BIOENERGETICS

FACTS:
1. Living organisms are not in equilibrium with their surroundings
Without energy input, cells break down into small building block
molecules and die (equilibrium state).
2. Continuous input of energy is required to keep processes from going to
equilibrium.
Cells burn fuel molecules (sugar, fat, amino acids) and use the released
energy to make ATP
ATP - adenosine triphosphate
 main energy currency of the cells
 used for building macromolecules from monomers & for other purposes
 produced in the ff.:
light reactions of photosynthesis (in chloroplasts of photosynthetic
eukaryotic organisms)
glycolysis (in the cytosol of all organisms)
aerobic respiration which includes the Krebs Cycle and electron
transport phosphorylation or chain (ETC) (in the mitochondria of
eukaryotic cells)
3. Cells are designed to use chemical energy rather than heat energy
The cell is not a heat engine- it runs at a constant low T
 BIOENERGETICS
4. Reasons for "food" requirement:
 as subunits to build the biomolecules of the organism
 provide E (ATP) for the maintenance and activities of the cell
Energy storage:
– The body cannot store much ATP as it interferes with many chemical reactions
– Most of the energy is stored in fats (triglycerides) & CHO (glycogen)
– ATP is generated from the fats & polysaccharides as needed  glycolysis & the
Krebs cycle
 Cell produces E by oxidizing or burning the stored energy-rich chemicals
 Some of the E goes off as heat, but most is trapped in the phosphate bonds of ATP
 Some electrical E is also stored as ion gradients
Chemical energy in the body is stored mainly as ATP , glycogen and triglycerides
A m o u n t A m o u n t
R a te o f U se
F u el S to red : S to red :
(P o w er)
T im e D ista n c e

en o u g h fo r
e n o u g h to g o Good for sprinting,
A T P & C P ab o u t
a b o u t 1 0 0 y ard s
fa s te st
jumping, lifting
1 0 sec

g ly c o ly sis Glycogen is stored in the

C a rb o h y d ra tes
en o u g h fo r
e n o u g h to g o m e d iu m fa st; muscles and liver;
(g ly c o g e n )
ab o u t
a b o u t 2 0 m il e s r e s p i ra t io n "hitting the wall" in a
2 h rs
slo w e r
marathon is due to
running out of glycogen
en o u g h fo r e n o u g h to g o
L ip id s
(tr igly c e rid e s)
ab o u t ab o u t 1 0 0 0 v e ry slo w
A lot of E stored as lipids
4 0 d ay s m iles but the amount varies
from person to person
 BIOENERGETICS

Review of Thermodynamics of Biological Systems

Cell function depends largely on molecules, such as proteins and
nucleic acids, whose formation requires a (+) free energy.
To carry out the thermodynamically unfavorable reactions, cells couple
them to other reactions that liberate free energy, so that the overall
process is exergonic

•The value of the changes in free energy, G

gives the needed information about spontaneity
•A spontaneous process is favored by energy-release (exergonic)
and increase in entropy
G = H - TS,
G < 0  spontaneous iff,
H is (+) but small or (-) & S is large & (+)
G > 0  nonspontaneous
 BIOENERGETICS

Review of Thermodynamics of Biological Systems

Energy coupling in mechanical and chemical processes

The Importance of Coupled Processes on Living Organisms

Many reactions required for living systems have an unfavorable ∆G or+ ∆G
They can be "forced" to proceed if they are coupled with a reaction with a
- ∆G  ∆Gnet is (-)
Example:
Phosphoenol pyruvate + H2O → Pyruvate + Phosphate ∆G = -78 kJ/mol
ADP + Phosphate → ATP + H2O ∆G = +55 kJ/mol
Phosphoenol pyruvate + ADP → Pyruvate + ATP ∆Gnet = -23 kJ/mol
 BIOENERGETICS

High energy or energy-rich molecules

Highly important in all biochemical processes; drive different
cellular processes such as synthesis of new chemical compounds,
membrane transport, mechanical work and many more.

Adenosine Triphosphate,
or ATP, is the principal
energy source of the cell.
Energy released by
hydrolysis of the
phosphoanhydride bonds
is the usual source of free
energy in coupled
biological reactions
 BIOENERGETICS

Some energy-containing compounds, and associated ∆G of hydrolysis

0
C o m p o u n d S tru c tu re  G ' o f
H y d ro ly s is
(k J /m o l)

P h o s p h o e n o l -6 2 .2
p y ru v a te

C re a tin e p h o s p h a te -4 3 .3

A c e ty l p h o s p h a te -4 3 .3

A d e n o s in e 5 ' -3 5 .7
trip h o s p h a te
2 +
-3 0 .5 (M g )

A d e n o s in e 5 ' -3 5 .7
d ip h o s p h a te

∆G°' (‘°' symbol 

standard state at
pH 7.0)
 BIOENERGETICS

Two general properties of high-E molecules

• not intended as a means to store energy long-term, but as a means to
transfer energy to drive coupled reactions
• not necessarily "unstable" molecules  key point: E required to break a
high energy bond < E released when a new, lower-energy bond is formed
 coupled reactions occur with a -∆G

How Some Release High E

1. High group transfer potential
the hydrolysis of a phosphate bond where it is then transferred to another
molecule in the coupled reaction releases E
ATP + H2O  ADP + Pi
∆Gº = - RT ln Keq
Keq = [ADP][Pi]/[ATP][H2O]
 group transfer potential in H2O
 BIOENERGETICS

2. Resonance stabilization
in ATP, the 3 terminal phosphate can have 3 resonance structures involving the
outer oxygen groups. But internal phosphates can have only 2 resonance
structures. After hydrolysis the released phosphate ion can have 3 resonance
structures, and the ADP terminal group can also have 3   availability of
resonance structures results in a lower E state for the molecules released after
hydrolysis.
for enol phosphates, like phosphoenol pyruvate (PEP), there is only a single
phosphate group  E released should be lower than in the hydrolysis of AMP
 PEP hydrolysis
produces
an unstable
enol form
of pyruvate
 -29 kJ/mol E
 Rapidl tautomeri-
zation to the
stable keto form
 -34 kJ/mol E
 E released upon
 hydrolysis of PEP is the sum of these two contributions
 BIOENERGETICS

Phosphoric Acid Anhydride Linkages

3. Other contributing factors

> destabilization of phosphoric acid anhydride bond due to
electrostatic repulsion. Each phosphate group in a phosphoric anhydride
carries a negative charge & the adjacent negative charges repel each
 repulsion is minimized by hydrolysis, which allows bond breakage and
separation of phosphate groups.
> entropic considerations at neutral pH.
 BIOENERGETICS

From the given reactions, which set/s can be coupled to the reaction
glucose + phosphate  glucose-6-phosphate + H2O G= +3.3
to bring about a net exergonic reaction?
G
maltose + H2O  2 glucose - 4.0
glucose-1-phosphate  glucose-6-phosphate - 1.7
glutamine + H2O  glutamate + NH4+ +3.4
pyruvate + ATP  phosphoeneol pyruvate + ADP +2.3
 BIOENERGETICS

Food For Thought

HOW DO CREATINE PHOSPHATE (CP) & ACETYL PHOSPHATE ACT AS
E-RICH MOLECULES?
 BIOENERGETICS

Food For Thought

HOW DO CREATINE PHOSPHATE (CP) & ACETYL PHOSPHATE ACT AS
E-RICH MOLECULES?
INTRO TO ELECTRON TRANSPORT CHAIN (ETC)
Electron Transport Chain
• Glycolysis  2 ATP Substrate level phosphorylation
• Kreb’s cycle  2 ATP

• Life takes a lot of energy to run, need to extract more energy than 4
ATP!
• Biological oxidations
- catalyzed by intracellular enzymes; to obtain more energy as ATP
 Electron Transport Chain

Remember the NADH & FADH2? Kreb’s cycle

Glycolysis
PGAL

8 NADH
2 FADH2

4 NADH

2005-2006
Electron Transport Chain
 Electron Transport Chain

Simplified Electron Transport