BIOLOGICAL OXIDATION

Electron Transport Chain

Dr. Dalia Shaalan
Lecturer of Medical Biochemistry
Faculty of Medicine – Mansoura University
 Electron Transport Chain
In non-biologic systems,
• Energy is produced in the form of heat by direct
reaction between hydrogen and oxygen,
• Then heat can be transformed into mechanical
or electric energy.
• This process is explosive, inefficient and
uncontrolled.
 Electron Transport Chain
In biologic systems,
• Cells use electron transport chain to transfer
electrons stepwise from substrates to oxygen.
• Thus producing energy gradually.
• This process is stepwise, efficient and
controlled.
 Electron Transport Chain
• Definition:
It is a chain of catalysts of increasing redox
potential that collects reducing equivalents
(hydrogen atoms and electrons) from substrates
transferring it stepwise to be oxidized in a final
reaction with oxygen to form water and energy.
• It is also known as redox chain or respiratory
chain.
 Electron Transport Chain

Components of the electron transport chain

1. Hydrogen and electron carriers.
2. Four membrane-bound enzyme complexes.

All are imbedded in the inner mitochondrial

membrane.
 Electron Transport Chain

FAD
NAD→ FMN→ Co Q→ Cyt b→ c1 → c → a → a3
Hydrogen and electron carriers
 Electron Transport Chain
Hydrogen and electron carriers
1- NAD+
• A coenzyme acts as a hydride ion carrier (H- =
Hydrogen atom with 2 electrons).
• It receives 2H from substrates as isocitrate,
malate, β-hydroxy acyl CoA and β-hydroxy
butyrate.
• Its reduced form (NADH+H+) passes both
hydrogens to flavoprotein containing FMN
 Electron Transport Chain
Hydrogen and electron carriers
2-Flavoproteins
• FAD and FMN are tightly bound to flavoproteins to
prevent their reduced form reacting with oxygen directly.
• Flavoprotein Fp1 containing FMN receives (2 H) atoms
from reduced NAD+ passing them to coenzyme Q.
• Flavoprotein Fp2 containing FAD receives (2 H) atoms
from substrates as succinate, acyl CoA and choline
passing them to coenzyme Q.
 Electron Transport Chain
Hydrogen and electron carriers
3- Ubiquinone (Coenzyme Q)
• It is a small molecule, freely mobile in the inner
mitochondrial membrane.
• collects reducing equivalents from more fixed
components (reduced FMN or FAD).
N.B: Ubiquinones are compounds containing quinine ring
(vary according to number of side chain isoprene units).
The most common ubiquinone is coenzyme Q that has
structural similarity to vitamin K.
 Electron Transport Chain
Hydrogen and electron carriers
3- Ubiquinone (Coenzyme Q)
• Receives 2 hydrogen atoms to form ubiquinol (reduced
coenzyme Q) or 1 hydrogen atom forming semiquinone.
• Reduced coenzyme Q passes the 2 e- to 2 cytochrome b
and releases 2H+ into the mitochondrial matrix.
• It is a bridge between flavoproteins, which can carry 2
hydrogen atoms, and cytochrome b, which can carry one
electron only.
 Electron Transport Chain
Hydrogen and electron carriers
3- Ubiquinone (Coenzyme Q)
Oxidation of ubiquinol involves 2 successive actions:
• Ubiquinol (coenzyme Q) dehydrogenase:
transfers electrons to (cyt b, FeS protein, cyt c1 which
are its coenzymes) then to cytochrome c .
• Cytochrome oxidase:
transfers electrons from cyt c to (cyt a, cyt a3 which are
its coenzymes) then to oxygen.
 Hydrogen and electron carriers

4- Cytochromes
• Electron carriers transfer only electrons from CoQ to O2.
• The letters; a, b and c according to their order of discovery.
• All ETC cytochromes are haemoproteins (differ in redox
potential).
• The haem in cytochromes differs from that of haemoglobin
as the Fe atom oscillates between oxidation and reduction
during the physiological action of cytochromes, while the Fe
of haemoglobin remains in the reduced form during its
physiological action.
 Electron Transport Chain
Hydrogen and electron carriers
4- Cytochromes
• Cytochrome c is a water soluble, peripheral membrane
protein. It is relatively mobile.
• Cytochrome a3 contains copper in addition to the
haeme group.
• N.B. the mobile components of the electron transport
chain include Co-Q and cyt c. They collect reducing
equivalents from the other fixed components.
 Electron Transport Chain
Hydrogen and electron carriers
5- Iron sulfur protein (FeS or none- haeme iron)
• associated with flavoproteins and cytochrome b.
• consists of cluster of cysteine residues which bind Fe by
covalent bonds (with S of cysteine).
• The S and Fe are thought to take part in the oxidation-
reduction mechanism between flavoprotein and
coenzyme Q as Fe atom in these complexes oscillates
between oxidation and reduction that allow them to
either give up or accept electrons.
Enzyme Complexes of the Electron Transport
Chain organized in the inner mitochondrial
membrane
 Electron Transport Chain
Enzyme Complexes of the Electron Transport Chain
• Complex I: NADH dehydrogenase (NADH-ubiquinone
oxidoreductase)
• It is a flavoprotein that contains FMN as well as FeS protein
as coenzymes.
• It transfers hydrogen atoms from NADH+H+ to ubiquinone.
 Electron Transport Chain
Enzyme Complexes of the Electron Transport Chain
• Complex II: Succinate dehydrogenase (succinate-
ubiquinone oxidoreductase)
• It is a flavoprotein that contains FAD as well as FeS
protein as coenzymes.
• It transfers hydrogen atoms from succinate to
ubiquinone.
 Electron Transport Chain
Enzyme Complexes of the Electron Transport Chain
Complex III: Ubiquinol dehydrogenase (ubiquinol-
cytochrome c oxidoreductase).
• It transfers electrons from ubiquinol to cytochrome c
using cyt b and cyt c1 as coenzymes.
Complex IV: Cytochrome oxidase (cytochrome-oxygen
oxidoreductase)
• It transfers electrons from cytochrome c to oxygen.
• It needs cyt a and cyt a3 as coenzymes.
 Electron Transport Chain
Enzyme Complexes of the Electron Transport Chain
N.B: In addition to these four enzyme complexes, there is
fifth complex (complex V) which is the ATP synthase
that responsible for biosynthesis of ATP from ADP and
inorganic phosphate.
Electron Transport Chain
 Electron Transport Chain
AH2 NAD FMNH2 Oxidized reduced Oxidized reduced

Coenzyme Q Cyt b (2 Fe +2) Cyt c1 (2 Fe +3) Cyt c (2 Fe +2)

NAD linked
Complex I Complex III
dehydrogenases
A NADH+H+ FMN reduced Oxidized reduced Oxidized
Coenzyme Q Cyt b (2 Fe +3) Cyt c1 (2 Fe +2) Cyt c (2 Fe +3)

2H+

reduced Oxidized reduced

½ O2
Cyt c (2 Fe +2) Cyt a (2 Fe +3) Cyt a3 (2 Fe +2)

Complex IV
O= H2O
Oxidized reduced Oxidized
Cyt c (2 Fe +3) Cyt a (2 Fe +2) Cyt a3 (2 Fe +3)

Sequence of events in the electron transport chain