Carbohydrates

Carbohydrates
• Most abundant class of biological
molecules on Earth
• Originally produced through CO2
fixation during photosynthesis
 Roles of Carbohydrates
• Energy storage (glycogen, starch)
• Structural components (cellulose, chitin)
• Cellular recognition
• Components of monomeric unit of DNA
and RNA,
• Glycoconjugates: glycoproteins, glycolipids
 Carbohydrates

• Carbohydrates are polyhydroxy aldehydes or

ketones, or substances that yield such compounds
on hydrolysis
• Carbohydrates (glycans) have the following basic
composition:

I
(CH2O)n or H - C - OH
I
Classification of Carbohydrates
 Monosaccharides - simple sugars with multiple OH
groups.

 Disaccharides - 2 monosaccharides covalently linked.

 Oligosaccharides - a few monosaccharides (upto 10)

covalently linked.

 Polysaccharides - polymers consisting of chains of

monosaccharide or disaccharide units.
 Monosaccharides
Aldoses (e.g., glucose) have Ketoses (e.g., fructose) have
an aldehyde group at one end. a keto group, usually at C2.
H O
C CH2OH

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH

D-glucose D-fructose
Monosaccharides
Stereoisomers and Stereochemistry

• Prefixes D- and L- in a monosaccharide name

identify one of two isomeric forms
– These isomers differ in the spatial arrangement of
atoms and are stereoisomers
• Stereochemistry is the study of different spatial
arrangements of atoms
• The stereoisomers D- and L- glyceraldehyde are
non-superimposable mirror image molecules and
are called enantiomers (a subset of stereoisomers)
 D vs L Designation

CHO CHO
D & L designations
H C OH HO C H
are based on the
configuration about CH2OH CH2OH
the single asymmetric D-glyceraldehyde L-glyceraldehyde
C in glyceraldehyde.
CHO CHO
The lower H C OH HO C H
representations are
CH2OH CH2OH
Fischer Projections.
D-glyceraldehyde L-glyceraldehyde
 Sugar Nomenclature

For sugars with more O H O H

than one chiral center, C C
D or L refers to the H – C – OH HO – C – H
asymmetric C farthest HO – C – H H – C – OH
from the aldehyde or H – C – OH HO – C – H
keto group. H – C – OH HO – C – H
CH2OH CH2OH
Most naturally occurring
D-glucose L-glucose
sugars are D isomers.
D & L sugars are mirror images of one another.

O H O H
C C
H – C – OH HO – C – H
HO – C – H H – C – OH
H – C – OH HO – C – H
H – C – OH HO – C – H
CH2OH CH2OH
D-glucose L-glucose
 Stereochemistry
Enantiomers Diastereomers Epimers
O O O O O O
H H H H H H
C C C C C C

HO C* H H C* OH HO C* H H C* OH H C* OH HO C* H

H C* OH HO C* H HO C* H HO C* H HO C* H HO C* H

HO C* H H C* OH H C* OH HO C* H H C* OH H C* OH

HO C* H H C* OH H C* OH H C* OH H C* OH H C* OH

CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH

L-glucose D-glucose D-mannose D-galactose D-glucose D-mannose

•Enantiomers = mirror images

•Pairs of isomers that have opposite configurations at one or more
chiral centers but are NOT mirror images are diastereomers
•Epimers = Two sugars that differ in configuration at only one
chiral center
16.3 Stereoisomers and Stereochemistry Enantiomers
 Chirality
• A carbon atom that has four different groups
bonded to it is called a chiral carbon atom
• Any molecule containing a chiral carbon can
exist as a pair of enantiomers

• Chirality in glyceraldehyde (the simplest carbohydrate)

is conveyed by a single chiral carbon
 Monosaccharides are chiral
• Aldoses with 3C or more and
ketoses with 4C or more are chiral

• The number of chiral carbons

present in a ketose is always one O
H
less than the number found in the C CH2OH
same length aldose H C* OH C O

HO C* H HO C* H
• Number of possible stereoisomers = H C* OH H C* OH
2n (n = the number of chiral
H C* OH
carbons) H C* OH

CH2OH CH2OH
D-glucose D-fructose
 Optical Activity
• Enantiomers are also called optical isomers
• Enantiomers interact with plane polarized
light to rotate the plane of the light in
opposite directions
– This interaction with polarized light is called
optical activity
– Optical activity distinguishes the isomers
– It is measured in a device called a polarimeter
 Polarized Light
• Normal light vibrates in an infinite number of
directions perpendicular to the direction of travel
– When the light passes through a polarizing filter
(Polaroid sunglasses) only light vibrating in one plane
reaches the other side of the filter

– A polarimeter allows the determination of the specific

rotation of a compound
• Measures its ability to rotate plane-polarized light
16.3 Stereoisomers and Stereochemistry
Schematic Drawing of a Polarimeter
Polarimeter
 Molecular Structure and Optical Activity
• When an enantiomer in a solution is placed in the
polarimeter, the plane of rotation of the polarized light is
rotated
– One enantiomer always rotates light in a clockwise (+)
direction
• This is the dextrorotatory isomer
– The other isomer rotates the light in a counterclockwise (-)
direction
• It is the levorotatory isomer
• Under identical conditions, the enantiomers always rotate
light to exactly the same degree, but in opposite directions
 Hemiacetal & hemiketal formation
An aldehyde can H H
react with an C O + R' OH R' O C OH
alcohol to form
R R
a hemiacetal.
aldehyde alcohol hemiacetal

A ketone can R R
react with an
alcohol to form C O + "R OH "R O C OH

a hemiketal. R' R'

ketone alcohol hemiketal

These reaction facilitates formation of ring structures

of monosaccharides
In aqueous solution, aldotetroses and all
monosaccharides with five or more carbon
atoms in the backbone occur predominantly as
cyclic (ring) structures.

In cyclic structures the carbonyl group has

formed a covalent bond with the oxygen of a
hydroxyl group along the chain.

The formation of these ring structures is the result

of a general reaction hemiacetals or hemiketals
reactions.
Cyclic Structures of common
monosaccharide

Haworth projections.
6-member pyranose ring, named after pyran
 1
CH2OH

2C O

HO C H
1 CH2OH
3 HOH2C 6 O
H C OH HO
4 5 H 2

H C OH H 4 3 OH
5
OH H
6
CH2OH

D-fructose (linear) -D-fructofuranose

Fructose forms either

 a 6-member pyranose ring, by reaction of the C2 keto
group with the OH on C6, or
 a 5-member furanose ring, by reaction of the C2 keto
group with the OH on C5.
 6 CH 2OH 6 CH 2OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D-glucose b-D-glucose

Cyclization of glucose produces a new asymmetric center at

C1. The hemiacetal (or carbonyl) carbon atom is called the
anomeric carbon. The 2 stereoisomers are called anomers, 
& b.
Haworth projections represent the cyclic sugar anomers as:
  (OH below the ring)
 b (OH above the ring).
The α and β anomers of D-glucose interconvert in
aqueous solution by a process called
mutarotation.

Thus, a solution of α-D-glucose and a solution of

β-D-glucose eventually form identical equilibrium
mixtures having identical optical properties.

This mixture consists of about one-third α-D-

glucose, two-thirds β-D-glucose, and very small
amounts of the linear and five-membered ring
(glucofuranose) forms.
 Reducing Sugars
• The aldehyde groups of aldoses are oxidized by
Benedict’s reagent, an alkaline copper(II) solution
• The blue color of the reagent fades as reaction occurs
reducing Cu2+ to Cu+ with a red-orange precipitate
forming as Cu2O results
• Test can measure glucose in urine

+ Cu2O (red-orange)
 Reducing Sugars
• All monosaccharides and the disaccharides
except sucrose are reducing sugars
• Ketoses can isomerize to aldoses and react also

CH2OH HO CH O CH
CO C OH H C OH
HO C H HO C H HO C H
H C OH H C OH H C OH
H C OH H C OH H C OH
CH2OH CH2OH CH2OH
D-fructose enediol D-glucose
Derivatives of Monosaccharides
Sugar Phosphates
 Deoxy Acids

Complex
Plant
Nucleic acid DNA oligosaccharides of
Polysaccharide
Glycolipids and
glycoproteins
Amino Sugars
Sugar alcohols
 Disaccharides
Disaccharides (such as maltose, lactose, and
sucrose) consist of two monosaccharides
joined covalently by an O-glycosidic bond,
which is formed when a hydroxyl group of
one sugar reacts with the anomeric carbon of
the other.
 Maltose
• Disaccharide of two glucose molecules.
• Has a α -1,4-glycosidic bond (between two α-glucoses).
• Is obtained from the breakdown of starches.
• Is used in cereals and candies.
• Is a reducing sugar (carbon 1 can open to give a free
aldehyde to oxidize).

CH2OH CH2OH
CH2OH CH2OH
O  -1,4-glycosidic
O
O O bond OH b
1 1
OH
OH
OH
+ 4
OH
OH
OH OH O
4
OH
OH
OH OH
OH OH
α-glucose α-glucose
b-
maltose
 Lactose
• Disaccharide of galactose and glucose.
• Has a β -1,4-glycosidic bond (between β-galactose and α-gulcose).
• Is found in milk and milk products (almost no sweet).
• Is a reducing sugar (carbon 1 can open to give a free aldehyde to
oxidize).

b-lactose
 Sucrose
• Is found in table sugar (obtained from sugar cane and
sugar beets).
• Consists of glucose and fructose.
• Has an α,β-1,2-glycosidic bond (between α-glucose and
b-fructose).
• Is not a reducing sugar (carbon 1 cannot open to give a
free aldehyde to oxidize).
 Invert Sugar
Invert or sugar syrup is a mixture of glucose and fructose.
It is obtained by splitting sucrose into these two components.
Compared with its precursor sucrose, inverted sugar is sweeter
and its products tend to retain moisture and are less prone to
crystallization.
Invert sugar is therefore valued by bakers.

C12H22O11 + H2O → C6H12O6 + C6H12O6

Sucrose Glucose Fructose
+66.5° +52.7° −92°
Polysaccharides

40
 Polysaccharides or glycans
1) Homoglycans: single type of monomer (Starch,
Cellulose, Glycogen, Dextrins or Inulin)

2) Heteroglycans : contain two or more different

kinds (Mucopolysaccharides)

Characteristics:
-polymers (MW from 200,000)
-White and amorphous products (glassy)
-not sweet
-not reducing; do not give the typical aldose or ketose
reactions
-form colloidal solutions or suspensions
41
 Homopoysaccharides
Homopoysaccharides are polymers composed of
a single type of sugar monomers

Homo polysaccharides

Fructosan Galactosan
e.g. Inulin e.g. Agar

Glucosans
e.g. Starch
Glycogen
Cellulose
42
 Glucosans /Glucans

1) Glycogen (Storage Polysaccharide)

-Also known as animal starch
-Stored in muscle and liver
-Present in cells as granules (high MW)
-Contains both α(1,4) links and α (1,6) branches at every
8 to 12 glucose unit
-Complete hydrolysis yields glucose
- With iodine gives a red-violet color
-Hydrolyzed by both α and β-amylases and by glycogen
phosphorylase

43
 Glycogen
-In the liver, glycogen synthesis and degradation are regulated
to maintain blood-glucose levels as required to meet the needs
of the organism as a whole. Glycogen serves as a buffer to
maintain blood glucose level.

-In contrast, in muscle, these processes are regulated to meet the

energy needs of the muscle itself.
- The concentration of glycogen is higher in the liver than in
muscle (10% versus 2% by weight), but more glycogen is stored
in skeletal muscle overall because of its much greater mass.

Structure of
Glycogen 45
 2) Starch (Storage Polysaccharide)
-Most common storage polysaccharide in plants
-Composed of 10 – 30% Amylose and 70-90% amylopectin
depending on the source
(a) Amylose is a linear polymer of α-D-glucose, linked
together by α 1→4 glycosidic linkages. It is soluble in water,
reacts with iodine to give a blue color and the molecular
weight of Amylose ranges between 50, 000 – 200, 000.

(b) Amylopectin is a highly branched polymer, insoluble in

water, reacts with iodine to give a reddish violet color. The
molecular weight ranges between 70, 000 - 1 000, 000.
Branches are composed of 25-30 glucose units linked by α
1→4 glycosidic linkage in the chain and by α 1→6
46
glycosidic linkage at the branch point.
Components of Starch

An (α1-6) branch point of

amylopectin.
47
 Starch

Suspensions of Amylose
in water adopt a helical
conformation

Iodine (I2) can insert in

the middle of the Amylose
helix to give a blue color
that is characteristic and
diagnostic for starch

Biochemistry for medics 48

 3) Dextrins
-Produced by the partial hydrolysis of starch along
with maltose and glucose
-Dextrins are often referred to as either amylodextrins,
erythrodextrins or achrodextrins
-Used as mucilages (glues)
-Used in infant formulas (prevent the curdling of milk
in baby’s stomach)
-Indigestible dextrin are developed as soluble fiber
supplements for food products
- Also Used as thickening agents in food processing

49
3) Dextrins
 4) Dextrans
-Products of the reaction of glucose and the enzyme
Transglucosidase from Leuconostoc mesenteroides
-Contains α (1,4), α(1,6) and α (1,3) linkages
-MW: 40,000; 70,000; 75,000
-Used as plasma expanders (treatment of shock)
-also used as molecular sieves to separate proteins and
other large molecules (gel filtration chromatography)
-Components of dental plaques

Biochemistry for medics 51

5) Cellulose (Structural Polysaccharide)

-Polymer of b-D-glucose linked by b(1,4) linkages

-Yields glucose upon complete hydrolysis

-Partial hydrolysis yields cellobiose

-Most abundant of all carbohydrates

-Gives no color with iodine

-Cellulose is tasteless, odorless and insoluble in water and

most organic solvents.

52
 Cellulose
Cellulose consists of β -D-glucopyranose units linked by
β 1 →4 bonds to form long, straight chains strengthened
by cross-linking hydrogen bonds.

Biochemistry for medics 53

 Cellulose- Digestion
Mammals lack any enzyme that hydrolyzes the β 1→ 4
bonds, and so cannot digest cellulose.

It is an important source of "bulk" in the diet, and the

major component of dietary fiber.

Microorganisms in the gut of ruminants and other

herbivores can hydrolyze the linkage and ferment the
products to short-chain fatty acids as a major energy
source.
 Significance of Cellulose

-Microcrystalline cellulose : used as binder-

disintegrant in tablets
-Methylcellulose: suspending agent and bulk
laxative
-Oxidized cellulose: hemostat
-Sodium carboxymethyl cellulose: laxative
-Cellulose acetate: rayon; photographic film;
plastics
-Cellulose acetate phthalate: enteric coating
-Nitrocellulose: explosives; collodion
(pyroxylin)
 Chitin- Structural Polysaccharide

-Chitin is the second most abundant carbohydrate

polymer of N- Acetyl Glucosamine
-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

56
 Inulin (Fructosan) Storage polysaccharide

-b-(1,2) linked fructofuranoses

-Linear ,no branching
-Lower molecular weight than starch
-Colors yellow with iodine
-Hydrolysis yields fructose
-Sources include onions, garlic, dandelions and Jerusalem
artichokes
-Used as diagnostic agent for the evaluation of glomerular
filtration rate (renal function test)

Biochemistry for medics 57

Jerusalem artichoke
 Uses of Inulin
-used clinically as a highly accurate measure of
glomerular filtration rate (GFR)
-Used as a soluble dietary fiber
-Used as appetite suppressant
-Used as a low glycemic index sweetener
-Also used as a fat/cream substitute

Biochemistry for medics 58

 Agar (Galactosan)
-Agar is a galactose polymer
-Obtained from the cell walls of some species of red algae or
seaweeds (Sphaerococcus Euchema ) and species of Gelidium

-Dissolved in hot water and cooled, agar becomes gelatinous;

-Its chief use is as a culture medium for microbiological work.
-Other uses are as a laxative,
-A vegetarian gelatin substitute,
-A thickener for soups, in jellies, ice cream and Japanese desserts,
-As a clarifying agent in brewing, and for sizing fabrics.

59
 Heteropolysaccharides/ Mucopolysaccharides

Mucopolysaccharides or Glycosaminoglycans are carbohydrates

containing a repeating disaccharide.

The disaccharide usually contains an acid sugar and an amino

sugar.
Acid sugar is generally D- Glucuronic acid or its C-5 epimer
Iduronic acid, while amino sugar is either D- Glucosamine or
D-Galactosamine, amino group is generally acetylated
eliminating its positive charge.
The amino sugar may be sulfated on non acetylated nitrogen.
Carboxyl groups of acid sugars together with sulfate groups give
Glycosaminoglycans strongly negative nature.

60
 Hyaluronic acid-(D-glucuronate + GlcNAc)n
Occurrence: synovial fluid, ECM of loose connective tissue.
Serves as a lubricant and shock absorber.
-Hyaluronic acid does not contain any sulfate and is not found
covalently attached to proteins.
-It forms non-covalently linked complexes with Proteoglycans
in the ECM.
-Hyaluronic acid polymers are very large (100 - 10,000 kDa)
and can displace a large volume of water.

61
 Dermatan sulfate
(L-Iduronate + GalNAc sulfate) n

Occurrence: skin, blood vessels, heart valves

Chondroitin sulfate
(D-glucuronate + GalNAc sulfate)n
Occurrence: cartilage, tendons, ligaments, heart valves and
aorta.
It is the most abundant GAG.

62
 Glycosaminoglycans of physiological
Significance

Heparin
(D-glucuronate sulfate + N-sulfo-D-glucosamine) n
Heparans have less sulfate groups than heparins
Occurrence:

Heparin : component of intracellular granules of mast cells lining the

arteries of the lungs, liver and skin ( Contrary to other GAGs that are
extra cellular compounds, it is intracellular). Acts as an anticoagulant.
Heparan sulfate : basement membranes, component of cell surfaces
 Glycosaminoglycans of Physiological
Significance
Keratan sulfate (Gal + GlcNAc sulfate) n

Occurrence: cornea, bone, cartilage;

Keratan sulfates are often aggregated with Chondroitin
sulfates.
 Neutral Mucopolysaccharides

- Found in Pneumococci capsule

- Act as blood group substances. Four monosaccharides ,
Galactose, Fucose, Galactosamine(Acetylated) and
Acetylated Glucosamine are present in all types of blood
group substances.
- Also found in egg protein- ovalbumin

65
 Proteoglycans (mucoproteins)

-are formed of glycosaminoglycans (GAGs) covalently

attached to the core proteins.
- are found in all connective tissues, extracellular
matrix (ECM) and on the surfaces of many cell types.
Proteoglycans are remarkable for their diversity

66
 Proteoglycan Monomer
-A Proteoglycan monomer found in cartilage consists of a core protein
to which the linear GAG chains are covalently linked.

-These chains which each may be composed of more than 100

monosaccharides, extend out from the core protein and remain
separated from each other because of charge repulsion.

The resulting structure resembles a ‘Bottle brush.

- In cartilage proteoglycans, the species of glycosaminoglycans

include Chondroitin sulfate and Keratan sulfate.

Biochemistry for medics 67

Structure of Proteoglycan Monomer

Biochemistry for medics 68

 Proteoglycan Aggregates

-The proteoglycan monomers associate with a molecule of

Hyaluronic acid to form Proteoglycan aggregates.

-The association is not covalent, but occurs primarily through

ionic interactions between the core protein and Hyaluronic acid.

-The association is stabilized by additional small proteins called

Link proteins.

Biochemistry for medics 69

Proteoglycan Aggregates

Biochemistry for medics 70

 Functions of Proteoglycans

GAG dependent functions can be divided into two classes: the

biophysical and the biochemical.
1) The biophysical functions :
-Act as constituent of extracellular matrix or ground substance-
Interact with collagen and Elastin
- contribute turgor to ECM acting as polycations and attracting
water.
-Act as barrier in the tissues
-Act as lubricant in the joints
- Help in the release of hormones

-
 Functions of Proteoglycans (Biophysical Contd.)

-Help in cell migration in embryonic tissues

- Present in the basement membrane of glomerulus of kidney,
play important role in the Glomerular filtration
-Heparin acts as an anticoagulant .
-Heparin helps in the release of lipoprotein lipase, also called
‘Clearing factor’.
-Components of cell membrane, act as receptors.
-Chondroitin sulfates and hyaluronic present in cartilages have a
great role in compressibility of cartilage in weight bearing
- Maintain shape of sclera
- Help in maintaining the transparency of cornea
-
 Functions of Proteoglycans
2)Biochemical functions of GAGs are mediated by
specific binding of GAGs to other macromolecules,
mostly proteins.
Proteoglycans participate in cell and tissue
development and physiology.

Biochemistry for medics 73

 Summary
-Homopoysaccharides are polymers of similar monomer
monosaccharides linked together by Glycosidic linkages.
Structurally they may be Glucosans, fructosan or Galactosan.
Functionally they may be storage or structural
polysaccharides
-Heteropolysaccharides are polymers of a repeating
disaccharide units with enormous diversity. They are
components of ECM, joints, cartilages, tendons, cornea and
sclera. Heparin is an anticoagulant.
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