Lyceum Northwestern University

Francisco Q. Duque Medical Foundation

COLLEGE OF MEDICINE
1st Semester – MED1

BIOCHEMISTRY LEC Dr. Redario C. Laygo

Bioenergetics & Biological Oxidation October 3, 2015

BIOENERGETICS
 Biochemical thermodynamics
 Study of energy changes accompanying biochemical
reactions

Laws of Thermodynamics
1. The total energy of its system, including its If ∆G is POSITIVE:
surrounding, remains constant  Endergonic reaction
2. Any system left alone to themselves approach a  Reaction proceeds only if free energy can be gained
state of maximum disorder (ENTROPY), until a state
of equilibrium is reached

DIRECTION AND EXTENT TO WHICH A CHEMICAL WILL PROCEED IS

DETERMINED BY:
a. Change in heat content
b. Change in entropy

CHANGE IN FREE ENERGY ∆G

 Portion of total energy change in a system available
for doing work
 Chemical potential in a chemical system

Total Energy Content and Work Done

H=W–Q If ∆G is ZERO:
∆H = Q – W  System is at EQUILIBRIUM
Where:  Rate of forward reaction = Rate of backward
H=enthalpy reaction
Q=amount of energy put into the system
W=work done COUPLED REACTIONS
 Thermodynamically unfavored reaction can be
ENTROPY (S) driven by being coupled to a thermodynamically
 Energy in a system not available for work favored reaction
 Extent of disorder or randomness of the system  Output of chemical energy from exergonic serve as
Q = T ∆S input of chemical energy that will drive endergonic
Then: reaction to completion
∆H = T ∆S – W
or Glucose + Pi GLUCOSE 6 PHOSPHATE + H2O
W = ∆H – T ∆S ∆Go’ = +3.3 Kcal/mole
but
∆G = -W therefore, ∆G = ∆H – T ∆S ATP + H2O ADP + Pi
∆Go’ = -7.3 Kcal/mole
Concepts on ∆G
If ∆G is NEGATIVE: Net reaction:
 Exergonic reaction Glucose + ATP GLUCOSE 6 PHOSPHATE + ADP
 Reaction proceeds spontaneously with loss of energy ∆Go’ = -4.0 Kcal/mole
 Mechanisms of Coupling
 Common obligatory intermediate
A+CIB+D
A B - EXERGONIC
C D - ENDERGONIC
I – INTERMEDIATE

 Dehydrogenation reaction coupled to

hydrogenation by an intermediate carrier

 Synthesize a compound of high energy potential

in exergonic reaction and to incorporate this
new compound into endergonic reaction REDOX REACTIONS
 A + BH2  AH2 + B

 Half reactions:
BH2 ⇆ B + e-
(B undergoes oxidation or donates e-)

A + e- ⇆ AH2
(A undergoes reduction or gains e-)

 Net redox potential = Eo of that undergoing

reduction - Eo of that undergoing oxidation
Standard Free Energy Change (∆Go )
 ∆G at one molar concentration of reactants at BIOLOGICAL OXIDATION
standard pressure and temperature Two Processes:
a. RESPIRATION
b. PHOSPHORYLATION
aA + bB  cC + dD
∆G = ∆Go + RT In [C]c [D]d
[A]a [B]b
HIGH ENERGY GROUP
 Reactant & product one molar each
In (1) = 0 therefore, ∆G = ∆Go + 0

 At equilibrium: ∆G = 0
∆Go’ = -RT In Keq or – 2.303 RT log Keq

 For redox reactions

∆Go = -nF (Eo’ net) + RTIn [OXIDATION]
[REDUCTANT]
LOW ENERGY PHOSPHATE COMPOUNDS o FAD
 Gives a P/O ratio of 2:1
 Accepts two protons and two electrons

CHEMIOSMOTIC COUPLING HYPOTHESIS (Peter Mitchell,

1961)
Electrochemical gradient of protons across
mitochondrial inner membrane serves as a means of
coupling energy flow of electron transport to ATP
formation

CONFORMATION COUPLING HYPOTHESIS (Paul Boyer, 1964)

A difference in hydrogen ion concentration across
ATP/ADP CYCLE the membrane drives the enzyme ATP synthase to
synthesize ATP

MAJOR SOURCES OF HIGH ENERGY PHOSPHATE

a. OXIDATIVE PHOSPHORYLATION
b. GLYCOLYSIS
c. TRICARBOXCYLIC ACID CYCLE (TCA or Krebs Cycle)

PHOSPHORYLATION
 Substrate level phosphorylation
-direct cleavage of high energy bonds
coupled to synthesis of ATP
 Oxidative phosphorylation
-transfer of reducing equivalents in the
electron transport chain (ETC) causes
capturing of free energy through
phosphorylation of ADP

Electrons enter the respiratory chain via these two points:

o NAD
 Gives a P/O ratio of 3:1
 Accepts one proton and two electrons
By: LCSagun2019