Carbohydrates

Dr.Samir Singh
Associate Professor &
Consultant Biochemist

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 Carbohydrate provides 4
Kcal/gm
 Each year, PHOTOSYNTHESIS
converts more than 100 billions
metric tons of CO2 and H2O into
CELLULOSE and other plant
products and stored as STARCH.
 SUGAR and STARCH are a
dietary staple in most parts of the
World and the OXIDATION of
Carbohydrates is the central
energy yielding pathway in
most nonphotosynthetic cells. 2
 Carbohydrates

The term carbohydrate was given by Karl Schmidt, which

literally means “hydrate of carbon”

Carbohydrates
 are defined as aldehyde or ketone derivatives of
polyhydric alcohols or as compounds which yield these
derivatives on hydrolysis.

 are the most abundant compounds found in nature

composed of carbon, hydrogen and oxygen in 1:2:1.
Some may also have nitrogen and sulphur beside CHO.

 also called saccharides, which means “sugars” 3

 Functions of CHO

 major dietary components, meeting 60-70% of energy

requirement.
 storage form of energy (e.g. glycogen and starch)
 intermediates in the biosynthesis of other basic
biochemical entities (fats and amino acids etc.)
 form structural tissues in plants and in
microorganisms (cellulose, lignin, murein etc.)
 linked to proteins and lipids (glycoconjugates)
 they are associated with diseases like diabetes
mellitus, galactosemia, lactose intolerance, glycogen
storage diseases etc.
Classification of Carbohydrates
 Monosaccharides, the simplest sugars which cannot be
hydrolyzed further into more simpler compounds.
 Disaccharides, which consist of two monosaccharides.
 Oligosaccharides, which contain 3-10 monosaccharides.
 Polysaccharides, which contain many monosaccharides (>10).

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 Monosaccharides (CnH2nOn)
 also known as simple sugars
 most are straight chain compounds
 D-glyceraldehyde is the simplest of the aldoses
(aldotriose)
 all other sugars have the ending ose (glucose, galactose,
ribose, fructose, mannose, etc…)
 glucose & fructose are most abundant monosaccharides.
Monosaccharides consist of
 3 to 6 carbon atoms, typically.
 a carbonyl group (aldehyde or ketone).
 several hydroxyl groups. 6
Aldoses
Aldoses are monosaccharides O
 With an aldehyde group. ║
 With many hydroxyl (─OH) C─H aldose
groups. │
triose (3 C atoms) H─ C─OH
tetrose (4 C atoms) │
pentose (5 C atoms) H─ C─OH
hexose (6 C atoms) │
CH2OH

Erythose, an aldotetrose
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Ketoses
Ketoses are monosaccharides CH2OH
 With a ketone group. │
 With many hydroxyl (-OH) C=O ketose
groups. │
H─ C─OH
triose (3 C atoms)
│
tetrose (4 C atoms) H─ C─OH
pentose (5 C atoms) │
hexose (6 C atoms) H─C─OH
│
CH2OH

Fructose, a ketohexose 8
Learning Check
Identify each as aldo- or keto- and as tetrose, pentose,
or hexose:
O
CH2OH
C H
C O
H C OH
HO C H
H C OH
H C OH
H C OH
H C OH
CH2OH
CH2OH
A B

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Solution
A. aldohexose

B. ketopentose

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 CONCEPTS OF ISOMERS
Two or more different compounds which contain the same
number and types of atoms and the same molecular weights.
The presence of a single chiral carbon (asymmetric carbon) gives
rise to stereoisomerism. Stereoisomerism have the same
molecular formula but differ only in spatial configuration.
A chiral carbon is one that has four different groups attached to
it.
The maximum number of stereoisomers is 2n where n= number
of chiral carbon atoms.
 Optical Stereoisomers
 Many carbohydrates exist as enantiomers – stereoisomers
that are mirror images.

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 D and L Isomerism
 All carbohydrates exist in D and L stereoisomeric form
 The −OH group on the chiral carbon farthest from the
carbonyl group determines an L or D isomer.
 Left is assigned the letter L for the L-isomer.
 Right is assigned the letter D for the D-isomer.

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 Polarity
 D and L enantiomers rotate polarized light in opposite
directions. Humans can only metabolize the D-isomers
of monosaccharides.

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Examples of D and L Isomers of
Monosaccharides
O
O
C H
C H O
HO H
H OH C H
H OH
HO H H OH
H OH
H OH H OH
H OH HO H
H OH
CH2OH CH2OH
CH2OH
D-glucose D-ribose L-galactose

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Learning Check
Identify each as the D or L isomer.
A. B. C.
O CH2OH

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

__-ribose __- threose __- fructose

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 Solution
Identify each as the D or L isomer.
A. B. C.
O CH2OH
C H O O
HO H C H HO H
HO H H OH H OH
HO H HO H H OH
CH2OH CH2OH CH2OH

L-ribose L-threose D-fructose

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 Carbohydrates

Structures of Monosaccharides

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Epimers

Sugars that differ only in their stereochemistry at a

single carbon.

Chapter 23 21
 D-Glucose
D-glucose is
 Found in fruits, corn
syrup, and honey.
 An aldohexose with
the formula C6H12O6.
 Known as blood sugar
in the body.
 The monosaccharide
in polymers of starch,
cellulose, and
glycogen.

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 Blood Glucose Level
In the body,
 Glucose has a normal
blood level of 70-110
mg/dL (fasting).
 A glucose tolerance
test measures blood
glucose for several
hours after ingesting
glucose.
 Renal threshold for
glucose:180 mg/dL
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D-Fructose
D-fructose
 Is a ketohexose CH2OH
C6H12O6. C O
 Is the sweetest HO C H
carbohydrate.
H C OH
 Is found in fruit
juices and honey H C OH
and called fruit CH2OH
sugar.
 Converts to glucose D-Fructose
in the body.
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D-Galactose
D-galactose is O
 An aldohexose C6H12O6. C H
 Not found free in nature. H C OH
 Obtained from lactose, a HO C H
disaccharide.
HO C H
 A similar structure to
glucose except for the H C OH
–OH on C4. CH2OH
D-Galactose

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Cyclic Structures of
Monosaccharides

CH2OH
O

OH
OH OH

OH

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Cyclic Structures
Cyclic structures
 are the prevalent form of monosaccharides with 5 or
6 carbon atoms.
O O

 Pyranose ring Furanose ring

 form when the hydroxyl group on C-5 reacts with the

aldehyde group or ketone group.

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Ring formation / Ring structure

An aldose: Glucose
A ketose: Fructose
Learning Check
Write the cyclic form of -D-galactose
O
C H
H C OH
HO C H
HO C H
H C OH
CH2OH

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Solution

CH2OH
O
OH

OH
OH

OH

-D-galactose

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 Pentose Sugars
The pentose (five-carbon) sugar
• in RNA is ribose.
• in DNA is deoxyribose with no O atom on carbon 2’.

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 Amino sugar
 Amino sugars have a hydroxyl group replaced by an amino
group. E.g. N-acetyl glucosamine, galactosamine, etc.
 Several antibiotics, e.g. erythromycin, carbomycin contain
amino sugar.
 Amino sugars are components of glycolipid (ganglioside),
glycoprotein and proteoglycans (glycosaminoglycans)
CH2OH CH2OH

H O H H O H
H H
OH H OH H
OH OH OH O OH
H NH2 H N C CH3
H
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-D-glucosamine -D-N-acetylglucosamine
Two or more monosaccharides are linked together
through an oxygen bridge known as O-glycosidic bond.
Glycosidic bonds are formed when the hemiacetal or
hemiketal hydroxyl group (of anomeric carbon) of a
carbohydrate reacts with a hydroxyl group of another sugar
or non-sugar (methyl alcohol, glycerol, phenol).
Carbohydrates
Disaccharides
e.g. maltose, lactose, sucrose

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 Maltose
Maltose is

 a reducing disaccharide also known as malt sugar.

 composed of two D-glucose molecules.
 neither present in human body nor exists as such in
nature
 only obtained from the hydrolysis of starch (by α-
amylase).
 linked by an -1,4-glycosidic bond.
 used in cereals, candies, and brewing.
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Formation of Maltose

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 Lactose
Lactose or milk sugar
 is a disaccharide of β-D-
galactose and α- or β-D-
glucose.
 contains a β -1,4-glycosidic
bond.
 is the only disaccharide
synthesized in human body
(lactating mammary glands) α-form
 Milk contain about 5-7%
lactose.
 Souring of milk results from
anaerobic oxidation of
lactose to lactic acid. 38
used in infant
formulations,
medium for
penicillin production
 Sucrose
Sucrose or table sugar
 is obtained from sugar cane and sugar beets, ripen fruits etc.
 is non reducing disaccharide consists of α-D-glucose and β-
D-fructose.
 has an α-1,2-glycosidic bond.
 used as table sweetener in food items like tea, coffee, milk
etc. and also used pharmaceutically to make syrups

α-D-glucose

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β-D-fructose
 Carbohydrates
Oligosaccharides
These sugars are composed of 3-10 monosaccharides
 Trisaccharide: raffinose (glucose, galactose and fructose).
Sugar beets are important source of raffinose.
 Trisaccharide: robinose (galactose and 2 rhamnose).
 Tetrasaccharide: stachyose (2 galactoses, glucose and
fructose)
 Pentasaccharide: verbascose (3 galactoses, glucose and
fructose)
Many glycoproteins like immunoglobulins, peptide hormones,
blood group antigens, etc. contain oligosaccharides
covalently attached to proteins.
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Carbohydrates
Polysaccharides

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Polysaccharides
more than 10 units
classification:

1. Homopolysaccharides
One type of units
starch, glycogen, cellulose
dextrins, chitin, Inulin, etc.

2. Heteropolysaccharides
Different type of units
gum, pectin, glycosaminoglycans
1. Homopolysaccharides
One type of units
starch, glycogen, cellulose
dextrins, dextrans, chitin, Inulin, etc.
Starch- composed of 2 kinds of glucose
polymer-Amylose and Amylopectin

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Amylose
Amylose is
 a polymer of α-D-
glucose molecules.
 linked by -1,4
glycosidic bonds.
 a continuous
(unbranched)
chain.
 water soluble

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Amylopectin
Amylopectin
 is a polymer of α-D-
glucose molecules.
 is a branched-chain
polysaccharide.
 has α-1,4-glycosidic
bonds between the
glucose units.
 has α-1,6 bonds to
branches.
 is water insoluble
 47
 Glycogen
Glycogen
 also known as animal starch
 is the polysaccharide that
stores glucose in liver and
muscle.
 is similar to amylopectin, but is
more highly branched.
 on complete hydrolysis yields
glucose
 hydrolyzed by both amylases
and by glycogen phosphorylase

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49
Cellulose (most abundant plant
polysaccharides)
Cellulose
 is a polysaccharide
of glucose units in
unbranched chains.
 has β-1,4-glycosidic
bonds.
 cannot be digested
by humans because
humans cannot
break down β-1,4-
glycosidic bonds.

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Learning Check
Identify the polysaccharides and types of glycosidic
bonds in each of the following:

A. B. C.

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Solution

A. Cellulose -1,4-glycosidic bonds

B. Amylose -1,4-glycosidic bonds

Amylopectin -1,4-and -1,6-glycosidic bonds

C. Glycogen -1,4-and -1,6-glycosidic bonds

(more branched than amylopectin)

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Inulin

 -(1,2) linked fructofuranoses

 hydrolysis yields fructose
 sources include onions, garlic,
 used as diagnostic agent for the
evaluation of glomerular filtration
rate (renal function test)
 Chitin
 Chitin is the second most
abundant carbohydrate next
to cellulose composed of
N-acetylglucosamine.

 Present in the cell wall of fungi

and in the exoskeletons of
crustaceans, insects and
spiders

 Chitin is used commercially in

coatings (extends the shelf life
of fruits and meats)
Dextrans

 Dextrans are bacterial and yeast polysaccharides

made of glucose.

 Dental plaque formed by bacteria growing on surface

of teeth is rich in dextrans.

 Sephadex (gel beads) used in Chromatography

2. Heteropolysaccharides
Different type of units
glycosaminoglycans, gum, pectin, etc.
 Glycosaminoglycans

 Also called as mucopolysaccharides

 Polysaccharides that are composed not only of a mixture of

simple sugars but also of derivatives of sugars such as amino
sugars and uronic sugars are called mucopolysaccharides.

 They are gelatinous substances of high molecular weights.

 Most of these act as structural support material for connective

tissue or mucous substances of the body.

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Glycosamino- Disaccharide Location Functions
glycans(GAG) unit

Hyaluronic acid N-acetyl Synovial fluid of Serve as a lubricant

glucosamine- joints,vitreous humour and shock absorber
Glucuronic acid of the eye, skin

Condroitin N-acetyl Tendons,cartilage, Provide an endosk-

sulfate galactosamine- bones, dentine and eletal structure helping
Glucuronic acid cementum of teeth, to maintain their
cornea, heart valves shape.
Keratan sulfate N-acetyl Cornea, loose con- Transparancy of
glucosamine- nective tissue, cartilage cornea
Galactose

Dermatan N-acetyl Skin, blood vessels and Transparancy of

sulfate galactosamine- heart valves cornea & maintain
L-lduronic acid shape of the eye

Heparin Glucosamine - Component of mast Serves as an anti-

Glucuronic acid cells,that line arteries in coagulant 58
or Iduronic acid liver,lung
 Glycoproteins

 Glycoproteins are proteins that contain

oligosaccharide chains (glycans) covalently attached
to their polypeptide side-chains.

 Monosaccharides commonly found in eukaryotic

glycoproteins include:

 Glucose, Galactose, Mannose, Fucose,

N-acetylglucosamine, N-acetylgalactosamine,
N-acetylneuraminic acid etc
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 Function Glycoproteins
Structural molecule Collagens
Lubricant and protective
Mucins
agent
Transport molecule Transferrin, Ceruloplasmin
Immunologic molecule Immunoglobins, histocompatibility antigens
Human chorionic gonadotropin (HCG),
Hormone
thyroid-stimulating hormone (TSH)
Enzyme Various, eg, alkaline phosphatase
Various proteins involved in hormone and
Receptor
drug action

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 Biomedical importance of CHO
 Glucose is chief source of energy.
 Fructose is a preferred as a source of energy for sperms
 D-ribose is a constituents of DNA, RNA, ATP, NAD, FMN
 Amino sugars are contituent of gangliosides,
glycoproteins, aminoglycosides etc.
 Cardiac glycosides (like digitonin) are used in treatment of
cardiac insufficiency.
 Inulin is used to determine GFR in kidney function test.
 Methycellulose is used to treat constipation.
 Hepatic glycogen serves as a constant source of blood
glucose, whereas muscle glycogen is a fuel reserve(muscles)
Plant Carbohydrate
Sources
 Simple carbohydrates: Fruit,
table sugar, sweets & sugar
sweetened cereals.
 Complex carbohydrates:
Vegetables, starchy
vegetables, grains, legumes, &
whole grain cereals.
Animal Carbohydrate
Food Sources
 Milk (& milk products yogurt & cheese)
contain lactose.
 Honey contains glucose, fructose &
small amounts of other sugars.
 Animal foods usually provide mostly
protein & fat.
 Milk & milk products also provide protein
& varying amounts of fat.
Dietary fibers are
Polysaccharides
 Dietary fiber or roughage is the indigestible portion of
food derived from plants.
 Nondigestible polysaccharides
 Provides no energy
 Classification
 Soluble
 Pectins, beta-glucan, some gums, mucilage
 Easily fermented by intestinal bacteria
• Carbon dioxide, methane, some fatty acids
 Insoluble
 Cellulose, lignin, some hemicelluloses
 Not easily fermented
Dietary fibers are Polysaccharides

 Soluble fiber, which dissolves in water, is readily

fermented in the colon into gases and
physiologically active byproducts, and can
be prebiotic and viscous. It delays gastric
emptying which in turn can cause an extended
feeling of fullness.
 Insoluble fiber, which does not dissolve in water,
is metabolically inert and provides bulking, or it
can be prebiotic and metabolically ferment in the
large intestine. Bulking fibers absorb water as they
move through the digestive system,
easing defecation.
Fiber Health Benefits
 Soluble fibers
 Slow gastric emptying and may delay absorption
of some nutrients
 Helps reduce serum cholesterol

 Improve appetite control

 Normalize blood glucose levels

 May help protect against colon cancer

 Insoluble fibers
 Relieves constipation
 Most plant foods contain both soluble and insoluble
fibers
Reactions of Carbohydrates

 Reduction

 Oxidation

 Dehydration

 Osazone formation

 Formation of esters

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 Reduction
 When treated with reducing agents such as sodium
amalgum, the aldehyde or keto group of monosaccharide
is reduced to corresponding alcohol.

D-Glucose D-Sorbitol

D-Fructose D-Mannitol + D-Sorbitol

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 Oxidation
 Depending upon the oxidizing agent used, the terminal
aldehyde or keto groups are oxidized.

D-Glucose Gluconic acid

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 Dehydration
 When treated with conc. sulfuric acid, the
monosaccharide undergo dehydration and give
hydroxymethyl furfurals. The furfurals can condense with
phenolic compounds (-napthol) to form coloured
products.

Molisch’s test

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 Osazone formation
 Phenylhydrazine in acetic acid, when boiled with
reducing sugars, forms osazones.

Glucose + Phenylhydrazine

Glucohydrazone

Phenylhydrazine

Glucosazone
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 Formation of esters
 The alcoholic groups of monosacharides may be
esterified by non-enzymatic or enzymatic reactions.
Esterification of carbohydrate with phosphoric acid is a
common reaction in metabolism.
 Glucose 6-phosphate and Glucose 1-phosphate are good
examples. ATP donates the phosphate moiety in ester
formation.

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