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Chapter 7 – Cellular Pathways that Harvest Chemical Energy Oxidation and Reduction Reactions A.e B A B.e An oxidation reaction involves the transfer of an electron from one compound to another. In this case, A loses an electron to B (small arrow indicates electron path). Thus, A is oxidized (loses electron) while B is reduced (gains electron). The molecule that accepts an electron is called the oxidizing agent while the molecule that donates the electron is called the reducing agent. The oxidation of a molecule releases energy while the reduction of a molecule stores energy. Since these reactions are coupled, the energy released in the oxidation is transferred to and stored by the reduced molecule. In metabolism, NAD+ and FAD are the oxidizing agents; then later NADH and FADH2 become the reducing agents. Stages of Respiration 1. glycolysis – 6C glucose converted to two 3C pyruvates 2. pyruvate converted to two CO2 molecules and two 2C sugars 3. citric acid cycle - 2C sugars added to oxaloacteate to form two 6C sugars, converted to 4 CO2 4. electron transport chain – electron carriers pass electrons to electron transport chain to make ATP Glycolysis The first five steps are: G3P ATP G DAP + G3P FBP ATP F6P G6P Glucose Time The first 5 steps of glycolysis require the input of energy in the form of 2 ATPs. Thus, these steps are endergonic and have a positive ∆G. The next five steps of glycolysis are exergonic. These steps produce 4 ATP, 2 NADH, 2 H+, and 2 H2O molecules per molecule of glucose. These steps also require the input of NAD+, Pi, and ADP. If any of these molecules are in short supply, the process stops. 2NAD+ + 2Pi 2 ADP 2 G3P 2 BPG G 2 3PG 2ADP 2 2PG 2 PEP 2NADH + 2H+ 2 Pyruvate 2ATP 2H2O Time 2ATP The net production of ATP by glycolysis is two: 4 ATP are produced and 2 ATP are used up. If cells are short on oxygen, and thus cannot go through the electron transport chain, they will speed up glycolysis in order to utilize the ATP it can produce. However, this is not very efficient because most of the energy in the glucose molecule is not harvested. Glycolysis occurs in the cytosol of the cell. The citric acid cycle and the electron transport chain occur in the mitochondria. In order to convert the NADH produced in glycolysis to ATP, the NADH needs to be transported into the mitochondria. This transport requires energy, so 1 ATP molecule is used up per NADH transported. This is energetically efficient because each NADH generates 3 ATP. Thus, for the two NADHs transported, a net of 2 ATP are produced. 2 NAD+ 2 Coenzyme A 2 Pyruvate Acetyl-CoA 2 NADH 2 CO2 The pyruvate produced in glycolysis is transported into the mitochondria matrix. Each pyruvate is oxidized to form one NADH and then is joined to coenzyme A to form acetylCoA. Depending on the energy needs of the cell, acetyl-CoA enters the citric acid cycle or is converted into fat for energy storage. Citric Acid Cycle The citric acid cycle occurs in the mitochondrial matrix. The two carbon acetyl-CoA is added to the four carbon oxaloactate to form the six carbon molecule citric acid. In the series of reactions that follow, the compound loses two carbon atoms to CO2, forms three NADH molecules and one FADH2 molecule, as well as one molecule of GTP. (Remember this is per pyruvate molecule. You need to double this to get the number per glucose!) The remainder of the cycle is dedicated to rearranging the atoms to regenerate oxaloacetate to allow the cycle to continue. Note that the two carbons that entered the cycle in acetyl-CoA are not the two carbons that form CO2. The carbons exiting the cyle came from the oxaloacetate molecule. (multiply each quantity by 2) Acetyl-CoA NADH OXAL CIT NAD+ MAL ISO H2O NAD+ FUM αKG NADH + CO2 CoA FADH2 NAD+ SUC SCA FAD GTP NADH + CO2 GTP + Pi Electron Transport Chain The electron transport chain occurs on the inner mitochondrial matrix. There, NADH and FADH2 pass their electrons to the embedded carriers. The electron is then passed down the series of cytochromes (yellow and blue), each one having a lower G than the one before it. Because of this change in G, the energy produced is used to pump hydrogen ions from the matrix to the intermembrane space. This creates an electrochemical gradient across the inner mitochondrial membrane; with the intermembrane space having a higher concentration of hydrogen ions. Oxygen accepts the electron from the final cytochrome in the chain, and it is reduced to water. The hydrogen ions leak back into the matrix through ATP synthase (purple), which couples the energy produced by the ion movement to the formation of ATP from ADP and P. This coupling of energy from electron movement to a chemical gradient is called chemiosmosis. The processes of proton pumping and ATP synthesis are coupled yet separate. Review experiment on page 142 to see how this was determined. Outer mitochondrial membrane H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ H+ e- e- Intermembrane space Inner mitochondrial membrane e- eNADH NAD+ H+ H+ ATP H+ O2 ADP + P H20 Q. Could ATP be made if the one of the mitochondrial membranes was not intact? Metabolism We tend to focus on metabolism as the formation of ATP from glucose. This is really only half of the process because metabolism consists of the sum of the catabolic and anabolic reactions. Catabolic reactions are those that breakdown simple molecules to form ATP. Anabolic reactions are those that consume ATP to produce larger molecules. Q. Why do NADH and FADH2 not pass their electrons and the energy they carry directly to O2? Q. Where are each of the ATP, NADH, FADH2, and GTP molecules produced (where in cell)? Be sure to account for all of the molecules.