Bioenergetics and Introduction to Metabolism

The transfer and utilization of energy in biologic systems

Faisal Khatib MD; PhD Faculty of Medicine, University of Jordan

Life requires both energy and matter

NO
What for Mechanical work Active transport Biosynthesis Heat

Energy Life

Sun is the ultimate source of energy for all living organisms

Glucose + O2

Photosynthetic Cells

Chemotrophic Cells

Heat

H2O + CO2

Heat

Energy generation is a major purpose of metabolism Other purposes of metabolism include Synthesis of building blocks Synthesis of macromolecules Degradation of biomolecules

Metabolism: Sum of all biochemical reactions in living organisms

Bioenergetics: Energy transformations in the cell

Chemical processes involved Quantitative aspects of energy transformation Concentration gradient Chemical energy Electrical gradient Mechanical energy Heat

Prediction of spontaneity of the reactions

Spontaneous : Favorable Which thermodynamic function can predict Enthalpy H (Heat content)
Heat can flow from system to surroundings or from surroundings to system
20 oC

50 oC

Exothermic and Endothermic reactions

CH4 + O2

CO2 + H2O +

213 kcal

Heat is liberated, products have lower heat content Bond energy Heat energy Most, but not all, exothermic reactions are spontaneous Endothermic reactions: Heat is absorbed

Most, not all, endothermic reactions are

nonspontaneous

Entropy (S): measure of randomness

In many spontaneous processes, there is a tendency for entropy increase

H2CO3

CO2 + H2O

Entropy as predictor of spontaneity

Second law of thermodynamics: in any spontaneous reaction, the entropy of system and surroundings increases. (Ssys + Ssurr)

Free energy change G

Combines enthalpy and entropy G = H - TS Can predict the direction of the reaction A B G = -ve = +ve = zero G tells nothing about reaction rate

G is a state function
Depends only on
initial state and final state

G = G final state G initial state For a chemical reaction, with a sequential steps, G of the reaction equals the sum of Gs of the individual steps. A B C GAB = GB - GA GBC = GC- GB GC GA = GAC

G is a state function
Is not affected by the mechanism of the reaction Combustion of glucose in calorimeter Glucose + O2 CO2 + H2O G = - 680 kcal/mol

In the cell Glucose CO2 + H2O G = - 680 kcal/mol

G is affected by concentration
A
A
A
B

G = - - G = G = zero G = ++

G measures the tendency of the reaction to proceed towards equilibrium

Standard free energy change Go

Concentrations of reactants and products = 1 mole/L G= Go + RT ln
[Products] [Reactants]

Standard free energy change Go and equilibrium constant Keq

Keq is obtained by dividing [product] by [reactants] when the reaction reaches equilibrium Keq = [Reactants] At equilibrium G = 0
[Products]

Exergonic reactions Gprod. < G react.

G = Gprod. Greact.

Spontaneous reaction

Endergonic reactions Gprod. > G react. G = Gprod. Greact. non Spontaneous reaction

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Standard free energy change Go and equilibrium constant Keq

G= Go + RT ln
[Products] [Reactants]
[Products] [Reactants

At equilibrium G =0

=Keq

0 = Go + RT ln Keq Go = - RT ln Keq

Go and equilibrium constant Keq

G= Go + RT 2.3 log
[Products] [Reactants]

At standard conditions G= Go + RT 2.3 log 1

G= Go

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Glucose 6- phosphate 0.66 mol/L

Fructose 6- phosphate 0.33 mol/L

G= Go + RT 2.3 log 0.33/ 0.66

Go = + 0.4 kcal/mol

Glucose 6- phosphate

Fructose 6- phosphate

Go = + 0.4 kcal/mol

G= Go + RT 2.3 log 0.09/0.9

G= - 0.96

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Glucose 6- phosphate 1 mol/L

Fructose 6- phosphate 1 mol/L G= Go + RT 2.3 log 1/1

G= Go

G and Keq
Keq 1 101 102 103 10-1 10-2 10-3 G 0 - 1.36 - 2.72 - 4.08 1.36 2.72 4.08 If Keq < 1, then G > 0 If Keq > 1, then G < 0 If Keq = 1, then G = 0

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Exergonic reactions in Biochemistry

Complex structures simple structures
amino acids n glucose CO2 + H2O Proteins Starch glucose + O2

More specifically
Hydrolysis reactions Decarboxylation reactions (release of CO2 ) pyruvate ( C3 ) acetyl- (C2) +CO2 Oxidation with O2

How can Endergonic reactions proceed?

Endergonic reaction can be driven by an exergonic reaction if the two can be coupled

A B

G = + 5 kcal/mol

C D G = - 9 kcal/mol When the two are coupled A+CB+D

G = - 4 kcal/mol

A+CIB+D

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Illustration of coupling an exergonic process with an endergonic one

Endergonic and exergonic reactions are indirectly coupled through ATP/ ADP cycle
ATP + H2O ADP + Pi

ADP ATP

+ Pi + H2O

G = - 7.3 G = + 7.3 G = - ? 2.3

ATP

ADP + Pi

? G = -1.7

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Energy released in exergonic reactions

Heat

Chemical energy in the products of endergonic reactions

Adenine + ribose

adenosine

+ 3 phosphate

ATP

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G for hydrolysis of some phosphorylated compounds

Compound +H2O Phosphoenol pyruvate Product + phosphate Pyruvate

G
-14.8 -11.8 - 10.3 - 7.3 -5.0 -3.3

1,3 bisphosphoglycerate 3 phosphoglycerate Creatine phosphate ATP Glucose 1- phosphate Glucose 6- phosphate Creatine ADP Glucose Glucose

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Phosphorylation of glucose
Glucose + Pi ATP Glc. 6 P + H20
G= +3.3

+ H2O ADP + Pi

G = -7.3

Glucose + ATP Glc. 6 P + ADP G = -4.0

CO2

O2

ATP is not a long term storage form of energy

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Approximate glucose uptake and ATP turnover by various tissues

Tissue
Approximate O2 consumption mole/ day

Equivalent glucose mole/ day

ATP turnover mole/day

Brain Heart Kidney Liver Muscle Total

3.4 1.9 2.9 3.6 3.3

0.57 0.32 0.49 0.6 0.54

20.4 11.4 17.4 21.6 19.8

15.1 2.52 Based on O2 consumption

90.6

Assuming glucose is the fuel use C6H12O6 + 6O2 6CO2 + 6H2O + 36ATP

Caloric value and free energy changes for complete oxidation of some fuels
Glucose + O2 Compound Glucose Palmitate Glycine

CO2 + H2O 686 kcal/mole Molecular weight 180 256 75 Caloric value 3.8 9.3 3.1

G kcal/mol 686 2380 234

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