Biochemistry - Diploma 2024

Basic - 1
 Carbohydrates chemistry

Def. → Aldehyde or ketone derivatives of polyhydric alcohol or as compounds which yield these derivatives on hydrolysis.

Classification of carbohydrates

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

Contain 1 sugar unit. Contain 2-10 sugar units. Contain more than 10 sugar units.
Cannot be hydrolyzed into a simpler sugar.

Monosaccharides (simple sugar)

General formula → Cn H2n On

According to number of Carbone atoms According to the presence of active group

Trioses Tetroses Pentoses Hexoses Aldose Ketose
Sugar contain Sugar contain Sugar contain Sugar contain Sugar contain aldehyde (CHO) group Sugar contain ketone (C=O) group
3C atoms 4C atoms 5C atoms 6C atoms
a- Trioses: → contain 3 carbon atoms.

1. Aldotriose: Glyceraldehyde (glcerose)

2. Ketotriose: Dihydroxy acetone.

b-Tetroses: → contain 4 carbon atoms

1. Aldotetrose: Erythrose
2. ketotetrose: Erythulose

c- Pentoses: → contain 5 carbon atoms

1. Aldopentose: Ribose, xylose
2. Ketopentose: Ribulose, xylulose

d- Hexoses: → contain 6 carbon atoms

1. Aldohexose: Glucose, Galactose, Mannose

2. Ketohexose: Fructose
 Isomerism in sugars
• Monosaccharides that consist of asymmetric carbon atoms show the tendency of isomerization.
• Asymmetric carbon atom is a carbon atom attached to four different groups or atoms.

Isomers: → substances which have the same structural formula and differ in configuration of
hydroxyl and hydrogen atoms.

• The number isomers is equal to [ 𝟐𝒏 ]

• Ex.
✓ Glucose → 4 asymmetric carbon atoms → has 16 isomers.
✓ Fructose → 3 asymmetric carbon atoms → has 8 isomers.
✓ Heptulose → 5 asymmetric carbon atoms → has 32 isomers.
 The most important type of isomerism in sugars
1- (Enantiomers) → mirror image

• The orientation of the -H and -OH groups around the carbon atom adjacent to the last primary
alcohol carbon → determines D or L series.
• Most of the Monosaccharides occurring in mammals are of the D-series

2- Optical isomerism

• The change of orientation of polarized light either to the right and called dextrorotatory (+) or to the left and called levorotatory (-)

3- Epimers:

• Change in configuration of 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)
4- Anomers:

• The orientation of hydroxyl group in the first carbon atom either to the right or downward is
called alpha anomer or to the left or upward is called beta anomers
• Anomeric carbon atom is the first carbon atom in carbohydrate molecule.

Fisher and Haworth projection:

• In solution and cellular level, the linear structure of carbohydrates is transferred in to cyclic
form according to aldose or ketose type of carbohydrates.
• The cyclic form of carbohydrates is either in pyran (hexagon) or furan (pentagon) form.

• Aldo, ketotriose and ketotetroses fail to produce both pyran and furan form.
• Aldotetrose and ketopentose can from only furan from.
 Mutarotation
• The observed change in angle of rotation of both alpha and beta anomers of glucose when dissolute in water, due to open ring
theory which state that the long storage of carbohydrate solution for a specific time, the angle of rotation of the anomer of sugar
changes by specific degree to transfer to other anomer.

• - glucose has an angle of + 112○ while β- glucose has an angle of +18○ but after a period of time, the degree of rotation becomes
constant at + 52○

5- Aldose and ketose → are consider isomers

 Properties of Monosaccharides and sugar derivatives
1-Optical activity

• All monosaccharides are optically active except Dihydroxyacetone due to presence of asymmetric carbon1 atom.

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 aldehyde 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 aldehyde and last alcoholic groups: Saccharic acid produced →→→ E.g: Glucose gives glucaric acid.
4- Reduction: → production of sugar alcohols
• Monosaccharides carries free aldehyde or ketone group that reduce alkaline reagent such as Fehling and benedict.
• E.g.
Glucose, Fructose →→→ Sorbitol
Mannose →→→ Mannitol.
Xylose →→→ xylitol
ribose →→→ ribitol

5- Condensation:

• Reaction of reducing sugars with phenyl hydrazine to form osazone crystals.

• Monosaccharides differing only in the first and second carbon atoms will produce similar osazone → so glucose and fructose give
the same osazone.

Importance of osazone test:

1) It is used to confirm the presence and absence of glucose in urine.

2) It is use to differentiate between glucose and other reducing sugars
present normally in urine of lactating female
E.g. → lactose in lactating female.

6- Amino sugar:

These are sugars in which OH group in 𝑐2 is replaced by NH2 group

E.g: Glucosamine and galactosamine

7- Deoxy-sugar:
These are sugars in which the-OH group on (𝐶2 ) or last carbon atom (C6) is replaced by a hydrogen atom.
E.g.: Ribose →→ deoxyribose.
L-galactose →→ L-fucose

8- Glycosides:

• These are compounds formed by a condensation reaction between sugar & OH group of second compound which may or may not be
another sugar.
• The linkage between the two residues is known as acetal linkage or O-glycosidic linkage.

The most important glycosides are

1) Cardiac glycosides: → treatment of heart failure. 3) Glycolipid: → containing sugar lactose.

2) Streptomycin: →antibiotic. 4) disaccharides

Sialic acid
✓ Derivatives of nine carbon atom monosaccharides.
✓ Its name is N-acetyl neuraminic acid (NANA), found in different tissue cells.

Biosynthesis:
Mannosamine + pyruvate → produce N -acetyl neuraminic acid (NANA).

Role:
1) Enhance metastasis of cancer. 3) Aid bacteria & viruses (Human Influenza) to bind with host receptors.
2) Used as a nutritive substance. 4) Brain development in infants
 Disaccharides
1- Maltose 2- Lactose

1. Called "malt sugar". 1. Called "milk sugar".

2. Two units of -D- glucose. 2. β-D-glucose + β-D-galactose.
3. Linked by -(1-4) O-glycosidic linkage. 3. Linked by β-(1-4) O-glycosidic linkage.
4. Reducing sugar due to presence of free aldehyde group. 4. Reducing sugar due to presence of free aldehyde group
5. Form osazone. 5. Form osazone.
6. Fermentable sugar. 6. Non-fermentable sugar so doesn't produce gases in small
7. It can be hydrolyzed by acids and maltase enzyme. intestine → no colic produced from ingestion.
7. It can be hydrolyzed by acids and lactase enzyme
8. It is not sweet sugar → baby drink much milk with no loss of
appetite.
3- Sucrose 4- Cellobiose
1. Called "cane or beet sugar. 1. Produced by a partial hydrolysis of cellulose.
2. -D- glucose + β-D-fructose. 2. Two units of β-D-glucose.
3. Linked by -(1-2) O-glycosidic linkage. 3. Linked by β-(1-4) O-glycosidic linkage.
4. non-reducing sugar due to absence of free aldehyde or 4. Reducing sugar due to presence of free aldehyde group
ketone group. 5. Form osazone.
5. Not form osazone. 6. Fermentable sugar.
6. Fermentable sugar. 7. It can't be digested in intestine of human.
7. Hydrolyzed by acid, invertase enzyme (in yeast) and 8. It can be digested in a large intestine of rabbits and rumen
sucrase enzyme. of ruminants by cellulase enzyme of bacteria.
Invert sugar:
• This is the hydrolytic mixture of sucrose.
• It is formed from equal amount of -glucose and β-fructose.
• Honey is a natural example of invert sugar.
• Called invert sugar as sucrose is dextrorotatory, but on hydrolysis it becomes levorotatory
 Polysaccharides
Classification of polysaccharide:
 Homogenous polysaccharides
1-Starch
• formed from two chief constituents

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 linkage Formed of -D- glucose units linked by -1-4 glycosidic linkage
and by -1-6 glycosidic linkage at point of branching
It give a blue color with iodine It give a violet color with iodine.
It form the inner part of granule It form 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- Dextrin
✓ Produce by hydrolysis of starch (amylopectin) → Include amylodextrin, erythrodextrin and achrodextrin.

3- Dextran
✓ Produced by bacteria, formed from α-D-glucose linked by α-1-3, α-1-4 and α-1-6 glycosidic linkage.
✓ Used in hypovolemia as fluid therapy for shock treatment.
✓ Used in emergency as supportive treatment.
4- Glycogen
✓ Called animal starch → main storage form of carbohydrates in animal tissues (liver and muscle).
✓ Formed from α-D-glucose units linked by α-1-4 glycosidic linkage and α-1-6 glycosidic linkage at point of branching
✓ It gives red color with iodine.

5- Cellulose
✓ The most abundant carbohydrate found in nature.
✓ Formed from β-D- glucose linked by β-1,4 glycosidic linkage.
It is insoluble in water
✓ Can’t be digested in carnivorous animals and human BUT important in stimulation of peristaltic movement.
✓ In herbivorous animals there are microorganisms have enzymes that can attack the β linkage.
✓ On hydrolysis cellobiose is produced.

6- Inulin
✓ Repeated units of α- D fructose joined by α 1-2 glycosidic linkage
✓ 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 found in exoskeleton of insects (invertebrates).
✓ It is formed from β-N-acetyl glucosamine units linked by β-1-4 glycosidic linkage.
✓ It is insoluble in water, acid and alkalis.
 Heterogenous polysaccharides
Pectin
• They are present in fruits of various plants.
• Mixture of galactouronic acid, rhaminose and arabinose, where carboxyl group of galacturonic acid might be methylated or
acetylated.

1- Hyaluronic acid

• 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 hydrolyzed by hyaluronidase enzyme present in heads of sperms and secreted by some bacteria.
2- Chondroitin sulfates

• 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) & position 6 (type C) of N–acetyl galactosamine.
• They are found in cornea, cartilage, skin and tendons
3- Heparin

• It is formed of sulphated Iduronic acid + sulphated N-acetyl glucosamine