2.

01a
July 7, 2016

BIOENERGETICS & OXIDATIVE PHOSPHORYLATION

Raymond Oliver D. Cruz, MD, FPAFP

o Entropy — extent of disorder or randomness of the system

TOPIC OUTLINE and becomes maximum as equilibrium is approached
I. Overview
II. Law of Thermodynamics
III. Changes in Free Energy in Biologic Systems
a. Application of the Formula
IV. Endergonic processes proceed by coupling to exergonic
Processes
V. Autotrophs vs Heterotrophs
VI. 3 sources of phosphate taking part in energy conservation
VII. The Role of ATP
a. ATP: The energy currency of the cell
b. Standard Free Energy of Hydrolysis of some
Organophosphates of Biochemical Importance
VIII. Low Energy Phosphates
IX. High Energy Phosphates
X. ATP Allows the Coupling of Thermodynamically
Unfavorable Reactions to Favorable Ones
a. Rate of ATP Synthesis is Dependent upon the CHANGES IN FREE ENERGY IN BIOLOGIC SYSTEMS
Substrate
XI. Rate of ATP Synthesis is Dependent upon Substrate  Computation of the 2 laws
XII. Adenylate Kinase (Myokinase)  Results in the ability to do work at constant temperature and
XIII. Other Nucleoside Triphosphates Participate in the Transfer pressure
of High-Energy Phosphate o ΔG = ΔH - TΔS (combines the 2 laws)
 where ΔG is the change in free energy
OVERVIEW  ΔH is the change in enthalpy (heat)
 ΔS is the change in entropy
 Bioenergetics
o Also called biological thermodynamics  T is the absolute temperature in degrees Kelvin
o Greek: bios = life and logikos = reason + Greek: thermos = heat and
dynamics = power NOTE: “I will not be asking to compute for the exam.” - Dr. Cruz
o Study of energy transformation in the biological sciences
A. Application of the Formula
 If ΔG is negative, the reaction proceeds spontaneously with loss of
free energy in the biological system called exergonic reaction.
 If ΔG is of great magnitude (highly negative), the reaction goes
virtually to completion and is essentially irreversible.
o Highly negative
 It is the case when the reactions are releasing a lot of
energy
 If ΔG is positive, the reaction proceeds only if free energy can be
gained in the biological system called endergonic reaction.
 If ΔG is of great magnitude with little or no tendency for a reaction
to occur, the system is stable.
o The system is stable, as long as you will not disturb the system,
unless you will be able to really provide energy for the reaction
to occur.

LAW OF THERMODYNAMICS
 The total energy of a system, including its surroundings, remains
constant.
 The total entropy of a system must increase if a process is to occur
simultaneously.

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TITLE OF LECTURE (NOTE: ALL CAPS) 3 SOURCES OF PHOSPHATE TAKING PART IN ENERGY
CONSERVATION
 Oxidative phosphorylation (aerobic)
o From respiratory chain using molecular O2 in mitochondria
 Glycolysis
o 2 ATP formed from the formation of lactate from glucose (no
oxygen)
 Citric acid cycle
o 1 ATP

THE ROLE OF ATP

(Illustrations of endergonic and exergonic reactions with regards to the

action progression)

 So at first, in an endergonic reaction, the activation energy to start

the reaction is very high ‘para kang umaakyat ng bundok,
nahihirapan ka bago ka mapunta sa iyong destination’.
o (at the peak of the slope) You will notice the energy level here
is much higher than the energy level at the start of the reaction
 In an exergonic reaction, the activation energy that is needed is
lower and then the energy level of the products of the reaction is
low
 This is the case, for example, in an endergonic reaction in the
synthesis of sucrose (table sugar) and if you are going to breakdown
glucose (main sugar energy source in the body) then you will be
synthesizing carbon dioxide and water via exergonic reaction with a
release of energy.
ENDERGONIC PROCESSES PROCEED BY COUPLING TO
EXERGONIC PROCESSES
 Adenosine triphosphate (ATP)
o To transfer free energy from the exergonic to the endergonic
processes
o To provide energy
 Because it contains a very important high energy acid
anhydride bonds which when broken will release a lot of
energy in the system
 Question: How many high energy phosphates are present in ATP?
o Answer: 2
 Al though there are 3 phosphates, the 2 phosphates is an
ester link to the sugar
 The energy is released by cleaving either a phosphate (Pi) or
pyrophosphate (PPi) unit from ATP, in hydrated conditions:
o ATP + H 2O → ADP (hydrated) + Pi (hydrated) + H + (hydrated)
 ΔG˚ = -30.54 kJ/mol (−7.3 kcal/mol)
o ATP + H 2O → AMP (hydrated) + PPi (hydrated) + H + (hydrated)
 ΔG˚ = -45.6 kJ/mol (−10.9 kcal/mol)
o PPi + H 2O → 2 Pi (-19.2 kJ/mol)

NOTE: Hydrolyze the ATP = energy will be reduced

You will notice that the energy released is negative so, it is exergonic and
this energy will be transformed or transferred to an endergonic system

A. ATP: The energy currency of the cell

 In the body, exergonic reactions are coupled to one another.
 So, you have an energy release reaction coupled to a reaction that
requires energy (exergonic energy to an endergonic reaction for the
processes to occur) this is what happens in biological systems.
 The ATP will be used in order to synthesize different
macromolecules in the body in an endergonic reaction

AUTOTROPHS VS HETEROTROPHS
 Autotrophic organisms (plants) utilize simple exergonic processes
such as obtaining energy from sunlight
 Heterotrophic organisms (animals) obtain free energy by coupling
their metabolism to the breakdown of complex organic molecules in
the environment (Structure of ATP)

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 The large release in energy makes the decomposition of ATP in

TITLE and
water extremely exergonic, OFhence
LECTURE (NOTE:
useful as a means for ALL CAPS)
chemically storing energy.
 All of the energy transformation that are happening will ultimately
end up with the synthesis of ATP

B. Standard Free Energy of Hydrolysis of some Organophosphates

of Biochemical Importance

(Standard table of free energy)

 ATP is somewhere in the middle because it is the energy currency

o Acts like a foreign currency where there is a mode of transfer
or mechanism for exchange ATP ALLOWS THE COUPLING OF
o Currency with which the high energy phosphates can transfer THERMODYNAMICALLY UNFAVORABLE REACTIONS
their inherent energy to the low energy phosphates TO FAVORABLE ONES
 Phosphoenolpyruvate is at the top of the list because it has the  The phosphorylation of glucose to glucose 6-phosphate, the first
highest yield of energy when it is broken down or hydrolyzed reaction of glycolysis is highly endergonic and cannot proceed under
 These other systems containing other phosphates are actually physiologic conditions.
different substrates in the different pathways which utilize ATP

LOW ENERGY PHOSPHATES

 Ester phosphates found in the intermediate of glycolysis
 Have G values lower than ATP  To take place, the first reaction must be coupled with another —
 Low energy phosphates have G values that are usually lower than more exergonic — reaction such as the hydrolysis of the terminal
the G values of your ATPs phosphate of ATP

HIGH ENERGY PHOSPHATES

 Act as energy currency of the cell
 High-Energy Phosphates Are Designated by ~P
o The symbol ~P indicates that the group attached to the bond,
on transfer to an appropriate acceptor, results in transfer of
the larger quantity of free energy
NOTE: It is seen in your textbook, encircled P means High Energy Phosphate
 When (1) and (2) are coupled in a reaction catalyzed by
hexokinase, phosphorylation of glucose readily proceeds in a highly
exergonic reaction that under physiologic conditions is irreversible.
 Many "activation" reactions follow this pattern.
 Biotransformation
o Phosphoenolpyruvate and high energy phosphate will
transfer their energy to ATP and then ATP will transfer energy
to different substrates that also contain the enzyme
phosphatase
 That’s why we have coupled reactions utilizing ATP as
energy source
 ATP will allow the coupling of thermally unfavorable reactions into
favorable ones
o For example:
 The conversion of glucose to glucose-6-phosphate is
not favorable because it has a ΔG that is positive, so, it
does not occur spontaneously.
 For this reaction to occur you will need energy from ATP
called thermodynamically unfavorable reaction.

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 Positive ΔG is endergonic so for a reaction to occur  Kinase → phosphate group (particularly synthesis)
you will need to couple it with an exergonic reaction.
 TITLE
Energy OF LECTURE
for reaction is provided by(NOTE:
ATP. ALL CAPS) OTHER NUCLEOSIDE TRIPHOSPHATES PARTICIPATE
IN THE TRANSFER OF HIGH-ENERGY PHOSPHATE
NOTE: The reaction Glucose to G-6-P is the first reaction in glycolysis for the
breakdown of glucose and rate of ATP synthesis is dependent upon the  By means of the enzyme nucleoside diphosphate kinase, UTP,
substrate GTP, and CTP can be synthesized from their diphosphates

A. Rate of ATP Synthesis is Dependent upon Substrate

 All of these triphosphates take part in phosphorylation in the cell

TRANSER’S MESSAGE

 The intermediate location of ATP allows it to play an important role

in energy transfer
 When ATP is hydrolyzed to AMP, inorganic pyrophosphate (PPi or
2Pi) is produced. This occurs in the activation of long-chain fatty
acids

 Many activation reactions or energy requiring reactions will follow

this reaction
 High energy phosphates could also be a source of energy
 The rate of ATP synthesis is dependent upon substrate
 Phosphocreatine seen in muscle needs a burst of energy
 Fatty acids have lowest energy rate but FAs are utilized for prolong
energy needs
o Example: If you are a runner or a sprinter your body will
require FA metabolism
 When ATP is hydrolyzed to AMP, you will release 2 inorganic
phosphate used to burn FA so you will need a lot of energy from the
breakdown of your FA

ADENYLATE KINASE (MYOKINASE)

 Present in most cells
 For interconversion of adenine nucleotides
 To create ATP from 2 ADPs

 In your muscles, we have Adenylate kinase reaction.

o When you breakdown ATP it will become ADP and it will
accumulate then it will result to inhibition of utilizing energy
 The body combines 2 ATPs, which have 1 high energy phosphate so
that you can synthesize ATP
 The AMP will signal that the energy is loaded so it will now facilitate
the synthesis of ATP in other reaction of the bodies
 The body will not wait for NAD to be broken down to AMP
 Other nucleotide triphosphates → transfer phosphates

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