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Bioenergetics High energy compounds- yields -7 to -15

H- represents Enthalpy kcal/mol upon hydrolyzing bonds


S- represents Entropy (randomness) Low energy compounds- yields greater* than -
Gibbs free energy (G)- amount of free energy 7 kcal/mol (*mas mathematically correct yung
available at anytime greater kasi as we get closer to zero, the value
G - determines EXTENT and amount of WORK goes up.)
done
G Sponteneity Release of Energy/ Heat 5 IMPORTANT HIGH ENERGY COMPOUNDS
-G Spontaneous Exergonic/ Exothermic Phosphoenolpyruvate (PEP)
+G Non- Endergonic/Endothermic Carboxylase Phosphate
spontaneous 1,3-Bisphosphoglycerate (1,3-BPG or 3-PG)
Creatine Phosphate
Mnemonic: NegaSponEx (Negative value,
ATP
Spontaneous, Exothermic/Exergonic)
Significance:
Biological Oxidation
A negative G LOSS of ENERGY, this energy is
- Biological production of energy
RELEASED as HEAT, meaning it is FAVORABLE
- 3 ways (from most common to least
for FORMATION OF PRODUCTS, and is more
common)
likely to OCCUR ON ITS OWN. (Spontaneous ito
o Remove e-
kasi kusa siyang nangyayari. Kaya siya negative
o Remove Hydrogen
kasi siya yung nagbigay.)
o Add Oxygen

A positive G- ABSORPTION of ENERGY, needs


(Opposite lang nito ung Reduction, add e-, add
an addition of energy for work to be done, NOT
Hydrogen and remove oxygen)
likely to OCCUR ON ITS OWN, TAKES UP HEAT.
LEORA- loss of e-, Oxidized, Reducing
(Kaya siya non-spontaneous, kailangan ng taga-
Agent
push. Positive naman to kasi tumanggap siya.)
GEROA- gain of e-, Reduced, Oxidizing
Agent
A G of 0 means the system is in equilibrium
H has the lowest redox potential
and both formation of reactants (backward
O has the highest redox potential (1/2
reaction) and production of products (forward
O2 is the FINAL ELECTRON ACCEPTOR
reaction) is equal.
due to this reason.)

Additive property
Electron Carriers
Simply put, a reaction with a + G, needs a
G that can overcome it so it will push the
NAD+/ NADP+ Hydride ion (H bearing
reaction towards the formation of products.
2 e-)
(Kailangan ng negative sum of G to push a FAD/FMN Direct e- (1e-)
reaction forwards. Kung inadd mo tapos CoEnzymeQ Direct e- (1 or 2 e-)
positive pa din, kulang yun to push the reaction. Fe-S and Cytochromes Direct 1 e-
Ginagamit ng + G yung ni-rerelease na energy
ng mga G.)

KLCB A 2019
Oxidative Phosphorylation
Substrate Level Oxidative Reducing equivalent- electron equivalent of one
Direct cleavage of Membrane bound proton
bonds (ATPADP + Pi) enzymes and
gradients of protons
Soluble enzymes and Oxidation of
chemical substrates in ETC
intermediates

Summary of ETC
Complex I *Complex II Complex III Complex IV
Enzyme NADH Succinate Cytochrome bc1 Cytochrome
dehydrogenase dehydrogenase complex (aka oxidase
(aka (only membrane Ubiquinone:Cytochrome
NADH:Ubiquinone bound enzyme in c oxidoreductase)
oxidoreductase) the TCA cycle)
Reaction Oxidation of NADH Oxidation of Oxidation of QH2 to Q Oxidation of 2
to NAD+ FADH2 to FAD+ mol Cyt c1
Reduction of 2 mol Cyt
Reduction of Q to c1 Formation of
QH2 water (1/2 O2 +
2H H2O)
H+ pumped into 4H+ - 4H+ 2H+
intermembrane
space
*FADH2 starts from Complex II only.
Recommend to watch: https://www.youtube.com/watch?v=vZz-KLK-X40 (very simple yet easily
understood explanation of the ETC)

ATP Synthesis
Mitchells Chemiosmotic Model
ATP Synthase- proton pore where protons pumped into the intermembrane space diffuses back to the
matrix
Parts of ATP Synthase:
F0- inner membrane portion, forms the pore
F1- headpiece projected toward the matrix
the subunit of the F1 contains the site for ATP synthesis

Proton-motive force- since protons are pumped out in the ETC, their concentration is higher in the
intermembrane space making it more positive, therefore, the protons move passively across their
concentration gradient.

Conversion factor: 4H+ translocated through the ATP Synthase = 1 ATP


Therefore, 1 mol NADH = 2.5 ATP and 1 mol FADH2 = 1.5 ATP

KLCB A 2019
ATP Regulation
Mass action ratio of ATP-ADP System- during energy-requiring processes, more ATP is broken down to
ADP and Pi, the rate of respiration increases because more ADP are available for phosphorylation.
(Also during energy-requiring processes, glycolysis, TCA and pyruvate oxidation increases to increase
the production of NADH and FADH2 to increase the e- entering the ETC, thereby increasing ATP
production)
High mass action ratio -> slow respiration
Low mass action ratio-> fast respiration
ATP is only generated as fast as it is needed.
Low Mass Action Ratio High Mass Action Ratio
During energy consuming activities Normal
More ADP More ATP
Fast respiration Slow Respiration
*the above will return the mass action ratio to
high and will stop producing ATP

Agents that interfere with Oxidative Phosphorylation

Interference Compound MOA


Inh e- transfer CN Inh cytochrome oxidase
CO
Rotenore Inh transfer of e- from Fe-S to Q
Amytal (Complex I)
Piericidin A
Inh ATP Synthase Oligomycin Inh F0 and F1
Uncoupling of phosphorylation FCCP Hydrophobic protein carriers
from e- transfer DNP (dinitrophenol)
Valinomycin
Inh ADP-ATP exchange Atractyloside Inh adenine nucleotide
translocase

Thermogenin- present in brown fat, uncoupling agent


-produces heat (sabi ni doc short circuit.)

Recommend to watch: https://www.youtube.com/watch?v=BHZhUbeI8FQ (simple explanation of


poisons and thermogenin)

KLCB A 2019

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