Principle of Bioenergetics

Chapter 13

Lehninger
Principles of
Biochemistry
by
Nelson & Cox

Principle of Bioenergetics

• Must perform work in order to:

• ____________
• ____________
• ____________

• The ability to _____________and to channel it

into biological work is a fundamental property of
all living organisms

• Variety of:
• energy transductions,
• conversion of one form to another
takes place in cell.

Principle of Bioenergetics
Chemical energy is used to:

- synthesize complex, highly ordered

macromolecules from _______ precursors.

- concentration/ electrical gradients

- motion

- Heat

- light (______, __________)

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Gibbs free energy, G:

The amount of energy capable of doing work

If the reaction proceeds with release of free (looses) energy

(∆G is Negative)
-______________

If system gains energy (∆G is positive)

-______________

∆G=0 (both forward and reverse reactions occur at equal

rates; the reaction is at _____________.

Enthalpy, H (Heat content of the reacting system)

- Number and kinds of __________________ in

reactants and products

Exothermic: heat is _________

(system looses) in a reaction.

Endothermic- Reacting system ________

up heat.

Entropy, S
(qualitative expression for the randomness or
disorder in the system)

• Gain in Entropy: Products are ____ complex and

______ disordered than reactants.

• The order created in a cell (as they grow) is

compensated by the _______ they create in their
surroundings.

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Relationship : Gibbs free energy, enthalpy &
entropy

∆G & ∆H are in joules/mole or calorie/mole

In biological system
(constant temperature and pressure):
- changes in free energy, enthalpy (H) and entropy (S)
are related to each other:

∆G = ∆H - T∆S

‘T’ is absolute temperature

Standard free energy is related to the

Equilibrium Constant

The composition of reacting system keeps changing

until _____________ is reached.

At equilibrium:

- the concentration of reactants and product, and the

- rate of forward and reverse reaction are _____________:

_________change in the system.

Cells Require Sources of Free Energy

Cells use free energy G which also allows to

predict the _________ of the reaction.

• Heterotrophic Cells get free energy from __________.

• Photosynthetic cell get it from _____________.

Both types of cells transform this energy into ____

and other energy rich compounds.

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 Standard free energy is related to the
Equilibrium Constant

Change in the ____________for reaction: ∆G

Standard free energy change : ∆G°

For biochemists : ∆G´°
Equilibrium constant : K´eq

(For more details and explanation refer to p 491)

E3
Standard free energy is related to the Equilibrium constant

If ∆G´° is negative = products have _______ free energy

(reaction is spontaneous) all chemical reactions tend to go in a

direction of decrease in free energy. Goes _______ direction.

If ∆G´° is positive = products have ________ free energy

(reaction will tend to go in _________ direction)

Standard free energy is related to the Equilibrium constant

If K’eq >1: chemical reactions proceed _______.

If K’eq <1: chemical reactions proceed _______.

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Slide 11

E3 Talk also about Equilibrium constant

ETSU, 8/20/2008
Activation energy

Some thermodynamically favorable

(∆G´° is large & negative) reactions do not occur at
measurable rates:

e.g. combustion of firewood to CO2 and H2O

Because activation energy for required for combustion is

__________ than energy available at RT (room temperature).

__________ will provide that activation energy.

In living cells, reaction will be extremely slow if uncatalyzed, -

- are made to proceed _____ by increasing heat

- but by _________ the activation energy.

Standard free energy are additive

In case of two sequential reaction the
A
B and B
C with ∆G´°1 and ∆G´°2

∆G´° values (1 & 2) are ________

For overall reaction A
C (B cancels: sequential)

∆ G´°total = ∆G´°1+ ∆G´°2

This can explain how a thermodynamically unfavorable

(____________) reaction can be driven in forward direction
by coupling it to a highly _____________- reaction through
a common intermediate.
Consider a example-

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Standard free energy are additive
Synthesis of Glucose 6-phosphate is first step in
the utilization of Glucose

• Glucose+ Pi
glucose 6-phosphate+ H2O

∆G´°= 13.8 kJ/mol
• While hydrolysis of ATP is very exorgonic
ATP+ H2O
ADP+ Pi ∆G´° = –30.5 kJ/mol

Both reaction have common intermediate: Pi and H2O

and if sequential will have a:

∆G´°=13.8 kJ/mol + (–30.5 kJ/mol)=–16.7 kJ/mol

the overall reaction is __________ (favorable).

Equilibrium constant K are multiplicative

∆G´° is additive but Equilibrium constant (K) are

__________________.

By coupling ATP hydrolysis to glucose 6-phosphate

synthesis, the K’eq for glucose 6-phosphate formation
has been raised by a factor of about 2x105

K’eq1=Glucose+Pi
glucose 6-phosphate= 3.9x10-3 M-1

ADP + Pi = 2.0x105M
K’eq2= ATP

For coupled reaction:

K’eq3=(K’eq1)(K’eq2)=(3.9x10-3 M-1)(2.0x105 M)
= ________

Phosphoryl Group Transfers and ATP

Heterotrophic cells obtain free energy in chemical form
by catabolism of nutrients and use that to make ___
from ______ and _____.

ATP then donates this energy to ________ processes

as:

• __________of metabolic intermediates and macromolecules

from smaller precursors

• Transport across membranes against concentration gradients

• mechanical motions

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 Phosphoryl Group transfers and ATP

Although the hydrolysis of ATP is highly exergonic but ATP is

kinetically _________ at pH 7, because
-activation energy needed is _______.

- An enzyme is needed to lower the activation energy.

The concentration of ADP &

Pi in cell are much ______
conc. at equilibrium,
favoring hydrolysis
reaction in cell.

Other Phosphorylated Compounds

PEP (Phosphoenolpyruvate) has phosphate ester bond that
hydrolyses to yield enol form of pyruvate which can immediately
tautomerizes to a stable keto form:

Product: more ____ than reactant due to its

existence in ____ forms.
Result: ______ standard free energy.

Other Phosphorylated Compounds

Another 3-C compound, 1,3-bisphosphoglycerate
Upon reaction with phosphoric acid:

The product loses a proton to give carboxylate

ion which has two equal ____________ forms.

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Other Phosphorylated Compounds
In Phosphocreatine, the P-N bond can be
hydrolyzed to generate free creatine and Pi.

The release of Pi and ________ stabilization of

creatine favors forward reaction.

In all these phosphate releasing reactions :

Several resonance forms available to __ stabilizes

the products relative to reactants thereby
contributing to already ______ standard free
energy.

Thioesters
Has sulphur atom which replaces oxygen in the
ester bond has large ∆G´°.

_______________ is one
of the many thioesters
Important in metabolism.

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 Hydrolysis reactions with large –ve standard
free energy, products are more ________.

ATP provides energy by ______ transfer and not

by simple _________.

While some processes do involve ______hydrolysis of

ATP

e.g. - Muscle contraction,

(Chemical energy is converted into kinetic energy)

- Movement of
- enzyme along DNA or of
- ribosomes along mRNA.

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Biological Oxidation-Reduction Reactions
1. Phosphoryl groups (_____, ____ etc.)
2. Electron transfer in oxidation-reduction:
involves loss/gain of electrons
loser = is _________
gainer = is _________

It is the direct/indirect result of flow of ________

which is responsible for ___________done in living
organisms.

Source of electron:
• heterotrophic cells: __________ compounds (food)

• Photosynthetic cells: Initial electron donor,

(a chemical species excited by light absorption)

Biological Oxidation-Reduction Reactions

Electrons move from metabolic intermediates to

specialized electron carriers which donate electrons
to acceptors with ______________, with release of
energy.

Biological system has glucose (________) as source

of electrons.

Biological Oxidations Involve Dehydrogenation:

Carbon in living cell exists in range of oxidation states due to
its ____________ sharing of electrons:

In most of the cases

when Carbon shares
an electron pair, is
_________ in favor of
more electronegative
atom (H<C<S<N<O)

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Biological Oxidations involve Dehydrogenation:

In biological system oxidation is synonymous to

___________.

There are also oxidation-reduction reactions which do

not involve carbon, e.g. Nitrogen to ammonia:

6H+ + 6e- + N2 → 2NH3 (N is reduced)

Electrons are transferred from donor to

acceptor in one of the following ways :

1. Directly as ___________
2. As hydrogens atoms
−
3. As a hydride (:H ), has 2 electrons
4. Through direct combination with _______.

(For More information p 513-514)

All four types occur in cells.

Cellular oxidation of Glucose to CO2

The oxidation of glucose supplies energy for

ATP production.

C6H12O6 + 6O2 → 6CO2 + 6H2O

∆G’° is -2840 kJ/mol

Energy needed for ATP synthesis (50-60 kJ/mol).

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Specialized carriers
C6H12O6 + 6O2 → 6CO2 + 6H2O

• Glucose to CO2 conversion is not in ____ high-energy

releasing reaction but ________ tightly controlled
reactions including some oxidation.

• Energy released in each step is sufficient for ATP

synthesis from ADP with some extra.

• Electrons removed in these oxidation are transferred

to specialized carriers:

e.g. NAD+ & FAD

Nicotinamide adenine dinucleotide
Flavin adenine dinucleotide

Universal Electron Carriers

• Only ____ types of universal electron carriers

- many enzyme catalyzed cellular oxidation.
- hundreds of different substrates.

• NAD, NADP, FMN and FAD: _____ soluble coenzymes

- NAD, NADP, readily ____ from one enzyme to another

- While FMN, FAD are ___________to enzymes c/a

flavoproteins.

Universal Electron Carriers

Some ______ soluble quinones:
(ubiquinone and Plastoquinone)

Act as electron carriers and proton

donors in __________ environment
(membranes).

Iron-sulphur proteins and

cytochromes:
water soluble or
integral membrane proteins.

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NADH and NADPH act with dehydrogenases as
soluble Electron Carriers

-NAD and NADP, are composed

of two nucleotides joined
together thru their phosphate
group.

Vitamin niacin (B3) is source

of nicotinamide moiety in
nicotinamide nucleotides.
Adenine

Vitamin B3: water soluble.

NADH and NADPH act with dehydrogenases as

soluble Electron Carriers

- In many cells ratio of NAD+ to NADH is high

which favors formation on NADH.

Role in oxidations in __________

- While NADPH is present in greater amounts

than NADP

Role in __________ reactions

Pellagra
Humans do not synthesize sufficient niacin (vitamin B3)
(synthesized from ______________).

Maize (corn) is a low

_____________ Diet.

This affects all the NAD(P)

dependent dehydrogenases.

Pellagra-Human
Black tongue - dogs
(dermititis, diarrhea &
Dimentia---death)—
Read (p519)

Role of Alcohol?

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Flavin Nucleotides are tightly bound in
Flavoproteins

Flavoproteins catalyze
reactions using flavin
mononucleotide (FMN) or
flavin adenine dinucletotide
(FAD)
- derived from vitamin
riboflavin (B2)

Flavoproteins can participate

either in ___- or ___-electron
transfers:
greater diversity

Flavin Nucleotides: tightly bound in Flavoproteins

Certain flavoproteins: act as ___________

Cryptochromes:

In plants: mediate effects of blue light

on plant ________________.

In animals: light on _________________.

Flavin Nucleotides: tightly bound in

Flavoproteins

Phytolyases (a flavoprotein) use light

energy for ________chemical defects in ___.

- are activated by _______ absorption.

- Can repair UV-induced DNA-damage.

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