Bioenergetics: Role of ATP
Biomedical Importance
• Bioenergetics or biochemical thermodynamics is the study of energy
changes in biochemical reactions.
• Biologic systems are isothermic and use chemical energy.
• The process of obtain fuel from food is essential in understanding
nutrition and metabolism.
• Starvation occurs when energy reserves are depleted.
• Malnutrition is energy imbalance or deficiency.
• Obesity on the other hand, is excess of energy which leads to CVD,
DM2 and lower life expectancy.
Free Energy is the useful energy
• GF is that portion of energy change available for doing work.
• First Law of Thermodynamics states that the total energy of a system
is constant – neither lost nor gained, only transferred or transformed.
• In living systems, chemical energy can be transformed into heat,
electrical, radiant or mechanical energy.
Second Law of Thermodynamics states that total entropy of a
systems must increase or occur spontaneously.
Free Energy is the useful energy
• Entropy is the extent of disorder and is maximum at equilibrium.
• H is enthalpy
• T is Temp
• In biochemical reactions, H approximates the total internal energy of
reaction E.
Free Energy is the useful energy
• If G is negative, the reaction is spontaneous with loss of free energy.
This reaction is exergonic.
• When the reaction has very large G, the reaction goes to completion
and is essentially irreversible.
• If G is positive, reaction proceeds if energy is gained. This reaction is
endergonic.
• When the reaction has very large G, the reaction is stable with almost
no product formed.
• If G is zero, the system is in equilibrium.
Free Energy is the useful energy
• G0 is the free-energy when reactions are present at 1.0 mol/L
concentrations.
• Biochemical reactions have a standard state at pH of 7.0.
• Standard free-energy can be calculated from the equilibrium constant
Keq.
• Actual G can be larger or smaller depending on concentrations of
reactants.
Endergonic Processes Proceed by Coupling to
Exergonic Processes
• Vital processes in the body obtain energy by coupling to oxidative
reactions.
Endergonic Processes Proceed by Coupling to
Exergonic Processes
• The terms exergonic and endergonic are used to denoted that there is
a loss or gain of energy, not necessarily heat.
• Endergonic processes cannot exist independently and must be
coupled with exergonic systems.
• Exergonic reactions are termed catabolism while those that build up
substances are called anabolism.
• Metabolism is the combination of the two.
Endergonic Processes Proceed by Coupling to
Exergonic Processes
• Reactions in biologic systems are coupled by having a common
obligatory intermediate.
• The intermediate I controls the rate of oxidation by allowing the rate
of utilization of D determined by the rate of oxidation of A.
• This is the basis of respiratory control which prevents an organism
from burning out of control.
Endergonic Processes Proceed by Coupling to
Exergonic Processes
Endergonic Processes Proceed by Coupling to
Exergonic Processes
• Another method of coupling involves synthesizing a high-energy
compound during the exergonic reaction and incorporate into the
endergonic reaction.
• The advantage of this is that the high-energy compound need not be
structurally related to the reactions or products.
• This allows the high-energy compound to serve as a transducer of
energy from a wide range of reactions.
• In cells, the principal high-energy compound is ATP.
High-Energy Phosphates Play a Central Role in
Energy Capture and Transfer
• Autotrophs utilize exergonic processes such as sunlight and
conversion of ferrous to ferric ions.
• Heterotrophs obtain energy by coupling their metabolism to the
breakdown of complex organic molecules.
• ATP is central in the transference of energy.
The Intermediate Value for the Free Energy of
Hydrolysis of ATP
• The group transfer potential is the tendency of each phosphate
group to transfer to a suitable acceptor which is obtained from the G0
of hydrolysis at 37oC.
• Low energy phosphate have low potential and includes intermediates
of hydrolysis.
• High energy phosphates high more negative G0 with a value higher
than ATP. This group includes anhydrides, enol phosphates and
phosphoguanidines.
The Intermediate Value for the Free Energy of
Hydrolysis of ATP
• ATP has high energy phosphoanhydride
bonds present in the phosphate groups.
• ATP is hydrolyzed to ADP + P in or AMP +
PP in more energy demanding reactions.
The Intermediate Value for the Free Energy of
Hydrolysis of ATP
• The high energy of ATP on hydrolysis is due to the relief of charge
repulsion of adjacent negatively charge oxygen as well as stabilization
of the reaction products as resonance hybrids.
• Other high energy compounds:
• Acetyl-CoA
• Acyl carrier protein
• Amino acid esters in protein synthesis
• S-adenosylmethionine
• Uridine diphosphate glucose (UDPGlc)
• 5-phosphoribosyl-1-pyrophosphate (PRPP)
ATP as Energy Currency of the Cell
• High group transfer potential.
• ADP can reform to ATP to maintain the energy
reserve.
• Rapid ATP/ADP pool cycle.
ATP as Energy Currency of the Cell
• Major sources of Pi:
• Oxidative Phosphorylation – major source
• Glycolysis
• Citric Acid Cycle
• Phosphagens act as storage forms:
• Creatine phosphate - vertebrates
• Arginine Phosphate - invertebrates
• Phosphagens act as ATP source in rapid consumption of energy. It is
then replenished if ATP/ADP ratio is high.
• When ATP donates a phosphate, the donated group becomes a low
energy phosphate group.
ATP allows Coupling of Unfavorable Reactions
to Favorable Ones
• Endergonic processes require energy input to occur.
Adenylyl Kinase Interconverts Adenine
Nucleotides
• This is enzyme is important in energy homeostasis:
• Allows ADP maintenance
• Extracts more anergy from AMP
• Allows AMP formation as a signal to increase catabolic reactions and in turn
generate more ATP
Inorganic Pyrophophate from AMP formation
• Accompanied by heat which ensures the process will proceed to the
right.
• Inorganic pyrophosphatase then splits PPi so that there are available
phosphate groups for adenine nucleotide conversion.
Other Nucleoside Triphosphates Participate in
Group Transfer
• Nucleoside Diphosphate (NDP) kinases allow synthesis of nucleoside
phosphates such as UTP, GTP and CTP.
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