CONTENTS

CARBOHYDRATE
 INTRODUCTION
 CLASSIFICATION OF CARBOHYDRATE
 METABOLISM AND REGULATION OF CARBOHYDRATE
CARBOHYDRATE

Carbohydrates are widely distributed in animal and plant, have important structure and metabolic role. In plant
glucose is synthesized by co2 and water by photosynthesis and store in the form of starch. Animal can synthe-
size carbohydrate from amino acid. Glucose is the most important carbohydrate and the major metabolic fuel of
mammal and natural fuel of fetus. Synthesis of all carbohydrate in the body like, glycogen for storage, ribose
and deoxyribose in nucleic acid, galactose for synthesis of lactose milk etc. Disease associated with carbohy-
drate metabolism includes diabetes mellitus, galactosemia, and glycogen storage disease. 5% of the weight of
cell membrane is the carbohydrate part of glycoprotein and glycolipids. Glucose is most important carbohydrate
in mammal because all carbohydrate in food is converted to glucose for metabolism. Sugars have large no. of
stereoisomer because they contain several symmetric carbon atoms. Carbohydrate is precursors for many organ-
ic compounds (fat, amino acids). They are most abundant dietary source of energy for all organisms. Carbohy-
drates participate in the structure of cell membrane and cellular functions such as cell growth, adhesion and fer-
tilization.

CARBOHYDRATES ARE POLYHYDROXYLATED DERIVATIVE OF ALDEHYD OR KETONE.

Carbohydrate is often referred to as saccharides. Carbohydrates are the key component of cell and form the
backbone of nucleic acid. They are simply called as SUGERS. THE BASIC FRAMEWORH HAS CARBON,
HYDROGEN, AND OXYGEN. The simplest carbohydrate is monosaccharide. Sugar with ketone group is
‘KETOSE’. Sugar with aldehyde group is ‘ALDOSE’.

CLASSIFICATION OF CARBOHYDRATE-

1. Monosaccharide
2. Disaccharide
3. Oligosaccharide
4. Polysaccharide

MONOSECCHARIDE:-
FORMULA = (CH2O) n
Where n are 3 or more
Monosaccharide basic unit of carbohydrate and cannot be further hydrolyzed into smaller carbohydrate. They
can be triose (c3), tetrode (c4), pentose (c5), hexose (c6). They consist of carbon chain of 3carbon atom contain-
ing hydroxyl group attached to every carbon except one (carbonyl group). The simplest carbohydrate compris-
ing of basic glucose unit is glyceraldehyde’s with one stereo genic center (any atom for which exchanging two
group creates a different stereoisomer. for example = Carbone 3 is a stereo genic center, because the two at-

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tached carbon chains are mirror image of each other and hence not identical.) based on the relative position of
the –OH group on the farthest stereo genic center, carbohydrates classified as D/L form.

Optical isomerism of monosaccharide:-

Many sugars can tend to plane of polarized light such sugars are called as optical isomerism sugar and it has
Asymmetrical carbons atoms. A carbon said to be asymmetrical in a compound when it has four different atoms
or groups attached to it. When a beam of polarized light is passed through optically active solution it may be
rotated either to the right or to the left.

Two sugars with same chemical formula and molecular weight but having different astrochemical arrangement
of atoms are known as Diastereoisomers.

The diastereoisomers that differ in configuration only around one chiral center are called as Epimers.

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Pair of stereoisomers that are mirror image of each other and are non- superimposable called enantiomers.
The configuration of all groups in one sugar should be opposite to that of other.

Cyclic structure of monosaccharide:-

In aqueous solution all monosaccharides with five or more carbon atom in the backbone occur predominantly as
cyclic structure. Ring form- A sugar with a six membrane ring known as pyranose and five membrane rings is
known as a furanose in analogy with pyran and furan, respectively.

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Disaccharide - disaccharide are the condensation product of 2 monosaccharide units ex= lactose, maltose, su-
crose, trehalose.

Polysaccharide: - consist of more than 10 monosaccharide units ex- starch, dextrin held together by glycosidic
bond. Polysaccharide linear as well as branched polymer. Occurrence of branches in polysaccharide is due to
the fact that glycoside linkages can be formed at one of the 2 hydroxyl group of monosaccharide. Animal access
glucose is stored as a large branched polysaccharide called glycogen where in most plants the storage form of
glucose is starch. Bacterial and yeast store glucose another form called dextran.

Type of polysaccharide:-

Homopolysaccharide :- which hydrolysis yield only a single type of monosaccharide . Their name based on
the nature of monosaccharide unit. Ex= starch, dextrin, inulin, glycogen.
Heteropolysaccharide:- also known as heteroglucans contain two or more different monosaccharide units. The
major heteroglycons include the connective tissue polysaccharide the blood group substances, glycoproteins
such as gamma globulin and glycolipids particularly found in the central nervous system of animals.
Ex= cellulose

Polysaccharide serve storage and structure function

Starch is a homopolymer of glucose forming α- glucosidic chain called glucon. Starch is the reserves of plants
starch are hydrolyzed by amylase to liberate dextrin and finally maltose and glucose units.

Glycogen is the storage form of animals and sometime called animal starch. It is more highly branched struc-
ture then amylopectin, with chain of 12 to 15 α-D glucopyranose residues (in α1 -4 glycosidic linkages) with
branching by means of α 1-6 glucosidic bond.
Inulin is a polysaccharide of fructose found in tubers and roots of dahlias, articholes, and dandelions. Used to
determine the glomular filtration rate but not hydrolyzed by intestinal enzymes is has no nutritional value.
Dextrins it is the breakdown product of starch by the enzyme amylases or dilute acids starch is sequentially hy-
drolyzed through different dextrin and finally to maltose and glucose.
Cellulose occurs in plants and it is the most abundant organic substance of plant. Cellulose is composed of β-d
glucose units linked by β (1-4) glycosidic bonds. Cellulose cannot be digest by the mammal due to the lack of

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enzyme that cleaves β-glycosidic bond. Certain ruminants and herbivorous animals contain microorganism in
the gut which produce enzymes that cleaved β-glycosidic bonds.
Chitin it is a complex resistant nitrogenous polymer. It is the most abundant bimolecular in biosphere after cel-
lulose. It is found in exoskeleton of arthropods (insects, crustaceans) and other invertebrates. Also found in fun-
gal cell wall and bacterial cell wall.

OLIGOSACCHARISES: - oligosaccharide is short chain of monosaccharide linked by glycosidic bond. In

case of oligosaccharide linked to proteins (glycoprotein) and lipid (glycolipids) the oligosaccharide. The most
important oligosaccharides found in appropriate quantities are sucrose, lactose, maltose and few others are-
cellobiose, treholose.

Oligosaccharides are two types:-

O-linked oligosaccharide: - attached protein via o-glycosides’ bonds to the group of serine or threcenine side
chain.

N-linked oligosaccharide: - attached protein via N-glycosidic bonds to the NH2 group of asparagines side
chain.

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 METABOLISM OF CARBOHYDRATE

Major pathway of carbohydrate metabolism

1) GLYCOLYSIS
Glycolysis is the major pathway of glucose metabolism; occur in the cytosol of all cells. Deoendind on the pres-
ence of oxygen it can function either aerobically or anaerobically. Lactate is the end product under the anaero-
bic condition. In the aerobic condition pyruvate is the end product. glycolysis is the major pathway for ATP
SYNTHESIS in tissue lacking mitochondria- ex- erythrocytes, lens etc. glycolysis is very essential for brain
which is depend upon glucose for energy. Intermediates of glycolysis are useful for the synthesis of amino acid
and fat. Glycolysis is regulated by three enzymes catalyzing no equilibrium reactions: HEXPKINASE,
PHOSPHOFRUKTOKINASE, and PYRUVATE KINASE.

Pathway of glycolysis

Regulation of glycolysis-
The three enzymes hexokinase, phosphofructokinase, pyruvate kinase, catalyzing the irreversible reaction
regulate glycolysis. HEXOKINASE – is inhibited by glucose 6- phosphate. These enzymes prevent the accu-
mulation of glucose 6- phosphate due to product inhibition.
Glucokinase, which specially phosphorylates glucose, is an inducible enzyme. The substrate glucose, probably
through the involvement of insulin induces glucokinase. PHOSPHOFRUCTOKINASE (PFK) - is the most
important regulatory enzyme in glycolysis. This enzyme catalysis the rate limiting committed step. PFK is an
allosteric enzyme regulated by allosteric effectors. ATP, citrate and H+ ions (low PH) are the most important
allosteric inhibitors where, fructose 2-6 bisphosphate, ADP, AMP, and Pi are the allosteric activators.

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PYRUVATE KINASE- also regulates glycolysis. This enzyme is inhibited by ATP and activated by F1, 6- BP.
Pyruvate kinase is active (a) in dephosphorylated state and inactive (b) in phosphorylated state. Inactivation of
pyruvate kinase by phosphorylation is brought about by cAMP- dependent protein kinase. The hormone gluca-
gon inhibits hepatic glycolysis by this mechanism.

REGULATION OF GLYCOLYTIC PATHWAY

2. CITRIC ACID CYCLE

The citric acid cycle is proposed by Hans Adolf Krebs in 1937, based on the studies of oxygen consumption in
pigeon breast muscle. The citric acid cycle is common pathway for the oxidation of carbohydrate, lipid, and

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protein because lipid, fatty acid and most amino acid are metabolized to actyle CoA. Abouth 65-70% of the
ATP is synthesized in krebs cycle. The enzyme of TCA are located in mitochondria matrix, in close proximity
to the electron transport chain. Cycle starts reaction between the acetyl moiety of acetyl-CoA and the four-
carbon dicarboxylic acid oxaloacetate, forming a six-carbon tricarboxylic acid, citrate. This is aerobic process.

Krebs cycle

Regulation of citric acid cycle:-

The cellular demands of ATP are crucial in controlling the rate of citric acid cycle. The regulation is brought
about either by enzymes namely citrate synthase, isocitrate dehyhroginase and α-ketoglutarate dehydro-
genase regulate citric acid cycle. Citrate synthase is inhibited by ATP, NADH, acetyl coA and succinl
coA. Isocitrate dehydrogenase is activated by ADP and inhibited by ATP and NADH. α-ketoglutarate de-
hydrogenase is inhibited by succinyl coA and NADH. Availability of ADP is very important for the citric ac-
id cycle to proceed. This is due to the fact that unless sufficient levels of ADP are available oxidation (coupled
with phosphorylation of ADP to ATP) of NADH and FADH2 will lead to inhibition of the enzymes and also
limits the supply of NAD+ and FAD which are essential for TCA cycle to proceed.

3. GLUCONEOGENESIS

Gluconeogenesis is the process of synthesizing glucose from no carbohydrate compound. The major substrate is

the lactate, pyruvate, glucogenic amino acids, glycerol. Gluconeogenesis mainly occurs in cytosol. Liver and

kidney are the major gluconeogenesis tissue. glucose supply is necessary especially for the nervous system and

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erythrocytes. Hypoglycemia causes brain dysfunction, which lead coma and death. Propionate is a product of

rumen metabolism of carbohydrates, and it is a major substrate for gluconeogenesis. Glu-

cagon and epinephrine, hormones that are responsive to decrease in blood glucose, inhibit glycolysis and

stimulate gluconeogenesis in the liver by increasing the concentration of cAMP. Glucose, galactose and fructose

that are transported to the liver via hepatic portal vein. Galactose and fructose are converted to glucose in the

liver. Gluconeogenesis closely resembles the reversed pathway of glycolysis; the seven reactions are common

for both glycolysis and gluconeogenesis. The formation of glucose via gluconeogenesis particularly uses amino

acids from protein breakdown and glycerol from fat breakdown. The first enzyme of gluconeogenesis is py-

ruvate carboxylase, and the last enzyme is glucose 6- phosphatase.

The pathway of gluconeogenesis

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Regulation of gluconeogenesis:-

The hormone glucagon and the availability of substrates mainly regulate gluconeogenesis is a hormone secret-
ed by α-cells. Stimulates gluconeogenesis by two mechanisms. Active form pyruvate kinase is converted to in-
active form through the medication of cyclic AMP, brought about by glucagon. Decreased pyruvate kinase
results in the reduced conversion of phosphoenol pyruvate to pyruvate and the former is diverted for the synthe-
sis of glucose. Glucagon reduces the concentration of fructose 2-6 bisphosphate. This compound allosterically
inhibits phosphofructokinase, both favor increased gluconeogenesis. Availability of substrates:- among the
various substrates, glucogenic amino acids have stimulating influence on gluconeogenesis. This is particularly
important in a condition like diabetes mellitus (decreased insulin level) where amino acids are mobilized from
muscle protein for the purpose of gluconeogenesis. Acetyl cOA promotes gluconeogenesis:- during starvation
due to excessive lipolysis in adipose tissue acetyl cOA accumulates pyruvate carboxylase resulting in enhanced
glucose production.

4. PENTOSE PHOSPHATE PATHWAY

PPP is also called Hexose monophosphate pathway or HMP shunt or Phosphogulconate pathway.

Alternative pathway of glycolysis and TCA cycle for oxidation of glucose. It does not lead the formation of
ATP but has a major function- the formation of NADPH for the synthesis of fatty acid and steroid and the for-
mation of ribose for the synthesis of nucleotide and nucleic acid.

PPP pathway is active in liver, adipose tissue, adrenal cortex, mammary gland. PPP occur in the cytosol . PPP is
more complex pathway than glycolysis. Three molecule of glucose 6- phosphate give rise to 3 molecule of co2
and 3, 5 c2 sugars. Glucose 6- phosphate dehydrogenase is the first enzyme of PPP. Genetic deficiency of
(G6PD) is a major cause of hemolysis of red blood cells, resulting in hemolytic anemia.

Reaction on HMP shunt devided into 2 phases-

Oxidative phase – glucose 6-phosphate dehydrogenase is an NADP dependent enzyme that convert glucose 6-
phosphate to 6- phosphogluconolactone. 6- phosphogluconolactone is hydrolysis by the enzyme gluconolac-
tone hydrolase in to 6- phosphogluconate. The next reaction involving the synthesis of NADPH is catalysed by
6-phosphogluconate dehydrogenase to produce 3- keto 6- phosphogluconate which then undergoes decarboxy-
lation to give ribulose 5- phosphate.
Non-oxidative phase – the non-oxidative reaction are conserned with the interconversio of three, four, five and
seven carbon monosaccharides. Ribulose 5- phosphate is acted upon by an epimerase to produce xylulose 5-
phosphate whilw ribose 5- phosphate ketoisomerase convertes ribulose5- pjosphate to ribuose 5-phosphate.

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Hexose mono phosphate shunt (Pentose phosphate pathway) Significance-

 Alternative route for metabolism of glucose.

 Major function generates NADPH and ribose 5- phosphate.
 No ATP generation.
 Pentose/derivative are useful for synthesis of nuclic acid.
 NADPH is required for the reductive biosynthesis of fatty acid and steroids.
 PPP generate NADPH one of the product.

5. GLYCOGENOLYSIS
This process provides immediate energy and maintains blood glucose level during fasting condition. Duration
of storage glycogen in liver and muscle. Enzyme present in the cytosol carry out glycogenosis glycogen is de-
graded by breaking α-1-4 and α 1-6 glycosidic bonds.

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Glycogen storage disease:-

6. CORI CYCLE
Under the limiting oxygen conditions during vigorous exercise, the formation of NADH by glycolysis exceed
the ability of the respiratory chain to oxidize it back to NAD+ . The pyruvate produce by glycolysis in muscle is
then converted to lactate by lactate dehydrogenase reaction degradation NAD+ and aloe glycolysis to continue
to produce ATP. Lactate is a metabolic dead end in that it cannot be metabolized further until it is converted
back to pyruvate. Lactate diffuse out of the muscle and it carry in the blood stream to the liver. It is diffuse into
liver cell and it is converted back to pyruvate by lactate dehydrogenase.
Pyruvate is then converted to glucose by gluconeogenesis and the glucose is released back into the blood stream
ready to taken up by muscle. This cycle is called Cori cycle.

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Significance of cori cycle –

The cycle’s importance is based on the prevention of lactic acidosin in the muscle under anaerobic conditions.
The cycle is also importance in producing ATP, an energy source, during muscle activity. The cori cycle is a
much more important source of substrate for gluconeogenesis than food. The excess lactate would be cleared
by the kidneys, but in patients with kidney failure, the kidneys cannot handle the excess lactic acid.

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