Biocatalysis in Green Solvents

Description

Biocatalysis in Green Solvents offers a pragmatic overview and instruction in biocatalysis and enzymology of green solvents for sustainable industries and medicine, running from concept to application. Here, international experts in the field discuss structure-function relationships of enzymes in ionic liquids (ILs) and examine how enzymes act as selective catalysts for fine biochemical synthesis in non-aqueous environments. Several integral green biochemical processes of biocatalytic transformation and pure product separation are described in detail. Application focused chapters discuss the role of biocatalysis in creating and implementing deep eutectic solvents, biomass derived solvents, sub and supercritical fluids, carbon dioxide biphasic systems, and enzymatic membrane reactors, as well as applying these biocatalytic processes in drug discovery and production. Cover Half Title Foundations and Frontiers in Enzymology Series Biocatalysis in Green Solvents Copyright Contents Dedication Foreword List of contributors Preface 1. Biocatalysis,solvents,and green metrics in sustainable chemistry 1.1 Introduction to green chemistry and sustainability 1.2 The role of catalysis 1.3 Advantages and limitations of biocatalysis 1.4 The metrics of waste minimization 1.5 Atom economy: every atom counts 1.6 The E-factor: the environmental footprint of chemicals 1.7 Intrinsic E-factors and system boundaries 1.8 The climate factor 1.9 The nature and environmental impact of wastes 1.10 The role of solvents: the medium is the message 1.11 Bio-based solvents 1.12 Water as a reaction medium 1.13 Aqueous biphasic catalysis 1.14 Surfactants in water: aqueous micelles as nanoreactors 1.15 Neoteric solvents: ionic liquids and deep eutectic solvents 1.16 Concluding remarks References 2. Nonconventional biocatalysis: from organic solvents to green solvents 2.1 Introduction 2.2 Biocatalysis strengths and weaknesses at industrial level 2.3 Whole cell biocatalysis 2.4 Isolation of new biocatalysts 2.5 Recombinant technologies and enzyme evolution 2.6 Immobilization of biocatalysts 2.7 Volume-confined biocatalysis 2.8 Solvent engineering: organic media 2.9 From organic solvents to green solvents 2.10 Solvent-free biocatalysis 2.11 Conclusions References 3. Activation and stabilization of enzymes using ionic liquid engineering 3.1 Introduction 3.2 How to use an ionic liquids as a solvent for enzymatic reactions 3.3 Activation of lipase-catalyzed reactions using ionic liquid enginee 3.4 Laccase-catalyzed reactions in ionic liquids 3.5 Conclusions and future perspective of enzymatic reaction using ionic liquids References Further reading 4. Refolding ability of ionic liquids against denatured proteins 4.1 Introduction 4.2 Structural aspects of ionic liquids and their important applications in various bioscientific fields 4.3 Protein folding/unfolding mechanism 4.4 Overview of protein stability in ionic liquids 4.5 Refolding ability of ionic liquids on the perturbed proteins 4.6 Ammonium-based ionic liquids acted as refolding additives for denatured proteins 4.7 Imidazolium-based ionic liquids acted as refolding additives for perturbed proteins 4.8 Cholinium-based ionic liquids acted as refolding additives for perturbed proteins 4.9 Pyridinium-based ionic liquids acted as refolding additives for perturbed proteins 4.10 Pyrrolidinium-based ionic liquids acted as refolding additives for perturbed proteins 4.11 Phosphonium-based ionic liquids acted as refolding additives for perturbed proteins 4.12 Morpholinium-based ionic liquids acted as refolding additives for perturbed proteins 4.13 Conclusions References 5. Stability and stabilization of biocatalysts by ionic liquids 5.1 Introduction 5.2 Enzyme stability in ionic liquids: controlling factors 5.2.1 Ionic liquids network structure 5.2.2 Ionic liquids polarity and hydrophobicity 5.2.3 Hydrogen-bond basicity and nucleophilicity of anions 5.2.4 Ion specificity and Hofmeister series 5.2.5 Viscosity 5.2.6 Surfactant effect 5.3 Enzyme stabilization by ionic liquids 5.3.1 Modifying enzyme’s microenvironment using ionic liquids 5.3.1.1 Water-in-ionic liquids microemulsions 5.3.1.2 Coating enzymes with ionic liquids 5.3.1.3 Chemical modification of enzymes with ionic liquids 5.3.2 Designing enzyme-compatible functionalized ionic liquids 5.4 Summary Acknowledgments References 6. Clean biocatalysis in sponge-like ionic liquids 6.1 Solvents, enzymes, and sustainable chemistry 6.2 Essentials of ionic liquids 6.3 Understanding biocatalysis in ionic liquids and beyond 6.4 Sponge-like ionic liquids: an enabling green tool to integrate reaction and separation processes 6.5 Biocatalytic production of flavor esters by using the sponge-like ionic liquid technology 6.6 Green biocatalytic production of biodiesel by using the sponge-like ionic liquid technology 6.7 Green biocatalytic production of monoacylglycerides by using the sponge-like ionic liquid technology 6.8 Conclusions Acknowledgements 7. Biocatalysis in biphasic systems based on ionic liquids 7.1 Introduction 7.2 Biocatalysis in biphasic systems 7.2.1 Ionic liquids as alternative solvents in biphasic systems 7.2.2 Deep eutectic solvents as alternatives solvents in biphasic sys 7.3 Biocatalysis in aqueous biphasic systems 7.3.1 Biocatalysis in ionic-liquid-based aqueous biphasic systems 7.4 Concluding remarks Acknowledgments 8. Biotransformations of carbohydrates in ionic liquids 8.1 Introduction 8.2 Ionic liquids 8.3 Ionic liquids can dissolve carbohydrates: properties and descriptions 8.4 Ionic liquids in carbohydrate synthesis 8.5 Enzymatic processes developed in ionic liquids for carbohydrate synthesis: lipases and glycosidases 8.5.1 Lipases in carbohydrate synthesis 8.5.2 Glycosidases in carbohydrate synthesis 8.6 Conclusions Acknowledgments References 9. Recent progress in ionic liquid assisted processing and extraction of biopolymers 9.1 Introduction 9.2 Ionic liquid-assisted dissolution and processing of biopolymers 9.2.1 Chitin and chitosan 9.2.2 Agar/agarose, guar gum, and starch 9.2.2.1 Agar/agarose 9.2.2.2 Guar gum 9.2.2.3 Starch 9.2.3 Silk and hydroxyapatite 9.2.3.1 Silk fibroin 9.2.3.2 Hydroxyapatite 9.2.4 Collagen and keratin 9.2.4.1 Collagen 9.2.4.2 Keratin 9.3 Relevant properties of ionic liquids for biopolymer dissolution and Processing 9.4 Conclusions and prospects Acknowledgments References 10. Ionic liquids for biomass biotransformation 10.1 Introduction 10.2 Ionic liquid pretreatment prior to enzymatic transformation of biomass 10.2.1 Ionic liquid pretreatment: the key to unlocking biomass recalcitrant structures 10.2.2 Understanding ionic liquids power to dissolve lignocellulosic biomass and chitin 10.2.3 Enhanced enzymatic hydrolysis of lignocellulosic biomass and chitin in ionic liquids 10.3 In situ enzymatic transformation of biomass in ionic liquid-aqueo 10.3.1 Concept and scientific challenge 10.3.2 Focus on enzymatic hydrolysis of polysaccharidic fractions from representative biomass in presence of ionic liquids 10.3.3 Focus on enzymatic depolymerization of lignin in aqueous-ionic solutions 10.3.4 Expanding enzymatic transformation in ionic liquid-aqueous media to chitinous biomass 10.4 Biopolymer esterification: a promising alternative of lignocellulosic biomass valorization 10.4.1 Chemical esterification versus bio catalysis 10.4.2 Nonconventional reaction media for enzymatic esterification of lignocellulosic biomass polymers: a double benefit References 11. Biocatalysis in ionic liquids for a low carbon future 11.1 Introduction 11.2 Biocatalysis in ionic liquids 11.2.1 Ionic liquids as a biocatalyst modifier 11.2.2 Ionic liquids as a solvent for isolated enzyme biocatalysis 11.2.3 Ionic liquids as an enzyme coating 11.2.4 Enzymes coentrapped with ionic liquids 11.3 Chemicals and liquid fuels from biomass 11.3.1 Why use ionic liquids in biomass biocatalysis? 11.3.2 Whole cell biocatalysis for biomass conversion 11.3.3 Isolated enzyme biocatalysis for biomass conversion 11.3.3.1 Ionic liquids as a modifier and/or solvent in isolated enzyme biocatalysis 11.3.3.2 Ionic liquids in enzyme immobilization, recycling and separation 11.4 Potential applications in a hydrogen economy 11.4.1 Hydrogen metabolism in nature 11.4.2 Enzymes for fuel cells 11.4.3 Other roles for enzyme electrodes 11.4.3.1 Hydrogen evolution 11.4.3.2 Ammonia production 11.4.3.3 Chemical synthesis 11.4.4 Potential roles for ionic liquids 11.5 Conclusion and future prospects Funding References 12. Application of ionic liquids in pharmaceutics and medicine 12.1 Introduction 12.1.1 Classification of ionic liquids in the context of pharmaceutic 12.1.1.1 Single or dual active ionic liquids derived from pharmaceutical ingredients (active pharmaceutical ingredient-ionic liquids) 12.1.1.1.1 Protic active pharmaceutical ingredient-ionic liquids from active pharmaceutical ingredients 12.1.1.1.2 Aprotic active pharmaceutical ingredient-ionic liquids from active pharmaceutical ingredients 12.1.1.2 Ionic liquids not derived from known active pharmaceutical ingredients 12.2 Physicochemical properties of ionic liquids of relevance for the 12.2.1 Polymorphism 12.2.2 Solubility and dissolution rate 12.2.3 Hygroscopicity 12.2.4 Chemical and thermal stability 12.2.5 Viscosity and density 12.2.6 Biodegradation 12.2.7 Toxicity 12.3 Bioactivity of ionic liquids 12.3.1 Active pharmaceutical ingredient-ionic liquids 12.3.1.1 Antimicrobial active pharmaceutical ingredient-ionic liquids 12.3.1.2 Antitumor active pharmaceutical ingredient-ionic liquids 12.3.1.3 Antioxidant agents 12.3.2 Ionic liquids not derived from active pharmaceutical ingredient 12.3.2.1 Antimicrobial agents 12.3.2.1.1 Ionic liquids derived from aromatic imidazolium and pyridinium cations 12.3.2.1.2 Ionic liquids derived from nonaromatic quaternary ammonium cations 12.3.2.1.3 Phosphonium ionic liquids 12.3.2.2 Ionic liquids as antitumoral agents 12.4 Ionic liquids as enhancers in the pharmaceutical industry 12.4.1 Ionic liquids in the synthesis of drugs 12.4.2 Ionic liquids in drug formulation. Controlled release systems 12.4.2.1 Drug delivery strategies based on active pharmaceutical ingredient-ionic liquids 12.4.2.2 Drug delivery strategies using ionic liquids not based on known active pharmaceutical ingredients 12.4.2.2.1 Ionic liquids as chemical enhancers 12.4.2.2.2 Surface-active ionic liquids as microemulsion carriers 12.4.2.2.3 Ionic liquids as formulation components in ionic liquid-in-oil, water/ionic liquids, ionic liquids/water microemulsion 12.4.2.2.4 Ionic liquids as ionogelators 12.5 Biological mechanism of interactions 12.6 Conclusions References 13. Biocatalysis in subcritical and supercritical fluids 13.1 Introduction 13.2 High-pressure reactors for biocatalysis 13.3 Biochemical reactions in supercritical fluids 13.3.1 Enzyme inactivation 13.4 Other applications of supercritical fluids in biocatalysis 13.4.1 Release of bioactive substances from microbial and plant cells 13.4.2 Scaffolds 13.4.3 Bleaching using enzymes and supercritical fluids 13.5 Conclusion: the state of the art References 14. Biocatalytic processes in ionic liquids and supercritical carbon dioxide biphasic systems 14.1 Green chemistry: biocatalysis in organic versus neoteric solvents 14.2 Supercritical fluids and supercritical carbon dioxide 14.3 Ionic liquids 14.4 Biocatalysts in nonaqueous environments 14.5 Biocatalysis in supercritical CO2 14.6 Essentials of biocatalysis in ionic liquids 14.7 Phase behavior of ionic liquids and scCO2 mixtures 14.8 Biocatalytic processes in ionic liquid/scCO2 biphasic systems 14.8.1 Pioneering works: a new strategy found 14.8.2 Kinetic resolution 14.8.3 Dynamic kinetic resolution 14.8.4 Biodiesel synthesis 14.8.5 Other applications 14.9 Conclusions Acknowledgments References 15. Enzymatic membrane reactors and nonconventional solvents 15.1 Introduction 15.2 Membrane separation processes 15.3 Integration of a membrane separation and a catalytic reaction 15.4 Enzymatic membrane reactors 15.5 Immobilization of enzymes 15.6 Enzymes immobilized on membranes 15.7 Enzymatic membrane reactors and nonconventional solvents 15.7.1 Enzymatic membrane reactors and supercritical carbon dioxide 15.7.2 Enzymatic membrane reactors and ionic liquids 15.8 Conclusions References 16. Applied biocatalysis in deep eutectic solvents 16.1 Introduction 16.2 Hydrolases 16.2.1 Hydrolases and deep eutectic solvents in hydrolytic reactions 16.2.2 Hydrolase-catalyzed nonhydrolytic conventional reactions 16.2.2.1 Esterification reactions 16.2.2.2 Aminolysis reactions and peptide synthesis 16.2.2.3 Transesterification and transphosphatidylation reactions 16.2.3 Nonconventional biotransformations using hydrolases as catalysts 16.2.3.1 Tandem oxidative reactions mediated by lipases in deep eutectic solvents 16.3 Redox enzymes 16.3.1 Reductions 16.3.2 Oxidations 16.3.3 Hydroxyfunctionalization and dioxygenation reactions 16.4 Lyases and transferases in single transformations using deep eutectic solvents as solvents 16.5 Multicatalytic transformations 16.5.1 Combination of enzymes and organocatalysts 16.5.2 Combination of enzymes and metal species 16.6 Conclusions and perspectives References 17. Biocatalysis and green solvents: trends, needs, and opportunities 17.1 On the need of using green solvents to reach truly sustainable processes 17.2 Solvent-free processes in biocatalysis: keeping things as simpler! 17.3 Biogenic solvents for biocatalysis: recent examples related to 2-methyltetrahydrofuran, cyclopentyl-methyl ether and cyrene 17.4 Deep eutectic solvents: from proof of concept to continuous biocatalytic processes 17.5 Concluding remarks References Index