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Redox reactions release energy when electrons move closer to electronegative atoms
Relocation of electrons releases energy in food, and this becomes ATP. Redox reactions Reactions with electron transfers. Oxidation Loss of electrons from one substance. Reduction Addition of electrons to another substance. Reducing agent Electron donor Oxidizing agent Electron acceptor An electron transfer requires a donor and an acceptor, so the two always occur together Not all redox reactions completely transfer electrons. Some change the type of electron sharing. Oxygen is really electronegative, so it is a very potent oxidizing agent. Energy must be added to pull an electron away. The more electronegative an atom, the more energy is needed to move an atom away.
The fall of electrons during respiration is stepwise, via NAD+ and an electron transport chain
Release of energy from fuel is difficult to harness efficiently. Cellular respiration doesnt oxidize glucose all at once. Glucose and other fuels are broken down gradually in a series of enzyme-catalyzed steps. NAD+ - Nicotinamide adenine dinucleotide Acceptor of hydrogens. At key steps, hydrogens are taken from glucose, but not directly given to oxygen, but given to NAD+ first. Dehydrogenases remove hydrogens from something, removing two protons and two electrons. Two electrons and one proton are given to NAD+. The other proton is released as a free hydrogen ion. NAD+ - Oxidized form, is positive. NADH is neutral because it got two negative electrons but only one positive proton. NAD+ is an electron acceptor, an oxidizing agent. This is the most versatile acceptor. Each NADH represents stored energy that can be trapped to make ATP when electrons fall from NADH to oxygen. Cellular respiration brings hydrogen and oxygen together to form water but in a special way. Hydrogen that reacts with oxygen is from molecules besides H2. Electron transport chain Used by respiration to break the fall of electrons to oxygen into several energy releasing steps. Instead of an explosion.
Consists of many molecules, mostly proteins, built into the insides of the mitochondrion. Electrons cascade downwards from one carrier to the next until they go to oxygen, the terminal electron acceptor. Each carrier is more electronegative than its uphill neighbor.
1. Glycolysis 2. The Krebs cycle 3. The electron transport chain and oxidative phosphorylation.
The first two steps are catabolic pathways that decompose glucose Glycolysis Begins degradation by breaking glucose into two pyruvates. In cytosol. Krebs cycle Decomposes derivative of pyruvate to carbon dioxide. Carbon dioxide represents fragmented organic molecules. Some steps are redox reactions that for NADH. Third step of respiration, electron transport chain accepts electrons from the earlier stages, and passes these from one molecule to another. At the end, these form water The energy released at each step is stored to form ATP. Oxidative phosphorylation This mode of ATP synthesis powered by redox reactions that process electrons. Accounts for almost .9 of ATP generated by respiration. Site of electron transport and oxidative phosphorylation is inner membrane of mitochondrion. Substrate-level phosphorylation Generates a small amount of ATP in glycolysis and the Krebs cycle. Occurs when an enzyme transfers phosphate from a substrate molecule to ADP. Substrate molecule is an organic molecule generated during catabolism of glucose. For each molecule of glucose degraded, about 38 ATP molecules are made.
The Krebs cycle completes the energy-yielding oxidation of organic molecules A closer look
Glycolysis releases less than 0.25 of the energy stored in glucose. Most remains in the pyruvate.
If oxygen is present, the pyruvate goes to the mitochondrion, where Krebs enzymes complete oxidation. Acetyl CoA Acetyl coenzyme A. Pyruvate is converted to this when it enters the mitochondrion. 1. Pyruvates oxidized carboxyl group is removed and released as CO2. 2. Remaining two carbon fragment is oxidized to form acetate. Extracted electrons forms another NADH. 3. Coenzyme A, a sulfur compound is attached to acetate in an unstable bond. Acetyl CoA is ready to go to Krebs cycle. Hands Krebs Namesake. Found most of it in 1930s. In the Krebs cycle, two carbons enter from acetate and leave in the from of CO2. Acetate joins the cycle by being joined to oxaloacetate, forming citrate. The citrate is decomposed, giving off CO2. Oxaloacetate regeneration is where the cycle comes from. Most energy harvested here is conserved in NADH. For each acetate, three NAD+ are reduced. At one point, electrons go to FAD, flavin adenine dinucleotide. At another point, ATP is formed directly. 1. Acetyl CoA adds two carbons to oxaloacetate, producing citrate. 2. Citrate is converted to an isomer by removal of one water and adding another. 3. Citrate loses one CO2, and the compound is oxidized, reducing one NAD+. 4. Another CO2 is lost, and the compound is oxidized again forming another NADH. 5. CoA is displaced by a phosphate, which is transferred to a GDP, forming GTP, then to ADP, forming an ATP in substrate-level phosphorylation. 6. Two hydrogens are transferred from FAD to FADH2 7. Addition of a water molecule rearranges bonds. 8. The substrate is oxidized, reducing NAD+ to NADH and regenerating oxaloacetate.
The inner mitochondrial membrane couples electron transport to ATP synthesis A closer look
Metabolic components of respiration produce only four molecules of ATP per glucose, all by substrate-level phosphorylation. NADH and FADH2 account for most extracted energy at this point. Electron Transport Collection of molecules embedded in inner membrane of mitochondrion. Folding increases surface area so thousands of chains can function. Most parts are proteins. Tightly bound to proteins Prosthetic groups. Essential to some catalytic functions. During transport, prosthetic groups alternate between reduced and oxidized states as they work with electrons. As electrons drop down the chain, free energy drops too. Electrons removed from food are transferred to NADH in the first molecule, a flavoprotein. Then, a flavroprotein returns to its oxidized form as it passes electrons to an iron-sulfur protein. Electrons then passed to ubiquinone, a lipid. Cytochromes (cyt) Most of the remaining electron carriers. Proteins. Prosthetic group, heme group, four organic rings around a single iron atom. Several different cytochromes in the chain, with different hemes. The last cytochrome, cyt a3 passes electrons to oxygen, which picks up hydrogen ions to form water. For two NADH molecules, one O2 is reduced to two molecules of water. Another sources of electrons is FADH2, adds electrons at a lower energy level. Provides about one third less energy for ATP synthesis.
ATP synthase Protein complex that actually makes ATP. Works like a reverse ion pump.
Ion pump would use ATP as an energy source to transport ions ATP uses energy of an ion gradient to power ATP synthesis. Driven by a proton/hydrogen ion gradient. How is the H+ gradient maintained? The electron transport chain does it. The chain is an energy converter that uses the exergonic flow of electrons to pump H+ into the membrane. The H+ leaks back into the intermembrane space, but only through the ATP synthases. Chemiosmosis The coupling mechanism where the H+ gradient is coupled with the redox reaction. Certain members of the electron transport chain accept and release protons along with electrons. Transfers cause H+ to be taken up and released. Arranged in such a way so that H+ is taken from the mitochondrial matrix and deposited in the inter-membrane space. Proton-motive force The H+ gradient. Emphasizing capacity of gradient to perform work. ATP synthase is a multi-subunit complex with four name parts Rotor, knob, internal rob, stator. Hydrogens flow between stator and rotor, causing rotor and rod to rotate. This activates catalytic sites where ATP is formed. Chemiosmosis is an energy-coupling mechanism that uses energy stored in H+ gradient across a membrane to drive cellular work. Chemiosmosis occurs elsewhere Chloroplasts, where light drives electron flow and gradient formation.
Cellular respiration generates many ATP molecules for each sugar molecule it oxidizes A review
Energy flows like this. Glucose to NADH to Electron transport chain to Proton-motive force to ATP. We can calculate the ATP produced in glycolysis, Krebs cycle and electron transport chain. Each NADH that transfers electrons to the transport chain contributes enough to yield about three ATPs. The average is really 2-3. FADH is worth a maximum of two molecules. Sometimes, NADH is produced by glycolysis in cytosol, and must be conveyed inside.
We can assume a maximum of 34 ATP produced to the net of 4 ATP from substrate-level phosphorylation for 38. This estimate is probably a bit high.
About 40% efficiency. The rest is lost as heat.
Fermentation enables some cells to produce ATP without the help of oxygen.
Oxidation is the loss of electrons to any acceptor. The oxidizing agent of glycolysis is NAD+. The process is also exergonic, so some of the energy produces two net ATPs. Aerobic/Anaerobic Whether oxygen is present or not. Glycolysis generates two ATPs regardless of oxygen. Anaerobic catabolism of nutrients can occur through fermentation. Extension of glycolysis that can generate ATP as long as there is NAD+. NAD+ is recycled in this case by transferring electrons from NADH to pyruvate. Fermentation is glycolysis plus NAD+ generating reactions by transferring electrons from NADH. Alcohol fermentation Pyruvate is converted to ethanol. First, carbon dioxide is released from pyruvate, which is converted to acetaldehyde. Then, acetaldehyde is reduced by NADH to ethanol, regenerating the NAD+ needed for glycolysis. Bacteria do this. Thats how we get yeast to make beer. Lactic acid fermentation Pyruvate is directly reduced by NADH to form lactate as a waste product without CO2 release. Used to make cheese and yoghurt. Human cells make ATP with lactic acid fermentation, like during strenuous exercise when there is not enough oxygen. Lactate accumulating causes fatigue and pain, but is gradually carried to the liver and converted back to pyruvate.
Respiration yields 19 times ATP. Facultative anaerobes Species that make enough ATP to survive by fermentation or respiration alone.
Our muscle cells do this.
Glycolysis and the Krebs cycle connect to many other metabolic pathways
Versatility of Catabolism Free glucose molecules are not common in diets. Most of our calories come from fats, proteins and saccharides. All of these can form ATP. Glycolysis can accept a wide range of carbohydrates. In digestive tract, starch becomes glucose. Glycogen can by hydrolyzed to glucose. Proteins can be used too, but must be broken into amino acids. Most are used to build new proteins. Amino acids in excess are converted to intermediates of glycolysis and amino groups are removed in deamination. Nitrogenous refuse is excreted in ammonia based urea. Catabolism can also harvest energy in fats. Glycerol is converted to an intermediate of glycolysis. Most energy stored in fatty acids. Beta oxidation Breaks fatty acids into two carbon fragments that can become acetyl CoA. Great fuel Twice as good as carbohydrate. Also means dieting is slow.