The biosynthesis of polysaccharides

1. The Nature of Polysaccharides.- A. General Introduction.- B. The Emerging View of Carbohydrate Structure.- C. The Sequencing of Oligo- and Poly-saccharides.- 1. The General Problem.- 2. Terminal Residues.- 3. Hydrolysis of Saccharides.- 4. Separation and Identification of Sugars.- 5. Detection and Estimation of Sugars.- 6. Degradation of Saccharides by Glycosidases.- 7. Chemical Techniques of Partial Fragmentation.- 8. Reassembly of Saccharide Sequences.- 9. Periodate Oxidation.- 10. Smith Degradation.- 11. Barry Degradation.- 12. Methylation.- 13. Lectins.- 14. Physical Methods.- D. Structures of Carbohydrates.- Further Reading.- 2. Sugar Nucleotides and Cyclitols.- A. Introduction.- B. The Discovery of Sugar Nucleotides.- C. The Detection, Analysis and Chemistry of Sugar Nucleotides.- D. Classes of Sugar Nucleotides.- E. The Use of 'Cell-Free' Systems in Studying Saccharide Assembly: Some Problems.- F. Mechanisms of Interconversion of Sugar Nucleotides.- 1. Some General Considerations.- 2. The Role of 4-oxo Intermediates.- 3. 4-Epimerase Reactions.- 4. The Formation of 4-amino Sugars.- 5. The Decarboxylation of Uronic Acids.- 6. The Formation of Apiose.- 7. Reactions Involving Reversals of Configuration of C-3 and C-5 and the Formation of Deoxy-sugars.- 8. Epimerisation about C-2.- 9. Evolutionary and Mechanistic Implications of Sugar Nucleotide Metabolism.- G. Cyclitol Metabolism.- H. The Fate and Re-use of Degradation Products of Glycoconjugates and Polysaccharides.- 1. Hexoses.- 2. Pentoses.- 3. Methyl Pentoses.- 4. Hexosamines.- 5. Uronic Acids.- 6. Sialic Acids.- I. Pathways of Sugar Nucleotide Interconversion.- Further Reading.- 3. Glycosylation in Bacteria.- A. The Structure of Bacterial Surfaces.- B. Bacterial Carbohydrates.- 1. Teichoic Acids.- 2. Teichuronic Acids.- 3. Peptidoglycan.- 4. Lipopolysaccharides.- 5. Polysaccharides.- C. The Strategy of Analysing Glycosyl Transfers in Bacteria.- D. Undecaprenol.- E. Synthesis of Teichoic Acids and Allied Polymers.- 1. Assembly of Sequences of the Form (-A-P-B-P-)n.- 2. Assembly of Sequences of the Form (-AB-P-AB-P-)n.- 3. Assembly of Sequences of the Form (-A-P-A-P-)n.- 4. Further Substitution of Teichoic Acids.- 5. Chain Initiation and Termination in Teichoic Acid Synthesis.- 6. Teichuronic Acid Synthesis.- F. Peptidoglycan Assembly.- 1. Part 1. The Assembly of UDPMurNAc-pentapeptide.- 2. Part 2. The Undecaprenyl Phosphate Cycle.- 3. Part 3. Cross-linking of the Peptidoglycan.- 4. The 'Priming' of Glycan Assembly.- 5. Variations Upon the Basic Mechanism of Peptidoglycan Assembly.- G. Lipopolysaccharide Synthesis (in Salmonella and Related Genera).- 1. Assembly of Lipid A.- 2. Core Assembly.- 3. Construction of the o-antigenic Side Chains.- H. Polysaccharide Synthesis.- 1. Bacterial Cellulose etc..- 2. Levans and Allied Polymers.- I. Organisational Aspects of Glycosyl Transfers in Bacteria.- Further Reading.- 4. Glycoprotein and Glycolipid Assembly and Related Processes in Eukaryotic Cells.- A. Glycosylation in Eukaryotes: General Schemes.- B. The Synthesis of N-Glycosidic Oligosaccharide 'Cores' in Higher Animals.- 1. Dolichol and Other Isoprenoids: Chemical Aspects.- 2. 'Core' Assembly.- 3. 'Core' Modification.- 4. Inhibitors of Glycosyl Transfer.- 5. Dolichol-dependent Glycosyl Transfers in vivo.- 6. Retinol-dependent Glycosyl Transfers and Glycoprotein Assembly.- C. The Initiation and Early Assembly of 'Mucin-type' Structures.- 1. The Tn-Antigen.- 2. M and N Blood Group Antigens.- D. The Formation of the Clc1,2Gal 1-Hyl Sequence in Collagens and Clq.- E. Construction of Saccharide Sequences by Mechanisms Independent of Dolichol.- 1. The Nature of Saccharide Assembly: General Views.- 2. I and P Blood Group Antigens.- 3. Glycopeptide Assembly by Artificial Systems.- 4. Chain Termination in Oligosaccharide Assembly.- F. Biosynthesis of Glycosphingolipids.- 1. The Patterns of Assembly of the Glycosphingolipids.- 2. Glucosylceramide and its Derivatives.- 3. Blood Group and Allied Glycolipids.- 4. Galactosylceramide and its Derivatives.- 5. Sphingoplasmalogens.- G. Glycerol-based Glycolipids.- H. Sulphated Glycolipids.- I. Complex Glycolipids of Lower Animals.- J. Fungal Cell Wall Mannans and Glycoproteins.- 1. N-Glycosidically Linked Fungal Mannan.- 2. O-Glycosidically Linked Fungal Mannan.- K. The Glycoproteins and Glycolipids of Plants.- 1. Structures of Plant Glycoproteins.- 2. Biosynthesis of Plant Glycoproteins.- 3. Plant Glycolipids.- Further Reading.- 5. Polysaccharide Assembly in Eukaryotes.- A. Introduction.- B. General Problems and Principles.- 1. The Initiation of Polymer Assembly: the 'Primer' Problem.- 2. The Conditions for Obtaining a Repeating Polymer.- 3. The Termination of Chains.- 4. The Problem of Irregular Heteropolymers.- 5. The Unusual Case of the Fructans or Glucofructans.- 6. Branching of Polysaccharides.- 7. Non-sugar Components of Polysaccharides.- 8. Are Similar Polymers of Similar Origin?.- 9. Are Polysaccharides Informational Macromolecules?.- C. Specific Polysaccharides.- 1. Glycosaminoglycans.- 2. Glucans.- 3. Mannans, Galactomannans, Glucomannans and Galacto-glucomannans.- 4. Galactans.- 5. Xylans.- 6. Pectic Substances.- 7. Alginic Acids.- 8. Chitin.- 9. Fructans.- Further Reading.- 6. Cytological Aspects of Glycosyl Transfer in Eukaryotes.- A. Basic ideas of Membrane Structure and Carbohydrates.- 1. Historical.- 2. The Fluid Mosaic Model.- 3. The Concept of the Unit Membrane and its Consequences.- 4. Membrane Flow.- 5. Autonomous Glycosyl Transfers and the Special Carbohydrates of Organelles.- 6. Carbohydrates as Determinants of Membrane Flow.- B. The Genetic Commitment to Glycosyl Transfer.- C. Self-assembly in Polysaccharide Structures.- D. The Integration of Glycosyl Transfer into General Metabolism.- 1. The Cell Walls of Higher Plants.- 2. The Cell Walls of Fungi.- Further Reading.- 7. Pathological Aspects of Glycosylation.- A. Introduction.- B. Catabolic Defects in the Metabolism of Glycoconjugates.- 1. Mucopolysaccharidoses.- 2. Glycolipidoses and Related Diseases.- 3. Glycogenoses.- C. Abnormal Glycosylation and Uptake of Glycoproteins.- 1. Wilson's Disease.- 2. Alpha-1-Antitrypsin Deficiency.- D. Defective Intracellular Targeting of Glycoconjugates.- 1. I-cell Disease.- 2. Other Diseases.- E. Defective Synthesis of Glycoconjugates.- 1. Studies on Mutant Cell Lines.- 2. Malignancy.- Further Reading.- Appendix: Terminology.- 1. Shape of Sugars.- 2. Derivatives of Simple Sugars.- (a) Deoxy-sugars.- (b) Amino- and Acetamido-sugars.- (c) Uronic Acids.- (d) Sugar Alcohols.- (e) Acyl, Ether and Sulphate Groups in Sugars.- 3. Sialic Acids.- 4. Notations for Sugars.- (a) Simple Sugars: Three-letter Notation.- (b) Uronic Acids.- (c) Amino-and Acetamido-sugars.- (d)' single-letter' Notation in Special Cases.- (e) Sulphates and Phosphates.- (f) Sialic Acids.- (g) D and L Sugars.- (h) Pyranose and Furanose Forms.- (i) Linkage.- (j ) Anomeric Configuration.- (k) Branching.- (1) Special Symbols.- 5. Special Nomenclature of Glycolipids.- 6. Special Nomenclature of Glycoproteins and Related Polymers.- (c) Glycosaminoglycans and Proteoglycans.- 7. Special Nomenclature of Polysaccharides.- References.