Biochemistry

Lecture 4

Łukasz Łopusiewicz PhD DSc Eng.

Associate Professor
School of Medical & Health Sciences
University of Economics and Human Sciences
in Warsaw
LIPIDS
Lipids
• Lipids (Greek: lipos–fat) are of great importance to the body as the main
concentrated storage form of energy, besides their role in cellular structure and
various other biochemical functions.
• As such, lipids are a heterogeneous group of compounds and, therefore, it is difficult
to define them precisely.
• Lipids may be regarded as organic substances relatively insoluble in water, soluble
in organic solvents (alcohol, ether, chloroform, benzene, etc.), actually or potentially
related to fatty acids and utilized by the living cells.
• Unlike the polysaccharides, proteins and nucleic acids, lipids are not polymers.
Further, lipids are mostly small molecules.
• Lipids constitute about 15-20% of the body weight in humans.
 Functions

 Storage form of energy (concentrated fuel reserve of the body )

 Important dietary components because of their high energy value and also because of the fat-
soluble vitamins (A, D, E, K) and the essential fatty acids contained in the fat of natural foods.
 Structural components of biomembranes
 Serve as thermal insulators in the subcutaneous tissues and around certain organs
 Nonpolar lipids act as electrical insulators, allowing rapid propagation of depolarization waves along
myelinated nerves
 Provide shape and contour to the body
 Act as metabolic regulators (as cellular metabolic regulators - steroid hormones and prostaglandins)
 Combinations of lipid and protein (lipoproteins) are important cellular constituents, occurring both in
the cell membrane and in the mitochondria, and transporting lipids in the blood.
 Following diseases are associated with abnormal chemistry or metabolism of lipids: Obesity,
Atherosclerosis, Diabetes Mellitus, Hyperlipoproteinemia, Fatty liver, Lipid storage diseases, ….

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CLASSIFICATION OF
LIPIDS
• Lipids are broadly classified (modified from Bloor) into simple,
complex, derived and miscellaneous lipids, which are further
subdivided into different groups
• 1. Simple lipids : Esters of fatty acids with alcohols. These are mainly
of two types
• (a) Fats and oils (triacylglycerols) : These are esters of fatty acids with
glycerol. The difference between fat and oil is only physical. Thus, oil
is a liquid while fat is a solid at room temperature. Fatty acid is a long
chain of carbon atoms with a carboxyl -COOH group at one end .
Glycerol is a three carbon alcohol with three -OH groups . Depending
on the number of fatty acid molecules attached to glycerol molecules
the esters are called mono , di , or triglycerides .
(b) Waxes : Esters of fatty acids (usually long chain) with alcohols other than glycerol. These
alcohols may be aliphatic or alicyclic. The carboxylic acid usually has an even number of
carbons from 16 through 36, while the alcohol has an even number of carbons from 24 through
36. Cetyl alcohol is most commonly found in waxes. The waxy protective coatings on most
fruits, berries, leaves, and animal furs have similar structures. Waxes are used in the
preparation of candles, lubricants, cosmetics, thickeners, ointments, polishes etc.
• 2. Complex (or compound) lipids : These are esters of fatty acids with alcohols containing
additional groups such as phosphate, nitrogenous base, carbohydrate, protein etc. They are
further divided as follows
• (a) Phospholipids : They contain phosphoric acid and frequently a nitrogenous base. This is in
addition to alcohol and fatty acids.
• (i) Glycerophospholipids : These phospholipids contain glycerol as the alcohol e.g., lecithin,
cephalin.
• (ii) (ii) Sphingophospholipids : Sphingosine is the alcohol in this group of phospholipids e.g.,
sphingomyelin.
• (b) Glycolipids : These lipids contain a fatty acid, carbohydrate and nitrogenous base. The
alcohol is sphingosine, hence they are also called as glycosphingolipids. Glycerol and
phosphate are absent e.g., cerebrosides, gangliosides.
• (c) Lipoproteins : Macromolecular complexes of lipids with proteins.
• (d) Other complex lipids : Sulfolipids, aminolipids and lipopolysaccharides are among the
other complex lipids.
• 3. Derived lipids : These are the derivatives obtained on the hydrolysis of
group 1 and group 2 lipids which possess the characteristics of lipids. These
include glycerol and other alcohols, fatty acids, mono-and diacylglycerols,
lipid (fat) soluble vitamins, steroid hormones, hydrocarbons and ketone
bodies.
• 4. Miscellaneous lipids : These include a large number of compounds
possessing the characteristics of lipids e.g., carotenoids, squalene,
hydrocarbons such as pentacosane (in bees wax), terpenes etc.
FATTY ACIDS
• FATTY ACIDS
• Fatty acids are carboxylic acids with hydrocarbon side chain. They are the simplest form of lipids.
• Fatty acids are aliphatic carboxylic acids
• Have the general formula R-(CH2)n-COOH
• They occur mainly as esters in natural fats and oils but do occur in the unesterified form as free fatty acids, a transport form
found in the plasma.
• Fatty acids that occur in natural fats are usually straight-chain derivatives containing an even number of carbon atoms.

• Occurrence
• Fatty acids mainly occur in the esterified form as major constituents of various lipids. They are also present as free
(unesterified) fatty acids. Fatty acids of animal origin are much simpler in structure in contrast to those of plant origin which
often contain groups such as epoxy, keto, hydroxy and cyclopentane rings.
• Even and odd carbon fatty acids
• Most of the fatty acids that occur in natural lipids are of even carbons (usually 14C – 20C). This is due to the fact that
biosynthesis of fatty acids mainly occurs with the sequential addition of 2 carbon units.
• Palmitic acid (16C) and stearic acid (18C) are the most common. Among the odd chain fatty acids, propionic acid (3C) and
valeric acid (5C) are well known.
Classification of fatty acids
• Fatty acids can be classified in many ways-
• 1) According to nature of the hydrophobic chain-
• Saturated
• Unsaturated
• Saturated fatty acids do not contain double bonds, while unsaturated fatty acids contain
double bonds
Saturated fatty acids
• Saturated fatty acids may be explained based on acetic
acid (CH3 —COOH) as the first member of the series in
which —CH2 — is progressively added between the
terminal CH3 — and —COOH groups.
• Fatty acids in biological systems usually contain an
even number of carbon atoms, typically between 14
and 24. The 16- and 18-carbon fatty acids are most
common.
Unsaturated fatty acids
• Unsaturated fatty acids may further be divided as follows-
• Monounsaturated (monoethenoid, monoenoic) acids, containing one double bond.
• Polyunsaturated (polyethenoid, polyenoic, PUFA) acids,
• containing two or more double bonds.
• The configuration of the double bonds in most unsaturated fatty acids is cis.
• The double bonds in polyunsaturated fatty acids are separated by at least one
methylene group.
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 Cis and Trans isomers in unsaturated fatty
-acids
Depending upon the orientation of the radicals around
the axis of the double bond-
- Cis- if the radicals are on the same side of the double
bond
- Trans- if the radicals are on the opposite side
- Oleic acid and Elaidic acid have the same formula but
Oleic acid is cis while Elaidic acid is Trans Fatty acid
-The hydrocarbon chains in saturated fatty acids are, fairly
straight and can pack closely together, making these
fats solid at room temperature.
Oils, mostly from plant sources, have some double bonds
between some of the carbons in the hydrocarbon tail.
Increase in the number of cis double bonds in a fatty acid
leads to a variety of possible spatial configurations of the
molecule—eg, Arachidonic acid,
with four cis double bonds, has "kinks" or a U shape. 16
- Because of the kinks (sharp curve) in
the hydrocarbon tails, unsaturated
fats can't pack closely together,
making them liquid at room
temperature.
- The membrane lipids, which must be
fluid at all
environmental temperatures, are
more unsaturated than storage lipids.
- The carbon chains of saturated fatty
acids form a zigzag pattern when
extended, as at low temperatures.
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 Trans fatty acids
Trans fatty acids are present in certain
foods arising as a by-product of the
saturation of fatty acids during
hydrogenation, or "hardening," of natural
oils in the manufacture of margarine.
- An additional small contribution comes
from the ingestion of ruminant fat that
contains trans fatty acids arising from the
action of microorganisms in the rumen.
- Naturally-occurring unsaturated
vegetable oils have almost all cis bonds,
but using oil for frying causes some of
the cis bonds to convert to trans bonds.
Properties of Fatty Acids
• Hydrogenation :The Good Gone Bad
• Hydrogenation is a chemical process that adds hydrogen to the unsaturated bonds on the
FA chains attached to the TAG backbone.
• In this way, an unsaturated fat can be turned into a saturated fat and increase its melting
point.

• Recall that the addition of hydrogen to an alkene (unsaturated) results in an alkane

(saturated). A simple hydrogenation reaction is:
• H2C=CH2+H2→CH3CH3
• alkene plus hydrogen yields an alkane
• Processing naturally occurring fats to modify their texture from liquid to semisolid and
solid forms results in the development of trans fats, which have been linked to an
increased risk for heart disease.

• Trans fats are used in many processed foods such as cookies, cakes, chips, doughnuts,
and snack foods to give them their crispy texture and increased shelf life.
Properties of Fatty Acids
• Halogenation:
• When treated with halogens under mild conditions, the unsaturated fatty acids can take
up two halogen atoms, at each double bond to form the halogenated derivative of the fatty
acid.
• For example, Oleic acid + I2 → Di-iodo oleic acid The number of halogen atoms taken up
will depend on the number of double bonds and is an index of the degree of unsaturation.
 Properties of Fatty Acids

Melting Point:
The short and medium chain fatty
acids are liquids, whereas long
chain fatty acids are solids at
25°C. The solubility in water
decreases, while melting and
boiling points increase, with
increase in chain length.
The unsaturated fatty acids have
lower melting point compared to
saturated fatty acids with the
same chain length.
Properties of Fatty Acids
• Salt Formation:
• Saturated and unsaturated fatty acids form salts with
• alkali.
• CH3—COOH + NaOH → CH3—COONa + H2O
• Sodium and potassium salts of long chain fatty acids are called soaps. Calcium and
magnesium soaps are insoluble.
• The saponification number indicates how much potassium hydroxide is needed to
saponify 1g fat.
Ester Formation:
Both saturated and unsaturated fatty acids form
esters with alcohols, especially with glycerol.
Fatty acids can form mono-, di- or tri- esters with
alcohol groups of glycerol.
Triglycerides or triacylglycerols are also known as
neutral fat.
 Properties of Fatty Acids

Oxidation of Fatty Acids:

All fatty acids undergo oxidation in the body to
give energy.
Beta-oxidation is the major process by which
acids are oxidized.
However, the unsaturated fatty acids can
undergo auto oxidation, due to the presence of
the highly reactive double bonds and a variety of
products.
Short chain-with 2-6 carbon atoms
Medium chain- with 8-14 carbon atoms
Long chain- with 16-18 carbon atoms
Very long chain fatty acids- with 20 or more
carbon atoms
Essential fatty acids
• Polyunsaturated fatty acids such as Linoleic and Linolenic acids are essential for normal
life functions. They are therefore characterized as essential fatty acids.
• Arachidonic acid is considered as semi essential fatty acid since it can be synthesized
from Linoleic acid .
• Essential polyunsaturated fatty acids can be classified as belonging to one of two
"families", the omega-6 family or the omega-3 family.
• Fatty acids belonging to these two families differ not only in their chemistry, but also in
their natural occurrence and biological functions.
Significance of essential fatty acids
• Components of cell membranes, structural elements of gonads and mitochondrial
membrane
• Required for brain growth and development
• Precursors of Eicosanoids
• Play important role in vision

• They have a cardio protective role- Lowerserum cholesterol and increase HDL
levels
• Prevent fatty liver formation

• Deficiencies of essential polyunsaturated fatty acids may cause a wide variety of

symptoms, including retarded growth in children, reduced fertility and pathologic changes
in the skin.
• Deficiency of EFA
• The deficiency of EFA results in phrynoderma or toad skin, characterized by the presence of horny eruptions
on the posterior and lateral parts of limbs, on the back and buttocks, loss of hair and poor wound healing.
• Hydroxy fatty acids
• Some of the fatty acids are hydroxylated. β-Hydroxybutyric acid, one of the ketone bodies produced in
metabolism, is a simple example of hydroxy fatty acids. Cerebronic acid and recinoleic acid are long chain
hydroxy fatty acids.
• Cyclic fatty acids
• Fatty acids with cyclic structures are rather rare e.g., chaulmoogric acid found in chaulmoogra oil (used in
leprosy treatment) contains cyclopentenyl ring.
• Eicosanoids
• These compounds are related to eicosapolyenoic fatty acids and include prostaglandins, prostacyclins,
leukotrienes and thromboxanes.
TRIACYLGLYCEROLS
• Triacylglycerols (formerly triglycerides) are the esters of glycerol with fatty acids. The fats and
oils that are widely distributed in both plants and animals are chemically triacylglycerols.
They are insoluble in water and nonpolar in character and commonly known as neutral fats.
• Fats as stored fuel
• Triacylglycerols are the most abundant group of lipids that primarily function as fuel reserves
of animals. The fat reserve of normal humans (men 20%, women 25% by weight) is sufficient
to meet the body's caloric requirements for 2–3 months.
• Fats primarily occur in adipose tissue
• Adipocytes of adipose tissue—predominantly found in the subcutaneous layer and in the
abdominal cavity—are specialized for storage of triacylglycerols.
• The fat is stored in the form of globules dispersed in the entire cytoplasm. And surprisingly,
triacylglycerols are not the structural components of biological membranes.
• Properties of triacylglycerols
• A few important properties of triacylglycerols, which have biochemical relevance,
are discussed below
• 1. Hydrolysis : Triacylglycerols undergo stepwise enzymatic hydrolysis to finally
liberate free fatty acids and glycerol. The process of hydrolysis, catalyzed by lipases
is important for digestion of fat in the gastrointestinal tract and fat mobilization from
the adipose tissues.
• 2. Saponification : The hydrolysis of triacylglycerols by alkali to produce glycerol and
soaps is known as saponification.
• 3. Rancidity : Rancidity is the term used to represent the deterioration of fats and
oils resulting in an unpleasant taste. Fats containing unsaturated fatty acids are
more susceptible to rancidity.
PHOSPHOLIPIDS
• These are complex or compound lipids containing phosphoric acid, in addition to fatty acids,
nitrogenous base and alcohol.
• There are two classes of phospholipids
• 1. Glycerophospholipids (or phosphoglycerides) that contain glycerol as the alcohol.
• 2. Sphingophospholipids (or sphingomyelins) that contain sphingosine as the
• alcohol.
• Glycerophospholipids
• Glycerophospholipids are the major lipids that occur in biological membranes.
• They consist of glycerol 3-phosphate esterified at its C1 and C2 with fatty acids.
• Usually, C1 contains a saturated fatty acid while C2 contains an unsaturated fatty acid.
• They include;
• 1. Phosphatidic acid : This is the simplest phospholipid. It does not occur in good concentration in the tissues. Basically,
phosphatidic acid is an intermediate in the synthesis of triacylglycerols and phospholipids.
• The other glycerophospholipids containing different nitrogenous bases or other groups may be regarded as the derivatives of
phosphatidic acid.
• 2. Lecithins (phosphatidylcholine): These are the most abundant group of phospholipids in the cell membranes. Chemically, lecithin
(Greek : lecithos— egg yolk) is a phosphatidic acid with choline as the base. Phosphatidylcholines represent the storage form of
body's choline.
• 3. Cephalins (phosphatidylethanolamine) : Ethanolamine is the nitrogenous base present in cephalins. Thus, lecithin and cephalin
differ with regard to the base.
• 4. Phosphatidylinositol : The steroisomer myo-inositol is attached to phosphatidic acid to give phosphatidylinositol(PI). This is an
important component of cell membranes. The action of certain hormones (e.g. oxytocin, vasopressin) is mediated through PI.
• 5. Phosphatidylserine .
• 6. Plasmalogens
• 7. Cardiolipin
• Sphingomyelins
• Sphingosine is an amino alcohol present in sphingomyelins (sphingophospholipids).
They do not contain glycerol at all. Sphingosine is attached by an amide linkage to a
fatty acid to produce ceramide. The alcohol group of sphingosine is bound to
phosphorylcholine in sphingomyelin structure
• Sphingomyelins are important constituents of myelin and are found in good quantity
in brain and nervous tissues.
• Ceramide, acts as a second messenger (signaling molecule) by regulating
programmed cell death (apoptosis), cell cycle and cell differentiation. A ceramide
containing a 30-carbon fatty acid is a major component of skin, and it regulates
skin's water permeability.
FUNCTIONS OF PHOSPHOLIPIDS
• 1. In association with proteins, phospholipids form the structural components of membranes and regulate membrane permeability.
• 2. Phospholipids (lecithin, cephalin and cardiolipin) in the mitochondria maintain the conformation of electron transport chain
components, and thus cellular respiration.
• 3. Phospholipids participate in the absorption of fat from the intestine.
• 4. Phospholipids are essential for the synthesis of different lipoproteins, and thus participate in the transport of lipids.
• 5. Accumulation of fat in liver (fatty liver) can be prevented by phospholipids, hence they are regarded as lipotropic factors.
• 6. Arachidonic acid, an unsaturated fatty acid liberated from phospholipids, serves as a precursor for the synthesis of eicosanoids
(prostaglandins, prostacyclins, thromboxanes etc.).
• 7. Phospholipids participate in the reverse cholesterol transport and thus help in the removal of cholesterol from the body.
• 8. Phospholipids act as surfactants (agents lowering surface tension). For instance, dipalmitoyl phosphatidylcholine is an important
lung surfactant. Respiratory distress syndrome in infants is associated with insufficient production of this surfactant.
• 9. Cephalins, an important group of phospholipids participate in blood clotting.
• 10. Phosphatidylinositol is the source of second messengers—inositol triphosphate and diacylglyceol, that are involved in the action
of some horomones.
GLYCOLIPIDS
• Glycolipids (glycosphingolipids) are important constituents of cell membrane and
nervous tissues (particularly the brain). Cerebrosides are the simplest form of
glycolipids.
• They contain a ceramide (sphingosine attached to a fatty acid) and one or more
sugars. Galactocerebroside (galactosylceramide) and glucocerebroside are the
most important glycolipids.
Lipoproteins
• Lipoproteins
• Lipoproteins are molecular complexes of lipids with proteins. They are the transport
vehicles for lipids in the circulation. There are five types of lipoproteins, namely
chylomicrons, very low density lipoproteins (VLDL), low density lipoproteins (LDL), high
density lipoproteins (HDL) and free fatty acid albumin complexes.
• Lipoproteins consist of a nonpolar core and a single surface layer of amphipathic lipids
• The nonpolar lipid core consists of mainly triacylglycerol and cholesteryl ester and is
surrounded by a single surface layer of amphipathic phospholipid and cholesterol
molecules
• These are oriented so that their polar groups face outward to the aqueous medium.
• The protein moiety of a lipoprotein is known as an apolipoprotein or apoprotein.

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Classification of Lipoproteins
Lipoproteins can be classified on the basis of density
Based on density- They are separated by Ultracentrifugation. Five major groups of
lipoproteins have been identified which are important physiologically and in clinical
diagnosis.
1. Chylomicons, derived from intestinal absorption of triacylglycerol and other lipids;
Density is generally less than 0.95 while the mean diameter lies between 100- 500 nm

2. Very low density lipoproteins (VLDL), derived from the liver for the export of
triacylglycerol; density lies between 0.95-1.006 and the mean diameter lies between 30-
80 nm.
3. Intermediate density lipoproteins (IDL) are derived from the catabolism of VLDL,with a
density ranging intermediate between Very low density and Low density lipoproteins i.e.
ranging between 1.006-
1.019 and the mean diameter ranges between 25- 50 nm.
4. Low-density lipoproteins (LDL), representing a final stage in the catabolism of VLDL; density
lies between 1.019-1.063 and mean diameter lies between 18-28 nm
5. High-density lipoproteins (HDL), involved in cholesterol transport and also in VLDL and
chylomicron metabolism. Density ranges between 1.063-1.121 and the mean diameter varies
between 5-15 nm.
Lipoproteins with high lipid content will have low density, larger size
and so float on centrifugation. Those with high protein content
sediment easily, have compact size and have a high density.
• Amphipathic lipids
• As per definition, lipids are insoluble (hydrophobic) in water. This is primarily due to
the predominant presence of hydrocarbon groups. However, some of the lipids
possess polar or hydrophilic groups which tend to be soluble in water.
• Molecules which contain both hydrophobic and hydrophilic groups are known as
amphipathic (Greek : amphi-both, pathos— passion).
• Examples of amphipathic lipids
• Among the lipids, fatty acids, phospholipids, sphingolipids, bile salts and
cholesterol (to some extent) are amphipathic in nature.
• Cholesterol
• Cholesterol, exclusively found in animals, is the most abundant animal
sterol. It is widely distributed in all cells and is a major component of cell
membranes and lipoproteins. Cholesterol (Greek : chole–bile) was first
isolated from bile. Cholesterol literally means ‘solid alcohol from bile.’
• Most important sterol in human body
• Molecular formula-C27H45OH, Possesses a cyclopentano
perhydrophenatherene ring nucleus. Has an -OH group at C3. A double bond
between C5 and C6. Two- CH3 groups at C10 and C13. And eight carbon
side chain attached to C17
• Functions of cholesterol
• Cholesterol is a poor conductor of heat and electricity, since it has a high
dielectric constant. It is present in abundance in nervous tissues.
• Cholesterol functions as an insulating cover for the transmission of electrical
impulses in the nervous tissue.
• Cholesterol performs several other biochemical functions which include its
role in membrane structure and function, in the synthesis of bile acids,
hormones (sex and cortical) and vitamin D
Forms of cholesterol
• Cholesterol occurs both as free form or in ester form
• In cholesteryl ester, the hydroxyl group on position 3 is esterified with a long-chain fatty
acid.
• Cholesterol esters are formed by the transfer of acyl group by Acyl transferases- Lecithin
Cholesterol Acyltransferase (LCAT) & Acyl-CoA Cholesterol O-Acyltransferase (ACAT)
• In plasma, both forms are transported in lipoproteins
• Plasma low-density lipoprotein (LDL) is the vehicle of uptakeof cholesterol and
cholesteryl ester into manytissues.
 Free cholesterol is removed from tissues by
plasma high-density lipoprotein (HDL) and
transported to the liver, where it is eliminated
from the body either unchanged or after conversion to
bile acids in the process known as reverse
cholesterol transport
A sum total of free and ester cholesterol in serum is

called serum total cholesterol
 Significance of cholesterol
Cholesterol is widely distributed in all cells of the body but
particularly in nervous tissue.
It is a major constituent of the plasma membrane
and of plasma lipoproteins.
It is synthesized in many tissues from acetyl-CoA and is the
precursor of all other steroids in the body, including
corticosteroids, sex hormones, bile acids, and vitamin D.
Cholesterol is a major constituent of gallstones.

Its chief role in pathologic processes is as a factor in the

genesis of atherosclerosis of vital arteries, causing
cerebrovascular, coronary, and peripheral vascular disease.
Other sterols of biological importance

7-dehydrocholesterol- also called as Provitamin D3

(Precursor of vitamin D)
Ergosterol-plant sterol (First isolated from Ergot- Fungus of
Rye)
Other steroids- Bile acids, adrenocortical hormones, gonadal
hormones, D vitamins and Cardiac glycosides.
CARBOHYDRATES
• Structure of Carbohydrates

• Carbohydrates consist of carbon, hydrogen, and oxygen.

• The general empirical structure for carbohydrates is (CH2O)n.
• They are organic compounds organized in the form of aldehydes or ketones with multiple hydroxyl groups coming off the carbon chain.
• The building blocks of all carbohydrates are simple sugars called monosaccharides.
• A monosaccharide can be a polyhydroxy aldehyde (aldose) or a polyhydroxy ketone (ketose).
• The carbohydrates can be structurally represented in any of the three forms:
• Open chain structure.
• Hemi-acetal structure.
• Haworth structure.
• Open chain structure – It is the long straight-chain form of carbohydrates.
• Hemi-acetal structure – Here the 1st carbon of the glucose condenses with the -OH group of the 5th carbon to form a ring structure.
• Haworth structure – It is the presence of the pyranose ring structure
• Some of their major functions include:

• Living organisms use carbohydrates as accessible energy to fuel cellular reactions. They are the most abundant dietary source of
energy (4kcal/gram) for all living beings.
• Carbohydrates along with being the chief energy source, in many animals, are instant sources of energy. Glucose is broken down
by glycolysis/ Kreb’s cycle to yield ATP.
• Serve as energy stores, fuels, and metabolic intermediates. It is stored as glycogen in animals and starch in plants.
• Stored carbohydrates act as an energy source instead of proteins.
• They form structural and protective components, like in the cell wall of plants and microorganisms. Structural elements in the cell
walls of bacteria (peptidoglycan or murein), plants (cellulose) and animals (chitin).
• Carbohydrates are intermediates in the biosynthesis of fats and proteins.
• Carbohydrates aid in the regulation of nerve tissue and is the energy source for the brain.
• Carbohydrates get associated with lipids and proteins to form surface antigens, receptor molecules, vitamins, and antibiotics.
• Formation of the structural framework of RNA and DNA (ribonucleic acid and deoxyribonucleic acid).
• They are linked to many proteins and lipids. Such linked carbohydrates are important in cell-cell communication and in interactions
between cells and other elements in the cellular environment.
• In animals, they are an important constituent of connective tissues.
• Carbohydrates that are rich in fiber content help to prevent constipation.
• Also, they help in the modulation of the immune system.
• HEALTH PROBLEMS
• Excess of sugar leads to nutrient deficiency and tooth decay
• Consuming high amount of sucrose or fructose may cause obesity by supply calories
• Diabetes: after food intake, blood glucose rises and is not regulated because of inadequate insulin. These high
glucose levels are believed to be at least one cause of the serious long-term consequences of untreated
diabetes—kidney failure, cardiovascular disease, blindness, and impaired wound healing
• Hypoglycemia: blood glucose drops dramatically, too much insulin, activity inadequate food intake, illness
• Lactose intolerance: an intolerance to lactose can occur in people who inherit or lose the ability to produce the
enzyme lactase that hydrolyses lactose into its monosaccharide units leads to diarrhea and flatulence
• Galatosemia: failure in converting glucose to galactose
• Glycogen storage disease
• Glucose is the principal fuel for the brain. When the amount of glucose reaching the brain is too low, the
consequences can be dire: lethargy, coma, permanent brain damage, and death
 Physical Properties of Carbohydrates

•Stereoisomerism – Compound shaving the same structural formula but

they differ in spatial configuration. Example: Glucose has two isomers with
respect to the penultimate carbon atom. They are D-glucose and L-glucose.
•Optical Activity – It is the rotation of plane-polarized light forming (+)
glucose and (-) glucose.
•Diastereo isomers – It the configurational changes with regard to C2, C3, or
C4 in glucose. Example: Mannose, galactose.
•Annomerism – It is the spatial configuration with respect to the first carbon
atom in aldoses and second carbon atom in ketoses.
 OPTICAL ACTIVITY
• Optical activity is a characteristic feature of compounds with asymmetric carbon atom.
When a beam of polarized light is passed through a solution of an optical isomer, it will be
rotated either to the right or left.
• The term dextrorotatory (d+) and levorotatory (l−) are used to compounds that respectively
rotate the plane of polarized light to the right or to the left.
• An optical isomer may be designated as D(+), D(−), L(+) and L(−) based on its structural
relation with glyceraldehyde.
• Racemic mixture
• If d− and l-isomers are present in equal concentration, it is known as racemic mixture or dl
mixture. Racemic mixture does not exhibit any optical activity, since the dextro-and
levorotatory activities cancel each other.
• In the medical practice, the term dextrose is used for glucose in solution. This is because of
the dextrorotatory nature of glucose.
• Epimers
• If two monosaccharides differ from each other in their configuration around a single specific carbon
(other than anomeric) atom, they are referred to as epimers to each other.
• For instance, glucose and galactose are epimers with regard to carbon 4 (C4-epimers). That is, they
differ in the arrangement of −OH group at C4. Glucose and mannose are epimers with regard to carbon
2 (C2- epimers).
Classification of carbohydrates
The simple carbohydrates include single sugars (monosaccharides) and polymers,
oligosaccharides, and polysaccharides.
Monosaccharides
•Simplest group of carbohydrates and often called simple sugars since they cannot
be further hydrolyzed.
•Colorless, crystalline solid which are soluble in water and insoluble in a non-polar
solvent.
•These are compound which possesses a free aldehyde or ketone group.
•The general formula is Cn(H2O)nor CnH2nOn.
•They are classified according to the number of carbon atoms they contain and also
on the basis of the functional group present.
•The monosaccharides thus with 3,4,5,6,7… carbons are called trioses, tetroses,
pentoses, hexoses, heptoses, etc., and also as aldoses or ketoses depending upon
whether they contain aldehyde or ketone group.
•Examples: Glucose, Fructose, Erythrulose, Ribulose.
• Monosaccharides are classified in two ways. (a) First of all, based on the number of
carbon atoms present in them and (b) secondly based on the presence of carbonyl
group.
• The naturally occurring monosaccharides contain three to seven carbon atoms per
molecule. Monosaccharides of specific sizes may be indicated by names composed
of a stem denoting the number of carbon atoms and the suffix -ose. For example,
the terms triose, tetrose, pentose, and hexose signify monosaccharides with,
respectively, three, four, five, and six carbon atoms
• Monosaccharides are also classified as aldoses or ketoses. Those
monosaccharides that contain an aldehyde functional group are called
aldoses; those containing a ketone functional group on the second
carbon atom are ketoses.
• Combining these classification systems gives general names that
indicate both the type of carbonyl group and the number of carbon
atoms in a molecule.
• Oligosaccharides

• Oligosaccharides are compound sugars that yield 2 to 10 molecules of the same or different monosaccharides on
hydrolysis.
• The monosaccharide units are joined by glycosidic linkage.
• Based on the number of monosaccharide units, it is further classified as disaccharide, trisaccharide, tetrasaccharide
etc.
• Oligosaccharides yielding 2 molecules of monosaccharides on hydrolysis is known as a disaccharide, and the ones
yielding 3 or 4 monosaccharides are known as trisaccharides and tetrasaccharides respectively and so on.
• The general formula of disaccharides is Cn(H2O)n-1and that of trisaccharides is Cn(H2O)n-2 and so on.
• Examples: Disaccharides include sucrose, lactose, maltose, etc.
• Trisaccharides are Raffinose, Rabinose.
• Among the oligosaccharides, disaccharides
are the most common. As is evident from the
name, a disaccharide consists of two
monosaccharide units (similar or dissimilar –
Homodisaccharides or
• Heterodisaccharides) held together by a
glycosidic bond.

• They are crystalline, water-soluble and

sweet to taste. The disaccharides are of two
types
• 1. Reducing disaccharides with free
aldehyde or keto group e.g. maltose, lactose.
• 2. Nonreducing disaccharides with no free
aldehyde or keto group e.g. sucrose, trehalose.
Disaccharides form when two monosaccharides undergo a dehydration reaction (also
known as a condensation reaction or dehydration synthesis).
During this process, the hydroxyl group of one monosaccharide combines with the
hydrogen of another monosaccharide, releasing a molecule of water and forming a
covalent bond.
A covalent bond formed between a carbohydrate molecule and another molecule (in
this case, between two monosaccharides) is known as a glycosidic bond.
Glycosidic bonds (also called glycosidic linkages) can be of the alpha or the beta
type.
• An alpha bond is formed when the OH
group on the carbon-1 of the first
glucose is below the ring plane, and a
beta bond is formed when the OH group
on the carbon-1 is above the ring plane.
• Maltose
• Maltose is composed of two α-D-glucose units held
together by α (1 → 4) glycosidic bond. The free aldehyde
group present on C1 of second glucose answers the
reducing reactions, besides the osazone formations
(sunflower shaped).
• Maltose can be hydrolysed by dilute acid or the enzyme
maltase to liberate two molecules of α-D-glucose.
• In isomaltose, the glucose units are held together by α (1
→ 6) glycosidic linkage.
• Cellobiose is another disaccharide, identical in structure
with maltose, except that the former has β (1 → 4)
glycosidic linkage. Cellobiose is formed during the
hydrolysis of cellulose.
• Sucrose
• Sucrose (cane sugar) is the sugar of commerce, mostly produced by sugar cane
and sugar beets. Sucrose is made up of α-D-glucose and β-D-fructose.
• The two monosaccharides are held together by a glycosidic bond (α1 → β2),
between C1 of α-glucose and C2 of β-fructose.
• The reducing groups of glucose and fructose are involved in glycosidic bond,
hence sucrose is a nonreducing sugar, and it cannot form osazones.
• Sucrose is an important source of dietary carbohydrate. It is sweeter than most
other common sugars (except fructose) namely glucose, lactose and maltose.
• Sucrose is employed as a sweetening agent in food industry. The intestinal
enzyme—sucrase—hydrolyses sucrose to glucose and fructose which are
absorbed.
• Lactose
• Lactose is more commonly known as milk sugar since it is the
disaccharide found in milk. Lactose is composed of β-D-galactose
and β-D-glucose held together by β (1 → 4) glycosidic bond.
• The anomeric carbon of C1 glucose is free, hence lactose exhibits
reducing properties and forms osazones (powderpuff or hedgehog
shape).
• Lactose of milk is the most important carbohydrate in the nutrition
of young mammals. It is hydrolysed by the intestinal enzyme
lactase to glucose and galactose.
• Lactulose
• Lactulose is a synthetic dissaccharide containing galactose and
fructose. It is neither digested nor absorbed in the intestine.
Lactulose is useful for the treatment of hepatic encephalopathy, a
disorder characterized by elevated plasma ammonium levels
(NH4+). Lactulose converts ammonia (NH3) in the lumen to
ammonium ion. This results in a reduction in the plasma NH3,
since ions are not easily absorbed.
Oligosaccharides as prebiotics
Prebiotics are compounds occur in food that induce the growth or activity of beneficial
microorganisms present in large intestine. It is healthy for host gastrointestinal tract.
Function:
 Increase desirable microbiota in colon.
 Decrease cancer risk.
 Improve glycemic control.
 Increase calcium and minerals absorption.
 Increase folate and vitamin B.
 Reduce caloric value.
 Increase immune response.
 Promote the growth of Lactobacilli and Bifidobacteria
 Lower colon pH
 Discourage growth of clostridia
 Prevent constipation and diarrhea
 Have low glycemic index
 Increase minerals absorption
 Increase digestion of lactose metabolism
 Decrease serum lipid and blood cholesterol
 Decrease blood pressure
Dietary oligosaccharides - These are included in prebiotics.
• Fructo-oligosaccharides (FOS), which are found in many vegetables, are short
chains of fructose molecules.
• Galacto-oligosaccharides (GOS), which also occur naturally, consist of short chains
of galactose molecules. These compounds cannot be digested in the human small
intestine, and instead pass through to the large intestine, where they promote the
growth of Bifidobacteria, which are beneficial to gut health.
• Mannan oligosaccharides (MOS) are widely used in animal feed to improve
gastrointestinal health. They are normally obtained from the yeast cell walls
of Saccharomyces cerevisiae.
POLYSACCHARIDES
• Polysaccharides (or simply glycans) consist of repeat units of
monosaccharides or their derivatives, held together by glycosidic bonds.
They are primarily concerned with two important functions-structural, and
storage of energy.
• Polysaccharides are linear as well as branched polymers. This is in contrast
to structure of proteins and nucleic acids which are only linear polymers. The
occurrence of branches in polysaccharides is due to the fact that glycosidic
linkages can be formed at any one of the hydroxyl groups of a
monosaccharide.
• Polysaccharides are of two types
• 1. Homopolysaccharides on hydrolysis yield only a single type of
monosaccharide. They are named based on the nature of the
monosaccharide. Thus, glucans are polymers of glucose whereas fructosans
are polymers of fructose.
• 2. Heteropolysaccharides on hydrolysis yield a mixture of a few
monosaccharides or their derivatives.
Homopolysaccharides
• Starch
• Starch is the carbohydrate reserve of plants which is the most important dietary source for higher animals,
including man. High content of starch is found in cereals, roots, tubers, vegetables etc.
• Starch is a homopolymer composed of D-glucose units held by α-glycosidic bonds. It is known as glucosan or
glucan.
• Starch consists of two polysaccharide components-water soluble amylose (15–20%) and a water insoluble
amylopectin (80–85%).
• Chemically, amylose is a long unbranched chain with 200–1,000 D-glucose units held by α (1 → 4) glycosidic
linkages. Amylopectin, on the other hand, is a branched chain with α (1 → 6) glycosidic bonds at the branching
points and α (1 → 4) linkages everywhere else.
• Amylopectin molecule containing a few thousand glucose units looks like a branched tree (20–30 glucose
units per branch).
• Starches are hydrolysed by amylase (pancreatic or salivary) to liberate dextrins, and finally maltose and
glucose units. Amylase acts specifically on α (1 → 4) glycosidic bonds.
• Glycogen
• Glycogen is the carbohydrate reserve in animals, hence often referred to as animal
starch. It is present in high concentration in liver, followed by muscle, brain etc. Stored in
liver(7% of wet weight) and skeletal muscle. Glycogenin is a primer protein present in
innermost core of glycogen.
• The structure of glycogen is similar to that of amylopectin with more number of branches.
Glucose is the repeating unit in glycogen joined together by α (1 → 4) glycosidic bonds,
and α (1 → 6) glycosidic bonds at branching points. More branched than amylopectin.
DIFFERENCE BETWEEN STARCH AND GLYCOGEN
Starch Glycogen
Plants Animals

Stored in tubers,grains, Stored in liver and muscle cells

legumes.

Less branched More branched

Glycogenin absent Glycogenin present

Molecular weight of 10 – 1000 1000-5000 kdal

kdal

Blue and violet complexes Red violet complex with

with iodine iodine
• Cellulose
• Cellulose occurs exclusively in plants and it is the most abundant organic
substance in plant kingdom. It is a predominant constituent of plant cell wall.
• Cellulose is totally absent in animal body. Cellulose is composed of β-D-
glucose units linked by β (1 → 4) glycosidic bonds . Cellulose cannot be
digested by mammals— including man— due to lack of the enzyme that
cleaves β-glycosidic bonds (α amylase breaks α bonds only).
• Certain ruminants and herbivorous animals contain microorganisms in the
gut which produce enzymes that can cleave β-glycosidic bonds. Hydrolysis of
cellulose yields a disaccharide cellobiose, followed by β-D-glucose.
• Cellulose, though not digested, has great importance in human nutrition. It is
a major constituent of fiber, the non- digestable carbohydrate. The functions
of dietary fiber include decreasing the absorption of glucose and cholesterol
from the intestine, besides increasing the bulk of feces.
• Dextrins
• Dextrins are the breakdown products of starch by the enzyme amylase or dilute acids. Starch is
sequentially hydrolyzed through different dextrins and, finally, to maltose and glucose. The
various intermediates (identified by iodine coloration) are soluble starch (blue), amylodextrin
(violet), erythrodextrin (red) and achrodextrin (no color).
• Dextrans
• Dextrans are polymers of glucose, produced by microorganisms. They are used as plasma volume
expanders in transfusion, and chromatography (e.g. gel filtration).
• Inulin
• Inulin is a polymer of fructose i.e., fructosan. It occurs in dahlia bulbs, garlic, onion etc. It is a low
molecular weight (around 5,000) polysaccharide easily soluble in water. Inulin is not utilized by
the body. It is used for assessing kidney function through measurement of glomerular filtration
rate (GFR).
• Chitin
• Chitin is composed of N-acetyl D-glucosamine units held
together by β (1 → 4) glycosidic bonds. It is a structural
polysaccharide found in the exoskeleton of some
invertebrates e.g. insects, crustaceans. Also in fungi.
Heteropolysaccharides
• Mucopolysaccharides
• Mucopolysaccharides are heteroglycans made up of repeating units of sugar
derivatives, namely amino sugars and uronic acids. These are more commonly
known as glycosaminoglycans (GAG).
• Acetylated amino groups, besides sulfate and carboxyl groups are generally present
in GAG structure. The presence of sulfate and carboxyl groups contributes to acidity
of the molecules, making them acid mucopolysaccharides.
• The important mucopolysaccharides include hyaluronic acid, chondroitin 4- sulfate,
heparin, dermatan sulfate and keratan sulfate
• Hyaluronic acid
• Hyaluronic acid is an important GAG found in the ground substance of synovial fluid
of joints and vitreous humor of eyes. It is also present as a ground substance in
connective tissues, and forms a gel around the ovum. Hyaluronic acid serves as a
lubricant and shock absorbant in joints.
• Hyaluronidase is an enzyme that breaks (β 1 → 4 linkages) hyaluronic acid and other
GAG. This enzyme is present in high concentration in testes, seminal fluid.
• Hyaluronidase of semen is assigned an important role in fertilization as this enzyme
clears the gel (hyaluronic acid) around the ovum allowing a better penetration of
sperm into the ovum. Hyaluronidase of bacteria helps their invasion into the animal
tissues.
• Chondroitin sulfates
• Chondroitin 4-sulfate (Greek : chondros- cartilage) is a major constituent of various mammalian tissues
(bone, cartilage, tendons, heart, valves, skin, cornea etc.). Structurally, it is comparable with hyaluronic acid.
Chondroitin 4-sulfate consists of repeating disaccharide units composed of D-glucuronic acid and N=acetyl
D-galactosamine 4-sulfate
• Heparin
• Heparin is an anticoagulant (prevents blood clotting) that occurs in blood, lung, liver, kidney, spleen etc.
Heparin helps in the release of the enzyme lipoprotein lipase which helps in clearing the turbidity of lipemic
plasma.
• Heparin is composed of alternating units of N- sulfo- D-glucosamine 6-sulfate and glucuronate 2-sulfate
• Dermatan sulfate
• Mostly found in skin, dermatan sulfate is structurally related to chondroitin 4- sulfate. The only difference is
that there is an inversion in the configuration around C5 of D-glucuronic acid to form L-iduronic acid