Carbohydrates

Learning Objectives

Role of carbohydrates in biosphere and their classification

Monosaccharides Cyclization

of glucose (lactose and sucrose) (starch, glycogen, cellulose)

Disaccharides

Polysaccharides

What Are Carbohydrates?

Carbohydrates (saccharides) are: - most abundant biological molecules - accumulators of the solar energy in biosphere - energy sources for heterotrophic organisms (including us) Carbohydrates contain carbon, oxygen and hydrogen atoms according to the formula (CH2O)n, where n 3. Plants use the solar energy to synthesize carbohydrates from CO2 and H2O. The energy is stored in carbohydrates in the form of chemical bonds. Plant-eating animals metabolize the carbohydrates, use the released energy, and return CO2 and H2O to the biosphere.

Monosaccharides
Monosaccharides are small carbohydrates that cannot be decomposed by hydrolysis. Monosaccharides are polyhydroxyalcohols containing at least three carbon atoms. Monosaccharides are classified according to: - the chemical nature of their carbonyl group - the number of carbon atoms Aldose is a monosaccharide with an aldehyde group (-COH ). Ketose is a monosaccharide with a keto group (-CO-). By the number of carbon atoms, monosaccharides are classified as trioses (3), tetroses (4), pentoses (5), hexoses (6), heptoses (7), etc.

D-Glucose
O
1

H C
2 3 4 5

D-Glucose

is: <>

H-C-OH HO-C-H H-C-OH H-C-OH

6

CH2OH

Carbohydrate Monosaccharide Aldose Hexose Aldohexose Compound with 4 chiral centers One of 16 possible stereoisomers of glucose

Epimers are sugars that differ only in the configuration of one carbon atom

D-Fructose
1

CH2OH
2

D-Fructose

is:

C=O

HO-C-H H-C-OH H-C-OH

6 5 4

CH2OH

Carbohydrate Monosaccharide Ketose Hexose Ketohexose Compound with 3 chiral centers One of 8 possible stereoisomers of fructose

D-Sugars are much more abundant than L-sugars. Sugars name that lacks the D/L prefix refers to the D-sugar.

Most Important Monosaccharides

Aldoses
Glyceraldehyde Ribose (pentose) Glucose (hexose) Mannose (C2-epimer of glucose) Galactose (C4-epimer of glucose) CHO H-C-OH CH2OH

Ketoses

CH2OH C=O

Dihydroxyacetone CH2OH Ribulose (pentose) Fructose (hexose)

Cyclization of Glucose
O
1 2

H C

When a sugar cyclizes, the carbonyl carbon becomes a chiral center. It is called the anomeric carbon

CH2OH
5

36%
O H
2

H-C-OH
3

< 0.1%
6

Anomeric carbon
CH2OH
5

H
4

H
1

H OH
3

HO H
1

HO-C-H
4

OH

H-C-OH
5

H
4

OH H
2

OH

H OH
3

C O

-D-Glucose

H-C-OH
6

HO

CH2OH

OH H
4

CH2OH
5

64%
O H
2

D-Glucose
O O

D-Glucose
-D-Glucose = -D-Glucopyranose -D-Glucose = -D-Glucopyranose -D-Fructose = -D-Fructofuranose

OH
1

H OH
3

HO H OH

Furan

Pyran

-D-Glucose

Cyclization of Fructose
1 2

CH2OH C=O
3 6

Anomeric carbon
HOH2C
5 1

HOH2C
5

O H
4

CH2OH OH
3 2

H OH H
4

HO-C-H
4

OH

CH2OH HO
3 2

OH

H-C-OH
5

C O

-D-Fructose

H-C-OH
6

CH2OH

OH

H
6

D-Fructose

D-Fructose

HOH2C
5

O H
4

OH OH
3 2

CH2OH
1

OH

-D-Fructose

Disaccharides
CH2OH HO H O H OH H H H OH OH H CH2OH O H OH H H H OH H2O H H OH OH HO CH2OH O H OH

Glycosidic bond
H O H
4

CH2OH O H OH H H H OH OH

+ HO

H 1

-Galactose

-Glucose

Lactose O--D-galactopyranozyl(14)-D-glucopyranose
CH2OH OH O H OH H H O OH OH H H CH2 H O OH CH2 OH H

CH2OH H HO H OH O H OH H H

OH CH2 H H OH H O OH CH2 HO H2O OH H

+ OH

-Glucose

-Fructose

OH

Sucrose O--D-glucopyranozyl(12)--D-fructofuranose (Table sugar)

Polysaccharides
Polysaccharides (glycans) consist of monosaccharides joined by glycosidic bonds. Starch is a mixture of amylose and amylopectin. Plants synthesize starch as their food reserve. CH OH
2

H O CH2OH H O H OH H H O OH H OH H H CH2OH O H OH H O H

O H OH H H

O OH CH2 H O

-(16)
branch point

Glucose

O H OH H H

H O

Glucose

Glucose

OH

-Amylose

Amylopectin

Glucose

Amylose
Fig. 8-10
CH2OH H O H OH H H O OH H OH H H CH2OH O H OH H O H

Glucose

Glucose

-Amylose

Amylopectin
CH2OH H O O H OH H H O OH CH2 H O H OH O H OH H O H H

-(16)
branch point

Glucose

Amylopectin

Glucose

Glycogen
Glycogen is the storage of polysaccharides in animals. Glycogen resembles amylopectin, but it is more branched. Glycogen is present in all cells. It is most prevalent in skeletal muscle and in liver. Highly branched structure of glycogen allows rapid mobilization of glucose

Cellulose
Cellulose is the primary structural component of plant cell walls. Cellulose accounts for over half of the carbon in biosphere. Cellulose is a linear homopolysaccharide with up to 15,000
D-glucose

residues linked by -(14) glycosidic bonds.

CH2OH H O H OH H H H OH

CH2OH

O H OH H H H OH O

Cellulose

Cellulose
Vertebrates lack enzymes capable of breaking the -(14) glycosidic bonds.

Fig. 8-9

Glycoproteins

O-linked oligosaccharides

N-linked oligosaccharides

Erythrocyte Surface
Fig. 8-20

Electron micrograph of erythrocyte surface with ~ 1400 -thick carbohydrate coat

Peptidoglycans
Fig. 8-16b

Bacterial Cell Walls

Fig. 8-15