Biocatalysis in Green Solvents

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 engineering
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
References
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 systems
7.3 Biocatalysis in aqueous biphasic systems
7.3.1 Biocatalysis in ionic-liquid-based aqueous biphasic systems
7.4 Concluding remarks
Acknowledgments
References
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-aqueous media
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 liquid 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 pharmaceutics and medicine
12.1.1.1 Single or dual active ionic liquids derived from pharmaceutical ingredients (active pharmaceutical ingredient-ioni...
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 pharmaceutical industry
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 ingredients with biological activity
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 microem...
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 simple as possible, but not simpler!
17.3 Biogenic solvents for biocatalysis: recent examples related to 2-methyltetrahydrofuran, cyclopentyl-methyl ether and c...
17.4 Deep eutectic solvents: from proof of concept to continuous biocatalytic processes
17.5 Concluding remarks
References
Index