Você está na página 1de 22

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

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

H-C-OH
6

CH2OH

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

D-Fructose
1

CH2OH
2

D-Fructose is: Carbohydrate Monosaccharide Ketose Hexose Ketohexose Compound with 3 chiral centers One of 8 possible stereoisomers of fructose

C=O

HO-C-H H-C-OH
4 5

H-C-OH
6

CH2OH

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
H

CH2OH
5

36%
O H
2

H
1

H-C-OH HO-C-H
4 3

< 0.1%
6

H OH
3

CH2OH
5

HO H
1

OH

H-C-OH
H-C-OH
6 5

H
4

OH H
2

OH

H OH
3

C O

-D-Glucose

Anomeric carbon

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
6

Anomeric carbon
HOH2C
5 1

HOH2C
5

O H
4

CH2OH OH
3 2

HO-C-H
4

H OH H
4

OH

CH2OH HO
3 2

OH

H-C-OH
H-C-OH
6 5

C O

-D-Fructose

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

CH2OH O H 4 OH H H H OH OH

+ HO

H 1

-Galactose

-Glucose

Lactose O- -D-galactopyranozyl(1 4)-D-glucopyranose


CH2OH OH O H OH H H 1 O OH OH H CH2
2 H

CH2OH H HO H O H OH H H

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

O OH

H CH2

+ OH

OH

OH

OH

-Glucose

-Fructose

Sucrose O- -D-glucopyranozyl(1 2)- -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

-(1 6) 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

-(1 6) 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 -(1 4) glycosidic bonds.

CH2OH H O H OH H H H OH O H

CH2OH O H OH H H H OH O

Cellulose

Cellulose
Vertebrates lack enzymes capable of breaking the -(1 4) glycosidic bonds.

Fig. 8-9

Glycoproteins

O-linked oligosaccharides

N-linked oligosaccharides

Erythrocyte Surface
Fig. 8-21

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

Oligosaccharides & Cell Recognition


Carbohydrates can link together in many possible ways For example, two different hexoses can combine in 36 different ways Lectins, ubiquitous proteins that bind to carbohydrates, often appear at the cell surfaces Protein-carbohydrate complexes have multiple intermolecular H-bonds Leucocytes bind to damaged tissue due to interactions of oligosaccharides with selectins Proteins on the surface of a spermatozoid recognize oligosaccharides on the ovum surface Various bacteria, viruses, and eukaryotic parasites bind to specific oligosaccharides expressed on the surface of target tissues

Fig. 8-22

Peptidoglycans
Fig. 8-17

Fig. 8-18

The cell wall of a bacteria consist of a helical cable composed of several peptidoglycan strands

Bacterial Cell Walls

Fig. 8-16

Hans Christian Joachim Gram, a Danish bacteriologist, the inventor of the Grams stain Crystal violet

Biomass
http://en.wikipedia.org/wiki/Biomass_(ecology)
There are ~ 40,000,000 bacterial cells in a gram of soil and ~ 1,000,000 bacterial cells in a milliliter of fresh water. There are ~ 5 1030 bacteria on Earth with a total biomass equaling that of plants. Some researchers believe the total biomass of bacteria exceeds that of all plants and animals.

Evolution: Time vs. # of Organisms


Prebiotic Era: ~ 1 x 109 years = 365 x 109 days = 876 x 1010 hours ~ 1013 generations of primordial cells There are ~ 5 1030 bacteria on Earth

Powers of Ten http://www.youtube.com/watch?v=0fKBhvDjuy0