Carbohydrates chemistry

Carbohydrates are aldhyde or ketone derivatives of polyhydric alcohol (contain more than one -OH group)

Classification of carbohydrates

1- Monosaccharides (simple sugar) 2- Oligosaccharides 3- Polysaccharides

They are the simplest units of sugars. Contain 2-10 simple sugar units. Contain more than 10 sugar units.
Cannot be hydrolyzed into a simpler form.

Monosaccharides (simple sugar) General formula Cn H2n On

a- Trioses:

They contain 3 carbon atoms.

1. Aldotriose: Glyceraldehyde. ( glcerose )
2. Ketotriose: Dihydroxy acetone.

b-Tetroses:

They contain 4 carbon atoms.

1. Aldotetrose: Erythrose.
2. ketotetrose: Erythulose

c- Pentoses:
They contain 5 carbon atoms

1. Aldopentose: Ribose , xylose C3

2. Ketopentose: Ribulose , xylulose C3

d- Hexoses:

They contain 6 carbon atoms

1. Aldohexose: Glucose , Galactose C4 , Mannose C2

2. Ketohexose: Fructose
Glyceraldehydes Dihydroxy acetone Erythrose Erythulose

Ribose xylose Ribulose xylulose

Glucose Galactose Mannose Fructose

  The pentose sugar present mainly in the heart muscle is Lyxose

Isomerism in sugars
Stereo Isomers: → are compounds that have the same structural formula and differ in spatial configuration.
 The presence of asymmetric carbon atoms allows the formation of isomers
 Asymmetric carbon atom is a carbon atom attached to four different groups or atoms.

 The number of possible isomers of compound depends on the number of asymmetric carbon atoms (n) and is equal to [ 𝟐𝒏 ]
 Glucose with 4 asymmetric carbon atoms therefore has 16 isomers.
 Fructose with 3 asymmetric carbon atoms therefore has 8 isomers.
 The most important type of isomerism in sugars
1- D and L isomers (Enantiomes) (mirror image):
• The designation of a sugar isomer as the D form or its mirror image.
• The orientation of the -H and -OH around the carbon atom adjacent to the terminal primary alcohol determines whether the sugar
belongs to the D- or L- series.
• In glucose the orientation of the -H and -OH groups around the carbon atom 5 adjacent to the terminal primary alcohol carbon
determines D or L series.
• When the -OH group on this carbon is on the right, the sugar a member of the D-series.
• When the -OH group on this carbon is on the left, the sugar is a member of the L-series.
• Most of the Monosaccharides occurring in mammals are of the D- configuration

2- Fisher projection and Haworth formula:

• The hemiacetal ring is called a Fisher projection , in which The carbon chain is written vertically

• A second way of representing the cyclic for representing the cyclic

forms of the sugar is the Haworth projection (formula).
3-Pyranose and furanose ring structures:
• In solution, Monosaccharides are found in ring structure.
In Aldohexose ( glucose )
→ 𝐶1 - 𝐶4 form furanose ring glucofuranose

→ 𝐶1 - 𝐶5 form pyranose ring glucopyranose (more stable)

 The predominant form of glucose in solution is Glucopyranose.

In ketohexoses ( fructose)
→ 𝐶2 - 𝐶5 form furanose ring fructofuranse (more stable)

→ 𝐶2 - 𝐶6 form pyranose ring fructopyranose

Note

 The smallest monosaccharide having furanose ring structure is Ribose, xylose.

4- - and β- isomers (Anomers):

 The orientation of hydroxyl group in the first carbon atom either to the right and called alpha anomer or to the left and called beta

anomers e.g. α-D-glucose and β-D-glucose.

 Formation of hemiacetal ring results in the creation of an anomeric carbon atom at C1 of an aldose or at C2 of ketose.
 The carbon atom which becomes asymmetric when the straight chain form of monosaccharide changes into ring form is known as

Anomeric carbon atom.

5- Epimers:

 Two sugars which differ from one another only in configuration around a single carbon atom.
 These are Monosaccharides differ in the position of the hydroxyl group at only one of their asymmetric carbon atoms.
 E.g.: glucose and galactose are 𝒄𝟒 epimers.
 E.g.: glucose and mannose are 𝒄𝟐 epimers.

Note:

Mannose and galactose are not epimers.

They differ in groups at two carbon atoms (2 and 4)
Optical activity:
• The presence of asymmetric carbon atoms also confers optical activity on the compound.
Optically active substances → are substances, which have the capacity to rotate the plane of polarized light (light that vibrates in one
direction) either to the right or to the left.
• If to the right side, the monosaccharide is dextrorotatory ( + ) or dextrose e.g. glucose.
• If to the left side, the monosaccharide is levorotatory ( - ) or levulose e.g. fructose.
• When equal amounts of dextrose and levulose isomers are present, the resulting mixture has no optical activity Since the activities of
each isomer cancel one another & Such a mixture is said to be Racemic

Mutarotation
• Mutarotation refers to change in Optical rotation.
• It is change in the angle of rotation of the beam of polarized light produced by a freshly prepared sugar solution when lefted for a
period of time.
• - glucose has an angle of + 115 while β- glucose has an angle of +19 but after a period of time , the degree of rotation becomes
constant at + 52.5
• The Explanation of this phenomenon is that the cyclic  and β-anomers of sugar in solution are in equilibrium with each other, and
can be interconvert through an open chain formula.
 Properties of Monosaccharides and sugar derivatives
1-Optical activity:
• Is due to presence of asymmetric carbon atom.
• All monosaccharides are optically active except Dihydroxyacetone.

2-Effect of acid:

Phosphoric acid: → sugar reacts with phosphoric acid to form ester of great importance.
Glucose + phosphoric acid → glucose-1-phosphate
Sulphuric acid: It removes water from the Monosaccharides giving a substance called furfural or hydroxyl methyl furfural.

3-Oxidation: →Means oxidation of Monosaccharides and production of sugar acids.

a- Oxidation of aldhyde group: Aldonic acid is produced →→→ E.g: Glucose gives gluconic acid
b- Oxidation of last alcoholic group: uronic acid is produced →→→ E.g: Glucose gives glucuronic acid.
c- Oxidation of both aldhyde and alcoholic groups: Saccharic acid produced →→→ E.g: Glucose gives glucaric acid.
Carboxylic acid derivatives of glucose are important including
1) D-glucuronic and L-Iduronic (in mucopolysaccharides synthesis)
2) L- gluconic (an intermediate in uronic acid pathway

and formation of vitamin C).

4- Reduction: → Means reduction of Monosaccharides and production of sugar alcohols

Examples
Glucose, Fructose →→→ Sorbitol xylose, xylulose →→→ xylitol
Mannose →→→ Mannitol. ribose →→→ ribitol

• D-Ribitol enters in the formation of vitamin B-complex or riboflavin (B2)

Inositol:

 It is a cyclic alcohol derived from glucose.

 It is present in muscle so called myo-inositol or muscle sugar.
 It can be regarded as a member of vitamin B-complex.
 It forms ester with phosphoric acid called phytic acid (Hexa phosphoric acid).
 Inositol is a lipotropic factor (prevent fatty liver).

5- Reducing agents:

 monosaccharides carry free aldehyde or Ketone group that reduces alkaline reagent such as fehling and benedict

6- Fermentation:

 Means decomposition of Monosaccharides due to some bacteria and yeast in the absence of oxygen producing 𝐶𝑂2 & ethyl
alcohol.
 Glucose, fructose and mannose are fermentable sugars.
 Pentoses, lactose and polysaccharides are non-fermentable sugars
7- Amino sugars:

These are sugars in which the -OH group on 𝑐2 is replaced by an amino group
E.g.: Glucosamine and galactosamine from glucose and galactose respectively

8- Deoxy-sugar:

These are sugars in which the-OH group on 𝐶2 or last carbon atom (C6) is replaced by a hydrogen atom

If 𝑐2 is replaced by a hydrogen atom, deoxy sugar is produced. E.g. : Ribose →→ deoxyribose.

If the last carbon atom 𝑐6 is replaced by a hydrogen atom, methylose is produced . E.g. : L-galactose →→ L-fucose (β,L 6-deoxy galactose)
9- Glycosides:

 These are compounds formed by a condensation reaction between a sugar and hydroxyl group of a second compound which may
or may not be another sugar.
 In these compounds, the linkage between the two residues is known as the acetal or O-glycosidic linkages.
 The carbohydrate residue is attached by the acetal linkage at the anomeric C-atom to the second sugar or non-sugar (aglycon)
residue.
 If the carbohydrate residue is glucose the resulting glycoside is known as glucoside and if it is a galactose we obtained a
galactoside.

The most important glycosides are

1) Cardiac glycosides: are glycosides used in treatment of heart failure.

2) Streptomycin: an important antibiotic.
3) Glycolipid: a glycoside containing sugar lactose.
4) disaccarides

Sugar + other compound

sugar non sugar

 Sialic acid
 Derivatives of nine carbon atom monosaccharides that named as neuraminic acid

 Its name is N acetyl neuraminic acid that is found in different tissue cells. (NANA)

 The structure of sialic acid is not fixed

i.e. amino group can carry acetyl group and hydroxyl groups might be variably substituted with acetyl, methyl, sulfate and
phosphate groups

Biosynthesis:

Mannosamine reacts with pyruvate to produce N acetyl neuraminic acid (NANA).

Role:

1) Expressed in cancer cell to enhance metastasis of cancer.

2) Used by different microorganisms as a nutritive substance.

3) Provide polarity in cell membranes (SIALIC acid on cell membrane bind with water)

4) Aids some bacteria and viruses to bind with host receptors (in Human Influenza infections)

5) Brain development in infants

 Chemical Properties of monosaccharides
Molish Test
Principle:
 H2SO4 is more dense than sugar solution so H2SO4 descends to the bottom & Sugar solution to upwards.
 Then H2SO4 absorbs the water from the sugar solution to give furfural (Non-Colored) & then by addition of α-napthol
will give with all monosaccharide → Reddish violet ring turns into dull violet color after shaking.

Note

 Molisch test is general test for detection of carbohydrates

 All monosaccharide and some disaccharides (maltose, cellobiose, lactose) have ability for reduction of alkaline agents → due to
presence of free aldehyde (CHO) or ketone (C=O) groups → In such a reaction, the sugar becomes a carboxylic acid

Fehling Test
 Give Reddish brown PPT or red PPT or orange PPT with all monosaccharide → depends on the amount of heating & amount of
sugar

Benedicts Test
 More sensitive and more accurate than Test.
 Give Reddish brown PPT or red PPT or orange PPT with all monosaccharide → depends on the amount of heating & amount of
sugar
Note

 Benedicts Test gives only with reducing sugars but fehling test give with reducing sugar and tartarate, oxalate & urate.

Barafoid Test
 This test is used for → distinguishing monosaccharides from disaccharides through:
1) Control PH
2) Control time of heat
 The test occurs in acidic medium – this makes monosaccharide reduce the Cu ions rapidly.
 But in prolonged heating → disaccharides will be hydrolyzed into monosaccharides.
 Give Yellow or Red PPT
 Before 5 min → glucose or fructose
 After 10 min → Lactose or Maltose

Specific tests
Ketose Test
 Depends on the presence of (C=O) group & this test differentiates between aldose & Ketose (Glucose, fructose)
 Give Orange color → Fructose or No orange Color → Glucose

Seliwanoff Test
 Depends on the presence of (C=O) group & this test is used in differentiation between aldose & Ketose (Glucose, fructose)
 Give Orange color → Fructose or No orange Color → Glucose
Osazone Test
 Reaction of reducing sugars with phenyl hydrazine to form ozazone crystals
 Monosaccharides differing only in the first and second carbon atoms will produce similar osazone
 Under light microscope we found

Its glucosazone Lactosazone maltosazone

Or fructosazone

Medical Importance of Osazone Test:-

① Confirm the presence of glucose in urine or not.

② Differ between glucose & other reducing sugars which is present normally in urine (Lactose in urine of lactating female)
 II- Oligosaccharides
 Oligosaccharides formed from 2-10 sugar units linked together by glycosidic linkage.

Disaccharides
These are sugars formed from two monosaccharide units
Examples: 1- Maltose 2- Cellobiose 3- Lactose 4- sucrose

1-Maltose
It is called "malt sugar" since it is a chief sugar of malt "germinating barely"
It is formed from two units of  -D- glucose linked together by  -(1-4) O-glycosidic linkage.
It is a reducing sugar due to presence of free aldhyde group.
It form osazone.
It can be hydrolyzed by acids and maltase enzyme in small intestine to give two molecules of - D- glucose.
It is a fermentable sugar.
2-Lactose
It is also called "milk sugar" since it is the main sugar of milk
It is formed in mammary gland from one molecule of β-D-glucose and another molecule of β-D-galactose linked together by
β-(1-4) O-glycosidic linkage.
It is a reducing sugar due to presence of free aldhyde group
It forms osazone.
It can be hydrolyzed by acids and lactase enzyme in small intestine to give one molecule of β-D-glucose and another molecule of
β-D- galactose.
It is non fermentable sugar so doesn't produces gases in small intestine of baby and so no colic is produced from ingestion
It is not sweet to enable the baby to drink much milk with no loss of appetite.
3- Sucrose
It is also called "cane or beet sugar" since it is obtained from cane and beet.
It is the ordinary sugar of diet.
It is formed from one molecule of -D- glucose and another molecule of β-D-fructose linked together by -(1-2) o-glycosidic linkage.
It is a non-reducing sugar due to absence of free aldhyde or ketone group
It does not form osazone
It can be hydrolyzed by acid , invertase enzyme (in yeast) and sucrase enzyme in small intestine to give one molecule of -D- glucose
and another molecule of β-D-fructose.
It is a fermentable sugar.
 Invert sugar:
This is the hydrolytic mixture of sucrose.
It is formed from equal amount of -D- glucose and another molecule of β-D-fructose.
It is called an invert sugar as sucrose is dextrorotatory (+) , but on hydrolysis it becomes levorotatory ( - ) , Since the levorotation of
fructose is more powerful than dextrorotation of glucose
Honey is a natural example of invert sugar .

4 - Cellobiose
It is a disaccharide produced by a partial hydrolysis of cellulose
It is formed from 2 molecules of β-D-glucose linked by β(1-4) glycosidic linkage.
It is a reducing sugar due to presence of free aldhyde group
It forms osazone.
It can't be digested in intestine of human due to absence of enzymes that hydrolyze β-(1-4) glycosidic linkage.
It can be digested in a large intestine of rabbits and rumen of ruminants due to presence of cellulase enzymes in bacteria
that hydrolyze β-(1-4) glycosidic linkage
Cellobiose is fermentale sugar
 Chemical Properties of Disaccharides
Chemical Properties
①𝑀𝑜𝑙𝑖𝑠ℎ 𝑇𝑒𝑠𝑡 → Give (+Ve) with all Disaccharides

②𝐹𝑒ℎ𝑙𝑖𝑛𝑔 𝑇𝑒𝑠𝑡 → Give (+Ve) with Disaccharides except sucrose (Non-Reducing sugar)

③𝐵𝑒𝑛𝑒𝑑𝑖𝑐𝑡𝑠 𝑇𝑒𝑠𝑡 → Give (+Ve) with Disaccharides except sucrose (Non-Reducing sugar)

④𝐵𝑎𝑟𝑎𝑓𝑜𝑖𝑑 𝑇𝑒𝑠𝑡 → Give (+Ve) after 10min

⑤𝐾𝑒𝑡𝑜𝑠𝑒 𝑇𝑒𝑠𝑡 → Give (+Ve) with sucrose after prolonged heating

⑥Seliwanoff Test → Give (+Ve) with sucrose after prolonged heating

 III- Polysaccharides(polymer)
 These are formed from more than 10 sugar units linked together by a glycosidic linkage

Classification of polysaccharide:
1. Homogenous polysaccharides: formed from the same types of repeating monosaccharide units.
2. Heterogonous polysaccharides: formed from the different types of repeating monosaccharide units.
 I- Homogenous polysaccharides
1-Starch
 It is a plant polysaccharide present in wheat, maize, sweet potatoes,...etc.
 It is a simple polysaccharide formed from -D- glucose units.
 It is formed from two chief constituents, which are amylose and amylopectin
Amylose Amylopectin
It is a straight chain and helical structure It is highly branched chain
The intervals of glucose units of each branch is 24-30.
Formed from -D- glucose units linked by - 1-4 glycosidic Formed of -D- glucose units linked by - 1-4 glycosidic linkage
linkages and by -1-6 glycosidic linkage at point of branching
It gives a blue color with iodine It gives a violet color with iodine.
It forms the inner part of granule It forms the outer part of granule
Constitutes 15-20% of starch granule Constitutes 80-85% of starch granule
Partial hydrolysis with amylase enzyme or acids gives various
types of dextrins.
Complete hydrolysis by amylase enzyme gives amylose.
Complete hydrolysis by acid gives glucose units.

2- Dextrins
They are the product of hydrolysis of starch (amylopectin).
They include amylodextrin, erythrodextrin and achrodextrin.
3- Dextrans
They are homogenous polysaccharides produced by certain type of bacteria when allowed to grow on certain type of media.
They are formed from α-D-glucose linked by α-1-3 , 1-4 and 1-6 glycosidic linkage.
They are used as plasma constituents in treatment of shock.
Used for intravenous infusion as plasma substitute.

4- Glycogen
Glycogen is often called animal starch.
It is the main storage form of carbohydrates in animal tissues (liver and muscle).
Its structure is similar to amylopectin of starch and formed from α-D-glucose units linked by α-1-4 glycosidic linkage and  1-6
glycosidic linkage at point of branching
It gives red color with iodine.

5- Cellulose
The most abundant carbohydrate found in nature.
It is a straight structure formed from β-D- glucose linked by β-1,4
glycosidic linkage.
It is insoluble in water

Can’t be digested in gastrointestinal tract of carnivorous animals and

human but can be digested by herbivorous animals.
In herbivorous animals there are microorganisms have enzymes that can attack the β linkage.
In carnivorous animals it is important in stimulation of peristaltic movement.
On hydrolysis cellobiose is produced.
6- Inulin
 It is found in tubers and roots of fruits.
 Repeated units of D fructose joined by 1-2 glycosidic linkage with a molecule of α- D glucose
 It is soluble in warm water.
 It is used in investigation of glomerular filtrations (GFR) as it is not absorbed by renal tubules.

7- Chitin
 It is an important structural polysaccharide of invertebrate.
 It is found in exoskeleton of insects.
 It is formed from β-N-acetyl glucosamine units linked
by β-1-4 glycosidic linkage.
 It is insoluble in water, acid and alkalis.
II- Heterogonous polysaccharides

1-Pectin 2-Mucopolysacchariden (Glycosaminoglycans)

They are present in fruits of various plants.
Mixture of galactouronic acid, rhaminose and arabinose
. A) Non-nitrogenous polysaccharides
. E.g.: hemicellulose (xylose, mannsose,

. glucose. galactose) and plant gum

B) Nitrogenous polysaccharides

A) Neutral: includes glycoproteins and blood group.

B) Acidic Glycoproteins: formed from hexoses and hexosamine
E.g.: a. Mucin of saliva
. 1-Sulfat-free b. (FSH, LH )
. mucopolysaccharides

E.g.: Hyaluronic acid . 2-Sulfate-containing

. mucopolysaccharides
. E.g.: Chondroitin sulfate .
. Heparin.
1- Hyaluronic acid
It is acidic and sulfate free mucopolysaccharides
It is formed from 400 to 4000 repeating disaccharide units
The repeating unit formed from β-glucuronic acid attached to β-N-acetyl glucosamine by β-1-3 and 1-4 glycosidic linkages.
It is present in subcutaneous tissues, synovial fluid, vitreous humor of the eye and umbilical cord

It can be hydrolyzed by hyaluronidase enzyme present in heads of sperms and secreted by some bacteria.
This enzyme enables bacteria to penetrate and spreads infection and facilitates penetration of ovum by spermatozoa for fertilization.
2- Chondroitin sulfates
They are acidic and sulfate containing mucopolysaccharides.
They formed from repeating units formed from β-glucuronic acid attached to β-N-acetyl galactosamine by β 1-3 & β 1-4 glycosidic
linkages.

They contain sulfate group in position 4 (type A) and position 6 (type C) of N –acetyl galactosamine.
They are found in cornea, cartilage, skin and tendons
3- Heparin
It is acidic and sulfate containing mucopolysaccharide.

It is formed of Iduronic acid, glucosamine and sulphate esters (attached to OH- group of 𝑐6 & NH2 of glucosamine and OH group 𝑐2 of
lduronic acid)
4- Dermatan sulphate
 Chemical Properties of Polysaccharides
Chemical Reaction:
①Molish Test → Give (+Ve) reddish violet ring

②Fehling Test→ Give(−Ve) No Red PPT

③Benedicts Test → Give (-Ve) No Red PPT

④Iodine Test: -

 Deep blue color → starch

 Violet color → Dextrin
 No Change → Gum Arabic