Carbohydrates (Part III)

Key Terminology

  • Monosaccharide:

    • A carbohydrate consisting of a single sugar unit.

  • Disaccharide:

    • A carbohydrate consisting of two covalently joined monosaccharide units.

  • Polysaccharide (Glycan):

    • A linear or branched polymer of monosaccharide units linked by glycosidic bonds.

  • Carbohydrate:

    • A sugar (monosaccharide), one of its dimers (disaccharide), or polymers (polysaccharide).

Characteristics of Natural Carbohydrates

  • Natural carbohydrates are primarily found as polymers.

  • Types of Polysaccharides:

    • Homopolysaccharides: Composed of one type of monosaccharide unit.

    • Heteropolysaccharides: Contain more than one type of sugar.

    • Linear and Branched forms.

  • Molecular Weight: Polysaccharides do not have a defined molecular weight, differing from proteins and DNA which use templates for synthesis.

Structure of Polysaccharides

  • Composition: may consist of 1, 2, or several monosaccharides in straight or branched chains of varying lengths.

  • Homopolysaccharides Examples: Starch, glycogen, collagen, chitin.

  • Heteropolysaccharides Examples: Agarose, peptidoglycans, glycosaminoglycans.

Starch

  • Structure: Mixture of two homopolysaccharides of D-glucose:

    • Amylose: Unbranched polymer with (α1 → 4) linked residues. Molecular weight varies from few thousands to over 1 million.

    • Amylopectin: Branched structure similar to glycogen; branch-points with (α1 → 6) linkers occur every 24–30 residues. Molecular weight can reach up to 200 million.

  • Hydrated: Starch is heavily hydrated due to a high number of exposed -OH groups.

  • Hydrolysis: Hydrolyzed by α-amylases.

Glycogen

  • Structure: Branched homopolysaccharide of glucose:

    • Glucose monomers form chains linked by (α1 → 4).

    • Branch-points occur every 8–12 residues via (α1 → 6) linkers, making it more compact than starch.

    • Molecular weight reaches several millions.

  • Function: Main storage polysaccharide in animals;

    • Found abundantly in the liver and skeletal muscle.

    • Contains ‘n’+1 non-reducing ends and 1 reducing end.

    • Glucose units are removed from the non-reducing ends by enzymes (glycosidases), hydrolyzing simultaneous branches, effectively converting the polymer to monosaccharides.

Dextrans

  • Description: Bacterial and yeast polysaccharides.

    • Poly-D-glucose forms chains linked by (α1 → 6).

    • Branch-points include (α1 → 3), and some contain (α1 → 2) and (α1 → 4) linkers.

    • Rich in dental plaque on teeth and commercially sold as synthetic dextrans (chemically cross-linked, forming insoluble materials with varying porosities).

Cellulose

  • Structure: Unbranched homopolysaccharide of glucose:

    • D-glucose forms chains linked by (β1 → 4) (10,000 – 15,000 residues).

    • Hydrogen bonds formed between adjacent monomers and between chains.

    • Results in a tough, water-insoluble structure; cellulose is the most abundant polysaccharide in nature, primarily found in cotton and wood.

  • Metabolism:

    • Cellulose is difficult to act on due to fibrous structure and water-insolubility, common in cell walls of plants.

    • Cellulases secreted by fungi, bacteria, and protozoa facilitate its breakdown, allowing them to utilize wood as a glucose source.

    • Most animals cannot digest cellulose because they lack the enzyme to hydrolyze (β1 → 4) linkages.

    • Ruminants and termites are exceptions, existing symbiotically with cellulase-producing microorganisms.

    • Cellulases are promising for biomass fermentation into biofuels.

Fungi, Ruminants, and Cellulose

  • Wood Fungi:

    • Utilize cellulases to hydrolyze the (β1 → 4) glycosidic bonds of cellulose, converting wood into metabolizable glucose.

  • Ruminants:

    • Only vertebrates that can use cellulose as a nutrient source. In the rumen, they have bacteria and protists that secrete cellulase.

  • Example: Trichonympha.

Chitin

  • Structure: Linear homopolysaccharide of N-acetylglucosamine (NAG):

    • NAG monomers linked by (β1 → 4) form chains.

    • Creates extended fibers akin to cellulose (hydroxyl group at C-2 replaced with an acetylated amino group).

    • Features: tough, flexible, water-insoluble, cannot be digested by vertebrates.

    • Found in the cell walls of mushrooms and exoskeletons of insects, spiders, crabs, and lobsters (making it the 2nd most abundant polysaccharide).

Agar and Agarose

  • Agar: Complex mixture of heteropolysaccharides containing modified galactose units, serving as a cell wall component in certain seaweeds.

  • Agarose: One component of agar with minimal charged groups, forming gels used in laboratories for growing bacteria and separating DNA by electrophoresis.

Glycosaminoglycans (GAGs)

  • Description: Linear polymers with repeating disaccharide units, unique to animals and bacteria, containing sulfate groups.

  • Role in Tissues: Extracellular matrix (ECM) in multicellular tissues holds cells together and facilitates nutrient and oxygen diffusion.

    • Specialized ECM: Basement membranes comprising collagens, laminin, and heteropolysaccharides (glycosaminoglycans).

Summary of Polysaccharides

  • Energy Storage: Starch and glycogen serve as stored fuel in plants and animals, respectively.

  • Structural Polysaccharides: Includes cellulose, chitin, and dextran, providing strength and rigidity to cell walls and exoskeletons.

  • 3D Folding: Homopolysaccharides can form helical structures (starch and glycogen) with interchain hydrogen bonding, while cellulose and chitin have long straight strands interacting with neighboring strands.

  • Strength of Cell Walls: Heteropolysaccharides like peptidoglycan and agar strengthen bacterial and algae cell walls.

  • Glycosaminoglycans: Provide extracellular support, often have high negative charge density, aiding in diffusion.

Overview of Carbohydrates

  1. Monosaccharides: Chemistry of sugars, carbonyl groups, and chiral centers.

  2. Forms of Monosaccharides: Open-chain and ring forms, including hemiacetals and hemiketals.

  3. Structures and Nomenclature: Important for understanding monosaccharides.

  4. Disaccharides: Structures and properties, including the glycosidic bond.

  5. Biological Functions: Importance of linear and branched homo- and heteropolysaccharides in nature.

  • Heparin Segment

Polysaccharides Quiz

  1. Which homopolysaccharide is an energy store in plants?

  2. Which homopolysaccharide is an energy store in animals?

  3. Which of these are polymers of α-glucose? (Starch, Glycogen, Cellulose, Chitin)

  4. Name a polymer of β-glucose.

  5. Name a homopolysaccharide which only has unbranched chains?

  6. True or False: Agarose is a homopolysaccharide.

  7. True or False: Glycosaminoglycans are polymers with repeating disaccharide units?