CARBOHYDRATES

Biochemistry
Studying the structure and behavior of the complex
molecules found in biological material and the ways these
molecules interact to form cells, tissues and whole
organism

Bio
molecules Biological
Carbohydrates Processes
 Carbohydrates are broadly defined as polyhydroxy
aldehydes or ketones and their derivatives or as substances
that yields one of these compounds

 The term saccharideis derived from the Latin word "

sacchararum" from the sweet taste of sugars.

 The name "carbohydrate" means a "hydrate of carbon."

The name derives from the general formula of carbohydrate
is Cx(H2O)y
Composed of carbon, hydrogen, and oxygen
Functional groups present include hydroxyl groups
 Biochemical Definition
Carbohydrates are poly-hydroxy carbonyl compounds
(aldehyde or ketone) and their derivative and the polymer that
give them on hydrolysis.

Example:
Biomedical Importance of Carbohydrates

1- Energy source for plants and animals (glucose).

One of the major source of energy in cell.
75% of energy in cell comes from CHO.
25% from others (fats)

1 g CHO =4 K.calories
1 g protein =4 K.calories.
1 g lipid =9K.calories.
 Why body not use lipid as major
energy source instead of CHO?

Lipids contain more energy but are not quicker source of energy, carbohydrates

though contain less energy but yield energy quite rapidly because their simpler

forms (monosaccharides) like glucose are reducing sugars means easily

oxidizeable and prove an efficient source of energy round the clock i.e in the

form of ATP, lipids' simpler forms like fatty acids have higher C-H content so

they are good at storing energy and yield energy slowly like in hibernation.
2- Cell membrane components:
eg. Glycolipid and glycoprotein

3- Form structural tissues in plants and in microorganisms

eg. (cellulose, chitin, murein)

4- Glucose is the precursor for synthesis of all other carbohydrates in the

body, including
Galactose in lactose of milk. Glycogen for storage; . (Store as glycogen in animals, and starch)
In plants. (storage form of energy).

Ribose and Deoxyribose in nucleic acids;

DNA –deoxy ribonucleic acid (deoxy sugar)
RNA –ribonucleic acid (ribose sugar).
 5-To describe the mechanism of some diseases related to CHO.

Diabetes Mellitus. Glactosemia Lactose intolerance

Caused by a lack of one of the enzymes A person becomes lactose intolerant when his or
Type 1 is a form of diabetes mellitus in which necessary for metabolizing galactose, a her small intestine stops making enough of the
very little or no insulin is produced by the sugar that is part of a larger sugar called enzyme lactase to digest and break down the
pancreas. lactose (milk sugar). lactose.
Type 2 noninsulin-dependent diabetes, is a
chronic condition that affects the way your
body metabolizes sugar (glucose)
 Classification of Carbohydrates
There are a variety of interrelated classification schemes. The most useful classification
scheme divides the carbohydrates into groups according to the number of individual
simple sugar units.

Carbohydrates are classified into four groups:

1.Monosaccharides: (saccharides means sugars)that cannot

be hydrolyzed into simpler carbohydrates.
2.Disaccharides: condensation products of two
monosaccharide units.

Note, all mono and disaccharides have the ending ose

(glucose, galactose, ribose, lactose, etc…)
3.Oligosaccharides are condensation products
of three to ten monosaccharides;
Maltotriose is an example.
4.Polysaccharides are condensation products
of more than ten monosaccharide units.

Homopolysaccharide are polysaccharides composed of a single type of sugar monomer. For

example, cellulose is an unbranched homopolysaccharide made up of glucose monomers
connected via beta-glycosidic linkages; glycogen is a branched form, where the glucose
monomers are joined by alpha-glycosidic linkages.

HeteropolysaccharideIf the polysaccharides molecules are formed by different kinds of

monosaccharides, they are considered heteropolysaccharides. Hyaluronic acid, formed by
thousands of alternative units of N-acetyl glucosamine and glucuronic acid, is an example
ofheteropolysaccharide.
Monosaccharides
are simple sugars, or the compounds which possess a free aldehyde (CHO) or
ketone (C=O) group and two or more hydroxyl (OH) groups. They are the
simplest sugars and cannot be hydrolysed further into smaller units.
Monosaccharides contain a single carbon chain and are classified on the basis of
number of carbon atoms they possess, and as aldoses or ketoses depending upon
their groups.
Monosaccharides are classified by:

1- the number of carbon atoms:

3C-Triose , 4C -tetroses , 5C-pentoses , 6C- hexoses and 7C –
heptoses.

2-the position or type of carbonyl group:

Aldehyde, aldose (terminal)
Ketone, ketose (middle )

3- Both number of carbon atom and type of carbonyl

E,g Aldotriose and Ketotriose
1- The number of carbon atoms:
Aldose sugars
H H H H H

C O C O C O C O C O

(H C OH)n H C OH H C OH H C OH H C OH

CH2OH CH2OH H C OH H C OH H C OH

Aldose Aldotriose CH2OH H C OH H C OH

n=1
Aldotetrose CH2OH
n=2 H C OH
Aldopentose
Glyceraldehyde CH2OH
n=3
Erythrose Aldohexose
And n=4
Threose
Ribose
Trioses Tetroses Pentoses
Ketose sugars (Top+Bottom CH OH) 2

CH2OH CH2OH
CH2OH
CH2OH
C O C O CH2OH
C O
C O
(H C OH)n H C OH C O
H C OH
CH2OH
CH2OH H C OH H C OH
CH2OH
CH2OH H OH
Ketose Ketotriose Ketotetrose
n=1 Ketopentose H C OH
n=0
n=2
Dihydroxyacetone
CH2OH

Erythrulose Ketohexose
Ribulose
n=3
Dihydroxyacetone Erythrulose Ribulose
Glyceraldehyde
 GLYCERALDEHYDE IS THE SIMPLEST
MONOSACCHARIDE(PARTICULARLY ALDOSES)

 IT CANNOT BE HYDROLYZED FURTHER.

 IT IS THE SMALLEST POSSIBLE STRUCTURE THAT IS A

CARBOHYDRATE CANNOT HAVE LESS THAN 3 CARBON
ATOMS.

 GENERAL FORMULA OF MONOSACCHARIDE: (C•H2O)N

 (WHERE N IS ANY NUMBER OF THREE OR GREATER)
Properties of monosaccharides
Carbohydrates with free carbonyl groups or in hemiacetal form
give positive tests to Benedict’s and Fehling’s reagents
without having been hydrolyzed are referred as ‘reducing’
sugars ; others (i.e., the acetal types) are then ‘non-reducing’
sugars
 Glucose Structure
The structure of Glucose can be represented in three ways:

Straight Chain Form Haworth Projection Chair Form

Ring Form is more stable

 Haworth Fischer projections

Haworth projection of the structures for α-D-

glucopyranose and α-L-glucopyranose.
A Haworth projection is a common way of writing
a structural formula to represent the
cyclic structure of monosaccharides with a simple
three-dimensional perspective. Organic chemistry and
especially biochemistry are the areas
of chemistry that use the Haworth projection the
most.
The Haworth projection was named after the English
chemist Sir Norman Haworth.

While Fischer projections are used for sugars in their open-

chain form
Isomers
are basically molecules that have the same
chemical formula but they differ in their chemical
structures.

Asymmetric Carbon is an important determinant

of Isomerism.

Asymmetric Carbon is that Carbon which is

attached with four different groups.
Forms of Isomerism

Monosaccharides exhibit various forms of isomerism: Because it have

asymmetric carbon atom

D and L Enantiomers.

Pyranose and Furanose ring structures.

Alpha and Beta anomers.

Epimers.

Aldose and Ketose isomerism.

Optical activity
Straight Chain Structure of Typical
Monosaccharide (Glucose)
Anomeric
Carbon

Epimeric
Carbons
Penultimate
Carbon

Terminal
Alcohol Carbon
Hemiacetal, Hemiketal, Acetal & Ketal
1- D & L isomers (enantiomers)

 Those monosaccharides that are of physiological significance exist

in the D-configuration, where the hydroxyl group is on the right
side .

 The mirror-image, called enantiomers, are in the L-configuration.

 They are related to glyceraldehyde which exists in

two isomers D and L
 Monosaccharides
L and D Enantiomers
It also called mirror images or Optical Isomers:
 The assignment of D or L is made according to
the orientation of the Penultimate Carbon

If the Hydroxyl Group is on the right

the molecule is a D sugar,
Otherwise It is an L sugar.

L-Sugar : D-Sugar
OH H
 2-pyranose and furanose ring
(isomer)

Monosaccharide with 5 or 6 carbon

atoms tend to cyclyze in solution.
This terminology indicate that the ring
structure of monosaccharide is similar
to either pyran or furan

Monosaccharides
2-Pyranose and Furanose
3 - α- and β anomers.(isomers)

Isomers that differ on the

position of OH
group around anomeric
carbon (which was
carbonyl carbon) when the
ring is formed
Alpha and Beta Anomers
4-Epimers (isomers)
 Two monosaccharide that differ from each
other by position of OH group on one
carbon. ( eg carbon 2,3 and 4 of glucose).

 glucose and galactose are epimers at carbon

4

 While glucose and mannose are carbon 2

epimers.
Epimers

Mannose Glucose Galactose

5-Aldose and Ketose Isomerism
Oxidation of Monosaccharides

• Aldehydes and ketones that have an OH group on

the carbon next to the carbonyl group react with a
basic solution of Cu2+ (Benedict’s reagent) to form
a red-orange precipitate of copper(I) oxide (Cu2O).

• Sugars that undergo this reaction are called

reducing sugars.
 What’s So Great About Chiral Molecules?

Molecules which are enantiomers of each

other have exactly the same physical
properties (melting point, boiling point,
index of refraction, etc.) but not their
interaction with polarized light.

• Polarized light vibrates only in one plane;

it results from passing light through a
polarizing filter.
Chiral molecules have the same relationship to each
other that your left and right hands have when
reflected in a mirror.
Optical activity
 The ability to rotate plane-polarized light to the
right (dextrorotatory) +sign Or to the left
(levorotatory) - sign
 Glucose is dexrtoratotry hence the name dextrose
in clinical practice eg IV fluid
 Fructose is levorotatory hence the name levulose

D-Glucose
Hexoses of Physiologic importance:

Glucose
 Fructose
Galactose
D-glucose
 Common names:
 glucose, grape sugar, dextrose

 Natural Source:
 Fruits, cereal starch hydrolysis, sugar hydrolysis, corn
syrup and honey.
 Importance:
The principal sugar used by the tissue.
 Building block for: disaccharides (such as sucrose, lactose
and maltose) and polysaccharides (starch, cellulose and
glycogen) converted to ribose and deoxyribose for DNA
and RNA synthesis.
D-galactose
 Natural Source:
 None for free form
 Formed by hydrolysis of lactose (milk sugar).
 Importance: converted to glucose, and used for the
synthesis of Milk.
 enter in cellular membranes of brain & nervous
system.
 Deficiency diseases:
 Galactosemia:
 Enzyme to metabolize galactose missing and levels
build in blood cause mental retardation, cataracts and
D-fructose

 Common names:
 Levulose and fruit sugar
 Natural Source:
 Fruit juice and honey
 Hydrolysis of cane and beat sugar
 Importance: converted to glucose in liver, source of
energy for spermatozoa
 Due to sweetness, used as sweetener.
Monosaccharide Derivatives of Biological
Importance

 Oxidation Products (Sugar Acids)

 Reduction Products (Sugar Alcohols).
 Amino Sugars.
 Sugar Phosphates.
 When oxidized under proper conditions, Aldoses may form
three types of acids (Sugar Acids):

Uronic Acids.
Uronic acids are a class of sugar acids with both carbonyl and carboxylic acid functional groups. They are
sugars in which the terminal carbon's hydroxyl group has been oxidized to a carboxylic acid.

Aldonic acid:

A molecule similar to an aldose, except that the aldehyde has been oxidized to a carboxylic acid.
Saccharic Acids.
Saccharic acid, also called glucaric acid, is a chemical compound with the formula C 6H10O8. It is derived by
oxidizing a sugar such as glucose with nitric acid. The salts of saccharic acid are called saccharates or
glucarates.
Uronic Acid Aldonic acid Saccharic Acid
Sugar Alcohols; Reduction Products

 Sugar Alcohols are obtained by reduction of

Monosaccharides (Both Aldoses and Ketoses) and
disaccharides.
 Sugar alcohols, also known as Polyols, Polyhydric
Alcohols, or Polyalcohols.
 Sugar Alcohols are the Hydrogenated forms of the Aldoses or Ketoses

H- C=O CH2OH
 
H-C-OH + H2 H-C-OH
 
OH-C-H OH-C-H
 
H-C-OH H-C-OH
 
H-C-OH H-C-OH
 
CH2OH CH2OH
Glucose
 Sugars with their Corresponding Alcohols

Glyceraldehyde & Glycerol

Dihydroxyacetone
Glucose Sorbitol (Glucitol)
Mannose Mannitol
Fructose Sorbitol & Mannitol
Galactose Dulcitol
Ribose Ribitol
Erythrose Erythritol
Xylose Xylitol
Lactose Lactitol
Maltose Maltitol
  Substitution of Amino Group for a
Amino Sugar: Hydroxyl Group of a Sugar Results
in the Formation of an Amino Sugar.
 The Amino Group is attached to
H-C=O
 Carbon 2.
H-C-OH
NH2 Common Examples of Amino Sugars (Aminosaccharides)

OH-C-H

H-C-OH
 Galactosamine Glucosamine
H-C-OH glycoprotein hormones
is part of the structure
 such as follicle-
stimulating hormon
of the polysaccharides,
chitosan, and chitin.
CH2OH
Sugar Phosphates

 Phosphate Esters formed by various Monosaccharides

are of Great Importance in Metabolic Reactions.
 Sugar phosphates of biological importance.

 Ribose and Deoxyribose in Nucleic Acids are

Phosphate Esters of these monosaccharides.
 Phosphates of Glucose, Fructose and Glyceraldehyde
etc. are important intermediate compounds in
carbohydrate metabolism of almost all the cells.
 Pentoses of Physiologic importance
Ribose inter the structure of Nucleic Acids

Ribose Deoxyribose
 Disaccharides
A disaccharide consists of two sugars joined by an O-glycosidic bond.

The three common Disaccharides are:

The disaccharides, just like monosaccharide are white crystalline, sweet solids. The
disaccharides are also optically active; they rotate the plane of polarized light. However,
even though they are soluble in water, they are too large to pass through cell
membranes.
 Glycosides
Glycoside is two substances connected by glycosidic bond.
Importance:
1- formation of disaccharide and other derivative.
2- cardiac glycoside (is a drug used in treatment of some heart disease)by
inhibiting Na-K ATPase pump. e.g Digitalis (contain sugar and
steroid)
3-Certain antibiotic like streptomycin.
 Aldehyde + Alcohol Hemiacetal

Maltose
Ketone + Alcohol Hemiketal

Commonly known as malt sugar.

 Present in germinating grain

Also known as malt sugar. It

is found in germinating grain
(such as barley), and is formed
during the hydrolysis of starch
to glucose during digestion.
It is a reducing sugar.

Produced commercially by hydrolysis of starch

 Lactose

Also known as milk sugar.

Lactose constitutes 5% of cow's
milk and 7% of human milk. It is
digested by the enzyme lactase.

Bacteria cause fermentation of lactose

forming lactic acid.

 When these reaction occur ,it

changes the taste to a sour one.
 Sucrose

Also known as table sugar. Both anomeric

carbons of glucose and fructose are tied
together in the glycosidic linkage; thus neither
ring can open, and sucrose is not a reducing
sugar. Sucrose is abundant in sugar cane
and sugar beets; maple syrup contains about
65% sucrose, with glucose and fructose This 50:50 mixture of
present as well; caramel is the solid residue glucose and fructose is
called invert sugar
formed from heating sucrose
because it reverses the
rotation of polarized light.
Reducing properties
In maltose
The aldehyde groups are at carbon 1 in each of the
original glucose molecules. Since the linkage is 1.4, one
free aldehyde group remains. Therefore, maltose acts as
a reducing sugar.
In sucrose
In sucrose the glucose part had the aldehyde at carbon 1, and the
fructose part had the ketone group at carbon 2. since the
linkage is 1,2, neither group is free. Therefore, sucrose is
not a reducing sugar.a
In lactose
Which has a 1,4-linkage, acts as a reducing sugar
because both of the original aldehyde group are on
carbon 1,
Fermentation
 Sucrose and maltose will ferment when
yeast is added because yeast contains the
enzyme sucrase and maltase.

 Lactose will not ferment because yeast

does not contain lactase.
 Many synthetic sweeteners are known

 The most common sugar substitutes

are:
1. Saccharin is made commercially
from o-toluenesulfonamide.
Saccharin
2. Cyclamates: they are not used
anymore because they might cause
cancer.

o-toluenesulfonamide
3. Aspartame became the first new sweetener Aspartic acid

to be approved by the U.S. Food and Drug

Administration (FDA).
It is about 160 times sweeter than sucrose.
Structurally, aspartame is the methyl ester of a
dipeptide of two amino acids that occur
naturally in proteins—aspartic acid and
phenylalanine—and is sold under the trade
name NutraSweet.

Aspartame is also one of the sugar substitutes used by

diabetics. non-carbohydrate sweetener,
 Isomaltulose

Prepared enzymatically
from sucrose
Enzyme is from
Protaminobacter rubrum

Uses
– Non-cariogenic α-D-Glucopyranosyl-(1-6)-D-fructofuranose
candies
– Specialty chocolate
– Chewing gum –
 Next Lecture

Oligosaccharide and Polysaccharides

Lecture 6

CARBOHYDRATES
Oligosaccharide and Polysaccharides
 Oligosaccharide
Oligo--Greek, few

 Higher order oligosaccharides are named tri-,

tetra-, penta-, etc.
 Structures may be predominately linear or
branched

Structural features
Types of Oligosaccharides
 Linear – Features a head-to-tail linkage – 1 reducing
end – 1 non-reducing end

 Branched – 1 reducing end – Several to many non-

reducing ends
 Oligosaccharides contain from 3 to 10 monosaccharide units.

Raffinose
An oligosaccharide found in peas
and beans; largely undigested until
reaching the intestinal flora in the
large intestine, releasing hydrogen,
carbon dioxide, and methane)
 The raffinose family of oligosaccharides (RFOs) are α-
galactosyl derivatives of sucrose.
 The most common are the trisaccharide raffinose , the
tetrasaccharide stachyose , and the pentasaccharide
verbascose.
 RFOs are almost ubiquitous in the plant kingdom, being
found in a large variety of seeds from many different
families, and they rank second only to sucrose in
abundance as soluble carbohydrates.
Cyclodextrins:
Cyclodextrins A family of compounds made up of sugar molecules
bound together in a ring: cyclic oligosaccharides. Cyclodextrins are
produced from starch by means of enzymatic conversion.
Used in: Food Pharmaceutical industry Chemical industry Agriculture
Environmental engineering
 α - cyclodextrin : β - cyclodextrin : γ - cyclodextrin :

six membered sugar seven membered sugar eight membered sugar

Cyclodextrins are produced from starch by enzymatic conversion. They

are used in food, pharmaceutical, drug delivery,] and chemical industries,
as well as agriculture and environmental engineering. α-Cyclodextrin is a
soluble dietary fiber used as an ingredient in commercial food products.
 POLYSACCHARIDES
 Polysaccharides consist of repeating units of
Monosaccharide or their derivatives held together by
glycosidic bond.
 These structures are often linear, but may contain
various degrees of branching.
 Polysaccharides are often quite heterogeneous,
containing slight modifications of the repeating unit
 Polysaccharides have a general formula of Cx
(H2O)y .

DEFINITION:- Polysaccharides are the complex carbohydrates. They are

made up of chains of monosaccharide (the sugars) which are linked
together by glycosidic bonds, formed by the condensation reaction.”
 TYPES AND STRUCTURAL FEATURES:-

1. Homopolysaccharides:-
 They are such polysaccharides which on
hydrolysis yield a single type of
monosaccharides.
 Thus, Glucans are polymers of glucose and
fructosans are polymers of fructose.
 When all the monosaccharides in a
polysaccharide are the same type the
polysaccharide is called a
homopolysaccharide or homoglycan.
SOME IMPORTANT HOMOPOLYSACCHARIDES ;-

STARCH

COMPOSITION OF STARCH
Starch consists of 2-polysaccharide
components, water soluble amylose(15-
20%) and water insoluble
amylopectin(80-85%).
Uses of Starch:-

1. Main constituents of food to produce heat.

2. Employed as an adhesive in book binding.
3. Manufacture of Glucose and alcoholic beverages.
4. Used as a gelatin in preparation of sweets.
5. In paper industry for sizing paper
 GLYCOGEN:

 Glycogen is the carbohydrate reserve in animals called as

animal starch.
 It is present in high concentration in liver followed by
muscle, brain, etc.
 Glycogen is also found in plants that do not possess
chlorophyll.

Structure of Glycogen:- GLYCOGEN

 The structure of Glycogen is similar to that of amylo pectin
with more no. of branches.
 Glucose is the repeating unit in the Glycogen joint together
by the- (1-4) glycosidic bonds and α-(1-6) glycosidic bonds at
branching points.

Uses of Glycogen:-
 It act as storage food reserve in animals and help in
glycolsis.
 Provides energy when needed.
GLYCOGEN
 Cellulose (Structural Polysaccharide)

Cellulose widely occurs in vegetables because it forms

fundamental constituent of cell walls and vegetable tissues.

Sources of cellulose:-
Cotton, wood, paper, jute, flax, hemp.
All of them contain small amount of mineral matter which is
left as residues when they are burnt.

Physical properties of Cellulose:-

 It occur in the form of hollow fiber which have
characteristics appearance and dimension.
 Cellulose is soluble in ammonical solution of cupric
hydroxide and insoluble in all organic solvents.
Significance of Cellulose
 Industrial Application of Cellulose:-

1. Textile Industry:- • Cellulose employed in manufacture

of cotton and linen. •Jute is employed in smaller extent.
•Flax in manufacture of Gunnies, Wrappings.
2. Explosives: • Gum, cotton which is cellulose tri-nitrate
is used as blasting and propellant explosives.
3. Celluloid:- • Synthetic plastic, manufactured by mixing
colloid on cotton with camphor in the presence of ether
or alcohol.
4. Artificial Silk:- Cellulose finds an extensive application
in manufacture of artificial silk
Chitin: Structural Polysaccharide
Composed of N-Acetyl, D-Glucosamine
units held together by β-(1-4) Glycosidic
bonds.

Structural polysaccharides found in the

exoskeleton of some invertebrates.
HEPARIN
Heparin, also known as unfractionated heparin (UFH),
is a medication which is used as an anticoagulant (blood
thinner). Specifically it is used to treat and prevent deep
vein thrombosis, pulmonary embolism, and arterial
thromboembolism. It is also used in the treatment of
heart attacks and unstable angina.
 BIOLOGICAL IMPORTANCE OF POLYSACCHARIDES

 These act as a metabolic reserve in plants and animals – starch, glycogen.

 They also serve as mechanical structures in plants and animals.

 Wood, cotton, paper are made of cellulose which are useful in our day to day life.

 Cellulose nitrates are used as explosives, lacquers, photograph.

 Films are used for packing materials.

 Xylan is also utilized in the cultivation of mushrooms.

 Agar-agar is a polysaccharide used for the preparation of food stuffs

 Heparin act as an anticoagulant for the prevention of blood, which is a polysaccharide.

 Source of energy and help to carry out certain metabolism.