The Carbohydrates

List of Contributors

Preface

I. Introduction: Structure and Stereochemistry of the Monosaccharides


1. General Relations


2. Some Definitions


3. Nomenclature


4. Development of Carbohydrate Chemistry


5. Structures of Glucose and Fructose


6. Stereochemistry

A. General Principles

B. Establishment of the Configuration of Glucose and Some Other Sugars

C. D- and L-Nomenclature


7. Ring Structures of the Sugars

A. Necessity for Ring Structures

B. Proof of Ring Structure

C. Configuration of the Anomeric Carbon Atom

D. The Representation of the Ring Structures of the Sugars

E. Nomenclature of Anomers (α-β Nomenclature)


8. Homomorphous Sugars

A. Homomorphology

B. Nomenclature for Higher Sugars and for Compounds with Numerous Asymmetric Atoms in a Carbon Chain


9. The Sugars in Solution

A. In the Absence of Strong Acids or Alkalies; Mutarotation

B. In the Presence of Acids

C. In the Presence of Alkalies

D. Behavior of the Sugars with Short Carbon Chains


10. Optical Superposition, the Isorotation Rules, and the Influence of Structure on Optical Rotation

II. Occurrence, Properties, and Synthesis of the Monosaccharides


1. Naturally Occurring Monosaccharides

A. Introduction

B. Origin and Preparation of Some Naturally Occurring Monosaccharides


2. Synthetic Sugars

A. Complete Synthesis of the Sugars

B. Methods for Lengthening the Carbon Chain of the Sugars

C. Methods for Shortening the Carbon Chain of Sugars

D. Methods Based on Changing the Configuration of Other Sugars

E. Methods for the Synthesis of Deoxysugars

F. Preparation of Ketoses by Biochemical Oxidation of Alcohols

G. Aldose to Ketose Conversion Utilizing the Osones

H. Methods for Isotope-Labeled Sugars

III. Esters

Part I. Acyl Derivatives


1. Acetate Esters


2. Benzoate Esters


3. O-Acylglycosyl Halides


4. Trihalogenoacetate Derivatives


5. Acyglycosyl Halides of Acyclic Structure


6. Partially Esterified Sugar Structures


7. Carbonates, Xanthates, Carbanilates


8. Galloyl Derivatives and Tannins


9. Aldonate Esters


10. Other Esters of Carboxylic Acids


11. Tosylates and Mesylates

Part II. Inorganic Esters


1. Nitrate Esters


2. Sulfate Esters


3. Boric Acid Esters


4. Halogeno Esters


5. Phosphate Esters

IV. Glycosides, Simple Acetals, and Thioacetals


1. Glycosides

A. Methods for Synthesis

B. Properties of Glycosides

C. Determination of Glycoside Structure


2. Glycosans

A. Preparation

B. Structures

C. Reactions

D. Diketohexose Dianhydrides


3. Acetal and Dithioacetal Derivatives of Acylic Sugars

A. Dithioacetals

B. Acetals


4. Reactions of Carbohydrates with Aldehydes and Ketones

A. Methylene (Formal) Derivatives

B. Benzylidene Derivatives

C. Condensation with Acetaldehyde and 2-Furaldehyde

D. Isopropylidene (Acetone) Derivatives

E. Acetoacetic Ester Derivatives

V. The Polyols

Part I. Acyclic Polyols (Alditols or Glycitols)


1. Configurations, Occurrence, and Preparation


2. Proofs of Structure and Configuration


3. Synthesis


4. Reactions

Part II. The Inositols and Related Compounds


1. Representation of Configuration and Nomenclature


2. Occurrence and Synthesis


3. Proofs of Structure and Configuration


4. Reactions


5. Biochemistry

VI. Acids and Oxidation Products


1. Preparation and Reactions

A. Aldonic Acids

B. Saccharic (or Aldaric) Acids

C. Uronic Acids

D. Keto Aldonic Acids

E. Ascorbic Acids

F. Osones

G. Dialdoses


2. Oxidative Agents

A. Halogen Oxidations

B. Reagents Cleaving Glycols

C. Nitric Acid and Nitrogen Oxides

D. Oxygen in Alkaline or Neutral Solution

E. Hydrogen Peroxide

F. Organic Per-Acids

G. Relatively Unspecific Oxidants

H. Microbial Oxidations

I. Enzymic Oxidations

VII. Ethers, Anhydro Sugars, and Unsaturated Derivatives


1. Ether Derivatives (External)

A. Alkylation Methods

B. Trityl Derivatives


2. Anhydro Derivatives

A. Methods of Preparation

B. Reactions of Anhydro Sugars


3. Unsaturated Derivatives

A. Glycals

B. Glycoseens and Alditoleens

VIII. Nitrogenous Derivatives


1. Glycosylamines

A. Unsubstituted Glycosylamines

B. N-Substituted Glycosylamines


2. Nucleotides

A. Preparation and Structures

B. Nucleoside Di- and Triphosphoric Acids

C. Biologically Important Substances Related to Nucleotides


3. Nucleic Acids


4. Combinations of Sugars with Amino Acids and Proteins

A. Preparation

B. Protein-Carbohydrate Compounds as Synthetic Antigens


5. Reactions of the Sugars With Substituted Hydrazines and Hydroxylamine

A. Hydrazones and Osazones

B. Oximes


6. Derivatives in Which an Amino Group Replaces a Primary or Secondary Hydroxyl Group

A. Amino Sugars (Glycosamines)

B. Glycamines and Aminodeoxyalditols

IX. Oligosaccharides


1. Synthesis of Oligosaccharides

A. Rearrangement and Degradation of Oligosaccharides

B. Condensation of Two Monosaccharide Units


2. Determination of Structure


3. Ease of Acid Hydrolysis


4. Preparation, Properties, and Structures of Some Oligosaccharides of Natural Origin

A. Disaccharides

B. Miscellaneous Disaccharides

C. Tri-, Tetra-, and Pentasaccharides

D. Miscellaneous Tri- and Tetrasaccharides


5. Enzymic Synthesis of Oligosaccharides

A. Synthesis of Sucrose by the Mechanism of Phosphorolysis

B. Synthesis of Analogs of Sucrose and Maltose by Sucrose and Maltose Phosphorylases

C. Synthesis of Disaccharides by Transglycosidation through the Action of Sucrose Phosphorylase

D. Synthesis of Oligosaccharides by Transglycosidation through the Action of Hydrolytic Enzymes

E. Miscellaneous Oligosaccharides

X. Naturally Occurring Glycosides and Glycosidases

Part I. Glycosides


1. Anthocyanidin, Flavanol, and Carotenoid Glycosides


2. Indican


3. Aglycons Related to Phenanthrene


4. Substituted-Phenyl Glycosides


5. Vanillin and Coumarin Glucosides


6. Cyanogenetic Glycosides


7. Hydroxyanthraquinone Glycosides


8. Sugar Components of Natural Plant Glycosides


9. Thioglycosides and Thiosugars


10. Streptomycin


11. Cerebrosides

Part II. Glycosidases


1. Introduction and Classification


2. Mechanism of Action


3. Chemical Composition of Glycosidases


4. Enzymes of Almond Emulsin


5. Occurrence and Specificity of Other β-Glucosidases


6. Alfalfa and Coffee Emulsins; β-Galactosidases


7. Yeast Glycosidases


8. β-Glucuronidases (β-D-Glucopyranosiduronases)


9. Enzymic Synthesis of Glycosides


10. In Vivo Synthesis of Glycosides


11. Bourquelot Biochemical Determination of Glycosides and Oligosaccharides in Plant Materials

XI. The Identification and the Quantitative Determination of Carbohydrates


1. Qualitative Identification

A. Separation of Sugar Mixtures

B. Color Reactions

C. Derivatives


2. Quantitative Determination

A. Optical Rotation

B. Reducing Sugar Methods

C. Colorimetric Procedures

D. Special Methods


3. Isotope Procedures

A. Synthesis of Labeled Sugars

B. Degradation of Labeled Sugars


4. Histochemistry of Carbohydrates

A. Purposes and Principles

B. Fixation and Preparation of Sections

C. Methods for the Histochemical Demonstration of Carbohydrates

D. The Use of Enzymes in the Identification of Carbohydrates in Tissues

XII. Polysaccharides

Part I. General Aspects and Phyto and Microbial Polysaccharides


1. Nomenclature and Classification


2. The Structures of Polysaccharides


3. Phytopolysaccharides (Phytoglycans)


4. Fungal and Bacterial Polysaccharides


5. General Reactions


6. Synthesis

Part II. Animal Polysaccharides (Zoopolysaccharides or Zooglycans) and Glycoproteins


1. Distribution and Classification


2. Reasonably Well-Defined Zoopolysaccharides


3. Glycoproteins, Mucoproteins, and Interactions of Zoöpolysaccharides


4. Glycolipides and Glycolipoproteins


5. The Problem of Sialic Acid

XIII. Photosynthesis and Metabolism of Carbohydrates


1. Photosynthesis

A. Introduction

B. Structural Aspects of the Photosynthetic Apparatus

C. Kinetic Studies on Photosynthesis

D. Bacterial Photosynthesis

E. The Hill Reaction

F. The Path of Carbon in Photosynthesis


2. The Biosynthesis of Carbohydrates by Plants

A. Monosaccharides

B. Oligosaccharides

C. Starch

D. Sugar Alcohols

E. Sugar Acids


3. Carbohydrate Biochemistry

A. Pathways for the Metabolism of Carbohydrates

B. Interconversion of the Sugars

C. Pathways of Pyruvate Metabolism

XIV. Carbohydrates in Nutrition

Part I. General Aspects


1. Caloric Value


2. Digestion and Absorption


3. Starches


4. Dextrins


5. Maltose


6. Sucrose


7. D-Glucose (Dextrose)


8. D-Fructose (Levulose)


9. D-Mannose


10. D-Galactose and Lactose


11. Cellobiose


12. Rare Sugars


13. Xylose Toxicity


14. Sugar Alcohols (Alditols)


15. Hexosamines


16. Cellulose and Related Substances


17. Sweetness and Flavoring Characteristics of Sugars


18. Appetite for Carbohydrate


19. Blood Glucose and the Urge to Eat


20. Synthesis of Vitamins by the Intestinal Microflora


21. Protein Sparing Action


22. Sugar in Candy and Carbonated Beverages


23. Carbohydrates and Weight Control


24. Carbohydrates in Parenteral Nutrition

Part II. Dental Aspects of Carbohydrates


1. Pre-eruptive Effects


2. Post-eruptive Effects


3. The Oral Clearance Factor


4. Saliva

XV. Some General References to Carbohydrate Compilations

Author Index

Subject Index