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Bart Dzudzor
Lecture Objectives:
• Be able to identify energy sources and there utilization.
• Be able to understand how Endergonic processes
proceed by Coupling to Exergonic processes.
• Be able to predict the spontaneity of biochemical
reactions based on the signs of ΔG, ΔH and ΔS.
• Be able to calculate standard free energy changes of
biochemical reactions given the equilibrium constant and
vice versa.
• How high-energy phosphates (ATP) play a central role in
energy capture and transfer and also acts as the “energy
currency” of the cell.
Some Biomedical Importance of
Bioenergetics
* Bioenergetics, or biochemical thermodynamics, is the
study of the energy changes accompanying biochemical
reactions.
* Death from starvation occurs when available energy
reserves are depleted.
* Certain forms of malnutrition are associated with energy
imbalance (marasmus).
* Thyroid hormones control the rate of energy release
(metabolic rate), and disease results when they
malfunction.
* Excess storage of surplus energy causes obesity, one of
the most common diseases of Western society.
Introduction to Metabolism
Metabolism = the sum of all chemical
reactions that take place
in a cell or organism.
Monomeric unit
Glycolysis
Acetyl-Coenzyme A
Learn to
c ogni z e this
re
molecule
E1 E2 E3
Principles of Metabolic Regulation
A ∆G1
B ∆G2
C D
∆G3
General features of metabolic pathways:
• Individual reaction steps may be reversible, but the overall
pathway is irreversible.
1. Cumulative
2. Concerted
3. Sequential
4. Isoenzymes for multiple effectors
Laws of Thermodynamics
• The first law of thermodynamics states that the total
energy of a system, including its surroundings,
remains constant.
∆ G=∆ H-
T∆ S
∆ H = ∆ U + P∆ V
G = Gibbs Free Energy
H = Enthalpy
S = Entropy
U = Internal Energy
Free Energy
• Hypothetical quantity - allows chemists to asses whether reactions will
occur
Exergonic:
Spontaneous processes with negative (-) ∆ G
Endergonic:
Processes that are not spontaneous with positive (+) ∆ G
Variation of Reaction Spontaneity (Sign of ∆ G)
with the signs of ∆ H and ∆ S
Page 56
Free Energy Calculations:
enzyme
aA + bB cC + dD , ∆Grxn
c d
[C] [D]
Standard free E change at pH 7 ∆G = ∆ G'o + RT ln [A]a [B]b
Biochemists use this
High-energy bonds
Why is ATP a “high-energy” compound ?
ATP is
kinetically
very
stable
ATP + H2O
Slow reaction
ADP + HPO42-
Garrett & Grisham
ATP in water is not readily converted Fig. 3.8
to ADP, but needs enzymes to mediate hydrolysis.
ATP the universal energy carrier
ATP
* More possible forms a molecule can exist
stabilizes the molecule
* Pi has more resonance forms than ATP
ADP Pi
(2) Charge separation in products
Similar electrostatic charges close
together in ATP compared to products
Creatine
Hydrolysis of energy rich compound can form an unstable compound
but can isomerize spontaneously to form stable compund
Stable form
Spontaneous isomerization
Consider a reaction: A + B C
Then:
∆ G = ∆ Go + RT ln ([C]/[A][B])
∆ Go = free energy change of the reaction under standard conditions
In "Chemistry":
The standard state convention defines the standard state of
solute as that with unit activity at 25oC and 1 atm. (So if H+ is a
reactant or product, pH = 0.)
In "Biochemistry":
The standard state convention is modified because most
reactions occur in dilute solutions near pH 7 with activities of
water and proton at unity
except
aA + bB cC + dD , ∆Grxn
c d
[C] [D]
Standard free E change at pH 7 ∆G = ∆ G'o + RT ln [A]a [B]b
Biochemists use this
c d
[C] [D]
∆G = ∆G' o + RT ln [A]a [B]b
K
c d
[C] [D]
∆G'o = -RT ln [A] [B]eqb
eq
a
eq
eq
@ equilibrium ∆ G = 0
Answer: K = 3300
Consider a reaction: A + B C
Go = free energy change of the reaction under standard conditions
∆ G = ∆ Go + RT ln Keq
∆ G = ∆ Go + RT ln([C]/[A][B])
At equilibrium, ∆ G = 0
mM.
Assuming1mMconcentrationandusingequation
∆ G = ∆ Go' + RT ln ([C][D]/[A][B])
∆ G = - 43.1 kJ/mol + (8.314 J/mol. K) (310 K) ln ([0.001][0.001]/[0.001])
∆ G = - 60.9 kJ/mol
-
-
-
-
Page 57
Free Energies of Formation of Some Compounds
of Biochemical Interest
Page 58
Page 58
Consider a reaction: A + B C
Go = free energy change of the reaction under standard conditions
∆ G = ∆ Go + RT ln Keq
∆ G = ∆ Go + RT ln([C]/[A][B])
At equilibrium, ∆ G = 0
A B + X ∆ G = + 50 kJ/mol
X Y + Z ∆ G = -100 kJ/mol
Overall reaction: A B + Y + Z
∆ G = - 50 kJ/mol
Values from human erythrocytes