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UERMMMCI College of Medicine

Subject: Biochemistry
Date: June 26, 2014
Title: (1.5) Bioenergetics
Lecturer: Dr. Catherine L. Co-Reportoso
Batch/section: 2018A
Sem/ A.Y.: 1st/A.Y. 2014-2015
Transcribers: Castro,C., Catana, A. Caton,K., Centeno,J., Chan,L., Cheng C.,
Trans Subject head: Evangelista, A. (9369390879/alanaevangelista@gmail.com)
BIOENERGETICS

OUTLINE

I. BIOENERGETICS
A. Metabolism
B. Laws of Thermodynamics
II. FREE ENERGY CHANGE
A. Exergonic and Endergonic Reactions
B. Standard Free Energy Change
III. Adenosine Triphosphate
A. Phosphoanhydride bonds
B. Hydrolysis of A TP
C. ATP from High Energy Phosphates
D. ATP from Low Energy Phosphates
IV. COUPLED REACTIONS
A. Additive Nature
B. Multiplicative Nature
V. KEY CONCEPTS

o Biochemical thermodynamics
o Field of biochemistry that concerns with the study of
energy changes accompanying biochemical reactions
in a living system
o Study of the fundamental role of energy in biological
processes such as metabolism

A. METABOLISM
Metabolism sum total of anabolic and catabolic
processes

OBJECTIVES
At the end of the lecture, the first year medical students
should be able to:
Define bioenergetics
Describe the general scheme used to regulate
metabolic pathways involved in bioenergetics
State the first and second laws of thermodynamics
Describe free energy change in relation to enthalpy
and entropy changes
Differentiate between actual free energy and
standard free energy changes
Differentiate between exergonic and endergonic
reactions
Explain ATP as currency of energy of the cell
Discuss coupled reactions

Figure 1. Anabolic and Catabolic Metabolism


Catabolic reactions- reactions that produce energybreakdown of large molecules to small molecules
Anabolic reactions- reactions that utilize energy biosynthetic reactions
Most Common energy produced: ATP

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

B. LAWS OF THERMODYNAMICS

The conversion of
metabolite A to
metabolite B occurs
with the release of
free energy and is
coupled to another
reaction in which free
energy is required to
convert metabolite C
to metabolite D.

First law of thermodynamics: The total energy of a


system remains constant
Energy can neither be created/gained nor
destroyed/lost, but can be converted to other forms
Ex. Solar energy chemical energy mechanical
energy
Second law of thermodynamics: The total entropy of a
system must increase if a process is to occur
spontaneously
Exergonic (Catabolic reactions)
Entropy (S) = measure of the degree of randomness in a
system
Ex. Ice (Ordered state) Water (Disordered State)
- due to increase in Entropy

- As the reaction progresses, reactant A is converted to


product B via a transition state
- Release of free energy; G is negative
o Free energy of A>B

**Note: Not sufficient to dictate the direction/spontaneity of


the reaction
FREE ENERGY CHANGE
Free Gibbs Energy Change (joules/mole or calories/mole)
Energy that is available to do work

o Product B Reactant A = -G
Hence, negative value: = Energy is Produced
= SPONTANEOUS reaction
= forward direction

G = actual free energy change


= portion of the total energy change in a system that is
available for doing work (ie, the useful energy a.k.a.
the chemical potential)
= direction of the reaction at any specified
concentration of reactants and products
G
= H
TS (Josiah-Gibbs equation)
Greaction = Gproducts - Greactants

Endergonic (Anabolic reactions)


Reactants have lower free energy than products o

Where:
G = change in free energy
H = change in enthalpy/heat content
T = TemperatureS = change in entropy
o
G = standard free energy change= energy change
under standard condition
o
(T = 25 C = 298 K, P = 1 atm, [C] = 1M reactants &
products, pH = 7.0

Product Reactant = +G
- Gain of free energy; G is positive
= Energy is used = NON-SPONTANEOUS reaction
= cannot proceed in a forward reaction/
direction but it can proceed in a reverse
direction


G = H TS

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

To see the relationship between the standard free


energy and actual free energy:
At equilibrium G = 0

G = free energy change in any condition


G

= standard free energy change

R = gas constant (1.98cal/mol/K)


T = temp (Kelvin)
o
Note: Many reactions have a + G . And yet, the
reaction is SPONTANEOUS. This happens when there is a

Where Keq = equilibrium constant

depletion of the products or maintenance of higher

G is negative

Exergonic reaction;

(G < 0, Keq > 1)

forward direction

NON

G is positive

Endergonic reaction;

SPONTANEOUS

(G > 0, Keq < 1)

reverse direction

EQUILIBRIUM

G = 0 (Keq = 1)

SPONTANEOUS

substrate or reactant concentration.

IN A STANDARD CONDITION:

**NOTE: For an Endergonic reaction to proceed in a


forward direction, it must be coupled with a reaction that is
more highly exergonic. E.g. Hydrolysis of ATP
ADENOSINE TRIPHOSPHATE (ATP)

AMP Adenosine monophosphate


ADP Adenosine diphosphate
ATP Adenosine triphosphate

where:
[][]
1
=
=1
[][]
1

o
G = G (at standard condition)
But there will be a time that the free energy falls down
up to 0, when all the net reactions stopped. The
reacting state now is in EQUILIBRIUM.

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

A. PHOSPHOANHYDRIDE BONDS
High energy bonds (- linkage, -Y linkage)
Represented by the ~ symbol
~P = phosphate group with a large - G of
hydrolysis
There are two phosphoanhydride bonds in an
ATP

Standard free energies of hydrolysis of some


phosphorylated compounds
HIGH ENERGY PHOSPHATES value is > ATP

B. HYDROLYSIS OF ATP
Hydrolysis Addition of H2O
An exergonic reaction
When an energy is needed in an anabolic reaction,
terminal phosphate is first hydrolyzed.

LOW ENERGY PHOSPHATES value is < ATP


ATP transfers from a higher energy potential group to
a lower potential energy group

C. ATP FROM HIGH-ENERGY PHOSPHATES


(1) Phosphoenolpyruvate to Pyruvate

catalyzed by pyruvate kinase

(2) 1,3 bisphosphoglycerate to 3 -phosphoglycerate


- catalysed by phosphoglycerate kinase

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

(3) Phosphocreatinine to Creatine

catalysed by creatine kinase

Phosphoenolpyruvate to
Pyruvate
1,3 bisphosphoglycerate
to 3 phosphoglycerate
Phosphocreatinine to
Creatine

II. PHOSPHOFRUCTOKINASE REACTION

pyruvate kinase
phosphoglycerate
kinase
creatine kinase

D. ATP FROM LOW ENERGY PHOSPHATES


I. GLYCOLYSIS (HEXOKINASE REACTION)

Hexokinase and Phosphofructokinase Reactions


- Endergonic as seen in the (+) values for G.
- These are therefore non-spontaneous reactions.
- For these two reactions to proceed liberated ATP & ADP
Are needed in a coupled reaction.

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

COUPLED REACTIONS
Liberation of energy in an exergonic (spontaneous)
reaction drives an endergonic (non-spontaneous) reaction
G of coupled reactions additive
Keq of coupled reactions multiplicative
A. ADDITIVE NATURE OF G
Phosphorylation of Glucose to Glucose 6-PO4
ATP + H2O ADP + Pi -7.3kcal/mol
Pi + glucose glucose-6-P +H2O +3.3kcal/mol

Coupled reaction:
ATP+glucose ADP+glucose-6-P -4.0kcal/mol
Phosphorylation of Glucose to Glucose-6-Phosphate can
now proceed in the forward reaction due to the coupling

SUMMARY OF KEY CONCEPTS

with the Hydrolysis of ATP


Phosphorylation of Fructose 6-PO4 to Fructose 1,6bisPO4
ATP = H2O ADP = Pi

-7.3kcal/mol

Pi + Fructose 6-PO4
Fructose 1,6-bisPO4 +H2O

+3.9kcal/mol

Coupled reaction:
ATP+ Fructose 6-PO4
ADP+ Fructose 1,6-bisPO4

-3.4 kcal/mol

Fructose 6-PO4 phosphorylated to Fructose 1,6- bisPO4


can now proceed in the forward reaction because it is now
an exergonic reaction.

a) Bioenergetics is the study of energy in living system


b) Catabolism (degradative/energy-releasing
process/exergonic)
c) Anabolism (biosynthetic/energy-requiring
process/endergonic)
d) First law of thermodynamics states that energy
remains constant
e) Second law of thermodynamics states that entropy
must increase for a process to occur spontaneously
f) G = net driving force in a reaction
g) G = criterion for spontaneity of a reaction
h) G=HTSi) Greaction = Gproducts Greactants
o
j) G = G + RT ln ([products]/[reactants]
k) G = -RT lnKeq ***(at equilibrium)
l) ATP acts as the energy currency of the cell
Higher energy lower energy
m) Exergonic reactions take place spontaneously
with loss of free energy (G is negative)
n) Endergonic reactions require the gain of free energy
(G is positive) and occur only when coupled to exergonic
reactions.

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

SOURCES
A. Textbook of Biochemistry by Thomas Devlin 7th ed chap14
pp. 542-548
B. Harper's lllustrated Biochemistry by Robert Muray, et al, 29th
ed. chap11
C.
1.2 Bioenergetics Class 2017 A Trans
D. Reportoso, C. Bioenergetics PPT Handout

Castro, C |Catana, A |Caton, K |Centeno, J |Chan, L |Cheng C


A.Y. 2014-2015

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Biochemistry 1.5 | Bioenergetics

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