Carbohydrate Chemistry: Chemical and Biological Approaches Volume 45 (Chemical and Biological Approaches, 45)

In many fields, most notably medicine and molecular biology, the understanding of the structure and function of carbohydrates and glycoconjugates remains vital. This new volume contains critical reviews covering the latest findings in both chemical and biological sciences, and demonstrates the interdisciplinary nature of modern carbohydrate research. This book addresses diverse applications that continue to be major challenges for carbohydrate chemists. The book starts with a review of Gérard Descotes contribution to the field as a pioneer of French modern carbohydrate chemistry. Green nanocatalytic oxidation of free sugars, photosensitive glycomacrocycles, the application of disaccharides in supramolecular chemistry, recent advances in the radiation chemistry of polysaccharides, and the cell wall pectic rhamnogalacturonan II, an enigma in plant glycobiology are just some of the diverse topics presented in Volume 45. This set of reports will certainly benefit any researcher who wishes to learn about the latest developments in the carbohydrate field. Cover Half Title Carbohydrate Chemistry. Chemical and Biological Approaches: Volume 45 Copyright Preface Gérard Descotes: a pioneer of Frenchmodern carbohydrate chemistry Acknowledgements Author biographies Contents Applications of fluorous tag methodology in carbohydrate synthesis 1. Introduction 2. Why use F-tags in carbohydrate synthesis? 3. Reducing sugar anomeric fluorous tags and ponytails 3.1 Cleavable anomeric fluorous tags 3.2 Non-cleavable anomeric fluorous ponytails 4. Terminal protecting group fluorous tags 5. Late-stage protecting group fluorous tags 5.1 Fluorous ester groups 5.2 Fluorous O-carbamates 5.3 Fluorous silyl groups 5.4 Fluorous cap and tag solid-phase oligosaccharide synthesis 5.5 Fluorous mixture synthesis of oligosaccharides 6. Iterative protecting group fluorous tags 6.1 Iterative double tag reducing-to-non-reducing oligosaccharide synthesis 7. Activatable fluorous thioglycoside groups 8. N-protecting groups 9. Phosphate protecting groups 10. Conclusions and future developments Note References Recent progress in the glycosylation of lupanes 1. Introduction 2. Glycosylation with glycosyl halides and orthoesters 3. Glycals as glycosyl donors 4. Glycosyl trichloroacetimidates as glycosyl donors 5. Synthesis of lupane bidesmosides 6. Miscellaneous glycosylation methods 7. Acyl migration and rearrangements during the synthesis of lupane saponins 8. Cytotoxic activity of lupane saponins 9. Conclusions Acknowledgements References Synthetic routes targeting agrocinopines, bacterial carbohydrate phosphodiesters, and their analogues 1. Introduction 2. Synthetic approaches towards agrocinopines and analogues 2.1 Agrocinopine A 2.2 Agrocinopine B 2.3 Agrocinopine C 2.3.1 D-glucos-2-yl sucros-6-yl phosphate 2.3.2 D-glucos-2-yl sucros-2-yl phosphate 2.4 Agrocinopine D 2.5 Arabinose 2-phosphate (A2P) and derivatives 2.6 D-Glucose 2-phosphate (G2P) and derivatives 2.7 Agrocin 84 3. Conclusions Acknowledgements Addition at the proof stage References Glycosylation in the green chemistry era 1. What is green chemistry? 2. Biological importance of glycosylation 3. General aspects of glycosylation chemistry 4. Chemical glycosylation 5. Synthesis of glycosides in environmentally benign solvents 6. Development of glycosyl donor chemistry 7. Enzymatic glycosylations 8. Electrochemical glycosylations 9. Photochemical glycosylations 10. Summary Acknowledgements References Sonogashira cross-coupling on carbohydrate templates 1. Introduction 2. Carbohydrate-connected medium- size cycles and macrocycles 3. Clusters/dendrimers containing carbohydrate units 4. Synthesis of natural products comprising a carbohydrate moiety 5. Functionalized glycals 6. C-Glycosides 7. Final considerations References Recent advances in the functionalization of unprotected carbohydrates 1. Introduction 2. Chemical glycosylation of free glycosides 2.1 O-glycosylation 2.2 N-glycosylation 2.3 C-glycosylation 2.4 Photocatalyzed glycosylation 3. Biocatalyzed glycosylation of free glycosides 3.1 Carbohydrate-active enzymes 3.2 Examples of enzymatic glycosylations 4. Chemical transformations in green solvents 4.1 Ionic liquids (IL) 4.2 Deep eutectic solvent (DES) 4.3 Water 5. Conclusions and outlook References Catalytic access to anhydrohexitols and their isomerization 1. Introduction: the industrial leading anhydrohexitols 2. The synthesis of isosorbide from sorbitol 2.1 Selectivity issues in the sorbitol anhydrisation steps 2.2 Homogeneous catalysts for sorbitol dehydration 2.3 Heterogeneous catalysts for sorbitol dehydration 3. The direct synthesis of isosorbide from cellulose 4. The synthesis of isomannide 5. The synthesis of isoidide 5.1 Laboratory scale synthesis of isoidide 5.2 Direct isomerization from isosorbide or isomannide 5.2.1 Heterogeneous organometallic catalysis 5.2.2 Homogeneous organometallic catalysis 5.2.3 Related intermediates to the oxidation step and further applications 5.2.3.1 Specific studies on the first step of oxidation 5.2.3.2 Applications 6. Conclusion References In situ formation of nucleotide-sugars from simple substrates for glycosyltransferase-catalyzed reactions 1. Introduction 2. Non-natural glycosyl donors 2.1 Glycosyl fluorides 2.2 Nitrophenyl glycosides 3. Natural saccharides as starting compounds 3.1 In vitro enzymatic coupling 3.2 Sugar-1-phosphate as intermediate 3.2.1 Glucose 3.2.2 Galactose 3.2.3 N-Acetylhexosamines 3.2.4 Glucuronic acid 3.2.5 Fucose 3.3 CMP-sialic acid synthetase 3.4 Sucrose synthase 4. Metabolic engineering 5. Conclusion References Enzymes as synthetic tools for the production of pentose-based molecules of interest 1. Introduction 2. The use of hemicellulases in synthesis 2.1 α-L-arabinofuranosidases 2.2 β-D-xylosidases 2.3 Xylanases 3. Lipases in the synthesis of pentose-based esters 4. An integrated approach from lignocellulosic biomass 5. Conclusions and perspectives Abbreviations Acknowledgements References Sugar- based organogelators 1. Introduction 2. Monosaccharides 2.1 Hexose-based organogelators 2.1.1 Glucoside derivatives 2.1.2 Galactoside derivatives 2.1.3 Mannoside derivatives 2.2 Pentoses and nucleosides 3. Disaccharides 4. Open forms 5. Structure/property relationships 6. Conclusions References Chemical synthesis of oligosaccharides on soluble support 1. Introduction 2. Polymeric supports 2.1 Linear MPEG 2.2 Polar dendrimers 2.3 Branched PEG 2.4 Poly(2-hydroxyethylmethacrylate) 2.5 Non polar dendrimer 3. Hydrophobic alkyl chains 3.1 Hydrophobic alkyl chains and liquid–liquid extractions 3.2 Hydrophobic alkyl chains and liquid solid partition 4. Ionic tags 5. Fluorinated supports 6. Conclusion References Disaccharides as building blocks for novel glycomacrocycles 1. Introduction 2. Macrocyclic receptors built on monosaccharides 3. Macrocyclic receptors built on disaccharides 3.1 Application of sucrose for the preparation of macrocyclic chiral receptors 3.2 Macrocyclic derivatives with sucrose scaffold 3.3 Macrocyclic dimers with sucrose scaffold 3.4 Connection of the terminal positions in sucrose via the long polyhydroxylated carbon bridge 4. Cryptands with saccharide platform 4.1 Cryptands and molecular cages containing disaccharide scaffold 5. Conclusion Acknowledgements References Synthesis and properties of photosensitive glycomacrocycles 1. Introduction 2. Fluorescent glycomacrocycles 2.1 Synthesis 2.2 Properties 2.2.1 Fluorescent chemosensors 2.2.2 DNA intercalators 2.2.3 Chiroptical and circularly polarized luminescence properties 3. Photochromic glycomacrocycles 3.1 Glycomacrocycles with azobenzene linked to the anomeric position 3.2 Glycomacrocycles with azobenzene linked to a monosaccharide 3.3 Glycomacrocycles with azobenzene linked to the 6-position of carbohydrate 4. Conclusion and outlook List of abbreviation References Cyclopeptides as glycan-presenting multivalent scaffolds 1. Introduction 2. Multivalent glycocyclopeptides as anti-adhesive molecules 2.1 Carbohydrate binding proteins from virus and toxins 2.2 Bacterial adhesins 3. Fully synthetic anticancer vaccines 4. Conclusion and perspectives Acknowledgements References FimH antagonists prevent biofilm formation on catheter surfaces 1. Introduction 2. Results 2.1 Concentration-dependent prevention of UPEC biofilm formation by FimH antagonists 2.1.1 Type 1 pili-dependent biofilm formation in human urine 2.1.2 Prevention of UPEC biofilm formation in urine 2.1.3 Prevention of UPEC biofilm formation on catheter surfaces 2.1.4 Enhanced effect of combination therapy on biofilm formation 3. Discussion 4. Materials and methods 4.1 Bacterial strains 4.2 Bacterial cultivation 4.3 Collection of human urine 4.4 96-well plate crystal violet (CV) staining assay 4.5 Microscopy 4.6 Catheter-associated biofilm model Funding information Acknowledgements References Recent progress in O-acetylated gangliosides analysis and functions in cancer 1. Introduction 2. Structure and biosynthesis of gangliosides 2.1 Ganglioside structure and biosynthesis 2.2 Regulation of glycosylation enzymes 2.3 O-acetylation of gangliosides 3. New approaches for the analysis of O-acetylated gangliosides 3.1 Use of mAbs and lectins to detect O-acetylated gangliosides 3.2 MS analysis of O-acetylated gangliosides 4. Expression and roles of O-acetylated gangliosides in cancer 4.1 Expression pattern of O-acetylated gangliosides in cancer 5. Use of O-acetylated gangliosides as targets for cancer immunotherapy 6. Conclusion References The cell wall pectic rhamnogalacturonan II, an enigma in plant glycobiology 1. Introduction 2. Distribution and structure of RG-II in the plant kingdom 3. Dimerization and conformation of RG-II 4. Biosynthesis of RG-II monosaccharides 5. Biosynthesis and dimerization of RG-II 6. Localisation of RG-II in the plant cell 7. Borate cross- linking of RG-II is required for plant development 8. Biological functions of RG-II 8.1 RG-II dimerization deficiency affects the cell wall ultrastructure 8.2 RG-II is required for cell elongation 9. Perspectives Abbreviations Acknowledgements References Diagnostic glycotools 1. Introduction 2. The specific glycans in pathological states 2.1 Glycans in microbial strains: viruses and bacteria 2.2 Glycans in tumor and inflammation 3. Diagnostic tools 3.1 Diagnostic tools functionalized with glycans 3.2 Tools functionalized with lectins and antibodies 4. Conclusions and perspectives Abbreviations References Recent advances in the radiation chemistry of destructured starch and other glucans as model compounds 1. Overview of the context 1.1 Status of starch-based materials amongst bioplastics 1.2 Chemical modification of polysaccharides: radiation-mediated processes as an alternative 1.3 Radiation chemistry of polysaccharides: basic aspects 2. Radiation-induced modification of destructured starch 2.1 Physical stabilization by radiation grafting of allyurea, as a reactive plasticizer 2.2 Radiation processing of thermoplastic starch–lignin blends 2.3 Surface properties and water sorption46 3. Influence of cinnamyl alcohol and glycerol on the behaviour of model glucans 3.1 Radiation effects on maltodextrin 3.2 Radiation effects on pullulan 4. Conclusion Acknowledgements References Polyester thermosets from carbohydrates 1. Introduction 2. Generality on polyesterification applied to thermosetting polymers 3. Polyester thermosets from carbohydrates in the literature 3.1 Crosslinked polysaccharides 3.1.1 Esterification of cotton cellulose 3.1.2 Esterification of starch films 3.1.3 Other natural materials 3.1.4 Mechanism of crosslinked reaction of polysaccharides through esterification 3.2 Crosslinked materials from hydrogenated carbohydrates 4. Toward thermosetting polymers from natural low transition temperature mixtures 4.1 Natural low transition temperature mixtures (NaLTTM) 4.2 Polymerization of NaLTTM 4.2.1 Na-LTTM from carbohydrates and polycarboxylic acids 4.2.2 Toward thermosets 5. Conclusion References