS -- REFERENCES -- 6: IONIC LIQUIDS AS (CO-)SOLVENTS FOR NONHYDROLYTIC ENZYMES -- NOMENCLATURE OF ILs -- 6.1 IONIC LIQUIDS AND NONHYDROLYTIC ENZYMES -- 6.2 USE OF ILs IN OXIDOREDUCTASE-CATALYZED ENZYMATIC REACTIONS -- 6.2.1 Dehydrogenases -- 6.2.2 Laccases, Peroxidases, Oxidases, and Oxygenases -- 6.3 ILs IN LYASE-CATALYZED REACTIONS -- 6.3.1 Aldolases -- 6.3.2 Oxynitrilases -- 6.4 PROSPECTS -- REFERENCES -- 7: IONIC LIQUIDS AND WHOLE-CELL-CATALYZED PROCESSES -- ABBREVIATIONS -- Abbreviations of Ionic Liquid Cations -- Abbreviations of Ionic Liquid Anions -- Abbreviation of Ionic Liquid -- List of Abbreviations -- 7.1 IONIC LIQUIDS COMPATIBLE WITH WHOLE-CELL BIOCATALYSIS: FUNDAMENTALS AND DESIGN -- 7.1.1 Biocompatibility -- 7.1.2 Availability and Purity -- 7.1.3 Stability -- 7.1.4 Process Design Criteria -- 7.1.4.1 Viscosity, Density, and Corrosiveness -- 7.1.4.2 Water Miscibility -- 7.1.5 Monophasic versus Biphasic Reaction Mode -- 7.1.6 Hazard Potential -- 7.1.6.1 Ecotoxicity -- 7.1.6.2 Biodegradability -- 7.1.7 Recyclability -- 7.1.8 Availability of Information -- 7.2 BIOCOMPATIBILITY, TOLERANCE, AND ACCUMULATION IN THE CELL -- 7.2.1 Methods -- 7.2.2 Tolerance -- 7.2.2.1 Composition of the Ionic Liquid and Organism Type -- 7.2.2.2 Other Factors of Influence -- 7.2.2.3 Comparison with Organic Solvents -- 7.2.3 Interaction Mechanism -- 7.2.3.1 Effect on the Cell Membrane -- 7.2.3.2 Accumulation inside the Cell -- 7.3 STATE OF THE ART -- 7.3.1 Asymmetric Reductions by Whole Cells in Ionic Liquids -- 7.3.2 Other Whole-Cell Biotransformations in Ionic Liquids -- 7.4 PROSPECTS -- REFERENCES -- 8: NONSOLVENT APPLICATIONS OF IONIC LIQUIDS IN BIOTRANSFORMATIONS -- 8.1 INTRODUCTION.

8.2 IONIC LIQUIDS AS ADDITIVES IN BIOTRANSFORMATIONS -- 8.3 IONIC LIQUIDS FOR COATING ENZYMES: THE ILCE CONCEPT -- 8.4 IONIC LIQUIDS COMBINED WITH MEMBRANES AND BIOTRANSFORMATIONS -- 8.5 IONIC LIQUIDS ANCHORING SUBSTRATES -- 8.6 IONIC LIQUIDS AND BIOELECTROCHEMISTRY -- REFERENCES -- PART III: IONIC LIQUIDS IN ORGANOCATALYSIS -- 9: IONIC LIQUIDS AS (CO-)SOLVENTS AND CO-CATALYSTS FOR ORGANOCATALYTIC REACTIONS -- 9.1 NONTRADITIONAL MEDIA IN ORGANOCATALYSIS -- 9.2 EARLY ORGANOCATALYTIC REACTIONS IN IONIC LIQUIDS -- 9.3 IONIC LIQUIDS AS SOLVENTS FOR ORGANOCATALYTIC REACTIONS -- 9.3.1 Aldol Reactions -- 9.3.2 Mannich Reactions -- 9.3.3 α-Amination and Aminoxylation of Carbonyl Compounds -- 9.3.4 Michael Additions -- 9.3.5 Miscellaneous Reactions -- 9.4 IONIC LIQUIDS AS CO-CATALYSTS FOR ORGANOCATALYTIC REACTIONS: TOWARD NEW REACTIVITIES AND SELECTIVITIES -- 9.5 KEY FACTORS IN CHOOSING IONIC LIQUIDS FOR ORGANOCATALYSIS AND PROSPECTS -- REFERENCES -- 10: "NONSOLVENT" APPLICATIONS OF IONIC LIQUIDS IN ORGANOCATALYSIS -- 10.1 INTRODUCTION -- 10.2 IMMOBILIZING IONIC LIQUIDS AND ORGANOCATALYSTS -- 10.2.1 Strategy 1a: Covalently Attached "Ionic Liquid" Moieties as Supports -- 10.2.2 Strategy 1b: Covalently Attached "Ionic Liquid" Moieties as Linkers -- 10.2.3 Strategy 1c: Covalently Attached "Ionic Liquid" Moieties as Organocatalysts -- 10.3 ANCHORING OF ORGANOCATALYST TO IONIC LIQUIDS -- 10.3.1 Aldol Reactions -- 10.3.2 Michael Reactions -- 10.3.3 Morita-Baylis-Hillman Reaction and Claisen-Schmidt Reaction -- 10.4 IONIC LIQUIDS AS ORGANOCATALYSTS -- 10.5 CONCLUSIONS -- REFERENCES -- INDEX.