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ELECTRON TRANSPORT CHAIN

– A series of biochemical reactions in which


electrons and hydrogen ions from NADH and
FADH2 are passed to intermediate carriers
and then ultimately react with molecular
oxygen to form water.
– NADH and FADH2 are oxidized in the process.
ELECTRON TRANSPORT CHAIN
– Electrons passed in each step of ETC lose some
energy.

– Some of these lost energy are used to make ATP


from ADP.
– Inner mitochondial membrane- enzymes and
electron carriers are located.
PROTEIN COMPLEXES:
Bound to membrane
❑COMPLEX I: NADH-coenzyme Q reductase

❑COMPLEX II: Succinate-coenzyme Q reductase


❑COMPLEX III: Coenzyme Q-cytochrome c reductase
❑COMPLEX IV: Cytochrome c oxidase
❑Coenzyme Q and Cytochrome -mobile electron carriers
COMPLEX I
– COMPLEX I: NADH-coenzyme Q reductase (NADH→ CoQ)

– LARGEST (40 subunits)


– FMN and Fe-S proteins (FESP)
STEPS:

1. Interaction of NADH with FMN.


– NAD is oxidized to NAD+, passes 2 H ions and e to FMN, forming
FMNH2
2. Transfer of e from FMNH2 through Fe-S proteins.
– FMNH2 releases 2 H ions to the solution.

– This needs 2 Fe-SP molecules to accommodate the release.


COMPLEX I
STEPS:

3. Fe(II)SP is reconverted into Fe(III)SP, as each two Fe(II)SP


units passes an e to CoQ (CoQ to CoQH2).
– CoQ and CoQH2 are lipid soluble and can move laterally
within the mitochondrial membrane.
– CoQH2 shuttles e to COMPLEX III.
COMPLEX III
– 11 subunits
– Contains FeSPs and Cytochromes
– Cytochrome: heme-containing protein in which
reversible oxidation and reduction of an iron atom
occur.
COMPLEX III
STEPS:

1. Oxidation of CoQH2 to CoQ


– 2H+ produced go into cellular solution.
– Electron transport proceeds from CoQH2 to an FeSP, to cyt
b, then to another FeSP, to cyt c1, and finally to cyt c.
– Cyt c can move laterally in the intermembrane space,
delivers its e to COMPLEX IV.

– Cyt c is the only water-soluble cytochrome.


COMPLEX IV
– 13 subunits, including 2 cytochromes
– Cyt c to Cyt a, then cyt a3.

– Electrons from cyt a3 and H+ ions from cellular solution


combine with Oxygen to form water.
– 95% of the oxygen used by cells serve as the final electron
acceptor for the ETC.
COMPLEX II
– 4 subunits, including 2 FESP molecules.
– Process FADH2

– CoQ is associated with the operations in COMPLEX II in a


manner similar to its actions in COMPLEX I.
– CoQ is the final recipient of the e from FADH2 (FeSP as
intermediaries).
– Complex I and II both produce CoQH2.
OXIDATIVE PHOPHORYLATION
– A biochemical process by which ATP is synthesized from ADP as
a result of the transfer of electrons and hydrogen ions from
NADH or FADH2 to O2 through the electron carriers involved in
the ETC.
– Couple reactions: pairs of biochemical reactions that occur
concurrently in which energy released by one reaction is used in
the other reaction.

– Oxidative phosphorylation and oxidation reactions of ETC are


coupled reactions.
OXIDATIVE PHOPHORYLATION
– COMPLEX I, III, & IV are also known as proton pumps

– For every 2 e- passed through ETC, 4 protons cross the


inner membrane through Complex I, 4 protons through
Complex III, and 2 through Complex IV.
– Proton flows causes buildup of H+ ions in the
intermembrane space.

– This high concentration of protons becomes the basis for


ATP synthesis.
OXIDATIVE PHOPHORYLATION
– Relationship of electron carriers and number of protons:

– Oxidation of NADH= 10 protons crossing the membrane


– Oxidation of FADH2= 6 protons crossing the membrane
– Proton flow= explained through CHEMIOSMOTIC COUPLING.

– CHEMIOSMOTIC COUPLING: coupling of ATP synthesis with ETC


reactions require a proton gradient across the inner mitochondrial
membrane.
OXIDATIVE PHOPHORYLATION
– Electrochemical gradient- electrical charge ion (proton H+) is higher
in concentration in the intermembrane space than in matrix.
– Spontaneous flow of protons from high concentration to low
concentration is facilated by ATPS synthase (inner mitochondrial
membrane).
– The flow powers up the synthesis of ATP, thus ATPS synthases are
coupling factors that link the OP and ETC.
OXIDATIVE PHOPHORYLATION
ATP Synthase
– 2 subunits: F0 and F1

– F0= channel of the proton flow


– F1=where formation of ATP takes place.
– The potential energy associated with the electrochemical
gradient is released and used in the F1 subunit for the synthesis
of ATP.
OXIDATIVE PHOPHORYLATION
– ATP must be moved from the matrix to the intermembrane
space before it can be used in the metabolic reactions.
– ATP is transported through the transport proteins
imbedded in the inner mitochondrial membrane.
OXIDATIVE PHOPHORYLATION
– 1 ATP molecule transported out of the matrix=

1 ADP
1 Pi
1 H+

Move in the opposite direction.


TAKE NOTE: 4 H+ powers the ATP synthesis

3 H+ from the gradient, 1 H+ as a result of movement of ATP out of the


matrix.
ATP PRODUCTION
– 1 NADH= pumps 10 protons= 2.5 moles ATP

– 3 NADH (1 cycle of TCA)=30 protons= 7.5 moles ATP


– 1 FADH2= pumps 6 protons= 1.5 moles ATP
– 1 GTP= 1 mole ATP

– TOTAL= 10 ATP

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