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Biological Oxidation

For first year mbbs

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28 views

Biological Oxidation

For first year mbbs

Uploaded by

airmacbook38
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Biological Oxidation

Terminologies
Oxidation-loss of electrons

Reduction-gain of electrons

Redox potential-electron transfer potential, E 0

Redox couple- ability of a substance to exist both in oxidized & reduced


state.

Biological oxidation:-Transfer of electrons from reduced coenzymes


through respiratory chain to molecular oxygen.

Cellular Respiration-process by which cells derive energy in the form of


ATP from controlled reactions of H 2 with O2 to form water.

Reducing equivalents:- used to designate a single electron equivalent


transferred in an oxidation-reduction reaction.
Oxidative phosphorylation & ETC

Oxidative phosphorylation/ biological oxidation


• Metabolic pathway.
• Oxidation coupled with phosphorylation.
• Occurs in mitochondria.
• Reduction of O2 to H2O with electrons donated by NADH and FADH2
(reducing equivalents) by series of electron carriers (ETC).
• Oxidation of food stuffs in body takes place by successive steps of
dehydrogenations.
• Energy released during transfer stored as ATP.
• Major source of ATP in aerobic organisms.
Mitochondria
• NADH cannot simply pass into mitochondria
for oxidation by the respiratory chain.
• Electrons from NADH & FADH2 are carried
across mitochondrial membrane by
(i)glycerol 3-phosphate shuttle
(ii) malate-aspartate shuttle.
glycerol 3-phosphate shuttle
glycerol 3-phosphate shuttle
Brain & skeletal muscles
LIVER, KIDNEY & SKELETAL MUSCLES
Electron transport chain
Final common pathway in aerobic cells by which electrons derived
from various substances are transferred to oxygen to form water.

Components
1. Complex I :- (NADH:ubiquinone oxidoreductase/NADH
dehydrogenase)
2. Complex II:- (succinate dehydrogenase)
3.Complex III:- Cytochrome bc1 complex or
ubiquinone:cytochrome c oxidoreductase
4.Complex IV:- Cytochrome oxidase
5. Complex V:- ATP synthase
• Oxidative phosphorylation begins with the entry of electrons into the
respiratory chain.
• Flow of electrons through a chain of membrane-bound carriers (ETC).
• Electron carriers embedded in inner mitochondrial membrane.
• Carriers arranged in the increasing order of redox potential.

• Three types of electron transfers occur in oxidative phosphorylation:


(1) direct transfer of electrons, (2) transfer as a hydrogen atom and (3)
transfer as a hydride ion(:H), which bears two electrons.

• Most of these electrons arise from the action of dehydrogenases.

• Each carrier is reduced by the gain of electrons from preceeding carrier &
is subsequently oxidized by loss of electrons to the carrier following it.
• Energy released as electrons move downhill along the chain.
• Free energy made available by this “downhill” (exergonic)
electron flow is coupled to the “uphill” transport of protons
across a proton-impermeable membrane.
• Transport of protons from inside to outside of inner
mitochondrial membrane creates a proton gradient across
the membrane.
• Accumulation of protons outside the membrane creates an
electrochemical potential difference (PMF).
For each pair of electrons transferred to O2,
4 protons are pumped out by Complex I
4 protons are pumped out by Complex III &
2 protons are pumped out by Complex IV.
• Inner mitochondrial membrane is impermeable to
protons.
• Protons reenter the matrix through proton-specific
channels.
• Proton-motive force drives protons back into the matrix
• This protein motive force provides the free energy for
synthesis of ATP by Complex V.
NADH
e-

NADH dehydrogenase/Complex I 4H+

e-
e- FADH2 Succinate dehydrogenase/
Complex II
CoQ
e-
Cyt bC1 complex/ Complex III 4H+

e-
Cyt C
e-
Cytochrome oxidase/Complex IV 2H+

e-
O2 H2O
Electron transport chain
Complex V/ATP synthase

 large enzyme complex of the inner mitochondrial


membrane.
 catalyzes the formation of ATP from ADP and Pi.
 two distinct components: F1 & F0
F1---- a peripheral membrane protein
------protrude into matrix.
-------ATP synthase activity
Fo -----present in the membrane.
Hypothesis for ATP generation-
Chemi osmotic theory
• ATP synthesis in mitochondria is based on the
hypothesis, introduced by Peter Mitchell in 1961.

• Provides insight into the processes of oxidative


phosphorylation.

• States that the electrochemical gradient developed across


IMM are utilized for ATP synthesis.
ATP production & P:O ratio

P:O ratio:-number of ATP’s generated for each


molecule of O2 consumed.
1 NADH=3 ATP
1 FADH2=2 ATP
Energetics

• Passage of 2 electrons from NADH to O2 drives the formation


of about 3 (2.5) ATP,
• Passage of two electrons from FADH2 to O2 yields about 2
(1.5) ATP.

ADP+Pi ATP requires 7.3Kcal/mol

1 NADH oxdn 52 kcal/mol


1 NADH=3 ATP=3 X 7.3= 21.9 Kcal
40% energy trapped. Rest released as heat.
Inhibitors of ETC
1.Complex I -Amobarbitol & Rotenone ,piercidin BAL

2.Complex II – Malonate, Carboxin

3.Complex III –Antimycin A, BAL

4.Complex IV-CO, CN-, H2S

5.Oxidative phosphorylation
-Atractyloside----binds Adenine nucleotide translocase -
Oligomycin----binds to F0 Subunit of ATP synthase
-Ionophores—valinomycin,gramicidin---increases permeability of IMM.

-Uncouplers- 2,4-DNP, pentachlorophenol, dinitrocresol


-Physiological uncouplers- Thyroxine, Ffa , bilirubin
Inherited disorders
• Leber’s heriditary optic neuropathy-complex
I enzyme def.
• MELAS: Mitochondrial encephalopathy with
lactic acidosis & stroke.
Def-complex III/Complex I.
Energy rich compounds
Pyrophosphates----ATP
Acyl phosphates—--1,3-BPG
Enol phosphates-----PEP
Thiolesters-----------Acetyl CoA
Phosphagens---------
Phosphocreatinine
ATP
• Most important high energy compound.
• Consists of Adenine, ribose & triphosphate.
• Serves as energy currency of cells.
• Free energy released during catabolic reactions are captured
in the form of ATP.
• 2 mechanisms for synthesis of ATP
I) Substrate-level phosphorylation----direct synthesis of ATP by
Glycolysis & TCA cycle.
II) Oxidative phosphorylation- synthesis of ATP by coupling of
oxidation with phosphorylation in mitochondria.
ATP-ADP cycle
Muscle contraction
OP ADP Pi
Active transport
Pi Biosynthesis
Phosphorylations

SP ATP
Pi

Creatinine Creatinine-P

Pi
Thank you
• A sedentary male of 70 kg ---requires about 8400 kJ (2000 kcal) for a day’s
worth of activity.
• To provide this much energy requires 83 kg of ATP.
• However, human beings possess only about 250 g of ATP at any given
moment.
• The disparity between the amount of ATP that we have and the amount
that we require is compensated by recycling ADP back to ATP.
• Each ATP molecule is recycled approximately 300 times per day.
• This recycling takes place primarily through oxidative phosphorylation.
Bioenergetics

Gibb’s Helmholtz Equation


△G =△H -T△S
△G- change in free energy
△H- change in enthalpy
△S- change in entropy

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