Ionic liquids in biotransformations and organocatalysis: solvents and beyond / ed. by Pablo Domínguez de María. - Hoboken: Wiley, 2012. - xviii, 435 p.: ill. - Incl. bibl. ref. - Ind.: p.419-435. - ISBN 978-0-470-56904-7  Место хранения:   031 | Институт катализа им. Г.К.Борескова CO РАН | Новосибирск

Оглавление / Contents

Foreword by Prof. Dr. Roger Sheldon .......................... xiii Preface ........................................................ xv Contributors ................................................. xvii PART I FUNDAMENTALS ............................................ 1 1 IONIC LIQUIDS: DEFINITION, APPLICATIONS, AND CONTEXT FOR BIOTRANSFORMATIONS AND ORGANOCATALYSIS ....................... 3 Pablo Domínguez de María 1.1 Ionic Liquids: Definition, Development, and Overview of Current Main Applications ............................... 3 1.2 On the Greenness of ILs: Toward the Third Generation of ILs and DES .......................................... 6 1.3 Context of ILs in Biotransformations and Organocatalysis ........................................ 12 References .................................................. 13 2 IONIC LIQUIDS AND PROTEINS: ACADEMIC AND SOME PRACTICAL INTERACTIONS ................................................ 15 Zhen Yang Abbreviations for Ionic Liquid Cations ...................... 15 Abbreviations for Ionic Liquid Anions ....................... 16 Abbreviations for Ammonium Ionic Liquids .................... 16 Other Abbreviations ......................................... 17 2.1 Introduction ........................................... 17 2.2 Ionic Liquids, Water, and Proteins ..................... 18 2.2.1 Ionic Nature of Ionic Liquids ................... 18 2.2.2 Protic and Aprotic Ionic Liquids ................ 19 2.2.3 Water Present in the Ionic Liquids .............. 21 2.2.4 Interactions of Water and Ionic Liquids with Proteins ........................................ 21 2.2.4.1 Effect of Water and Water Activity ..... 22 2.2.4.2 Effect of Ionic Liquids ................ 26 2.3 Hofmeister Effects on Biocatalysis ..................... 26 2.3.1 Hofmeister Effects of Inorganic Salts ........... 27 2.3.1.1 Quantification of Hofmeister Series .... 28 2.3.1.2 Effect of Ions on Protein Stability .... 29 2.3.1.3 Effect of Ions on Enzyme Activity ...... 30 2.3.2 Hofmeister Effects of Ionic Liquids ............. 34 2.3.2.1 Effect of Ionic Liquid Ions on Enzyme Performance in Aqueous Solution ........ 34 2.3.2.2 Kinetic Studies of Enzymes in Ionic Liquid-Containing Aqueous Solution ..... 38 2.3.2.3 Enzyme Performance in Ionic Liquid- Dominating Reaction Systems ............ 39 2.4 Impact of Ionic Liquids on Enzymes and Proteins ........ 41 2.4.1 Effect of Ionic Liquids on Enzyme Activity and Stability ................................... 41 2.4.1.1 Hydrophobicity and Log P ............... 41 2.4.1.2 Nucleophilicity and H-bond Basicity .... 44 2.4.1.3 Viscosity .............................. 45 2.4.2 Effect of Ionic Liquids on Protein Structure and Dynamics .................................... 46 2.4.3 Effect of Ionic Liquids on Protein Refolding and Renaturation ................................ 50 2.4.4 Effect of Ionic Liquids on Protein Crystallization and Fibrilization ............... 52 2.5 Protein Extraction by Means of Ionic Liquids ........... 52 2.5.1 Aqueous/Ionic Liquid-Liquid Extraction Systems .. 52 2.5.2 Ionic Liquid-Based Aqueous Biphasic Systems ..... 53 2.5.3 Water-in-Ionic Liquid Microemulsion Systems ..... 56 2.6 Proper Selection of Ionic Liquids for Biocatalysis ..... 57 2.6.1 Amino Acid Ionic Liquids ........................ 57 2.6.2 Ammonium and Phosphonium Ionic Liquids .......... 58 2.6.3 Design of Ionic Liquids for Biocatalysis ........ 59 2.6.4 Proposed Guidelines for Selecting/Designing Biocompatible Ionic Liquids ..................... 64 2.7 Concluding Remarks ..................................... 65 References .................................................. 66 PART II IONIC LIQUIDS IN BIOTRANSFORMATIONS ................... 73 3 IONIC LIQUIDS IN BIOTRANSFORMATIONS: MOTIVATION AND DEVELOPMENT ................................................. 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 References .................................................. 98 4 IONIC LIQUIDS AND OTHER NONCONVENTIONAL SOLVENTS IN BIOTRANSFORMATIONS: MEDIUM ENGINEERING AND PROCESS DEVELOPMENT ................................................ 103 Pedro Lozano and Eduardo García-Verdugo 4.1 Introduction: Toward Greener Catalytic Processes ...... 103 4.2 The Importance of the Medium Engineering in Biotransformations .................................... 106 4.2.1 Enzymes in Nonaqueous Environments ............. 106 4.3 Biocatalysis in Monophasic ILs Systems ................ 110 4.3.1 Medium Engineering in Monophasic ILs System .... 110 4.3.2 Isolation and Recyclability Issues in Monophasic ILs System .......................... 115 4.4 (Bio)catalytic Processes in SCFs ...................... 118 4.4.1 Properties of SFCs ............................. 118 4.4.2 Medium Engineering in Supercritical Biocatalysis ................................... 119 4.4.3 Processes Design for SCF Biocatalysis .......... 122 4.5 Multiphase Biotransformations .......................... 124 4.5.1 Biocatalytic Processes in Biphasic Fluorous Solvents ....................................... 125 4.5.2 Bioprocesses in Water/scCO2 Systems ............ 126 4.5.3 Bioprocesses in Biphasic ILs System ............ 128 4.5.3.1 Biphasic ILs/Water System ............. 128 4.5.3.2 Phase Behavior of IL/scCO2 Biphasic Systems ............................... 132 4.5.3.3 Bioprocesses in IL/scCO2 Biphasic Systems ............................... 134 4.6 Prospects 140 Acknowledgments ......................... 140 References 5 IONIC LIQUIDS AS (CO-)SOLVENTS FOR HYDROLYTIC ENZYMES ...... 151 Hua Zhao Nomenclature of ILs ........................................ 151 Cations .................................................... 151 Anions ..................................................... 152 5.1 Introduction .......................................... 152 5.1.1 Type of Hydrolases ............................. 152 5.1.2 Properties and Applications of ILs ............. 154 5.2 State-of-the-art: Lipases, Esterases, Proteases in ILs as (co-)Solvents .................................. 155 5.2.1 Effect of Physical Properties of ILs on Hydrolase Activity and Stability ............... 156 5.2.1.1 IL Polarity ........................... 156 5.2.1.2 Hydrogen-bond (H-bond) Basicity and Nucleophilicity of Anions ............. 157 5.2.1.3 IL Network ............................ 160 5.2.1.4 Ion Kosmotropicity .................... 161 5.2.1.5 Viscosity ............................. 165 5.2.1.6 Hydrophobicity ........................ 165 5.2.1.7 Enzyme Dissolution .................... 170 5.2.2 Other Factors Influencing Hydrolase Activity and Stability .................................. 171 5.2.2.1 Halide Impurities in ILs .............. 171 5.2.2.2 Water Activity ........................ 172 5.2.3 Methods to Improve Hydrolase Activity and Stability ...................................... 174 5.2.3.1 Enzyme Immobilization ................. 174 5.2.3.2 PEG-Modification ...................... 176 5.2.3.3 EPRP .................................. 177 5.2.3.4 Water-in-IL Microemulsions ............ 178 5.2.3.5 Coating Enzymes with ILs .............. 179 5.2.3.6 Designing Hydrolase-Compatible ILs .... 179 5.3 Use of ILs for (dynamic) Kinetic Resolutions ((D)KRs) .............................................. 183 5.3.1 Kinetic Resolutions via Hydrolysis in Aqueous Solutions of ILs ............................... 183 5.3.1.1 Enantioselective Hydrolysis of Amino Acid Esters ........................... 183 5.3.1.2 Enantioselective Hydrolysis of Other Esters ................................ 184 5.3.2 Kinetic Resolution via Synthesis in Nonaqueous Solutions of ILs .................... 187 5.3.2.1 Evaluating Hydrolase's Enantioselectivity via the Kinetic Resolution of 1-phenylethanol ......... 187 5.3.2.2 Kinetic Resolutions of Other Alcohols .............................. 188 5.3.2.3 Kinetic Resolutions of Amines ......... 199 5.3.2.4 Kinetic Resolutions Integrated with Supported IL Membranes (SILMs) or Microfluidic Separation ............... 199 5.3.2.5 Kinetic Resolution Using IL/scCO2 Biphasic Systems ...................... 202 5.4 Hydrolase-Catalyzed Esterifications of Saccharides and Cellulose Derivatives in ILs ...................... 205 5.5 ILs for Glycosidases .................................. 210 5.5.1 Glycosidase-Catalyzed Synthesis in ILs ......... 210 5.5.2 Cellulase-catalyzed Hydrolysis in ILs .......... 211 5.6 Prospects ............................................. 212 Acknowledgments ............................................ 213 References ................................................. 213 6 IONIC LIQUIDS AS (CO-)SOLVENTS FOR NONHYDROLYTIC ENZYMES ... 229 Daniela Gamenara, Patricia Saenz Méndez, Gustavo Seoane, and Pablo Domínguez de María Nomenclature of ILs ........................................ 229 6.1 Ionic Liquids and Nonhydrolytic Enzymes ............... 231 6.2 Use of ILs in Oxidoreductase-Catalyzed Enzymatic Reactions ............................................. 232 6.2.1 Dehydrogenases ................................. 232 6.2.2 Laccases, Peroxidases, Oxidases, and Oxygenases ..................................... 247 6.3 ILs in Lyase-Catalyzed Reactions ...................... 253 6.3.1 Aldolases ...................................... 253 6.3.2 Oxynitrilases .................................. 254 6.4 Prospects ............................................. 256 References ................................................. 256 7 IONIC LIQUIDS AND WHOLE-CELL-CATALYZED PROCESSES ........... 261 Danielle Dennewald and Dirk Weuster-Botz Abbreviations .............................................. 261 Abbreviations of Ionic Liquid Cations ...................... 261 Abbreviations of Ionic Liquid Anions ....................... 262 Abbreviation of Ionic Liquid ............................... 262 List of Ahhrpifintin ....................................... 262 7.1 Ionic Liquids Compatible with Whole-Cell Biocatalysis: Fundamentals and Design ................. 263 7.1.1 Biocompatibility ............................... 264 7.1.2 Availability and Purity ........................ 265 7.1.3 Stability ...................................... 265 7.1.4 Process Design Criteria ........................ 265 7.1.4.1 Viscosity, Density, and Corrosiveness ......................... 266 7.1.4.2 Water Miscibility ..................... 266 7.1.5 Monophasic versus Biphasic Reaction Mode ....... 266 7.1.6 Hazard Potential ............................... 268 7.1.6.1 Ecotoxicity ........................... 268 7.1.6.2 Biodegradability ...................... 269 7.1.7 Recyclability .................................. 271 7.1.8 Availability of Information .................... 271 7.2 Biocompatibility, Tolerance, and Accumulation in the Cell .................................................. 272 7.2.1 Methods ........................................ 272 7.2.2 Tolerance ...................................... 273 7.2.2.1 Composition of the Ionic Liquid and Organism Type ......................... 273 7.2.2.2 Other Factors of Influence ............ 276 7.2.2.3 Comparison with Organic Solvents ...... 277 7.2.3 Interaction Mechanism .......................... 278 7.2.3.1 Effect on the Cell Membrane ........... 279 7.2.3.2 Accumulation inside the Cell .......... 280 7.3 State of the Art ...................................... 281 7.3.1 Asymmetric Reductions by Whole Cells in Ionic Liquids ........................................ 282 7.3.2 Other Whole-Cell Biotransformations in Ionic Liquids ........................................ 304 7.4 Prospects ............................................. 308 References ................................................. 310 8 NONSOLVENT APPLICATIONS OF IONIC LIQUIDS IN BIOTRANSFORMATIONS ......................................... 315 Pablo Doménguez de Maria and Christina Kohlmann 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 Biotransformations .................................... 321 8.5 Ionic Liquids Anchoring Substrates .................... 321 8.6 Ionic Liquids and Bioelectrochemistry ................. 324 References ................................................. 329 PART III IONIC LIQUIDS IN ORGANOCATALYSIS ................... 331 9 IONIC LIQUIDS AS (CO-)SOLVENTS AND CO-CATALYSTS FOR ORGANOCATALYTIC REACTIONS .................................. 333 Štefan Torna and Radovan Šebesta 9.1 Nontraditional Media in Organocatalysis ............... 333 9.2 Early Organocatalytic Reactions in Ionic Liquids ...... 334 9.3 Ionic Liquids as Solvents for Organocatalytic Reactions ............................................. 335 9.3.1 Aldol Reactions ................................ 335 9.3.2 Mannich Reactions .............................. 341 9.3.3 α-Amination and Aminoxylation of Carbonyl Compounds ...................................... 342 9.3.4 Michael Additions .............................. 343 9.3.5 Miscellaneous Reactions ........................ 351 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 Organocatalysis and Prospects ......................... 355 References ................................................. 356 10 "NONSOLVENT" APPLICATIONS OF IONIC LIQUIDS IN ORGANOCATALYSIS ............................................ 361 Michelangelo Gruttadauria, Francesco Giacalone, Paola Agrigento, and Renato Noto 10.1 Introduction .......................................... 361 10.2 Immobilizing Ionic Liquids and Organocatalysts ........ 363 10.2.1 Strategy 1a: Covalently Attached "Ionic Liquid" Moieties as Supports ................... 363 10.2.2 Strategy 1b: Covalently Attached "Ionic Liquid" Moieties as Linkers .................... 369 10.2.3 Strategy 1c: Covalently Attached "Ionic Liquid" Moieties as Organocatalysts ............ 372 10.3 Anchoring of Organocatalyst to Ionic Liquids .......... 378 10.3.1 Aldol Reactions ................................ 379 10.3.2 Michael Reactions .............................. 393 10.3.3 Morita-Baylis-Hillman Reaction and Claisen- Schmidt Reaction ............................... 405 10.4 Ionic Liquids as Organocatalysts ...................... 405 10.5 Conclusions ........................................... 414 References ................................................. 414 Index ......................................................... 419