Stick / Williams Carbohydrates: The Essential Molecules of Life

2. Auflage 2010
ISBN: 978-0-08-092702-2
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 496 Seiten

This book provides the 'nuts and bolts' background for a successful study of carbohydrates - the essential molecules that not only give you energy, but are an integral part of many biological processes.
A question often asked is 'Why do carbohydrate chemistry?' The answer is simple: It is fundamental to a study of biology. Carbohydrates are the building blocks of life and enable biological processes to take place.
Therefore the book will provide a taste for the subject of glycobiology.
Covering the basics of carbohydrates and then the chemistry and reactions of carbohydrates this book will enable a chemist to gain essential knowledge that will enable them to move smoothly into the worlds of biochemistry, molecular biology and cell biology.
* includes perspective from new co-author Spencer Williams, who enhances coverage of the connection between carbohydrates and life
* describes the basic chemistry and biology of carbohydrates
* reviews the concepts, synthesis, reactions, and biology of carbohydrates

Robert Stick is a Queenslander by birth and completed his undergraduate and higher degrees at the University of Queensland. Following post-doctoral studies with Ray Lemieux and Sir Derek Barton, he took a faculty position at The University of Western Australia in 1975 and has since spent sabbatical leaves with Bert Fraser-Reid (Duke University), and with Bill Cullen and Steve Withers (both of the University of British Columbia).

Autoren/Hrsg.

Stick, Robert V.

Williams, Spencer

Inhaltsverzeichnis

1;Front Cover;1
2;Carbohydrates: The Essential Molecules of Life;4
3;Copyright Page;5
4;Table of Contents;8
5;Preface and Acknowledgements;18
6;Abbreviations;20
7;CHAPTER 1: The 'Nuts and Bolts' of Carbohydrates;24
7.1;The Early Years;24
7.2;The Constitution of Glucose and Other Sugars;30
7.3;The Cyclic Forms of Sugars, and Mutarotation;38
7.4;The Shape (Conformation) of Cyclic Sugars, and the Anomeric Effect;46
7.5;References;55
8;CHAPTER 2: Synthesis and Protecting Groups;58
8.1;Esters;59
8.1.1;Acetates;59
8.1.2;Benzoates;61
8.1.3;Chloroacetates;62
8.1.4;Pivalates;62
8.1.5;Levulinates;62
8.1.6;Carbonates, borates, phosphates, sulfates and nitrates;63
8.1.7;Sulfonates;64
8.2;Ethers;65
8.2.1;Methyl ethers;65
8.2.2;Benzyl ethers;66
8.2.3;4-Methoxybenzyl ethers;67
8.2.4;Allyl ethers;68
8.2.5;Trityl ethers;68
8.2.6;Silyl ethers;68
8.3;Acetals;70
8.3.1;Cyclic acetals;72
8.3.2;Benzylidene acetals;73
8.3.3;4-Methoxybenzylidene acetals;76
8.3.4;Isopropylidene acetals;77
8.3.5;Diacetals;80
8.3.6;Cyclohexylidene acetals;81
8.3.7;Dithioacetals;81
8.3.8;Thioacetals;81
8.3.9;Stannylene acetals;82
8.4;The Protection of Amines;84
8.5;Orthogonality;89
8.6;References;90
9;CHAPTER 3: The Reactions of Monosaccharides;98
9.1;Oxidation;98
9.2;Reduction;103
9.3;Halogenation;107
9.3.1;Non-anomeric halogenation;108
9.3.2;Anomeric halogenation;112
9.4;Alkenes and Carbocycles;116
9.4.1;Non-anomeric alkenes;116
9.4.2;Anomeric alkenes;117
9.4.3;Carbocycles;119
9.5;Anhydro Sugars;121
9.5.1;Non-anomeric anhydro sugars;122
9.5.2;Anomeric anhydro sugars;124
9.6;Deoxy, Amino Deoxy and Branched-chain Sugars;128
9.6.1;Deoxy sugars;128
9.6.2;Amino deoxy sugars;130
9.6.3;Branched-chain sugars;134
9.7;Miscellaneous Reactions;135
9.7.1;Wittig reaction;135
9.7.2;Thiazole-based homologation;136
9.7.3;Mitsunobu reaction;137
9.7.4;Orthoesters;138
9.8;Industrially Important Ketoses;140
9.8.1;D-Fructose;140
9.8.2;L-Sorbose;142
9.8.3;Isomaltulose;142
9.8.4;Lactulose;143
9.9;Aza and Imino Sugars;144
9.10;References;147
10;CHAPTER 4: Formation of the Glycosidic Linkage;156
10.1;General;158
10.1.1;The different glycosidic linkages;158
10.1.2;The mechanism of glycosidation;159
10.1.3;Ion pairs and the solvent;159
10.1.4;The substituent at C2;160
10.1.5;The 'armed/disarmed' concept;160
10.1.6;The 'torsional control' concept;161
10.1.7;The 'latent/active' concept;162
10.1.8;Activation of the glycosyl acceptor;162
10.1.9;The concept of 'orthogonality';163
10.1.10;'Reciprocal donor/acceptor selectivity';163
10.2;Hemiacetals;164
10.3;Glycosyl Esters;167
10.4;Glycosyl Halides and Orthoesters;168
10.4.1;The Koenigs–Knorr reaction (1,2-trans);169
10.4.2;The orthoester procedure (1,2-trans);171
10.4.3;Halide catalysis (1,2-cis);173
10.4.4;Glycosyl fluorides (1,2-cis and 1,2-trans);175
10.5;Glycosyl Imidates (1,2-cis and 1,2-trans);176
10.6;Thioglycosides (1,2-cis and 1,2-trans);179
10.7;Seleno- and Telluroglycosides;183
10.8;Glycosyl Sulfoxides (sulfinyl glycosides; 1,2-cis and 1,2-trans);185
10.9;Glycals;187
10.10;4-Pentenyl Activation (1,2-cis and 1,2-trans);189
10.11;ß-D-Mannopyranosides (1,2-cis);192
10.11.1;Glycosyl halides;192
10.11.2;Glycosyl sulfoxides (and thioglycosides);193
10.11.3;ß-D-Glucopyranoside to ß-D-mannopyranoside;194
10.11.4;Intramolecular aglycon delivery;195
10.11.5;Other methods;196
10.12;ß-Rhamnopyranosides (1,2-cis);197
10.13;2-Acetamido-2-deoxy Glycosides;197
10.14;2-Deoxy Glycosides;201
10.15;Sialosides;203
10.16;Furanosides;204
10.17;Miscellaneous Methods;205
10.17.1;Alkenyl glycosides;205
10.17.2;Remote activation;206
10.18;C-Glycosides;209
10.18.1;The addition of carbanions to anomeric electrophiles;210
10.18.2;The addition of electrophiles to anomeric carbanions;211
10.18.3;Glycosyl radicals;213
10.18.4;Miscellaneous;214
10.19;References;214
11;CHAPTER 5: Oligosaccharide Synthesis;226
11.1;Strategies in Oligosaccharide Synthesis;226
11.1.1;Linear syntheses;227
11.1.2;Convergent syntheses;229
11.1.3;Two-directional syntheses;229
11.1.4;'One-pot' syntheses;230
11.2;Polymer-supported Synthesis;233
11.2.1;Types of polymers;234
11.2.2;Linkers;235
11.2.3;Attachment of the sugar to the linker/polymer;236
11.2.4;The glycosyl donors used;236
11.2.5;Insoluble versus soluble polymers;236
11.2.6;Trichloroacetimidates;237
11.2.7;Pentenyl glycosides;238
11.2.8;Glycosyl sulfoxides;238
11.2.9;Thioglycosides;239
11.2.10;Glycals;239
11.2.11;Automated oligosaccharide synthesis;240
11.2.12;Combinatorial synthesis and the generation of 'libraries';240
11.3;References;242
12;CHAPTER 6: Monosaccharide Metabolism;248
12.1;The Role of Charged Intermediates in Basic Metabolism;248
12.2;Glucose-6-phosphate: a Central Molecule in Carbohydrate Metabolism;249
12.3;Glycolysis;250
12.4;The Fate of Pyruvate in Primary Metabolism;253
12.4.1;Under aerobic conditions;253
12.4.2;Under anaerobic conditions;253
12.5;Gluconeogenesis;254
12.6;The Pentose Phosphate Pathway;255
12.7;The Glyoxylate Cycle;257
12.8;Biosynthesis of Sugar Nucleoside Diphosphates;258
12.8.1;Nucleotidylyltransferases;258
12.8.2;Biosynthesis of UDP-glucose, UDP-galactose and galactose;259
12.8.3;Biosynthesis of UDP-glucuronic acid and UDP-xylose;261
12.8.4;Biosynthesis of GDP-mannose;262
12.8.5;Biosynthesis of UDP-N-acetylglucosamine and UDP-N-acetylgalactosamine;263
12.8.6;Biosynthesis of UDP-N-acetylmuramic acid;265
12.8.7;Biosynthesis of GDP-fucose;265
12.8.8;Biosynthesis of furanosyl nucleoside diphosphates: UDP-galactofuranose and UDP-arabinofuranose;266
12.9;Biosynthesis of Sialic Acids and CMP-Sialic Acids;267
12.10;Biosynthesis of myo-Inositol;269
12.11;Biosynthesis of L-Ascorbic Acid;270
12.12;References;272
13;CHAPTER 7: Enzymatic Cleavage of Glycosides: Mechanism, Inhibition and Synthetic Applications;276
13.1;Glycoside Hydrolases;276
13.2;Retaining and Inverting Mechanisms;278
13.2.1;Sequence-based classification of glycoside hydrolases;278
13.2.2;Mechanism of inverting glycoside hydrolases;279
13.2.3;Mechanism of retaining glycoside hydrolases that use carboxylic acids as nucleophiles;279
13.2.4;Mechanism of retaining glycoside hydrolases that use tyrosine as a catalytic nucleophile;281
13.2.5;Mechanism of retaining glycoside hydrolases that use substrate-assisted catalysis;281
13.3;Unusual Enzymes that Catalyse Glycoside Cleavage;282
13.4;Transglycosidases;285
13.5;Structure-based Studies of Glycoside Hydrolases;286
13.6;Reagents and Tools for the Study of Glycoside Hydrolases;288
13.7;Non-covalent Glycoside Hydrolase Inhibitors;291
13.8;Exploitation of Glycoside Hydrolases in Synthesis;295
13.8.1;Thermodynamic control (reversed hydrolysis);296
13.8.2;Kinetic control (transglycosidation);296
13.9;Glycosynthases: Mutant Glycosidases for Glycoside Synthesis;299
13.10;Thioglycoligases: Mutant Glycosidases for Thioglycoside Synthesis;301
13.11;Hehre Resynthesis/Hydrolysis Mechanism;302
13.12;References;303
14;CHAPTER 8: Glycosyltransferases;308
14.1;Classification and Mechanism;308
14.1.1;Classification;309
14.1.2;Mechanism;309
14.2;Glycosyltransferases and the 'One-enzyme One-linkage' Hypothesis;314
14.3;Sequence-based Classification and Structure;315
14.4;Reversibility of Glycosyl Transfer by Glycosyltransferases;316
14.5;Inhibitors of Glycosyltransferases;317
14.5.1;'Direct' inhibition of glycosyltransferases;317
14.5.2;Therapeutically-useful glycosyltransferase inhibitors;322
14.5.3;'Indirect' inhibition of glycosyltransferases by metabolic interference;324
14.6;Chemical Modification of Glycoconjugates Using Metabolic Pathway Promiscuity;326
14.7;Use of Glycosyltransferases in Synthesis;328
14.7.1;Enzymatic synthesis using glycosyltransferases and sugar (di)phosphonucleoside donors;329
14.7.2;Multienzyme systems including sugar (di)phosphonucleoside generation and recycling;334
14.7.3;Synthesis using glycosyltransferases in engineered whole cell systems;337
14.8;References;339
15;CHAPTER 9: Disaccharides, Oligosaccharides and Polysaccharides;344
15.1;Cellulose and Cellobiose;344
15.2;Starch, Amylopectin, Amylose and Maltose;347
15.3;Glycogen;349
15.4;Cyclodextrins;350
15.5;Sucrose, Sucrose Analogues and Sucrose Oligosaccharides;351
15.6;Lactose and Milk Oligosaccharides;354
15.7;Fructans;356
15.8;Chitin and Chitosan;357
15.9;Trehalose and Trehalose Oligosaccharides;358
15.10;1,3-ß-Glucans;360
15.11;Mannans;361
15.12;References;362
16;CHAPTER 10: Modifications of Glycans and Glycoconjugates;366
16.1;Epimerization;367
16.2;Sulfation;368
16.2.1;Sulfotransferases;368
16.2.2;Sulfatases;368
16.2.3;Sulfated glycosaminoglycans;369
16.2.4;Heparin;370
16.2.5;Nodulation factors;372
16.2.6;Sulfated carbohydrates from halophilic bacteria;372
16.2.7;Mycobacterial sulfoglycolipids;373
16.2.8;Sulfated nucleosides;374
16.2.9;Sulfation in inflammation;374
16.2.10;Sulfatide and seminolipid;375
16.3;Phosphorylation;376
16.3.1;Mannose-6-phosphate;376
16.3.2;Phosphoglycosylation in Leishmania and other protists;377
16.3.3;Teichoic acids;378
16.3.4;Other phosphoglycans;379
16.4;Carboxylic Acid Esters;380
16.4.1;Acylated bacterial antigens;380
16.4.2;Mycobacterial fatty acid esters;382
16.4.3;Carboxylic acid esters in hemicelluloses;383
16.5;Modifications of Sialic Acids;385
16.6;Other Carbohydrate Modifications;386
16.7;References;387
17;CHAPTER 11: Glycoproteins and Proteoglycans;392
17.1;N-Linked Glycosylation;393
17.1.1;Biosynthesis of the lipid-linked oligosaccharide;394
17.1.2;Transfer of the lipid-linked oligosaccharide;395
17.1.3;N-Glycan trimming and the calnexin/calreticulin cycle;396
17.1.4;Golgi processing of N-linked glycans;397
17.1.5;ER-associated protein degradation;398
17.1.6;Diversity of N-linked glycans;399
17.1.7;Inhibitors of N-linked glycoprotein biosynthesis;400
17.2;Modification of N-Linked Glycans for Lysosomal Targeting;401
17.3;O-Linked Mucins/Proteoglycans, Blood Group Antigens and Xenorejection;402
17.3.1;'Mucin-type' O-linked glycosylation;402
17.3.2;The blood group antigens;405
17.3.3;Xenotransplantation and the a-1,3-Gal epitope;409
17.4;O-Linked N-Acetyl-ß-D-glucosamine;410
17.5;Glycosylphosphatidylinositol Membrane Anchors;412
17.6;Other Types of Protein Glycosylation;415
17.6.1;O-Fucose;415
17.6.2;C-Mannose;416
17.6.3;O-Mannose glycans;416
17.6.4;Rare protein modifications;417
17.7;Proteoglycans and Glycosaminoglycans;418
17.7.1;Hyaluronan;419
17.7.2;Chondroitin sulfate/dermatan sulfate;420
17.7.3;Keratan sulfate;421
17.7.4;Heparin and heparan sulfate;422
17.8;Lysosomal Degradation of Glycoconjugates;425
17.8.1;N-Linked glycoprotein degradation;426
17.8.2;Glycosaminoglycan degradation;427
17.8.3;Treatment of lysosomal storage disorders with imino sugar inhibitors;431
17.9;References;433
18;CHAPTER 12: Classics in Carbohydrate Chemistry and Glycobiology;436
18.1;The Immucillins: Transition-state Analogue Inhibitors of Enzymic N-Ribosyl Transfer Reactions;436
18.2;Development of a Candidate Anti-toxic Malarial Vaccine;445
18.3;Synthetic Carbohydrate Anti-tumour Vaccines;451
18.4;New and Improved Anticoagulant Therapeutics Based on Heparin;458
18.5;References;465
19;APPENDIX I;468
19.1;Reagents for O-Protecting Group Removal;468
19.2;Reagents for N-Protecting Group Removal;469
20;APPENDIX II;470
20.1;Carbohydrate Nomenclature;470
20.2;The Literature of Carbohydrates;470
20.2.1;Reference literature;470
20.2.2;Primary literature;471
20.2.3;Monographs and related works;471
20.2.4;Recent edited works;472
20.2.5;Recent textbooks;473
20.2.6;Miscellaneous;474
21;EPILOGUE;476
22;INDEX;484