Electron Transport Chain and ATP Synthesis in Biochemistry

 
BIOCHEMISTY
 
BINITA RANI
ASSOCIATE PROFESSOR (DAIRY CHEMISTRY)
FACULTY OF DAIRY TECHNOLOGY
S.G.I.D.T., BVC CAMPUS,
P.O.- BVC, DIST.-PATNA-800014
 
ELECTRON TRANSPORT CHAIN AND
 ATP SYNTHESIS
 
Course No.-DTC-111,    Credit Hours – 2 (1+1)
 
•In 
eukaryotes
 => Electron transport and oxidative
phosphorylation => inner 
mitochondrial
 membrane.
 
• These processes => 
re-oxidize NADH and FADH2 
<= from the
citric acid cycle (mitochondrial matrix ), glycolysis (cytoplasm )
and fatty acid oxidation ( mitochondrial matrix ) and => trap the
energy  released as ATP.
 
Oxidative phosphorylation 
=> 
major source of ATP 
in the
cell.
 
In 
prokaryotes 
=> electron transport and oxidative
phosphorylation components 
=> in the 
plasma membrane
.
 
      
Redox Potential
 
 Oxidation => 
loss
 of electrons.
 
 Reduction =>
 gain 
of electrons.
 
 In chemical reaction 
:
 
 if one molecule is oxidized => another must be reduced
 
 i.e. oxidation-reduction reaction => 
transfer of electrons
.
 
 
 
 
.
 
 when  
NADH
 => oxidized to 
NAD+ 
=> it loses electrons.
 
 When 
molecular oxygen 
=> reduced to 
water
 => it gains
electrons :
 
Oxidation-reduction potential, E, 
(
redox potential
)
 a measure of 
affinity of a substance for electrons 
and
 is measured relative to 
hydrogen
.
 
 
Positive
 
redox potential
 substance => 
higher affinity 
=> 
electrons
 than hydrogen
 so would 
accept electrons 
from hydrogen,
 
e.g.,
 Oxygen
 , a strong 
oxidizing agent
 
Negative
 
redox potential
 
 substance has a 
lower affinity 
for 
electrons
 than does hydrogen
 
 would 
donate electrons 
to 
H+, 
forming hydrogen,
 
e.g.,
 NADH
 , a strong 
reducing agent
 
For biological systems
,
standard redox potential 
for a substance (
E0’
)
 
measured at 
pH 7
 &  expressed in 
volts
.
 
 In oxidation-reduction reaction
 
 electron transfer is occurring
 
 
total
 
voltage change 
of the reaction (
change in electric potential, ΔE
)
=> is the 
sum
 
of voltage changes  
of  individual oxidation-reduction
steps.
 
 
Standard free energy change 
of a reaction at 
pH 7 
=> 
ΔG0’
=>
calculated from the 
change in redox potential 
ΔE0’ of substrates
and products:
ΔG0’ = -n F ΔE0’
Where, 
n     
  -- 
number of electrons transferred
,
            
ΔE0’  
-- in 
volts 
(V),
            ΔG0’ 
-- in 
kilocalories
 per mole (kcal mol-1) and
            
F      
 -- 
constant
 called 
Faraday
 (23.06 kcal V-1 mol-1).
 
A reaction with a 
positive ΔE0’ 
has a 
negative ΔG0’ 
(i.e., is
exergonic
).
Thus for the reaction:
 
 
Electron Transport from NADH
 
NADH oxidation 
and 
ATP synthesis 
 not occur in a single
step.
 
 Electrons 
 
not transferred 
from NADH 
 oxygen directly.
 
Electrons are transferred from NADH 
 oxygen 
 
along a
chain of electron carriers 
 called 
electron transport chain
(
respiratory chain
).
 
Organisation of Electron Transport Chain complexes
 
Electron Transport Chain
Consists of 
3 large protein complexes 
embedded in 
inner
mitochondrial membrane :
• NADH dehydrogenase complex 
(Complex I)
 
• Succinate Q reductase
 
• The cytochrome bc1 complex 
(Complex II)
 
• cytochrome oxidase 
( 
Complex II
I)
 
Electrons
 flow from NADH to oxygen through these three
complexes
Each complex contains 
 several electron carriers 
 work
sequentially  
 carry electrons down the chain.
 
2
 
free electron carriers 
are also needed to link these large
complexes:
Ubiquinone
 {
coenzyme Q (CoQ)}
 • cytochrome c
 
ATP Synthesis (Oxidative Phosphorylation)
 
NADH
 and
 FADH2 
are 
oxidized
 by 
electron
 
transport
 through 
respiratory chain 
 Synthesis of ATP
.
 
Energy liberated 
by electron transport => used to create a 
proton
gradient 
across the mitochondrial inner membrane => that is used to
drive ATP synthesis 
(chemiosmotic hypothesis
)
 i
n presence of 
ATP
synthase 
.
 
Thus the 
proton gradient 
couples electron transport and ATP
synthesis
 .
    (not a chemical intermediate as in substrate level
phosphorylation.)
 
 
(enzyme 
 originally 
 
ATPase
 because 
 
without input of
energy 
from electron transport 
 the reaction can reverse and
actually 
hydrolyzes ATP
.)
 
Summary
• Electron transport down the respiratory chain 
 from 
NADH
oxidation 
=> causes 
H+ ions 
to be 
pumped out 
 into the 
inter
membrane space 
by 
 
three H+ pumps
 
 
 
NADH dehydrogenase
,
cytochrome bc1 complex
 
and 
cytochrome oxidase
.
Free energy change 
=> in transporting an electrically charged ion =>
across a membrane => leads to 
formation of   
electrochemical proton
gradient
.
 
The pumping out of H+ ions 
 generates a 
higher concentration of H+
ions 
 in inter membrane space 
and 
an electrical potential
 
the side of
the inner mitochondrial membrane facing the inter membrane space 
positive
.
Protons flow back 
 
mitochondrial matrix 
according to electrochemical
gradient
 
through
 
ATP synthase 
 
drives ATP synthesis
.
 The 
ATP synthase 
is driven by 
proton-motive force
 
 which is the 
sum
 of
pH gradient 
(the chemical gradient of H+ ions) and 
membrane potential
(electrical charge potential across the inner   mitochondrial membrane).
 
 
FADH2
 is re oxidized 
 via 
ubiquinone
 
 its oxidation causes H+
ions to be pumped out only by the 
cytochrome
 
bc1 complex
and 
cytochrome oxidase 
 so the amount of ATP made from
FADH2 is 
less
 than from NADH.
Measurements 
 
show that 
2.5 ATP 
molecules are synthesized
per NADH 
oxidized whereas 
1.5 ATPs 
are synthesized 
per FADH2
oxidized.
 
 
Summary of Electron Flow
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This course delves into the intricacies of electron transport and oxidative phosphorylation in biochemistry, elucidating how NADH and FADH2 are re-oxidized to generate ATP in eukaryotes and prokaryotes. It explores redox potential, oxidation-reduction reactions, and the role of standard redox potential in biological systems. The content highlights the transfer of electrons and how substances with positive and negative redox potentials interact in cellular processes. A comprehensive study on the essential concepts of energy transfer and electron affinity in biological systems is presented in a clear and concise manner suitable for students and professionals alike.

  • Biochemistry
  • Electron Transport Chain
  • ATP Synthesis
  • Redox Potential
  • Oxidation-Reduction

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  1. BIOCHEMISTY Course No.-DTC-111, Credit Hours 2 (1+1) ELECTRON TRANSPORT CHAIN AND ATP SYNTHESIS BINITA RANI ASSOCIATE PROFESSOR (DAIRY CHEMISTRY) FACULTY OF DAIRY TECHNOLOGY S.G.I.D.T., BVC CAMPUS, P.O.- BVC, DIST.-PATNA-800014

  2. In phosphorylation => inner mitochondrial membrane. eukaryotes => Electron transport and oxidative These processes => re-oxidize NADH and FADH2 <= from the citric acid cycle (mitochondrial matrix ), glycolysis (cytoplasm ) and fatty acid oxidation ( mitochondrial matrix ) and => trap the energy released as ATP. Oxidative phosphorylation => major source of ATP in the cell. In prokaryotes => electron transport and oxidative phosphorylation components => in the plasma membrane.

  3. Redox Potential Oxidation => loss of electrons. Reduction => gain of electrons. In chemical reaction : if one molecule is oxidized => another must be reduced . i.e. oxidation-reduction reaction => transfer of electrons.

  4. when NADH => oxidized to NAD+ => it loses electrons. When molecular oxygen => reduced to water => it gains electrons :

  5. Oxidation-reduction potential, E, (redox potential) a measure of affinity of a substance for electrons and is measured relative to hydrogen. Positive redox potential substance => higher affinity => electrons than hydrogen so would accept electrons from hydrogen, e.g., Oxygen , a strong oxidizing agent

  6. Negative redox potential substance has a lower affinity for electrons than does hydrogen would donate electrons to H+, forming hydrogen, e.g., NADH , a strong reducing agent

  7. For biological systems, standard redox potential for a substance (E0 ) measured at pH 7 & expressed in volts. In oxidation-reduction reaction electron transfer is occurring total voltage change of the reaction (change in electric potential, E) => is the sum of voltage changes of individual oxidation-reduction steps.

  8. Standard free energy change of a reaction at pH 7 => G0=> calculated from the change in redox potential E0 of substrates and products: G0 = -n F E0 Where, n -- number of electrons transferred, E0 -- in volts (V), G0 -- in kilocalories per mole (kcal mol-1) and F -- constant called Faraday (23.06 kcal V-1 mol-1).

  9. A reaction with a positive E0 has a negative G0 (i.e., is exergonic). Thus for the reaction:

  10. Electron Transport from NADH

  11. NADH oxidation and ATP synthesis not occur in a single step. Electrons not transferred from NADH oxygen directly. Electrons are transferred from NADH oxygen along a chain of electron carriers called electron transport chain (respiratory chain).

  12. Organisation of Electron Transport Chain complexes

  13. Electron Transport Chain Consists of 3 large protein complexes embedded in inner mitochondrial membrane : NADH dehydrogenase complex (Complex I) Succinate Q reductase The cytochrome bc1 complex (Complex II) cytochrome oxidase ( Complex III)

  14. Electrons flow from NADH to oxygen through these three complexes Each complex contains several electron carriers work sequentially carry electrons down the chain. 2 free electron carriers are also needed to link these large complexes: Ubiquinone {coenzyme Q (CoQ)} cytochrome c

  15. ATP Synthesis (Oxidative Phosphorylation) NADH and FADH2 are oxidized by electron transport through respiratory chain Synthesis of ATP. Energy liberated by electron transport => used to create a proton gradient across the mitochondrial inner membrane => that is used to drive ATP synthesis (chemiosmotic hypothesis) in presence of ATP synthase .

  16. Thus the proton gradient couples electron transport and ATP synthesis . (not a chemical intermediate as in substrate level phosphorylation.) (enzyme originally ATPase because without input of energy from electron transport the reaction can reverse and actually hydrolyzes ATP.)

  17. Summary Electron transport down the respiratory chain from NADH oxidation => causes H+ ions to be pumped out into the inter membrane space by three H+ pumps NADH dehydrogenase, cytochrome bc1 complex and cytochrome oxidase. Free energy change => in transporting an electrically charged ion => across a membrane => leads to formation of electrochemical proton gradient.

  18. The pumping out of H+ ions generates a higher concentration of H+ ions in inter membrane space and an electrical potential the side of the inner mitochondrial membrane facing the inter membrane space positive. Protons flow back mitochondrial matrix according to electrochemical gradient through ATP synthase drives ATP synthesis. The ATP synthase is driven by proton-motive force which is the sum of pH gradient (the chemical gradient of H+ ions) and membrane potential (electrical charge potential across the inner mitochondrial membrane).

  19. FADH2 is re oxidized via ubiquinone its oxidation causes H+ ions to be pumped out only by the cytochromebc1 complex and cytochrome oxidase so the amount of ATP made from FADH2 is less than from NADH. Measurements show that 2.5 ATP molecules are synthesized per NADH oxidized whereas 1.5 ATPs are synthesized per FADH2 oxidized.

  20. Summary of Electron Flow

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