Carbohydrates

Chapter 7 (Part II)

Carbohydrates and Glycobiology

• Glycogen is the major form of stored carbohydrate in animals. This crucial molecule is a
homopolymer of glucose in α–(1,4) linkage; it is also highly branched, with α–(1,6) branch linkages
occurring every 8-12 residues. Glycogen is a very compact structure that results from the coiling of
the polymer chains. This compactness allows large amounts of carbon energy to be stored in a
small volume, with little effect on cellular osmolarity.

• Starch is the major form of stored carbohydrate in plant cells. Its structure is identical to glycogen,
except for a much lower degree of branching (about every 24–30 residues). Unbranched starch is
called amylose (α1→4)Glc, linear) ; branched starch is called amylopectin (α1→6)Glc, branched).
Carbohydrates and Glycobiology
Carbohydrates and Glycobiology
Epimers and isomers
• Isomers:

Have same chemical formula but different structures.

• Epimers:

Differ in configuration around only one carbon atom (except the carbonyl carbon)

• For example, fructose, glucose, mannose, and galactose are all isomers of each other, having the
same chemical formula, C6H12O6.
• However, galactose and mannose are NOT epimers—they differ in the position of -OH groups at
two carbons (2 and 4) and are, therefore, defined only as isomers
Isomers and epimers

galactose glucose Mannose

epimers epimers
Carbohydrates and Glycobiology
Enantiomers
• All carbohydrates contain asymmetrical (chiral) carbon and are optically active.

• If a pair of sugars are mirror images of each other (enantiomers)

• Designated as D- and L-sugars.

• Majority of sugars in humans are D-sugars.

• OH group on the asymmetric carbon:

• in the D-isomer is on the right

• in the L-isomer it is on the left.

• Enzymes known as racemases are able to interconvert D- and L-isomers.

Carbohydrates and Glycobiology
Enantiomers
• In the D isomeric form, the OH group on the asymmetric carbon (a carbon linked to four different atoms
or groups) farthest from the carbonyl carbon is on the right, while in the L-isomer it is on the left
Carbohydrates and Glycobiology
Cyclization of monosaccharides
<99% of monosaccharides (5 carbons) are in a ring (cyclic) form

The aldehyde (or ketone) group has reacted with an alcohol group on the same sugar, making the
carbonyl carbon asymmetric.

Anomeric
Carbon
Carbohydrates and Glycobiology
Cyclization of monosaccharides
<99% of monosaccharides (5 carbons) are in a ring (cyclic) form

The aldehyde (or ketone) group has reacted with an alcohol group on the same sugar, making the
carbonyl carbon asymmetric.

Anomeric
Carbon
 N- and O-glycosides

• Complex carbohydrates can be attached to non-carbohydrates:

• Purine and pyrimidine bases.

• Aromatic rings

• Proteins

• Lipids

• If the group attached to sugar is -NH2 group, the structure is an N-

glycoside, and the bond is N-glycosidic link.

• If the group is an -OH, the structure is an O-glycoside, and the bond

is O-glycosidic link
Carbohydrates and Glycobiology

• Mouth

• Digestion begins by breaking some -(1→4) glycosidic bonds by salivary α-amylase

enzyme

• Stomach

• Digestion stops because high acidity inactivates the amylase

• Small intestine
1. Pancreatic -amylase completes starch digestion
2. Brush border enzymes digest disaccharides and polysaccharides
Carbohydrates and Glycobiology

• End products of carbohydrate digestion

• Glucose, fructose, galactose
• Absorbed into blood stream

• Fibers are not digested, excreted in feces