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
Monosaccharides: Chemistry of sugars, carbonyl groups, and chiral centers.
Forms of Monosaccharides: Open-chain and ring forms, including hemiacetals and hemiketals.
Structures and Nomenclature: Important for understanding monosaccharides.
Disaccharides: Structures and properties, including the glycosidic bond.
Biological Functions: Importance of linear and branched homo- and heteropolysaccharides in nature.
Heparin Segment
Polysaccharides Quiz
Which homopolysaccharide is an energy store in plants?
Which homopolysaccharide is an energy store in animals?
Which of these are polymers of α-glucose? (Starch, Glycogen, Cellulose, Chitin)
Name a polymer of β-glucose.
Name a homopolysaccharide which only has unbranched chains?
True or False: Agarose is a homopolysaccharide.
True or False: Glycosaminoglycans are polymers with repeating disaccharide units?