Biological oxidation.

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Caloric Value of Food

A Calorie (kcal) is the amount of energy needed to raise the
temperature of 1 kilogram of water by 1 degree Celsius.
the energy accumulated in food substances (proteins, fat, and carbohydrates); the energy value of
foodstuffs, expressed in calories (cal) or kilocalories (kcal).
The caloric value is determined by the presence of unoxidized atoms of carbon and hydrogen. A
molecule of fat contains more unoxidized atoms of carbon and hydrogen than a carbohydrate
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molecule or a molecule of protein. One g of fat yields 9.3 kcal (1 kcal = 4.1868 × 10 joules); 1 g of
carbohydrate, 4.1 kcal; and 1 g of protein, 4.1 kcal.

Oxidation of foodstuff: Macro food molecule is breakdown into smaller

units to yield energy which is need for cellular work.
cells require a constant supply of energy to generate and maintain the biological
order that keeps them alive. This energy is derived from the chemical bond
energy in food molecules.

Food Molecules Are Broken Down in Three Stages to Produce ATP

The breakdown will takes place in 3 steps:

Stage 1 in the enzymatic breakdown of food molecules is therefore digestion,

which occurs either in our intestine outside cells, or in a
specialized organellewithin cells, the lysosome.
In either case, the large polymeric molecules in food are broken down during
digestion into their monomer subunits—proteins into amino acids,
polysaccharides into sugars, and fats into fatty acids andglycerol—through the
action of enzymes.
After digestion, the small organic molecules derived from food enter the cytosol
of the cell, where their gradual oxidation begins.
stage 2 a chain of reactions calledglycolysis converts
each molecule ofglucose into two smaller molecules of pyruvate. Sugars other
than glucose are similarly converted to pyruvate after their conversion to one of
the sugarintermediates in this glycolytic path
g pyruvate formation, two types ofactivated carrier molecules are produced—ATP
and NADH. The pyruvate then passes from the cytosol into mitochondria.
There, each pyruvate molecule is converted into CO2 plus a two-
carbon acetyl group—which becomes attached to coenzyme A(CoA),
forming acetyl CoA.

Stage 3 of the oxidative breakdown of food molecules takes place entirely in

mitochondria.
The acetyl group in acetyl CoA is linked to coenzyme A through a high-
energy linkage,
After its transfer to the four-carbonmolecule oxaloacetate, the acetyl group
enters a series of reactions called the citricacid cycle.
the acetyl group is oxidized to CO2 in these reactions, and large amounts of
the electron carrierNADH are generated.
NADH are passed along an electron-transport chain within the
mitochondrial inner membrane, where the energy released by their transfer is
used to drive a process that produces ATP and consumes molecular oxygen (O2).

Cellular metabolism
All of the chemical reactions that take place inside of a cell are collectively
called the cell’smetabolism.
It may be Catabolism and Anabolism
Catabolism: Catabolism Breaking down of large complex molecules.
E.g. Respiration –Glucose + Oxygen – carbon dioxide + water
E.g. Hydrolysis –Starch – Maltose – GlucoseDNA – Mononucleotides

 Reactions are usually EXERGONIC (give off energy).

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Anabolism: Anabolism Synthesis of large complex molecules from small molecules.
E.g. Protein synthesis –Amino Acids – ProteinsE.g. Polymerisation –Mononucleotides – DNA.

 Reactions are usually ENDERGONIC (take in energy).

ATP: Adenosine tri phosphate composed of base adenine,ribose auger and

3molecule of phosphate.
It is called universal energy currency , because energy is usually stored in molecules
of ATP. Whenever something needs energy within the body usually ATP supplies it with
energy by removing one of its phosphate groups leaving it as ADP.

ATP hydrolysis
ATP hydrolysis is the catabolic reaction process by which chemical energy that
has been stored in the high-energy phosphoanhydride bonds in adenosine
triphosphate (ATP) is released by splitting these bonds.
The product is adenosine diphosphate(ADP) and an inorganic phosphate,
orthophosphate (Pi). ADP can be further hydrolyzed to give energy, adenosine
monophosphate (AMP), and another orthophosphate (Pi).
ATP+H2O -> ADP + Pi
Hydrolysis of the phosphate groups in ATP is especially exergonic, because the
resulting orthophosphate group is greatly stabilized by multiple resonance
structures, making the products (ADP and Pi) much lower in energy than the
reactant (ATP).
Hydrolysis of the terminal phosphoanhydridic bond is a highly exergonic process.
The amount of released energy depends on the conditions in a particular cell.
Specifically, the energy released is dependent on concentrations of ATP, ADP and
Pi. As the concentrations of these molecules deviate from values at equilibrium,
the value of Gibbs free energy change (ΔG) will be increasingly different. In
standard conditions ( ATP, ADP and Pi concentrations are equal to 1M, water
concentration is equal to 55M) the value of ΔG is between -28 to -34 kJ/mol.[3][4]
The range of the ΔG value exists because this reaction is dependent on the
concentration of Mg2+ cations, which stabilize the ATP molecule.

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 Glycolysis
Glycolysis – Glucose Catabolic Pathway:
Glycolysis is divided into two phases

1. Preparative phase (Step 1 to 5)

2. Pay off Phase (Step 6 to 10)
Preparative Phase:
This is the first phase of Glycolysis. In this Glucose is converted into Glyceraldehyde-3-
Phosphate and DHAP (Dihydroxy Acetone Phosphate). This phase contains 5 Steps.

Step 1: Phosphorylation :
Glucose (C6H12O6) + hexokinase + ATP → ADP + Glucose 6-phosphate (C6H11O6P1)
Step 2: Isomerization :
Glucose 6-phosphate (C6H11O6P1) + Phosphoglucoisomerase
→ Fructose 6-phosphate (C6H11O6P1)
Step 3: Phosphorylation:
Fructose 6-phosphate (C6H11O6P1) + Phosphofructokinase + ATP
→ ADP + Fructose 1, 6-bisphosphate (C6H10O6P2)
Step 4: Condensation:

Fructose 1, 6-bisphosphate) + aldolase →

Dihydroxyacetone phosphate (C3H5O3P1) + Glyceraldehyde phosphate (C3H5O3P1)
Step5:Isomerization:

Dihydroxyacetone phosphate (C3H5O3P1)-> Glyceraldehyde phosphate (C3H5O3P1)

Pay-off Phase:
This is the second phase of Glycolysis. In this phase Glyceraldehyde-3-Phosphate is
converted into Pyruvate molecules. This phase have 5 steps.

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Step 6: Dehydrogenation:
hydrogenase + 2 H– + 2 NAD+ → 2 NADH + 2 H+
B. Triose phosphate dehydrogenase + 2 P + 2 glyceraldehyde phosphate (C3H5O3P1)
→ 2 molecules of 1,3-bisphosphoglycerate (C3H4O4P2)
Step 7: Substrate level Phosphorylation:
2 molecules of 1,3-bisphoshoglycerate (C3H4O4P2) + phosphoglycerokinase + 2 ADP
→ 2 molecules of 3-phosphoglycerate (C3H5O4P1) + 2 ATP
Step 8: Dehydration (Intramolecular rearrangement):
2 molecules of 3-Phosphoglycerate (C3H5O4P1) + phosphoglyceromutase
→ 2 molecules of 2-Phosphoglycerate (C3H5O4P1)
Step 9 : Enolyzation :
2 molecules of 2-Phosphoglycerate (C3H5O4P1) + enolase
→ 2 molecules of phosphoenolpyruvic acid (PEP) (C3H3O3P1)
Step 10: Substrate level Phosphorylation:
2 molecules of PEP (C3H3O3P1) + pyruvate kinase + 2 ADP
→ 2 molecules of pyruvic acid (C3H4O3) + 2 ATP

Stochiometric Equation:
Glucose + 2ATP +4ADP+ 2 NAD++ H3PO4 –> 2 Pyruvate + 2 ADP + 4 ATP + 2 NADH +
H+ + H2O

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Kreb's cycle

The citric acid cycle, also known as the Krebs cycle or tricarboxylic acid (TCA)
cycle, is the second stage of cellular respiration. This cycle is catalyzed by several
enzymes and is named in honor of the British scientist Hans Krebs who identified
the series of steps involved in the citric acid cycle.

The first phase of cellular respiration, called glycolysis, takes place in the cytosol
of the cell's cytoplasm. The citric acid cycle, however, occurs in the matrix of
cell mitochondria.

In eukaryotic cells, the citric acid cycle uses one molecule of acetyl CoA to
generate 1 ATP, 3 NADH, 1 FADH2, 2 CO2, and 3 H+.

Since two acetyl CoA molecules are generated from the two pyruvic acid
molecules produced in glycolysis, the total number of these molecules yielded in
the citric acid cycle is doubled to 2 ATP, 6 NADH, 2 FADH2, 4 CO2, and 6 H+.

The NADH and FADH2 molecules produced in the citric acid cycle are passed
along to the final phase of cellular respiration called the electron transport chain.
Here NADH and FADH2 undergo oxidative phosphorylation to generate more
ATP.

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Fermentation
There are two main fermentation pathways: lactic acid fermentation and alcoholic fermentation.
Both of these pathways begin with pyruvate, the end product of glycolosis, are anaerobic (require no
oxygen), and allow glycolysis to proceed aerobically. A relatively small amount of ATP is generated in
the pathway, but that’s about the best that can be accomplished in the absence of O2 and
mitochondrial respiratory chain reactions.

 Lactic acid fermentation (cheese- and yogurt-making; anaerobic muscle activity)

CH3COCO2H + NADH→ CH3CH(OH)CO2H + NAD+
pyruvic acid → lactic acid with regeneration of 1 mole of NAD+ per pyruvate, or two moles
of NAD+ per mole of glucose
Catalyzed by lactic acid dehydrogenase (operating in the reverse of the normal direction).
 Alcoholic fermentation (beer- and wine-making)
CH3COCO2H + NADH → CO2 + CH3CH2OH + NAD+
pyruvic acid → carbon dioxide + ethanol with regeneration of 1 mole of NAD+ per
pyruvate or two moles of NAD+ per mole of glucose
This is a two-step process, catalyzed by pyruvate decarboxylase (forming acetaldehyde +
CO2) and alcohol dehydrogenase (forming ethanol).

The Catabolism of Fats

Fatty acid oxidation is initiated on the outer mitochondrial membrane. There the fatty acids, which
like carbohydrates are relatively inert, must first be activated by conversion to an energy-rich fatty
acid derivative of coenzyme A called fatty acyl-coenzyme A(CoA). The activation is catalyzed
by acyl-CoA synthetase. For each molecule of fatty acid activated, one molecule of coenzyme

A and one molecule of adenosine triphosphate (ATP) are used,

The fatty acyl-CoA diffuses to the inner mitochondrial membrane, where it combines with a carrier
molecule known as carnitine in a reaction catalyzed by carnitine acyltransferase. The acyl-
carnitine derivative is transported into the mitochondrial matrix and converted back to the fatty
acyl-CoA.

Steps in the β-Oxidation of Fatty Acids

Further oxidation of the fatty acyl-CoA occurs in the mitochondrial matrix via a sequence of four
reactions known collectively as β-oxidation because the β-carbon undergoes successive
oxidations in the progressive removal of two carbon atoms from the carboxyl end of the fatty acyl-
CoA

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The first step in the catabolism of fatty acids is the formation of an alkene in an oxidation reaction
catalyzed by acyl-CoA dehydrogenase. In this reaction, the coenzyme FAD accepts two
hydrogen atoms from the acyl-CoA, one from the α-carbon and one from the β-carbon, forming
reduced flavin adenine dinucleotide (FADH2).

The FADH2 is reoxidized back to FAD via theelectron transport chain that supplies energy to form
1.5–2 molecules of ATP.

Next, the trans-alkene is hydrated to form a secondary alcohol in a reaction catalyzed by enoyl-
CoA hydratase. The enzyme forms only the L-isomer.

The secondary alcohol is then oxidized to a ketone byβ-hydroxyacyl-CoA dehydrogenase, with

NAD+ acting as the oxidizing agent. The reoxidation of each molecule of NADH to NAD+ by the
electron transport chain furnishes 2.5–3 molecules of ATP.

The final reaction is cleavage of the β-ketoacyl-CoA by a molecule of coenzyme A. The products
are acetyl-CoA and a fatty acyl-CoA that has been shortened by two carbon atoms. The reaction
is catalyzed bythiolase.

The shortened fatty acyl-CoA is then degraded by repetitions of these four steps, each time
releasing a molecule of acetyl-CoA. The overall equation for the β-oxidation of palmitoyl-CoA (16
carbon atoms) is as follows:

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The fate of the acetyl-CoA obtained from fatty acid oxidation depends on the needs of an
organism. It may enter the citric acid cycle and be oxidized to produce energy, it may be used for
the formation of water-soluble derivatives known as ketone bodies, or it may serve as the starting
material for the synthesis of fatty acids. .

In the liver, most of the acetyl-CoA obtained from fatty acid oxidation is oxidized by the citric acid
cycle. However, some of the acetyl-CoA is used to synthesize a group of compounds known
asketone bodies: acetoacetate, β-hydroxybutyrate, and acetone. Two acetyl-CoA molecules
combine, in a reversal of the final step of β-oxidation, to produce acetoacetyl-CoA. The
acetoacetyl-CoA reacts with another molecule of acetyl-CoA and water to form β-hydroxy-β-
methylglutaryl-CoA, which is then cleaved to acetoacetate and acetyl-CoA. Most of the
acetoacetate is reduced to β-hydroxybutyrate, while a small amount is decarboxylated to carbon
dioxide and acetone.

Key Takeaways
 Fatty acids, obtained from the breakdown of triglycerides and other lipids, are oxidized
through a series of reactions known as β-oxidation.
 In each round of β-oxidation, 1 molecule of acetyl-CoA, 1 molecule of NADH, and 1
molecule of FADH2 are produced.
 The acetyl-CoA, NADH, and FADH2 are used in the citric acid cycle, the electron transport
chain, and oxidative phosphorylation to produce ATP.

Catabolism of proteins
Protein catabolism is the breakdown of proteins intoamino acids in order to produce ATP.
This first step to protein catabolism is breaking the protein down into amino acids by cleaving their
peptide bonds, also known asproteolysis. The peptide bonds are broken up by theproteasome,
which is able to hydrolyze the peptide bonds by using ATP energy, with utilization of protease
enzyme.
Oxidative deamination is the first step to breaking down the amino acids so that they can be
converted to sugars. The process begins by removing the amino group of the amino
acids(deamination by deaminase enzyme).
The amino group becomes ammonium as it is lost and later undergoes the urea cycle to become
urea, in the liver. It is then released into the blood stream, where it is transferred to the kidneys,
which will secrete the urea as urine.
The remaining portion of the amino acid becomes oxidized, resulting in an alpha-keto acid. The
alpha-keto acid will then proceed into the TCA cycle, in order to produce energy. The acid can also
enterglycolysis, where it will be eventually converted intopyruvate.

Protease. Deamination

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Protein -------------amino acid -----------keto acid .
Transamination leads to the same end result as deamination: the remaining acid will undergo either
glycolysis or the TCA cycle to produce energy that the organism's body will use for various
purposes. This process transfers the amino group instead of losing the amino group to be converted
into ammonium. The amino group is transferred to alpha-ketoglutarate, so that it can be converted
toglutamate. Then glutamate transfers the amino group to oxaloacetate. This transfer is so that the
oxaloacetate can be converted to aspartate or other amino acids. Eventually, this product will also
proceed into oxidative deamination to once again produce alpha-ketoglutarate, an alpha-keto acid
that will undergo the TCA cycle, and ammonium, which will eventually undergo the urea cycle.[3]

Transaminases are enzymes that help catalyze the reactions

Interrelationship b/w catabolic pathways:

All organisms utilise the three major foodstuffs to form acetyl CoA or the metabolites of
the Krebs cycle. These, in turn, supply energy upon subsequent oxidation by the cycle. A
brief summary of the interrelationships of the metabolic pathways is given in Fig. 8.91.

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