Redox reactions are crucial for harvesting chemical energy from fuels.
Cellular Respiration:
Reaction: C6H12O6 + 6O2 → 6CO2 + 6H2O
Free energy change (ΔG) = -686 kcal/mol
Glucose and organic molecules are oxidized during cellular respiration.
Oxygen (O2) functions as an electron acceptor and gets reduced.
Reaction: C6H12O6 + 6O2 → 6CO2 + 6H2O + Energy
Oxidation and Reduction:
Glucose gets oxidized while oxygen gets reduced.
Oxygen is a powerful oxidizing agent.
Energy needs to be released slowly and controlled for effective capture.
Reaction: C6H12O6 + 6O2 → 6CO2 + 6H2O involves multiple enzyme-mediated steps in glycolysis and the citric acid cycle.
Phosphorylation Process:
An enzyme transfers a phosphate group from a substrate to ADP, forming ATP.
Reaction: substrate-P + ADP → substrate + ATP
This is a slow reaction.
Electron Carrier Molecules transfer H+ and e-:
Catalyzed by dehydrogenases.
Reactions for carriers:
NAD+ + H+ + 2e- → NADH (stores energy for later ATP production)
FAD + 2H+ + 2e- → FADH2.
Electrons carried by NADH and FADH2 enter the electron transport chain.
Redox reactions occur, releasing energy in small amounts.
Controlled energy release is essential for ATP production.
Overview of Respiration:
Glycolysis: initial breakdown of glucose.
Citric Acid Cycle: completes the breakdown of glucose.
Oxidative Phosphorylation: final ATP synthesis stage.
Energy Investment Phase:
Uses 2 ATP.
Energy Payoff Phase:
Produces 4 ATP through substrate-level phosphorylation and generates 2 NADH.
Net Gain: 4 ATP produced - 2 ATP used = 2 ATP net gain.
Key Enzymes and Intermediates in Glycolysis:
Hexokinase, Phosphofructokinase, Pyruvate Kinase, Glyceraldehyde 3-phosphate Dehydrogenase, etc.
Process includes: conversion of glucose to glucose-6-phosphate, fructose-6-phosphate, and ultimately pyruvate.
If oxygen is present: Pyruvate enters mitochondria for further processing.
If oxygen is absent: Pyruvate undergoes fermentation:
Reduced to lactic acid or ethanol.
This process regenerates NAD+.
Process of Alcoholic Fermentation:
Releases CO2 from pyruvate, produces acetaldehyde.
Acetaldehyde gets reduced, moving electrons from NADH to form ethanol and regenerate NAD+.
No ATP is produced during fermentation, but NAD+ allows glycolysis to continue.
Lactic Acid Fermentation:
Pyruvate is directly reduced from NADH.
Produces NAD+ and lactate (lactic acid).
Like alcoholic fermentation, no ATP is made, but NAD+ allows continued glycolysis.
At the conclusion of glycolysis:
Yield: 2 ATP, 2 NADH, and 2 Pyruvate.
ATP can be utilized immediately; NADH and pyruvate are transported into the mitochondria for further processing.
Pyruvate must be converted into acetyl CoA to enter the citric acid cycle.
Catalyzed by the enzyme pyruvate dehydrogenase.
For each pyruvate, products are: 1 CO2, 1 NADH, and 1 acetyl CoA.
Key Steps in the Citric Acid Cycle:
Enzymes include citrate synthase, aconitase, isocitrate dehydrogenase, and others.
Cycle includes conversion of acetate to citrate and follows further reactions to produce CO2, NADH, and FADH2.
Components of ETC:
4 protein complexes in the inner mitochondrial membrane.
Electrons are transferred from one protein complex to another.
The released energy from these transfers is utilized to pump H+ ions into the intermembrane space.
Carrier Molecules involved in ETC:
Cytochromes: proteins containing iron heme group.
Ubiquinone (Q): hydrophobic electron carrier, shuttles electrons between complexes in the electron transport chain.
Each protein and carrier in ETC alternates between:
Reduced State: Accepts electrons.
Oxidized State: Donates electrons.
Energy is released in each redox reaction.
Detailed functions of complex interactions:
Complex I: receives 2 e- from NADH, pumps H+ into the intermembrane space.
Complex II: receives 2 e- from FADH2, does not pump.
Complex III: receives e- from Complexes I and II, pumps H+.
Complex IV: receives e- from Complex III, pumps H+.
Complex IV: Transfers e- to O2, producing water.
Reaction: 4H+ + 4e- + O2 → 2H2O.
ATP Generation: Not produced directly by the electron transport chain.
Instead, a H+ gradient is established (High [H+] vs Low [H+]).
Mechanism of ATP synthesis:
Chemiosmosis: uses the flow of H+ ions to drive ATP synthesis.
ATP Synthase: enzyme that turns as H+ flows, activating catalytic sites to convert ADP + P into ATP.
Ideally produces 32-34 ATP per glucose.
Under normal cellular conditions, realistically produces about 26-28 ATP per glucose molecule.
Overall Reaction: C6H12O6 + 6O2 → 6CO2 + 6H2O
Glucose is utilized in glycolysis and the citric acid cycle.
CO2 released during the citric acid cycle; O2 consumed and water produced in the electron transport chain.
In anaerobic conditions, the citric acid cycle stops since O2 is not available.
Cells can utilize various fuel sources:
Amino Acids: modified after removing the amino group to enter the citric acid cycle.
Glycerol: converted to G3P, can be broken down or synthesized into glucose.
Fatty Acids: undergo beta oxidation to be broken into acetyl CoA.
Feedback Inhibition is used to modulate the rate of cellular respiration:
Low levels of ATP lead to an increased rate of cellular respiration.
High levels of ATP result in a decreased rate of cellular respiration.
This mechanism prevents unnecessary energy expenditure when ATP is abundant.