Deep Eutectic Solvents

Diego J. Ram??n is full professor at the University of Alicante, Spain, since 2010. His current research interests lie in the eld of organometallic chemistry and asymmetric synthesis. Gabriela Guillena is full professor and Head of the Department of Organic Chemistry at the University of Alicante, Spain. Her research is focused on new methodologies and asymmetric organocatalysis.

• Preface xiii1 Synthesis and Properties 1Karine De Oliveira Vigier and Francois Jerome1.1 Introduction 11.2 Synthesis 21.3 Properties 41.3.1 Freezing Point (Tf) 41.3.2 Density 51.3.3 Viscosity 111.3.4 Ionic Conductivity 161.3.5 Polarity 191.3.6 Surface Tension 191.4 Summary and Conclusions 21References 212 Structure and Implications 25Oliver S. Hammond and Karen J. Edler2.1 Introduction 252.2 Nanostructure of DES 262.2.1 Complex Ion Model 262.2.2 An Extended Hydrogen Bond Network Model: “Alphabet Soup” 272.2.3 Non‐cholinium DES 362.3 Conclusions and Implications 38Abbreviations 40References 403 Toxicity and Biodegradability of Deep Eutectic Solvents and Natural Deep Eutectic Solvents 43Zhen Yang3.1 Introduction 433.2 Toxicity to Microorganisms 443.2.1 Toxicity to Bacteria 443.2.2 Toxicity to Other Microorganisms 473.3 Toxicity to Animals 483.3.1 In Vitro Toxicity Tests on Vertebrates and Invertebrates 483.3.2 Cytotoxicity 493.3.3 In Vivo Acute Toxicity Tests and Pharmacokinetics 533.4 Toxicity to Plants 553.5 Biodegradability 563.6 Summary and Conclusions 57Abbreviations 58References 594 Natural Deep Eutectic Solvents: From Their Discovery to Their Applications 61Henni Vanda, Robert Verpoorte, Peter G. L. Klinkhamer, and Young H. Choi4.1 Introduction 614.2 Natural Deep Eutectic Solvents is a Concept Based on How Physicochemical Features Could Be Used for Biological Functions 634.3 Extraction and Solubilization of Non‐water‐Soluble Metabolites 664.4 Solvents for Macromolecules 694.4.1 Application of ILs and DES to Macromolecules 694.4.2 Recent NADES Application for DNA, RNA, and Proteins 704.5 Application to Enzyme Reactions 754.6 Pharmaceutical Applications 764.7 Perspective of NADES 76Abbreviations 79References 795 Hydrophobic Deep Eutectic Solvents 83Samah E.E. Warrag and Maaike C. Kroon5.1 Introduction 835.2 Physiochemical Properties of Hydrophobic DESs 845.2.1 Density 855.2.2 Viscosity 865.3 Thermal Stability Window 865.4 Applications of Hydrophobic DESs 875.4.1 The Extraction of Fatty Acids and Biomolecules from Water 875.4.2 The Removal of Transition Metal Ions from Water 895.4.3 Impregnation in Membranes 905.4.4 The Removal of Pesticides from Water 905.4.5 CO2 Capture 905.5 Prediction of the Hydrophobic DESs Phase Behavior 915.5.1 The Use of PC‐SAFT 915.6 Outlook and Recommendations 92Abbreviations 92References 936 Deep Eutectic Solvents: Exploring Their Role in Nature 95Rita Craveiro, Francisca Mano, Alexandre Paiva, and Ana Rita C. Duarte6.1 (Introduction) DES in Nature 956.2 Honey 976.2.1 Behind Beehive: How Honey is Really Produced? 986.2.2 Honey and Its Properties 996.2.3 Honey as the First THEDES 996.3 Maple Syrup: How is Maple Syrup Produced? 1006.3.1 Maple Syrup Nutraceutical Value 1016.3.2 Maple Syrup and NADES 1026.4 Sugar Beet 1026.5 Resurrection Plants 1066.6 Summary and Conclusions 107Abbreviations 107Acknowledgments 108References 1087 Organic Synthesis in DESs 111Filippo M. Perna, Paola Vitale, and Vito Capriati7.1 Introduction 1117.2 DESs in Organocatalysis 1127.3 DESs in the Synthesis of Heterocycles 1167.3.1 Synthesis of Nitrogen‐ or Nitrogen‐ and Oxygen‐Containing Rings in DESs 1177.3.2 Synthesis of Thiophenes in DESs 1197.3.3 Synthesis of Benzo‐Condensed Rings in DESs 1207.4 Multicomponent Reactions in DESs 1237.4.1 Multicomponent Reactions in the Synthesis of Heterocycles 1237.4.2 Synthesis of Betti Bases in DESs 1287.4.3 Ugi and Passerini Reactions 1287.5 Miscellaneous Transformations in DESs 1297.6 Conclusion and Perspective 130Abbreviations 131References 1328 DES as Catalyst 135Mehran Shahiri‐Haghayegh and Najmedin Azizi8.1 Introduction 1358.2 DES Promoted Organic Transformations 1368.2.1 Fischer Indole Synthesis 1368.2.2 Carbon–Carbon Bond Formation 1388.2.3 Synthesis of Pyrroles 1418.2.4 Oxidation Reactions 1418.2.5 “Green” Multicomponent Reactions 1428.2.5.1 Isocyanide‐Based MCRs 1438.2.5.2 Mannich‐Type Reactions 1448.2.5.3 Biginelli Reaction 1478.2.5.4 Synthesis of Chromene, Pyran, and Spiroxindole Derivatives 1498.2.5.5 Multicomponent Synthesis of Pyrrole and Pyrazole 1498.2.5.6 Synthesis of Quinazoline 1538.2.5.7 A3‐Coupling Reaction 1538.3 Desulfurization of Fuels 1548.3.1 Olefin Alkylation of Thiophenic Sulfur 1558.3.2 Oxidative Desulfurization of Fuels 1568.4 Biodiesel Production 1578.4.1 Transesterification of Triglycerides 1588.4.2 Esterification of Free Fatty Acids 1598.4.3 Hydrolysis/Dehydration of Carbohydrates 1608.5 CO2 Chemical Fixation 1618.6 Chemical Recycling of Polymers 1638.7 Epoxy Resin Crosslinking 1658.8 Supramolecular Macrocyclic Host Synthesis 1668.9 Conclusion 166References 1679 Metal‐Promoted Organic Transformation in DES 171Cristian Vidal and Joaquin Garcia‐Alvarez9.1 Introduction 1719.2 Design of New Synthetic Sustainable Organic Procedures Coupling Deep Eutectic Solvents and Highly‐Polarized Organometallic Reagents (RLi and RMgX) 1739.3 Transition‐Metal‐Catalyzed Organic Reactions in Deep Eutectic Solvents 1779.3.1 Palladium Catalyzed C–C Coupling Reactions in DESs 1779.3.2 Ruthenium Catalyzed Isomerization of Allylic Alcohols and Design of One‐Pot Tandem Reactions in DESs 1799.3.3 Gold Catalyzed Cycloisomerizations of Unsaturated Organic Substrates in DESs 1809.4 Summary and Conclusions 181Abbreviations 182Acknowledgments 182References 18310 Polymerizations 187Josue D. Mota‐Morales10.1 Introduction 18710.2 Deep Eutectic Solvents and Green Chemistry 18810.3 The Role of Deep Eutectic Solvents in Polymerizations 18910.3.1 Polymerizations Carried Out in Deep Eutectic Solvents 18910.3.2 Polymerization of Monomers Containing Deep Eutectic Solvents: DES Monomers 19110.3.3 DES as Cosolvents and Auxiliaries in Polymerizations 19210.3.4 Cooperative Hydrogen Bonding Network of Water Added to DESs 19410.4 Mechanisms of Polymerization Explored 19410.4.1 Polycondensation 19410.4.2 Free‐Radical Polymerization 19710.4.3 Ring Opening Polymerization 20710.4.4 Other Mechanisms of Polymerizations 20910.5 Outlook and Future Directions 210Abbreviations 212References 21211 Extraction of Bioactive Compounds 217Mohamad H. Zainal‐Abidin, Maan Hayyan, Gek C. Ngoh, Won F. Wong, and Adeeb Hayyan11.1 Introduction 21711.2 The Main Features of DESs as an Extractive Agent 21811.2.1 Effect of Water Addition on Extraction Efficiency 21911.3 DESs in the Bioactive Compound Extractions 22111.3.1 Phenolic Compounds 22211.3.1.1 Flavonoid Compounds 22511.3.2 Polysaccharides 22611.3.3 Proteins 22711.3.4 Hydrophobic Compounds 22811.4 Summary 230Abbreviations 230References 23112 Processing of Biomass in Deep Eutectic Solvents 235Miao Zuo, Xianhai Zeng, Yong Sun, Xing Tang, and Lu Lin12.1 Introduction 23512.2 Chemical Process of Products Extraction from Biomass in DESs 23512.2.1 Extraction and Solubility of Lignocellulose in DESs 23512.2.2 Value‐Added Products Extraction from Biomass in DESs 23812.3 Modification of Cellulose in DESs 24012.4 Catalytic Conversion of Carbohydrates in DESs 24212.4.1 Catalytic Conversion of Carbohydrates in Neat DESs 24212.4.2 HMF Production from Carbohydrates in Bio‐Based DESs 24412.4.3 Carbohydrates Dehydration in Biphasic DES/Organic Solvent Systems 24612.4.4 Carbohydrates Dehydration to Other Value‐Added Products in DESs 24912.5 Conclusions and Prospects 251Abbreviations 252Acknowledgments 252References 25313 Enzyme Catalysis: In DES, with DES, and in the Presence of DES 257Pablo Dominguez de Maria, Nadia Guajardo, and Selin Kara13.1 DESs as “Non‐Conventional Media” and “Non‐Conventional Solutions” for Biocatalysis 25713.2 Hydrolases and Deep Eutectic Solvents 25913.3 Oxidoreductases and Deep Eutectic Solvents 26413.4 Other Biocatalytic Concepts in Deep Eutectic Solvents 26613.5 Conclusions 267Abbreviations 268References26814 Nanoscale and Functional Materials 273Diego A. Alonso, Alejandro Baeza, Rafael Chinchilla, Cecilia Gomez, and Isidro M. Pastor14.1 Introduction 27314.2 Nanoparticulated Materials 27414.3 Nanofilms and Nanolayers 28214.4 Carbonaceous Materials 28314.5 Porous Materials 28714.6 DNA Manipulation 29014.7 Summary and Conclusions 291Abbreviations 292References 29215 Carbon Dioxide Capture 297Yingying Zhang, Xiaohua Lu, and Xiaoyan Ji15.1 Introduction 29715.2 Properties of DESs 29915.2.1 Thermophysical Properties 29915.2.1.1 Gas Solubility 29915.2.1.2 Viscosity 30515.2.1.3 Molar Heat Capacity 30915.2.2 Kinetic Property 31215.3 Screening and Evaluation of DESs for CO2 Separation 31315.3.1 Property‐Based Method 31315.3.2 Thermodynamic Analysis‐Based Method 31315.3.3 Process Simulation‐Based Method 31415.4 Further Conversion with DESs 31415.5 Conclusions 314Abbreviations 315References 31616 DES‐Mediated Approaches Toward Green Analytical Chemistry 321Federico J.V. Gomez, Magdalena Espino, Maria de los A. Fernandez, Joana Boiteux, and Maria F. Silva16.1 Introduction 32116.2 Extraction Techniques and Deep Eutectic Solvents 32316.2.1 Ultrasound Assisted Extraction (UAE) 32416.2.2 Microwave Assisted Extraction (MAE) 32516.2.3 Liquid Phase Microextraction (LPME) 32516.2.4 Solid Phase Microextraction (SPME) 32616.3 Separation Techniques and DES 32616.3.1 Gas Chromatography and DES 32716.3.2 Liquid Chromatography and DES 32716.3.3 Capillary Electrophoresis and DES 32816.4 DES Detection Techniques Compatibility 32816.5 Future Trends and Challenges for Green Solvents in Analytical Chemistry 330Abbreviations 331Acknowledgments 332References 33217 Electrochemistry 335Zhimin Xue, Wancheng Zhao, and Tiancheng Mu17.1 Introduction 33517.2 Conductivity 33617.3 Electrochemical Stability 34717.4 Electrochemical Applications 35017.4.1 Electrodeposition 35017.4.2 Electropolishing 35717.5 Summary and Conclusions 359Abbreviations 359Acknowledgments 360References 360Index 363