Carbohydrate Chemistry and Biochemistry: Structure and Mechanism

This monograph is aimed at providing researchers new to the subject with information on the structure and mechanisms in the chemistry, biochemistry or processing of carbohydrates. The book contains everything the reader needs to know about a non-synthetic carbohydrate research project. It gives excellent coverage of carbohydrate chemistry and biochemistry, particularly including the principles of reactivity in the process industries, such as pulp, paper and food. It also employs use of the same concepts to describe enzymic and non-enzymic reactivity.

Table of Contents:
Chapter 1: Structures of the open-chain forms of reducing sugars, and nucleophilic additions to the carbonyl group; 1.1 Definitions and Structures; 1.1.2 R,S Stereochemical designations in carbohydrate chemistry - prochirality; 1.2 Nucleophilic additions to carbonyl groups of sugars; 1.2.1 Additions of water, and OH groups of the same sugar.; 1.2.1.1 Equilibria; 1.2.1.2 Kinetics of mutarotation; 1.2.1.3. General acid and base catalysis of mutarotation; 1.2.1.4 Isotope effects on mutarotation; 1.2.1.5 Mutarotation of 5-thioglucose; 1.2.1.6 Synchronous catalysis of mutarotation ?; 1.2.1.7 Mutarotases; 1.2.2. Reaction with low molecular weight alcohols - the Fischer glycoside synthesis.; 1.2.3. Formation, anomerisation, and hydrolysis of glycosylamines.; 1.3 Cyclitols; Chapter 2: Conformations of monosaccharides; 2.1 Differences between conformational analysis of carbohydrates and other organic molecules.; 2.2 The gauche effect.; 2.3 Conformations of acyclic sugars; 2.4 Description of the conformations of sugar rings.; 2.5 Analysis of carbohydrate conformation and configuration by NMR - the key role of the Karplus equation; 2.6 The anomeric effect; 2.7 Conformational free energies in pyranoses.; 2.8 Rationalisation of the composition of aqueous solutions of reducing sugars; Chapter 3: Non-enzymic nucleophilic substitution at the anomeric centre.; 3.1 Stereochemistry of oxocarbenium ions; 3.2. Lifetimes of intermediates; 3.2.1. The Jencks clock; 3.3 The methoxymethyl system; 3.3.1 alpha Hydrogen isotope effects in the methoxymethyl system; 3.4 Geminal effects and development of conjugation; 3.4.1 Geminal effects; 3.4.2 Development and loss of conjugation; 3.5 Spontaneous hydrolysis of glycosyl derivatives; 3.5.1 Departure of anionic oxygen leaving groups from sugars; 3.5.2 Departure of pyridines; 3.6 Lifetimes of glycosyl cations in water and bimolecular displacements at the anomeric centre.; 3.7 Acid-catalysed hydrolysis of glycosides; 3.7.1 Specific acid catalysis; 3.7.2 Site of productive protonation; 3.7.3 Differences in structure-reactivity patterns in acid-catalysed and spontaneous hydrolyses - effect of the pre-equilibrium protonation.; 3.7.4 Acid-catalysed hydrolysis of nucleosides.; 3.7.5 Intermolecular general acid catalysis of glycoside hydrolysis; 3.7.6 Intramolecular general acid catalysis of glycoside hydrolysis; 3.8 Electrophilic catalysis of glycoside hydrolysis.; 3.9 Hydrolysis of thioglycosides and thioacetals.; 3.10 Heavy atom and remote hydrogen kinetic isotope effects in glycosyl transfer.; 3.10.1 Measurement of small isotope effects; 3.10.2 Inductive and steric effects of isotopes of hydrogen; 3.10.3 ¯-Hydrogen kinetic isotope effects; 3.10.4 Heavy atom kinetic isotope effects.; 3.10.5. Transition state structure determination from multiple kinetic isotope effects; 3.11 Hydrolyses of ketosides; 3.11.1 Hydrolysis of sialic acid (neuraminic acid) derivatives; 3.12 Neighbouring group participation in glycoside hydrolyses; 3.12.1 Participation by acetamido; 3.12.2 Participation by carboxylate and phosphate. Electrostatic catalysis?; 3.12.3. Participation by ionised sugar hydroxyls - base-catalysed hydrolysis of glycosides.; 3.13 Reactions in organic media.; 3.13.1. Solvolyses; 3.13.2 Synthesis of glycosides; 3.13.2. 1. Reaction of phenoxides with glycosyl halides in organic and aqueous-organic solutions; 3.12.2.2 Leaving groups; 3.12.2.3 Effect of protecting groups.; 3.13.2.4 Effect of solvent; Chapter 4: Primary structure and conformation of oligosaccharides and polysaccharides; 4.1 Introduction - depiction and isolation of polysaccharides; 4.2 Determination of structure and conformation of oligo- and polysaccharides; 4.2.1 Determination of constituent sugars and substitution pattern; 4.2.2. Mass spectrometry; 4.2.3 Diffraction by single crystals, crystal powders and fibres; 4.2.4 The role of Fourier transforms; 4.2.5 Use of NMR pulse sequences in the determination of sequence - an example; 4.2.6 High-Resolution Solid State 13C NMR - CP-MAS; 4.2.7 Atomic force microscopy; 4.3 Description of oligosaccharide and polysaccharide conformation.; 4.4 The exo-anomeric effect; 4.5 Polysaccharides in solution; 4.5.1 Separation on the basis of molecular size.; 4.5.2 Rheological properties of polysaccharides.; 4.5.3 Laser light scattering, and related techniques; 4.5.4 Chiroptical methods; 4.6 Some Important Polysaccharides; 4.6.1. 1,4-Linked diequatorial pyranosides; 4.6.1.1. Undecorated, fibrous, 1,4-diequatorial polysaccharides; 4.6.1.1.1 Cellulose; 4.6.1.1.2 Chitin; 4.6.1.1.3 Chitosan.; 4.6.1.2 Decorated 1,4-diequatorially linked polysaccharides - the plant hemicelluloses; 4.6.1.3 Conformationally mobile, originally 1-4 diequatorially linked polysaccharides.; 4.6.2. 1,4 Linked equatorial-axial pyranosides; 4.6.2.1 Starch ; 4.6.2.1.1 Amylose; 4.6.2.1.2 Derivatisation of cycloamyloses and catalysis; 4.6.2.1.3 Amylopectin; 4.6.2.1.4 Biosynthesis of starch; 4.6.2.1.5 Interaction of starch and water - cooking and retrogradation; 4.6.3. 1, 4-Diaxially linked pyranosides.; 4.6.3.1 Marine galactans; 4.6.3.2. Pectin; 4.6.3.2.1 Homogalacturonan; 4.6.3.2.2 Rhamnogalacturonan I; 4.6.3.2.3 Rhamnogalacturonan II; 4.7.3.2.4. Biosynthesis and biodegradation of pectin.; 4.6.4 1,3-Diequatorially linked pyranosides.; 4.6.4.1 ¯(1-3) glucans; 4.6.4.2 ¯(1-3) galactans; 4.6.5 (1-3) Linked axial-equatorial pyranosides; 4.6.6 (1-2) Pyranosidic homopolymers.; 4.6.7 Pyranosidic homopolymers without direct linkages to the ring.; 4.6.8. Furanosidic Homopolymers; 4.6.8.1 Inulin; 4.6.8.2 Phleins, levans and fructans.; 4.6.9 Polysaccharides from one sugar but with more than one linkage in the main chain.; 4.6.10 Heteropolysaccharides with several sugars in the main chain; 4.6.10.1 Glycosaminoglycans.; 4.6.10.1.1 Initial polymer chains and their biosynthesis; 4.6.10.1.2 Hyaluronan; 4.6.10.1.3 Sulfation and epimerisation.; 4.6.10.1.4 Chondroitin, dermatan and their sulfates; 4.6.10.1.5 Heparan sulfate and heparin.; 4.6.10.2 Marine galactans.; 4.6.10.3 Industrially and commercially important bacterial exopolysaccharides; 4.6.10.3.1 Xanthan family; 4.6.10.3.2 Gellan family; 4.6.10.4 Bacterial cell wall peptidoglycans and related material.; Chapter 5: Enzyme-catalysed glycosyl transfer; 5.1. Types of enzyme-catalysed glycosyl transfer; 5.2 Stereochemistry and steady- state kinetics of enzymic glycosyl transfer; 5.3 Reversible inhibition; 5.3.1 Competitive inhibition; 5.3.2 Transition state analogues and adventitious tight-binding inhibitors; 5.3.3 Anticompetitive inhibition; 5.4 The determination of the mechanism of enzymic glycosyl transfer - modification of tools from small-molecule physical organic chemistry, and new tools from protein chemistry.; 5.4.1 Temperature dependence of rates and equilibria.; 5.4.2 Effect of change of pH; 5.4.3. Determination of stereochemistry.; 5.4.4. Kinetic isotope effects; 5.4.5 Structure-reactivity correlations.; 5.4.5.1 Variation of substrate structure; 5.4.5.2 Variation of enzyme structure - site-directed mutagenesis; 5.4.5.3 Large kinetic consequences of remote changes in enzyme or substrate structure: intrinsic binding energy and the Circe effect; 5.4.6 The use and misuse of X-ray crystallographic data in the determination of enzyme mechanism; 5.5 Enzymes with multiple subsites such as polysaccharidases; 5.6 General features of O-glycohydrolases.; 5.6.1 Reactions with enol ethers; 5.7 Inverting O-glycosidases; 5.7.1 Evidence from action on the ""wrong"" fluorides; 5.7.2 Mutation of catalytic groups; 5.7.3 Some inverting glycosidase families; 5.7.3.1 GH6; 5.7.3.2 GH 8; 5.7.3.3 GH 9 ; 5.7.3.4 GH 14; 5.7.3.5 GH 15 Glucoamylase; 5.7.3.6 GH 28; 5.7.3.7 GH 47; 5.7.3.8 GH 48; 5.7.3.9 GH 67.; 5.8 Reaction of N-glycosides with inversion; 5.9 Retaining O-glycosidases and transglycosylases; 5.9.1 Inactivation of glycosidases - exo and paracatalytic activation; 5.9.2. Direct observation of glycosyl-enzyme intermediates; 5.9.3 Effect of mutation of the nucleophilic carboxylate.; 5.9.4 The acid-base catalytic machinery.; 5.9.5 Effects of mutation of the catalytic acid/base.; 5.9.6 Retaining glycosidase families; 5.9.6.1 GH 1; 5.9.6.2 GH 2; 5.9.6.3 GH 7; 5.9.6.4-Non-chair pyranosyl-enzyme intermediates - GH 11, 26, 29, 31 and 38; 5.9.6.5 GH 13; 5.9.6.6 The many activities of GH16; 5.9.6.7 Nucleophilic Assistance by vicinal trans-acetamido group of substrate - mechanisms of GH 18, GH20, GH56, GH84, GH102, GH103, GH104 and sometimes GH23; 5.9.6.8 GH 22-lysozyme.; 5.9.6.9 GH 31; 5.9.6.10 Sialidases (neuraminidases); 5.9.6.11 GH 32 and 68: Fructofuranosidases and transfructofuranosylases.; 5. 10 Carbohydrate binding modules and the attack of glycosidases on insoluble substrates.; 5.10.1 Occurrence of CBM's; 5.10.2 Methods of study of CBM's; 5.10.3 Types of CBM; 5.10.4 CBM Type A Function.; 5.10 .5 Type B CBM Function; 5.10.6 Type C CBM's; 5.11 Retaining N-glycosylases and transglycosylases.; 5.11.1 Retaining NAD+-glycohydrolases and cyclases; 5.11.2.tRNA transglycosylases; 5.11.3 2'-Deoxyribosyl transferases.; 5.12 Glycosyl transferases; 5.12.1 Inverting glycosyl transferases.; 5.12.1. 1 GT 63; 5.12.1.2 GT1; 5.12.1.3 GT2; 5.12.1.4 GT 7; 5.12.1.5 GT9 and GT13.; 5.12.1.7 GT28; 5.12.1.8 GT 42, sialyl transferases.; 5.12.1.9 GT 43 - glucuronyltransferases; 5.12.1.10 - GT 66, oligosaccharyl transferase.; 5.12.2 Retaining glycosyltransferases.; 5.12.2.1 GT 5.; 5.12.2.2 GT6; 5.12.2.3 GT 8; 5.12.2.4 GT 15; 5.12.2.5 GT 20; 5.12.2.6 GT 27; 5.12.2.7. GT35 - Glycogen phosphorylase; 5.12.2.8 GT 44; 5.12.2.9 GT64; 5.12.2.10 GT 72; 5.12.3 UDPGlcNAc epimerase.; 5.12.4 UDP Galactopyranose mutase.; Chapter 6: Heterolytic chemistry other than nucleophilic attack at the anomeric or carbonyl centre.; 6.1 Rearrangements of reducing sugars.; 6.1.1 Types of rearrangements; 6.1.2 Isomerisation by enolisation - the classic Lobry de Bruyn - Alberda van Eckenstein reaction.; 6.1.2.1 Non-enzymic enolisation.; 6.1.2.2 Enzymic enolisation - the classic aldose/ketose phosphate isomerase mechanism.; 6.1.3 Isomerisation of reducing sugars by hydride shift.; 6.1.4 The BÝlik and related reactions.; 6.1.5 Beyond the Lobry de Bruyn - Alberda von Eckenstein rearrangement - deep-seated reactions of sugars in base.; 6.2 Further reactions of glycosylamines.; 6.2.1 The Amadori and Heyns rearrangement; 6.2.2 Osazone formation; 6.2.3 The Maillard reaction.; 6.3 Aromatisation.; 6.4 Acidic and basic groups in carbohydrates.; 6.5 Nucleophilic reactions of OH groups.; 6.5.1. Alkylation.; 6.5.2 Silylation.; 6.5.3. Acylation and deacylation.; 6.5.3.1 Non-enzymic acylation, deacylation and migration; 6.5.3.2 Enzymic acylation, deacylation and transesterification; 6.5.3.2.1 Serine carbohydrate esterases and transacylases; 6.5.3.2.2 Zn++-dependent carbohydrate esterases; 6.5.3.2.3 Aspartic carbohydrate esterases; 6.5.3.2.4 Twin group VIII metal esterases (urease type); 6.5.4. Carbohydrate esters of carbonic anhydride, and their nitrogen and sulfur analogues.; 6.5.5 Acetals of carbohydrates.; 6.5.6 Borates and boronates.; 6.5.7 Nitrites and Nitrates; 6.5.8 Phosphorus derivatives; 6.5.8.1 General considerations; 6.5.8.2 Phosphonium intermediates in the activation of OH to nucleophilic substitution.; 6.5.8.3 Phosphite esters; 6.5.8.4 Phosphates; 6.5.8.4.1 Mechanistic features of phosphoryl transfer, and methods of investigation.; 6.5. 8.4.2 Mechanisms of biological phosphate transfer to and from carbohydrates.; 6.5.9 Sulfites, sulfates and sulfonates; 6.5.10 Stannylenes; 6.6 Oxidations; 6.6.1. Oxidations of individual OH groups; 6.6.1.1 By valence change of an oxyacid ester or related species; 6.6.1.2 By hydride transfer.; 6.6.1.2.1 Non-enzymic hydride abstraction from carbohydrates; 6.6.1.2.2. NAD(P)-linked enzymic oxidations; 6.6.2 Oxidations of diols.; 6. 7 Eliminations and additions; 6.7.1 General considerations; 6.7.2 Electrophilic additions to glycals; 6.7.3 SN' Reactions at the anomeric centre- the Ferrier rearrangement; 6.7.3.1 Nature of the reaction; 6.7.3.2 Substrate reactivity and substrate and product conformation.; 6.7.3.3. Product stereochemistry and regiochemistry.; 6.7.4. Epimerisations alpha, and eliminations alpha,beta to the carboxylates of uronic acids.; 6.7.4.1 Non-enzymic epimerisations and eliminations; 6.7.4.2 Polysaccharide lyase families; 6.7.4.2.1 Polysaccharide lyase Family 8 (PL 8); 6.7.4.2.2 Pectin and pectate lyases ; 6.7.4.2.3 Alginate lyase; 6.7.4.2.4 . PL9 - Both chondroitin and alginate lyase.; 6.7.4.2.5. PL 18 Hyaluronan lyase; 6.7.5. C5 Uronyl residue epimerases; 6.8 Biological oxidation-elimination-addition sequences; 6.8.1 S-Adenosylhomocysteine hydrolase; 6.8.2 Biosynthesis of nucleotide diphospho 6-deoxysugars.; 6.8.3 GH Family 4; 6.8.4 L-Myoinositol 1-phosphate synthetase; Chapter 7: One-electron chemistry of carbohydrates.; 7.1 Classes of radical reactions of carbohydrates.; 7.2. Methods of investigation of radicals in carbohydrate chemistry and biochemistry.; 7.2.1 Electron spin resonance -aspects of importance to carbohydrates; 7.2.2 Conformations of carbohydrate radicals as determined by ESR; 7.2.3 Kinetics of radical elementary steps.; 7.3 Generation of radicals.; 7. 3. 1 By direct transfer of electrons; 7.3.1.1. Reducing sugar assays; 7.3.1.2. Ascorbic acid, the natural antioxidant ; 7.3.1.3. Glucose oxidase and related enzymes; 7.3.1.4. Pyrroloquinoline quinone (PQQ)-dependent glucose dehydrogenase.; 7.3.2 By hydrogen abstraction.; 7.3.2.1 Abstraction of hydrogen by hydroxyl and alkoxyl and related species, and reactive oxygen species. The autoxidation of carbohydrates.; 7.3.2.2 Hydrogen abstraction by halogens; 7.3.2.3 Selective oxidation of hydroxymethyl groups; 7.3.2.3.1 Galactose oxidase; 7.3.3 By fission of weak bonds.; 7.3.3.1 Radical deoxygenation.; 7.3.3.2 Radicals from carboxylic acids; 7.4 Reactions of radicals; 7.4.1 Stereochemistry of atom transfer to oxygenated radicals.; 7.4.2 Heterolysis of carbohydrate radicals.; 7.4.2.1 Ribonucleotide reductase; 7.4.3. Acyloxy and related rearrangements.; 7.5 Carbohydrate carbenes.; Appendix: Structures of amino acids, and parallel and antiparallel strand and -helix;

Review :
"the overall view of the text is favorable, since it covers so many varied topics, some perhaps unfamiliar to even the most seasoned glycoscientists" "..an invaluable companion and introduction to the primary literature of the field." "...this is an excellent treatment of carbohydrate chemistry. It belongs in libraries and on the bookshelves of carbohydrate chemists and biochemists." "useful addition to the library of individuals with interests in theglycoscience field, as well as students wishing to learn moreabout this area." "...the book provides an excellent and authoritative reference resource for beginning and established researchers interested in structural and mechanistic aspects of carbohydrate (biochemistry)"