Definition of Bioenergetics

It is a study of the energy changes that accompany

biochemical reactions
Fuel essential metabolic processes in the body
Bioenergetics

Energy in biological systems is described in terms of

free energy
Biologic systems conform to the general laws of
thermodynamics
Gibbs free energy is the most important
thermodynamic function in biochemistry

S is (+) change in entropy

H is (-) heat content
If G < 0
Process is feasible
(exergonic)
If G = 0
Equilibrium prevails
(isoergonic)
If G > 0
Process not feasible
(endergonic)
Equilibrium constant
aA + bB
K eq

cC + dD
=

_[C] c [D] d __
[A] a [B] b

Gibbs Free Energy

Gibbs change in free energy ( G) is the amount of

energy capable of doing work during a chemical
reaction , at constant temperature and pressure

A. First Law of Thermodynamics

The total energy of a system, including its
surroundings, remains constant
energy is never destroyed, merely conserved,
transforming from one form to another
B. Second Law of Thermodynamics
The total entropy of a system including its
surroundings must increase if a process is to occur
spontaneously
Concepts:
Enthalpy (H)
Heat content of the reacting system
In exothermic reactions:
Heat content of products > reactants
H is negative
In endothermic reactions:
Heat is taken from surroundings
H is positive
Entropy (S)
Extent of disorder or randomness of a system
Becomes maximum as equilibrium is
approached
Becomes maximum as equilibrium is approached
When products of a reaction are disordered than the
reactants, the reaction is said to proceed with a gain
in entropy
When entropy, S is positive
Formula:
G = H - T(S)

G
H
T
S

G is always negative for a spontaneously reacting

system
Favorable conditions:

free energy change

change in enthalpy (heat)
absolute temperature
change in entropy

Equilibrium
When equilibrium is reached, no net change in the
concentration of the reactants and products occur
When a reacting system is not at equilibrium, the
tendency to move towards equilibrium represents a
driving force (tendency to move towards equilibrium)
The force driving the system toward equilibrium is
defined as the standard free energy change, G0
The biochemical standard state :
25C
Concn of reactants and products = 1M
pH = 7
Free energy change is directly related to the
equilibrium constant
The standard free energy change of a chemical
reaction is an alternative mathematical way of
expressing its equilibirum constant

G0 = -RTlnKeq
Where:
R = 8.315 J/mol (gas constant)
T = 298 K (25C) (absolute temp.)
ln = natural logarithm

 In contrast, equilibrium constants are multiplicative

Example:
G0 (kJmol-1)

Pi + glucose
Glucose-6-P + H2O +13.8
ATP + H2O
ADP + Pi
- 30.5
ATP + glucose ADP + Glucose-6-P - 16.7

Keq

3.9 x 10-3 M
2 x 105 M
7.8 x 102

The relationship between G0 and Keq is

logarithmic

Common intermediates
Pi and H2O
Used by all living cells in the synthesis of metabolic
intermediates & cellular components
This works only if compounds such as ATP are
continuously available

ATP

(CATABOLISM)

(ANABOLISM)
Energy utilization
Synthesis of
macromolecules
Muscle contraction
Active ion transport
Thermogenesis

Energy
production
Carbohydrate
Lipid

G and G0

Protein

G0 - concerned with the direction a reaction will

take for proceeding toward equilibrium
The rate at which this reaction will occur could not
be predicted
G - depends on reactant and product concentrations,
and the prevailing temperature

ADP + Pi

G0
Standard free energy values are additive
Example: Phosphorylation of Glucose to Glucose 6-P
0
G (kJmol
1

Endergonic Pi + glucose
Glucose-6-P + H2O
Exergonic ATP + H2O
ADP + Pi
Overall
ATP + glucose ADP + Glucose-6-P
Coupled

+13.8
- 30.5
- 16.7

Reaction

G0 of hydrolysis of some organophosphates of

biochemical significance
Keq

Compound
(kcal/mol)

G0

Phosphoenolpyruvate
Carbamoyl phosphate
1,3 Biphosphoglycerate
( to 3-phosphoglycerate)
Creatine phosphate
ATP AMP + PPi
ATP ADP + Pi
Glucose 1-phosphate
Pyrophosphate
Fructose 6-phosphate
Glucose 6-phosphate
Glycerol 3-phosphate

- 14.8
- 12.3
- 11.8
- 10.3
- 7.7

Oxidative phosphorylation
Adenylate kinase reaction
The process by which cells derive energy in the form
of ATP is called cellular respiration

Biologic Oxidation

- 7.3

- 5.0
- 4.6
- 3.8
- 3.3
- 2.2

Oxidation = removal of electrons

Reduction = gain of electrons
Free energy change may also be expressed in terms
of the redox potential
Enzymes involved are called oxidoreductases

Oxidoreductases

Low energy and high-energy phosphates

Low-energy phosphates - include ester phosphates

found in the intermediates of glycolysis pathway
(carb metab)
High-energy phosphates( - include ATP, anhydrides,
enolphosphates (phosphoenolpyruvate) and
phosphoguanidines (creatine phosphate and arginine
phosphates)

Oxidases
Dehydrogenases
Hydroperoxidases
Oxygenases

Oxidases
Catalyze removal of H from a substrate using
oxygen as a hydrogen acceptor

Sources of high-energy phosphates

AH2

Oxidative phosphorylation
Glycolysis
The citric acid cycle

1/2 O2

AH2

Oxidase
A

H2O

O2
Oxidase

H2O2

Rate of ATP Turnover

ATP is continuously being hydrolyzed & regenerated

Brain cells have only a few seconds supply
Muscle & nerve cells have a high ATP turnover but
have a free energy reservoir that functions to
regenerate ATP rapidly

ATP Regeneration
Endergonic PEP + H2O
Exergonic ADP + Pi
Overall
PEP + ADP
Coupled
Reaction

Pyruvate + Pi
ATP + H2O
Pyruvate + ATP

G0 (kJ/mol-1)

- 61.9
+ 30.5
- 31.4

ATP is regenerated by coupling its synthesis from

ADP & Pi to the even more exergonic hydrolysis of
phosphoenolpyruvate (PEP)

Dehydrogenases

Act as storage forms of high-energy phosphate

Include:
Creatine phosphate (found in skeletal
muscle, heart, spermatozoa, brain)
Arginine phosphate (invertebrate muscle

Formation of ATP

Substrate level phosphorylation

Transfer of hydrogen from one substrate to another in

a coupled redox reaction
Function as components in the respiratory chain of
electron transport

Dehydrogenases & Nicotinamide Coenzymes

Phosphagens

Cytochrome oxidase
Terminal component of the chain of
respiratory carriers found in mitochondria
Transfers electrons to final oxygen acceptor
Flavoprotein enzymes
L-amino acid oxidase
Xanthine oxidase

NAD-linked dehydrogenases catalyze redox reactions

in:
Glycolysis
Citric acid cycle
Respiratory chain of mitochondria
NADP-linked dehydrogenases catalyze reactions in
reductive pathways:
NADP-linked dehydrogenases catalyze reactions in
reductive pathways:
Fatty acid synthesis
Steroid synthesis
Pentose phosphate pathway

Glucose

Hydroperoxidases

Fatty acids
Acetyl CoA

Use H2O2 or an organic peroxide as a substrate

Protect the body against harmful peroxides which
could lead to free radical formation
Include peroxidase and catalase

Citric acid
cycle

2H

ATP

Oxygenases

Catalyze direct transfer and incorporation of oxygen

into a substrate molecule
Dioxygenases incorporate both atoms of molecular
O2 into the substrate
Monooxygenases incorporate only one atom of
molecular O2 into the substrate

2CO2
Oxidation of NADH and FADH2
Electron transport chain

Monooxygenases

Also called mixed function oxidases or hydroxylases

Notable example is the superfamily of hemecontaining monooxygenases cytochrome P450
(metabolism of many drugs)
Both NADH & NADPH donate reducing equivalents
for the reduction of these cytochromes

Electron transport chain

Complex I
Complex IV
NADH

Act to generate a proton (H) concentration gradient

across a membrane
Discharge of this gradient is enzymatically coupled to
formation of ATP from ADP & Pi (the reverse of ATP
hydrolysis)

Mitochondria and enzyme compartments

Inner membrane:
Electron carriers (complexes I - IV)
ATP synthase
Membrane transporters
Mitochondrial matrix
Outer membrane
Metabolic pathways oxidizing glucose & fatty acids

b562 b566

a3

Substrate Level Phosphorylation

ATP may be formed from phosphoenolpyruvate by
direct transfer of a phosphoryl group from a high
energy compound to ADP
These reactions most commonly occur in the early
stages of carbohydrate metabolism
Oxidative phosphorylation

FMN-(Fe-S)7

Complex III

O2
Fe-S

c1

CuA CuB
Succinate FAD-(Fe-S)3

Respiratory Chain components

The flow of electrons through complexes I, III & IV

results in the pumping of protons from the matrix
across the inner mitochondrial membrane into the
intermembrane space
ATP synthase spans the membrane and acts like a
rotary motor using the potential energy of the proton
gradient to synthesize ATP
Impermeability of the inner mitochondrial membrane
to protons and other ions necessitates exchange
transporters
Substrate shuttles: glycerophosphate, malate &
creatine phosphate

Thanks to i_bitealittle for the upload!

- geLowfish -