Carbohydrates :

Physical and Chemical Properties

By

drg. Prasetyo Adi, MS

Objectives
To Understand : The importance of carbohydrates for organisms The classification of carbohydrates The physical and chemical properties of carbohydrates Reference : March and Bettelheim,1995; Introduction to General,Organic & Biochemistry, 4th edition, Saunders College

Whats carbohydrate ?
Compound containing C, H, O General formula : Cx (H2O)y Polyhydroxylated aldehydes aldose Polyhydroxylated ketones ketose In plants, simple carbohydrate (glucose) is synthesized from carbon dioxide and water by photosynthesis

CARBOHYDRATES:
POLYHYDROXY ALDEHYDES OR KETONES

SIMPLE CARBOHYDRATES MOLECULES ARE SYNTHESIZED

CHIEFLY BY CHLOROPHYL-CONTAINING PLANTS AS LONG AS THE SUN IS SHINING

PHOTOSYNTHESIS

6 CO2 + 6 H2O

LIGHT KHOLOROFIL

C6H12O6 + 6 O2

The Importances of carbohydrates

Give structure to cell walls and cell membrane (e.g. cellulose) Humans: Provide the majority of energy A source of carbon atoms for synthesis of many compounds nucleic acids and connective tissue Comprise large portions of nucleic acids that form DNA and RNA (e.g. ribose, deoxyribose) Comprise some portions of connective tissues

Classification
Based on : 1. Number of sugar units in total chain 2. Number of carbon atoms in the chain 3. Stereochemistry

Classification of carbohydrate based on the number of sugar units :

Monosaccharides : single sugar unit e.g. glucose, fructose, galactose Disaccharides : 2 sugar units e.g. lactose, sucrose Oligosaccharides : 3-10 sugar units e.g. maltotriose Polysaccharides : > 10 sugar units e.g. starch, cellulose

Monosaccharides classifisation based on the number of carbon atoms

Stereoisomer
Stereochemistry : study of the spatial arrangement of the molecules Stereoisomers have : - the same order and types of bonds - different spatial arrangements - different properties Many biologically important chemicals, like sugars, exist as stereoisomers.

Enantiomers
Pairs of isomers (stereoisomers) that are nonsuperimpossable mirror images of each other It must have at least 1 assymmetric carbon ( a chiral carbon)

H C F

Br OH

CH3CH2

Mirror
CH3CH2

Br

Br H H

CH3CH2

CH3CH2

a non chiral C

H
H H

Br
Br

CH3CH2

Mirror
CH3CH2

CH3 H

Br

Br

CH3 H

CH3CH2

CH3CH2

Chiral C

H
CH3 H

Br
Br

CH3

Functional groups
Double bond
Hydroxyl Carbonyl Carboxyl C C C

OH
O O C

OH Sulfhidril
Amine SH
NH2

O C H H C OH H C OH H D(+) GLISERALDEHID

H2C C

OH O

H C OH H DI HIDROKSIASETON

Aldehyde ( aldose ) derivates :

H H

O C H

C C
C H

OH OH

D(+) GLISERALDEHID

O C H H H

O C H HO H C C C C H OH

OH OH

CH2OH
D(-) ERITHROSE

CH2OH
D(-) THREOSE

O C H H H H C C OH OH OH HO H H

O C H

O C H H HO H C C C C C C OH H OH HO HO H

O C H C C C C C C H H OH

C C
C C C C

H OH OH

C C
C C

CH2OH
D-RIBOSE

CH2OH
D-ARABINOSE

CH2OH
D-XILOSE

CH2OH
D-LIXOSE

D - Alosa

D - Glukosa

D - Gulosa

D - Galaktosa

D - Manosa D - Altrosa

D - Idosa

D - Talosa

Structure of carbohydrates
Open Chain Forms Cyclic Forms
CH2OH H H OH OH H OH O H OH H

Glucose

PHYSICAL PROPERTIES OF MONOSACCHARIDES

sweetness solubility optical rotation

Table. Comperative Sweetness of Some Sugars and Artificial Sweeteners.

Sugar or Artificial Sweetener Lactose Galactose Maltose Glucose Sweetness Relaitive to Sweeteners 0,16 0,32 0,33 0,74 Disaccharide Monoccharide Disaccharide Monoccharide Type

Sucrose
Invert sugar Fructose Aspartame Acesulfame-K Saccharin

1,00
1,25 1,74 100 150 200 450

Disaccharide
Mixture of Glucose and Fructose Monoccharide Artificial sweetener Artificial sweetener Artificial sweetener

Solubility
At room temperature : carbohydrates are solids Because of the many OH groups as well as the oxygen of the aldehyde or ketone groups carbohydrates are soluble in water these groups form hydrogen bonds with the solvating water molecules

Optical Rotation
All three forms of D-glucose (alpha, beta, and open-chain) rotate the plane of polarized ligth to the right D-(+)-glucose L-glucose rotate the plane of polarized ligth to the left L-(-)-glucose There is no simple relationship between configuration and rotation D-(+)-glucose = dextrose D-(-)-glucose = levulose

CHEMICAL PROPERTIES OF MONOSACCHARIDES

Cyclic forms Oxydation Glycoside formations

O C H H HO H H C C C C OH H OH OH HO H H

CH2OH C C C C O H OH OH

CH2OH D(+) Glucose

CH2OH D-Fructose

CH2OH H H OH OH H OH O H OH

CH2OH

H
H

O OH

CH2OH

OH OH H

Pyranose

Furanose

H H HO OH OH H OH CH2OH H H C O
Rotate C4 - C5

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

CH2OH H H OH OH H OH O H

H OH O

O OH

OH

Oxidation
All of monosaccharides are reducing sugars Aldehydes and OH groups are easily oxidized Aldehydes are oxidized to carboxylic acids

Dissaccharides
2 units of monosaccharides
Glycoside bonds From carbon 1 to - OH groups (C4 position). or position from C1 of 1st unit 1 to OH group C4 of 2nd unit

H OH
6 4 5

1,4- or 1,4- linkage

H OH H
2

O
4 1

6 5 3

HO HO
3

H
2

O
1

O HO H

H H

OH H

OH

OH

1,4- linkage

Maltose.
It is a dissaccharide
Contains 2 glucose units connected in a 1 4 linkage, from hydrolisis of starch by enzymes/acid Ex. : Enzyme 1,4 - glukan 4- glucanohydrolase in saliva Enzyme 1,4 - glukan maltohydrolase in malt

1 Maltose
H
4 5 6

- glukosidase

2 D-Glucose

HOH2C H
2

O
1

HO HO
3

H
4

H HOH2C

6 5

H H

OH O

H
2

O
1

HO

1,4- a linkage
H

OH

OH

Cellubiose
A dissaccharide

From hydroliysis of cellulose by enzyme -glukosidase

Connected by 1,4 glycoside linkage Cellubiose hydroliysis with acid produces and -D-glucose

HOH2C

H H O O HO H H H OH HOH2C H O OH

HO HO H H OH

Lactose
A dissaccharide Connected by 1,4 glycoside linkage
Lactose hydrolysis D - glucose and D - galactose, D - glucose

Source : * mammalian milk 5% Lactose

OH HOH 2C H HO H H OH H H O O HO

H HOH 2C H O H H H OH OH

Sucrose.
Contains : glucose and fructose. The glycoside linkage is from C-1 of D-glucose (an aldose) to C-2 of D-fructose (a The differences of sucrose from other dissaccharides are : 1. There are 2 anomeric carbon that used for glycoside linkage.
2. Glucose and fructose in sucrose have no hemiacetal group, because sucrose isnt an equilibrium state with forms aldehyde or keton in water .

3. Sucrose have no mutarotation and isnt reducing sugar.

H2OH H OH OH H CH2OH H H OH H OH O O H H

ALPHA-GLUKOPIRANOSE

BETA-FRUKTOFURANOSE

O OH CH2OH

Poly saccharide
1. Amylose
Repeated condensation of 1,4 a-D-glucose

Polyglucose Contains 1000 to 2000 glucose units

It has 1,4 glycoside linkage It has flexibility to form conformation

O O O O

Coil / helix

HO

Amylose
O O

2. Amylopectin.

A polymer of -D- glucose It isnt entirely a straight-chain molecule, but has random branches with 1,6 glycoside linkage There are 20 25 glucose units in the straigth chain form with 1,4 glycoside linkages A Macromolecule contains 105 to 106 glucose units Test with Iodine ( I2 ) gives deep purple colour.

CH 2OH

CH 2OH

O
O OH OH O OH

Amylopectin
OH O CH 2

n
CH 2OH

O
O OH OH O OH

O
O OH

Glycogen

( also called animal starch)

Glycogen is similar to amylopectin, has 1,6 glycosidic linkage at branching points and 1,4 glycosidic libjkage at the straigth-chain portions.
The structural difference between glycogen and amylopectin is in the degree of branching. There are 10 to 12 glucose units at straight chain. It is a giant molecule, containing about 106 glucose units.

Cellulose.
A linear polymer containing D-glucose units, all in the 1,4 glycosidic linkage The structural difference between cellulose and amylose : in cellulose all the 1,4 glycosidic linkages are . Cellulose is the most abundant molecule in living tissues.
CH 2OH

O
CH 2OH

OH

O
CH 2OH

OH OH

O
OH

OH OH

OH
OH

Cellulose

Acidic Polysaccharides
The important role : in the structure and function of connective tissue
The tissues are matrix between organs and cells that provides:

mechanical strength
filters the flow of molecular information between cells.

Specialized form Examples : Cartilage, bone, synovial fluid, skin, tendons, blood vessel walls, intervertebral disks and cornea.

Hyaluronic acid.
A typical and the simplest (structurally) acidic polysaccharide of connective tissue
A giant molecul : molecular weigth 105 107, contains from 300 to 100 000 repeating units, depending the organ in which it occur.

Most abundant in embryonic tissue and in specialized connective tissues such as :

- The synovial fluid : acts as lubricant

- The vitreous of the eye : its function is to provide a clear, elastic gel that maintains the retina in its proper position.

Molecular structure of hyaluronic acid :

Composed of D glucuronic acid linked to N acetyl glucosamine by 1,3 linkage, the latter in turn is linked to
the next glucuronic acid by 1,4 linkage.
N-Acetylglucosamine

CH2OH

O O O
OH OH

CH2OH

CH2OH

OH O NH n C O CH 3

O O
OH OH
Glucoronic acid

Glucoronic acid

Hyaluronic acid

Heparin.
It is one of the most acidic polysaccharides, ocuurs in such tissues as lung, liver, skin and intestinal mucosa
Biological function : anticoagulant activity prevents blood clotting.

O C OO OH O OSO3O

CH2OSO3H O OH O NHSO3H COOOH OSO3O O

CH2OSO3-

OSO3NH C O CH3

HEPARIN

THANK YOU !!!