Topics in Current Chemistry Also Available Electronically 7
Aims and Scope 7
Preface 9
References 11
Contents 13
Sucrose: A Prospering and Sustainable Organic Raw Material 15
1 Introduction 16
2 Sustainability Efforts in Industrial Sugar Production 16
3 Reaction Pathways of Sucrose Towards Organic Chemicals 18
3.1 Degradation of the Sucrose Framework 19
3.1.1 Bioethylene Based on Sucrose 19
3.1.2 Access to 1,2-Propylene Glycol and Other Polyhydric Alcohols 20
3.1.3 5-(Hydoxymethyl)furfural and Its Derivatives 21
3.1.4 Levulinic Acid 23
3.2 Derivatization by Maintaining the Sucrose Skeleton 23
3.2.1 Sucrose Esters 24
3.2.2 Polyurethanes 25
3.2.3 Sucralose 26
3.3 Reactions and Rearrangements Maintaining the Carbohydrate Structure 27
3.3.1 Inversion of Sucrose 28
3.3.2 Novel Carbohydrates, e.g., Isomaltulose (Palatinose) and Trehalulose 29
3.3.3 Inulin, Fructooligosaccharides and Levan, Neo-Amylose, and Dextran 30
4 Outlook 33
References 33
Sucrose-Utilizing Transglucosidases for Biocatalysis 38
1 Introduction 39
2 Potential of Native Sucrose-Utilizing Transglucosidases for Glucoside Synthesis 40
2.1 A General Mechanism 41
2.2 Natural Promiscuity Is at the Heart of Large Product Diversity 44
2.2.1 Polysaccharide Synthesis 44
2.2.2 Exogenous Acceptor Glucosylation 45
3 Engineering Novel Sucrose-Utilizing Transglucosidases 50
3.1 Enzyme Engineering Strategies 51
3.2 Improving and Controlling Natural Enzyme Reactions 51
3.2.1 Altering Biocatalyst Properties 51
3.2.2 Controlling Biopolymer Product Size and Structure 52
3.3 Opportunities for Applications Through the Use of Engineered Enzymes 53
3.3.1 Synthesis of Novel Biopolymer Structures 53
3.3.2 Chemo-Enzymatic Synthesis of Antigenic Carbohydrates 54
4 Conclusion: Future Directions 56
References 57
Difructose Dianhydrides (DFAs) and DFA-Enriched Products as Functional Foods 62
1 Introduction 63
2 Natural Occurrence of Di-d-Fructose Dianhydrides 64
2.1 DFAs in Higher Plants 65
2.2 DFA-Producing Microorganisms 65
3 Synthetic Strategies to DFAs 67
3.1 DFA Formation by Treatment of Fructose and Fructose-Containing Oligo- and Polysaccharides with Mineral Acids 67
3.2 Activation of Fructose, Sucrose, Glycosylfructoses, and Inulin with Anhydrous Hydrogen Fluoride and HF-Reagents 68
3.3 Protecting Group Strategies: Intermolecular d-Fructose Dimerization 71
3.4 Rigid Spacer-Mediated Strategies: Intramolecular Spiroketalization 73
3.5 Enzymatic Strategies Towards the Synthesis of DFAs 77
4 DFAs in Nutrition 78
4.1 DFAs as Oligosaccharide Components of Caramel 79
4.2 Identification and Quantification of DFAs in Food Products by Analytical Methods 79
4.3 Preparation of DFA-Enriched Products 81
4.4 DFAs as Functional Foods 85
5 Concluding Remarks 86
References 87
Development of Agriculture Left-Overs: Fine Organic Chemicals from Wheat Hemicellulose-Derived Pentoses 91
1 Introduction 92
2 Hemicelluloses: From Wheat Bran and Straw to Pentoses 93
2.1 Wheat: Composition, Transformation and By-Products 93
2.2 Hemicelluloses: Composition, Extraction, Hydrolysis 94
3 Pentoses-Derived Surfactants 96
3.1 Alkyl Polypentosides Based on Fischer-Type Glycosylation 96
3.2 Pentose-Based Surfactants from Palladium-Catalyzed Butadiene Oligomerization 98
3.3 Pentose-Based Surfactants: Properties, Applications, and Environmental Profile 98
4 d-Xylose and l-Arabinose as Starting Materials for Fine Organic Chemistry 100
4.1 Enantiopure Building-Blocks 100
4.1.1 Masked 1,2,4-Triols 100
4.1.2 d-Xylose: A Synthon with a Latent Plane of Symmetry 101
4.1.3 Transformations of d-Xylose via Reductive Opening of a 5-Iodo-d-Xylofuranoside 101
4.1.4 Use of Mixture of d-Xylose and l-Arabinose as Starting Materials 103
4.1.5 Chain Elongation 104
4.1.6 d-Xylose-Derived Glycodendrimers 104
4.2 Synthesis of Compounds of Biological Interest 105
4.2.1 d-Xylosides as Primers of the Biosynthesis of Glycosaminoglycan Chains 105
4.2.2 Synthesis of Carbocyclic Compounds from d-Xylose 107
4.2.3 Synthesis of Sugar Analogs: Iminosugars and Thiosugars 107
4.2.4 Synthesis of l-Nucleosides 111
5 Chemistry of Furfural 112
5.1 Furfural as Starting Material for the Synthesis of Bulk Chemicals 112
5.2 Furfural as Starting Material for Fine Chemicals 114
6 Conclusion 119
References 120
Cellulose and Derivatives from Wood and Fibers as Renewable Sources of Raw-Materials 128
1 Cellulose and Hemicelluloses 129
2 Sources of Cellulose and Hemicelluloses 131
3 Cellulose and Derivatives 132
3.1 Wood to Paper 132
3.2 Chemical Modification of Cellulose 132
3.2.1 TEMPO-Mediated Oxidation 132
3.2.2 Enzymatic Modifications 135
3.3 Pharmaceutical Applications 136
3.4 Metal Absorbents 136
3.5 Cellulosic Fibers and Biocomposites 136
3.6 Cellulose Nanopaper 137
3.7 Biofuels 137
4 Conclusion 138
References 138
Olive Pomace, a Source for Valuable Arabinan-Rich Pectic Polysaccharides 140
1 Olive Fruits as Raw Materials 141
2 Olive Polysaccharides 141
3 The Olive Pomace 143
4 Olive Pomace Pectic Polysaccharides 146
5 Conclusion and Perspectives 151
References 151
Oligomannuronates from Seaweeds as Renewable Sources for the Development of Green Surfactants 153
1 Oligomannuronates as Innovative Renewable Raw Materials 154
1.1 Alginate as a Source of Mannuronate 154
1.2 Depolymerization of Polymannuronate Blocks 157
1.3 Direct Route to Oligomannuronates from Alginate 159
1.4 Direct Route to Oligomannuronates from Marine Algae 160
2 Chemical Transformations of Oligomannuronates into Surfactants 161
2.1 Synthesis of Butyl Monosaccharide and Disaccharide Mannuronates 161
2.2 Double-Tailed Surfactants 163
2.3 Single-Tailed Surfactant Acids and Salts 165
2.4 Uronamide-Type Surfactants 166
3 Physicochemical Properties of Alginate-Derived Surfactants and Potential Applications 167
3.1 CMC and Surface Tension Measurements 167
3.2 Foaming Behavior 169
3.3 Emulsification Properties 170
4 Conclusion and Perspectives 172
References 173
From Natural Polysaccharides to Materials for Catalysis, Adsorption, and Remediation 175
1 Introduction 176
1.1 Why Use These Biopolymers for Catalysis? 176
1.2 Why Use These Biopolymers for Metal Recovery? 177
2 Polysaccharides Hydrocolloids 178
2.1 Alginates 178
2.2 Chitosan 179
2.3 Carrageenans 180
3 Shaping 180
3.1 Gel Beads 181
3.2 Fiber and Hollow Fiber 181
3.3 Membranes 182
4 From Hydrocolloids to Porous Materials 182
4.1 Drying 182
4.2 Control of the Structural Properties 186
4.2.1 Alginates 186
4.2.2 Chitosan 188
4.3 Accessibility of the Functional Groups 189
4.3.1 Accessibility in the Gas Phase 190
4.3.2 Accessibility in the Liquid Phase 191
5 Perspectives Within Sustainable Development 192
5.1 Applications in Metal Remediation 192
5.1.1 Sorption Mechanisms 192
Chelation/Complexation Mechanisms 192
Ion Exchange/Electrostatic Attraction Mechanisms 194
5.1.2 Controlling Parameters 195
5.1.3 Is There Another Life for These Biopolymer-Metal Ions Composite After Metal Sorption? 196
5.2 Applications in Catalysis 197
5.2.1 Chitosan as a Catalyst 197
5.2.2 Polysaccharide Aerogels as Supports for Catalysts in Aqueous Phase 199
5.2.3 Polysaccharide Aerogels as Supports for Bifunctional Catalysts 200
5.2.4 Functionalized Chitosan as Support for Catalysts 201
5.2.5 Polysaccharide Aerogels as Supports for Metal Particles 202
6 Conclusion 203
References 204
Index 208