Chapter 14 – Electron Transport

Overview of oxidative energy

generation

 Relatively little ATP is generated per mole

of glucose in stages 1 and 2

 Stages 1 and 2; however, convert 10 moles

of NAD+ to NADH and 2 moles of FAD to
FADH2 per mole of glucose

 Reoxidation of NADH and FADH2 in stage

3 (cellular respiration) provides most of
the energy used for ATP synthesis
Major mitochondrial compartments and the
principal pathways found in them
 Oxidative phosphorylation takes place on the inner
mitochondrial membrane

Complexes I, III and IV pump protons into the intermembrane space, creating an energy
gradient. Complex V, ATP synthase, uses the energy stored in this gradient to drive ATP
synthesis.
• Final stages of aerobic oxidation of biomolecules in eukaryotes
occur in the mitochondrion

•Reduced coenzymes NADH and FADH2 from:

(1) Aerobic oxidation of pyruvate by the citric acid cycle

(2) Oxidation of fatty acids and amino acids

•Electron Transport Chain is the process by which NADH and FADH2

are oxidized and a proton gradient is formed.
Oxidative phosphorylation is the
process of making ATP by using the
proton gradient generated by the
ETC.

Respiration by mitochondria
• Oxidation of substrates is coupled
to the phosphorylation of ADP
• Respiration (consumption of
oxygen) proceeds only when ADP is
present
• The amount of O2 consumed
depends upon the amount of ADP
added
Location of mitochondrial complexes

• Inner mitochondrial membrane:

a. Electron transport chain: oxidizes reduced coenzymes
b. ATP synthase: machinery to synthesize ATP

Electron transport and oxidative phosphorylation capture the

energy in the redox potential of NADH and FADH2 – 2 separate
processes that are COUPLED to result in ATP production

Extensive folding of Inner mitochondrial membrane provides a

large surface area on the matrix side to form lots of assemblies
of proteins to maximize ATP production
(1) Respiratory electron-transport chain (ETC) Series of
enzyme complexes embedded in the inner
mitochondrial membrane, which oxidize NADH and FADH2.

Oxidation energy is used to transport protons creating a proton

gradient – protons pumped from matrix to intermembrane space
across Inner mitochondrial membrane

(2) ATP synthase uses the proton gradient energy to produce

ATP; It is the release of the energy in the gradient back
through the membrane through the protein ATP Synthase that
drives ATP synthesis
 Electron carriers in the
respiratory chain

 The respiratory chain catalyzes the flow

of electrons from low reduction potential
carriers to high reduction potential
carriers (exergonic)
 Uses a variety of electron carriers
 Flavoproteins contain flavin
mononucleotide (FMN) or flavin
adenine dinucleotide (FAD)
 Iron-sulfur proteins contain non-
heme iron clusters such as FeS and
Fe4S4 (I, II, III)
 Coenzyme Q (ubiquinone, Q)
 Cytochromes contain hemes (b, c, or
a) (II and III – three b-type
cytochromes; III – cytochrome c1; IV
– a and a3; cytochrome c is membrane
associated 100-mer)
 FOUR protein complexes in the Inner mitochondrial
membrane make up the Electron transport chain

- Complexes I, II, III, IV

- Work together in succession to catalyze redox reactions

- Electrons are transferred to molecular oxygen that is then

reduced to water

- Electrons move through the complexes in order

• Electrons from NADH enter at Complex I
• Electrons from FADH2 enter at Complex II

- Flow of electrons is spontaneous and thermodynamically

favorable because the next carrier has greater affinity
for electrons than the previous

• In each reaction, an electron donor is oxidized and an

electron acceptor is reduced
– Areduced + Boxidized ↔ Aoxidized + Breduced
 Standard reduction potentials of major electron carriers
in the respiratory chain

 Transport of electrons through the respiratory chains can be visualized

as a series of coupled exergonic reactions
 Three steps are sufficiently exergonic to drive ATP synthesis
 Free energy available from the oxidation of NADH by O 2 is converted
into a proton gradient that powers the synthesis of ATP from ADP and P i

 these data are from standard conditions and may be very different
from those in the mitochondrion
Co-factors in Electron Transport
• Complexes contain enzymes with electron carrying
groups or oxidation – reduction components
• Protein components use metal containing prosthetic
groups or flavins to carry electrons
• Metal-containing groups such as iron-sulfur clusters,
copper ions, hemes
• Flavins:
• (Complex I) FMN - FMNH2
• (Complex II) FAD - FADH2
 Mobile electron carriers – serve as links between Electron transport
chain complexes
1. Ubiquinone (Q)
• Also called coenzyme Q
• A membrane-soluble low molecular weight compound
• Long hydrophobic tail keeps Q anchored in the mitochondrial inner
membrane
• Q is a lipid soluble molecule that diffuses within the lipid bilayer, and
shuttles electrons from Complexes I and II and pass them to III
• Not a part of any complex
2. Cytochrome c
• A peripheral membrane protein associated with the outer face of the
membrane, transports electrons from III to IV
• Cytochromes are heme-containing proteins – contains Fe
• Not a part of any complex
• Shuttles electrons and protons from Complex III to Complex IV
 Coenzyme Q

 Lipophilic electron carrier

 Benzoquinone linked to isoprene-containing

tail

 Can transfer two electrons in one electron

steps (via a stable semiquinone
intermediate)

 Coenzyme Q provides a link between two-

electron carriers such as NADH and one-
electron carriers such as cytochromes
 Cytochromes
 Cytochrome c and c1 hemes are
covalently bound to the protein
component
 Cytochrome a and a3 hemes are
noncovalently attached to protein and
contain formyl group (red) and
isoprenoid (blue) modifications

 Cytochromes are
Cytochrome c and c1 classified based
on their
absorption
spectra
 The absorption
spectra of the
reduced forms of
cytochromes b, c
and a are shown
to right
Cytochrome a and a3 heme
 Overview of Electron Transport

• Complexes I – where NADH electrons enter the chain

• Complex II – Where FADH2 electrons enter the chain
• Electrons passed from Complex I or II to Coenzyme Q
• Coenzyme Q shuttles electrons to complex III
• Complex III shuttles electrons to cytochrome C
• Cytochrome C shuttles electrons to Complex IV
• Complex IV transfers electrons to O2 which is then reduced to water
• Flow through Complexes I, III and IV release energy which is used to
pump protons across the IMM and form a “proton gradient”
• Proton gradient has lots of potential energy
• When the energy is released (protons flow back into matrix through ATP
synthase), the energy drives ATP synthesis
Overview of the multienzyme complexes involved in the
mitochondrial respiratory chain

Red arrows denote electron flow, gray arrows denote energy released from complexes I,
III and IV used to drive ATP synthesis
NADH–coenzyme Q reductase structure

FMN

iron-sulfur
clusters
(8 total)
 Coenzyme Q collects electrons from multiple flavoproteins for
transfer to complex III

CoQ accepts electrons not only from complexes I and II, but also ETF:ubiquinone oxidoreductase (ETF-
QO) and glycerol-3-phosphate dehydrogenase
SUMMARY OF ELECTRON TRANSPORT CHAIN
© PEARSON EDUCATION LTD 2015. COPYING PERMITTED
FOR PURCHASING INSTITUTION ONLY.