POLYSACCHARIDES

- Polysaccharides are polymers comprising many monosaccharide units connected together by glycosidic bonds.
- Common Properties:
1. Amorphous powder in appearance
2. Does not impart sweet taste
3. Can be hydrolyzed but do not undergo fermentation
4. All polysaccharides are non-reducing although they usually have a free anomeric carbon at the end. However, this single free
anomeric carbon is not enough compared to the molecular size of a polysaccharide.
5. They have limited solubility in water due to their size, however the–OH in their structures can individually be hydrated with
water molecule resulting in a thick colloidal suspension of a polysaccharide in water.
- Factors in identifying polysaccharides:
1. type of monosaccharide units
2. type of glycosidic linkages
3. length (how many monosaccharide units)
4. degree of branching
- Polysaccharides can be classified as:
1. Homopolysaccharides – containing similar monosaccharide units
2. Heteropolysaccharides – containing different monosaccharide units

A. Storage Polysaccharides
- These polysaccharides function as storage forms of monosaccharides and are used as energy source in cells.
- Monosaccharides are often stored in the cell as polysaccharides to lower osmotic pressure inside the cell.
- The most important storage polysaccharides are your starch and glycogen.

Starch
- Energy storage in plants
- A homopolysaccharide of α-D-glucose units
- Contains only α-linkages in between glucose units which give rise to a chain that folds in a helical form

- Starches are composed of 2 types of glucose polymers – amylose and amylopectin

1. Amylose
- accounts for 10-20% of starch and can solubilize when treated with boiling water
- composed of 300-500 glucose units with α(14) glycosidic bonds forming an unbranched long chain with a molecular weight of
400,000 Da or more.

2. Amylopectin
- accounts for 80-90% of starch and cannot be dissolved in boiling water, but instead forms paste like gel
- is highly branched unlike your amylose with molecular weight more than 1 million.
- The linear glucose units in amylopectin is also linked by α(14) glycosidic bonds, and the branching involves α(16) glycosidic
bonds.

- Notice that all glycosidic bonds between each glucose units in amylose and amylopectin are α type. This is the reason why starch has
nutritional value in humans as we have enzymes capable of hydrolyzing α linkages in glucose units (α-glucosidase).

Glycogen
- also known as animal starch as this serve as energy storage in animals
- found mostly in liver cells and muscle cells in humans
- A homopolysaccharide of α-D-glucose units
- has similar structure as your amylopectin, all glycosidic linkages are α(14) and α(16) linkages; but glycogen is more branched
than amylopectin
- When glucose in blood is present in excess amount, liver and muscle cells convert the excess glucose to glycogen. When glucose level
drops, some of the stored glycogen are hydrolyzed back to glucose.
B. Structural Polysaccharides
- These polysaccharides serve as structural component in plant cell walls and animal exoskeletons.
- The most important structural polysaccharides are cellulose and chitin.

Cellulose
- structural component in plant cell walls
- most abundant naturally occurring polysaccharides
- A homopolysaccharide of β-D-glucose units
- It has unbranched structure like your amylose, however the glucose units in cellulose are linked together by β(14) linkages which
give rise to a long linear chain.
- When aligned side by side, the linear chains of cellulose become water insoluble fibers because of inter-chain hydrogen bonding of
the hydroxyl groups.

- Although cellulose is a polymer of glucose, it does not have nutritional value to humans, because we lack enzymes capable of
hydrolyzing β linkages between glucose units.
- The intestinal tracts of grazing animals such as cows and sheep, however, have bacteria that produce enzyme cellulase capable of
hydrolyzing β linkages between glucose units.
- Despite its indigestibility, cellulose is still an important component of a balanced diet as dietary fibers. They serve as roughage in the
excretion of digestive wastes.

Chitin
- structural component in animal exoskeleton
- second most abundant natural polysaccharides
- A homopolysaccharide of N-acetyl-β-D-glucosamine (NAG) units
- It has structure similar to cellulose, where monosaccharide units are linked together by β(14) linkages; except that the
monosaccharide unit is NAG rather than D-glucose itself.

C. Acidic Polysaccharides
- a.k.a. mucopolysaccharides or glycosoaminoglycans
- a heteropolysaccharide containing alduronic acids and amino sugars, where one or both monosaccharide components has a
negative charge due to the presence if sulfate group or carboxyl group.
- Two of the most well-known acidic polysaccharides are hyaluronic acid and heparin.

Hyaluronic acid
- present in connective tissues, tendons, synovial fluid and vitreous humor
- contains alternating residues of N-acetyl-β-D-glucosamine (NAG) and D-glucuronate (an ion obtained when D-glucuronic acid loses
its acidic H.
- The glycosidic bonds in hyaluronic acid are alternating β(13) and β(14).

β(13) β(14)

Heparin
- blood anticoagulant which are naturally present in mast cells and is released at the site of tissue injury.
- commonly used as anticoagulant when taking blood for clinical studies.
- Commercial heparin is obtained from slaughterhouse animal lung tissues (pigs and cows)
- contains alternating unit of D-glucuronate-2-sulfate and N-sulfo-D-glucosamine-6-sulfate
- The repeating units are linked by α(14) glycosidic bonds.

Hydrolysis of Starch
- Like disaccharides, polysaccharides are also capable of hydrolysis.
- Hydrolysis of starch is an important process in the digestion of carbohydrates in humans, as starch is our primary source of energy.
- Starch can be hydrolyzed by acids and enzymes.

Acid Hydrolysis of Starch

- When starch is heated with a strong acid, it will produce small fragments gradually.
Starch

Amylodextrin

Erythrodextrin

Achrodextrin

Maltose

Enzymatic Hydrolysis of Starch

- Enzymatic hydrolysis of starch is carried out in the of amylases.
- Amylase is an enzyme capable of attacking the α(14) glycosidic bond in starch.
- There are 2 types of amylases – α-amylase and β-amylase. Note that the α and β in amylases do not signify anomeric forms in
this case.

Action of β-amylase
- β-amylase is an exoglycosidase that cleaves starting from the glucose ends of starch releasing maltose consecutively.
- β-amylase is not present in humans, it is present in plants (germinating seeds and ripening fruits).
- When 𝛽-amylase acts on amylopectin, maltose units are liberated from the ends of the branches of amylopectin, until the
action of enzyme is blocked at the α(16) glycosidic linkage.
- The action of 𝛽-amylase stops at branching points, leaving a large molecule, called limit dextrin or residual dextrin.

Action of α-amylase: Digestion of Starch in Humans

- Salivary amylase and pancreatic amylase in humans are both α-amylase.
- α-amylases act randomly on α(14) glycosidic linkages to split starch into smaller units (dextrins) and finally to maltose.

- Chemical digestion of starch starts in the mouth by the action of salivary amylase resulting in branched and unbranched
oligosaccharides (dextrin), and some maltose.
- Salivary digestion occurs briefly though, because it is interrupted by the acidic environment of the stomach.
- When the acidic stomach contents reach the small intestine, they are neutralized by bicarbonate secreted by the pancreas, and
pancreatic α-amylase continues the process of starch digestion.
- Digestion by pancreatic amylase results in maltose.
- The final digestive processes occur primarily at the mucosal lining of the upper jejunum, and include the action of several brush-border
enzymes (disaccharidase).