One of 3 major organic compounds in living organisms

Carbohydrates Lipids Proteins

Definition Carbohydrates are aldehydes or ketones derived from polyhydric alcohols O and H present in same proportion as in water 2:1

Carbohydrates polyhydroxy alcohols having either aldehyde group or ketone group

Glycerol Ployhydric Alcohol

CHOH

Aldehyde

Ketone CHOH

CHO

C=O

Glycerol

CHOH

Aldehyde

Ketone

1. Major source of energy as glucose and glycogen. 2. Structural material in plants (cellulose). 3. Biosynthesis of essential compounds inside body as purines, pyrimidines (DNA and RNA). 1. Glycolipids and glycoproteins enter in structure of cell membrane.

Classification
1- Monosaccharides (simple sugars) as glucose.

2- Oligosaccharides = 2 to 6 monosaccharides units linked together as sucrose. 3- Polysaccharides More than 6 monosacharides linked together as glycogen.

Classification of Monsaccharides 1- Number of carbon atoms No of Carbons Name Triose: Glyceraldehyde and dihydroxy acetone 3 4 5 6

Pentose: Ribose Hexose: glucose, galactose, mannose and fructose

2- According to presence of aldehyde or ketone group. Aldose Aldehyde group: CHO Ketose Ketone group: C=O.

Nomenclature of Monsaccharides 1- Aldoses and ketoses aldehyde and ketone. contain

2- Triose, tetrose, etc. denotes number of carbons

3- According to number of carbons and presence of aldehyde or ketone group Aldotriose Ketotriose

Trioses
Ketone

Aldehyde

Dihydroxy acetone

Ketone

Aldehyde

ose

Erythrose

Erythrulose

ulose

Pentoses

Ribose enter in structure of nucleic acids

( DNA, RNA) and ATP, GTP and coenzymes as NADH.

D-ribulose

important in pentose phosphate pathway in glucose oxidation.

L-arabinose in gums.

Aldopentoses

OH

D-Ribose

D-Xylose

Pentoses

Ribose

enter in the structure nucleic acids ( DNA, RNA) and ATP, and coenzymes.
D-Ribose

Ketopentoses

OH
C=O OH

OH
C=O

D-Ribulose

D-Xylulose

Hexoses

OH OH OH OH OH

Glucose

Mannose

Galactose

KetoHexose

Fructose

OH

Numbering of carbon atoms

Beginning at end of chain nearest carbonyl group.
1 2 3 4 5 6

1 2 3 4 5 6 Fructose

Glucose

D-Glucose

Most common carbohydrate D-glucose called dextrose

dextrorotatory.

as

it

is

D-Glucose

Present in fruits and vegetables Grape sugar Produced by hydrolysis of starch Concentration in blood 100 mg/dl.

D-Fructose

Ketohexose. D-fructose called

levorotatory.

levulose

as

it

is

Fruit sugar. Very sweet sugar. . Main sugar in semen. It

is present in disaccharide (sucrose) and polysaccharide inulin.

dextrorotatory. Present in lactose of milk

D-Galactose

Less sweet than glucose. Enter in structure of galactolipids

D-Mannose
Enter in structure of glycoproteins

Cyclic structure of sugar Sugars exist in aqueous solution as cyclic form. 2 forms of sugar present in and forms. 1- If OH of C1 on right side, it is sugar. 2- If OH of C1 on left side, it is sugar. Cyclic form of glucose is pyranose Cyclic form of fructose is furanose


H C H C OH HO C H H C OH H C OH CH OH 2 O H C H C OH HO C H H C OH H C CH OH 2 O OH HO

H C H C OH HO C H H C OH H C CH OH 2 O

or

Cyclic forms create anomeric carbons alpha has OH down. beta has OH up Fisher projection
H C H C OH HO C H H C OH H C CH OH 2 O OH

Haworth formula H H H H OH H

CH OH 2 C O HO C H H C OH H C OH CH OH 2 D-Fructose

CH OH 2 HO C HO C H H C OH H C CH OH 2 b-D-Fructose O or

CH OH 2 OH C HO C H H C OH H C CH OH 2 a-D-Fructose O

a - D - Fructofuranose HOCH 2 H O HO OH OH H CH 2OH

Some properties of sugars Asymmetric carbon atom Optical activity Muarotaion

Asymmetric carbon atom

Carbon atom attached to 4 different

groups

All monosacchardides have asymmetric carbon atom except dihydroxyacetone

The configuration of such

molecule is chiral.

Asymmetric carbon atom

Optical activity Optical isomers

Isomer

Structure

exist in either right-handed configuration or left-handed configuration.

Left hand

Right hand

Not superimposable

Rotating molecule B this time shows that it is exactly the same as molecule A. You only get optical isomers if all four groups attached to central carbon are different.

All sugars exist as pair of enantiomers: D- and L- Form

Stereoisomers non-identical, mirror images of each other are enantiomers )(optical isomers
Isomers Ability of substance to present in more than one form

pair of enantiomers

Mirror image Cannot be superimposed on one another

D- monosaccharide is a monosaccharides has same configuration at carbon before the end as D-glyceraldehyde (OH group at the right).

L- monosaccharide monosaccharides has same configuration at carbon before end as L-glyceraldehyde(OH group at the left).

To determine D or L, look at chiral carbon before end

If it has same configuration as Dglyceraldehyde (OH group on right) D sugar. D-sugars Common in nature.

D- and L-glyceraldehydes reference points for configuration to other aldoses and ketoses Glyceraldehydes is Reference Sugar

(D)

(L)

D-

L-

D-Sugar

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

CH2OH

CH2OH

D-glucose

L-glucose

How many asymmetric carbon atoms in glucose, fructose

A- Optical activity The ability of substance to rotates polarized light either to right or to left.
Plane polarized light vibrate in on e direction only

plane-

Ordinary light

dextrorotatory ( right ) + or d Angle of rotation

Solution of optically active substance levorotatory ( left) - or l

Racemic mixture Mixture contain equal amounts of 2 optically active sugars, one dextrorotatory and other levorotatory, so it produces no effect on plane polarized light and no optical activity and no rotation Example: Equal amounts of D-glucose and L-glucose.

Isomers
Definition Ability of substance to present in more than one form.

1- Optical isomers or enatiomers

Substance has one asymmetric carbon atom has 2 isomers. Substance has 2 or more asymmetric carbon atoms has 2 n isomers where (n) is the number of asymmetric carbon
atoms.

CHO CHO H HO H H C C C C OH H OH OH H C C C C CH2OH OH C H2O H

1- Glucose O 4 C has asymmetric carbon C H 24 HO atoms isomers 16 H C isomers. OH

2- Fructose OH 3 H C has asymmetric CH2OH CH2OH carbon atoms 2 3 F ir s t a s y m m e t r ic c a r b o n F r u c t o s e8 h 3 s a isomers isomers. a to m o f g lu c o se G lu c o s e h a s f o u r

a sy m m e tr ic c a r b o n a to m s

a s y m m e t r ic c a r b o n a t

Glyceraldehyde has one asymmetric carbon atom so it has L and D mirror image or optical isomers. Most of monosaccharides are present in D-form. D-means OH before last carbon on right. L-means the OH before last carbon on left.

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

H C C C C C H OH H H

CH2OH

CH2OH

D-glucose

L-glucose

2- Anomers isomers obtained from change of position of OH attached to anomeric carbon (C1 in aldose and C2 in ketose). and glucose are anomers.

H C H HO H H C C C C

OH OH H OH O or

HO C H HO H H C C C C

H OH H OH O

CH OH 2 -glucose

CH OH 2 -glucose

anomers

3- Epimers
Change in the position of OH around epimeric carbon. Epimeric carbon is any asymmetric carbon atom other than anomeric carbon. Glucose and galactose are epimers at C4 Glucose and mannose are epimers at C2

Epimers at C2 CHO HO HO H H C C C C OH H OH OH C2 H HO H H CHO C C C C OH H OH OH

Epimers at C4 CHO H HO HO H C4 C C C C OH H OH OH

CH2OH Mannose

CH2OH Glucose

CH2OH Galactose

Mutarotation

It is gradual change in specific rotation of optically active substance. -glucose freshly dissolved in water has specific rotation of +112. -glucose freshly dissolved in water has specific rotation of +19.

when both anomers of glucose, dissolved in water left for some time and changed into an equilibrium mixture of glucose (36% alpha and 64% beta) with specific rotation of +52.5.

Monosaccharide Derivatives
1- Sugar acid
1. Aldonic acid: mild oxidation. Oxidation of C1 Glucose ----------> D-gluconic acid 2. Uronic acid: moderate oxidation Oxidation of C6. Glucose ----------> D-glucouronic acid 3. Aldaric (saccharic): strong oxidation by HNO3 Oxidation of C1 and C6. Glucose ----------> D- glucaric acid

2- Sugar Alcohols Reduction of carbonyl group results in sugar alcohol 1. 2. Glucose -------> Mannose-------> sorbitol mannitol sorbitol+

3. Fructose -------> mannitol

3- Amino Sugars

Hydroxyl group (OH) at the C-2 position is replaced by amino group (NH2).
Glucosamine
- Enter in structure of heparin.

4- Sugar Esters
Sugar phosphate

5- Deoxy Sugars OH at C2 is replaced by H atom as deoxyribose which enter in structure of DNA.

Chemical Properties of Monosaccharides

1- Reducing sugars Sugars containing free aldehyde or ketone group can reduce reagents as cupric ions in Benedict's test to cuprous ions

2- Reaction of monosacchardies with acids 1- It gives phosphate ester with phosphoric acid. B- Reaction with sulfuric acid (concentrated non-oxidizing acid) H2SO4 removes 3 molecules of H2O from
sugar and forms furfural with pentoses and hydroxyl methyl furfural with hexoses.

3- Osazone Formation Characteristic yellow crystals resulted from reaction of sugars with phenylhydrazine. All sugars have free aldehyde or ketone group can form osazone. Importance of osazone Detect presence or absence of glucose and lactose in urine and differentiate between them.

Disaccharides Formed of 2 molecules of monosaccharides. Types

1- Reducing : maltose, cellobiose. 2- Non-reducing: sucrose lactose,

Maltose= glucose + glucose ( 1 glycosidic bond). 4 Lactose= glucose + galactose ( 1 glycosidic bond). 4 Sucrose= glucose + fructose ( 1 glycosidic bond) 2

Maltose Sources Digestion of starch by amylase enzyme. Properties It contains a free carbonyl carbon so it is: 1) Reducing sugar. 2) Can form osazone. 3) Can present in alpha and beta forms. 4) Can show mutarotation.

Lactose (milk sugar)

Sources Milk. Properties as maltose

Sucrose (Table sugar) Sources Cane and beet Properties It does not contain a free carbonyl carbon so its properties is opposite to maltose

Polysaccharides Starch Glycogen Dextrins Cellulose

Function 1- Starch and glycogen are storage form of energy. 2- Cellulose are structural molecules.

Starch- 1

Formed of inner part amylose and outer part amylopectin Source: Potatoes.

Starch

Amylose

Amylopectin

Digestion of starch occurs in stages:

to dextrins and to maltose to glucose

Amylose

Glycogen- 2

Glycogen constitutes 10% of liver mass and 1-2% of muscle mass. Glycogen is energy storage in animals. It is similar in structure to amylopectin.

3- Dextrins
HYDROLYTIC PRODUCTS OF STARCH STARCH

----------> erythrodextrin ----------> acrodextrins ----------> maltose ----------> 2 alpha glucose.

----------> amylodextrin

4- Cellulose
1- Structure

Consists of long non branching chains of glucose linked with (1-4). 2- Source of cellulose. It is present in plants as wood and cotton.

Digestion of cellulose No enzyme can digest (1-4) bonds so it is not digested in human. It digested in herbivorous animal that have this enzyme. So, cellulose passes in stool and prevent constipation.

Heteroploysaccharides 1- Glycosaminoglycans or mucopolysaccharides 2- Glycoproteins 3- Proteoglycans Structure Polymers of repeating disaccharides. Site GAG are present in extracellular spaces, particularly connective tissue. Function Lubricants and cushions for other tissues as they hold large quantity of water.

1- Glycosaminoglycans or mucopolysaccharides
Classification 1- Sulfate free mucopolysaccharides: Hyaluronic acid Repeating disaccharide consisting of glucuronic acid & N-acetyl-glucosamine linked

2- Sulfate containing mucopolysaccharides 1- Chondroitin Sulphate Glucouronic acid & N-acetyl-galactosamine with sulphate at C4 or C6 2- Heparin Iduronic acid with sulphate at C2 and N-acetyl glucosamine with sulphate on C2 and C6. 3- Dematan sulfate L- iduronic acid and N-acetyl-glucosamine with sulphate on C 4.

2- Glycoproteins Monosaccharides that are attached to proteins. PROTEOGLYCANS Chains of glycosaminoglycans attacched to protein.