Pathways That Harvest Chemical Energy

7 Pathways That Harvest Chemical Energy 7.1 How Does Glucose Oxidation Release Chemical Energy? 7.2 What Are the Aerobic Pathways of Glucose Metabolism? 7.3 How Is Energy Harvested from Glucose in the Absence of Oxygen? 7.4 How Does the Oxidation of Glucose Form ATP? 7.5 Why Does Cellular Respiration Yield So Much More Energy Than Fermentation? 7.6 How Are Metabolic Pathways Interrelated and Controlled?

7.1 How Does Glucose Oxidation Release Chemical Energy? Fuels: molecules whose stored energy can be released for use. The most common fuel in organisms is glucose. Other molecules are first converted into glucose or other intermediate compounds.

7.1 How Does Glucose Oxidation Release Chemical Energy? Principles governing metabolic pathways: Complex chemical transformations occur in a series of reactions. Each reaction is catalyzed by a specific enzyme. Metabolic pathways are similar in all organisms. In eukaryotes, metabolic pathways are compartmentalized in organelles. Each pathway is regulated by key enzymes.

7.1 How Does Glucose Oxidation Release Chemical Energy? Burning or metabolism of glucose: Glucose metabolism pathway traps the free energy in ATP:

7.1 How Does Glucose Oxidation Release Chemical Energy? ΔG from complete combustion of glucose = –686 kcal/mole Highly exergonic; drives endergonic formation of many ATP

Three metabolic pathways involved in harvesting the energy of glucose Figure 7.1 Energy for Life Three metabolic pathways involved in harvesting the energy of glucose

7.1 How Does Glucose Oxidation Release Chemical Energy? If O2 is present, four pathways operate: Glycolysis, pyruvate oxidation, citric acid cycle, and electron transport chain. If O2 is not present, pyruvate is metabolized in fermentation.

Figure 7.2 Energy-Producing Metabolic Pathways

7.1 How Does Glucose Oxidation Release Chemical Energy? Redox reactions: one substance transfers electrons to another substance Reduction: gain of one or more electrons by an atom, ion, or molecule Oxidation: loss of one or more electrons Also applies if hydrogen atoms are gained or lost.

7.1 How Does Glucose Oxidation Release Chemical Energy? Oxidation and reduction always occur together. The reactant that becomes reduced is the oxidizing agent. The reactant that becomes oxidized is the reducing agent.

Figure 7.3 Oxidation and Reduction Are Coupled

7.1 How Does Glucose Oxidation Release Chemical Energy? In combustion of glucose, glucose is the reducing agent, O2 is the oxidizing agent. Energy is transferred in a redox reaction. Energy in the reducing agent becomes associated with the reduced product.

7.1 How Does Glucose Oxidation Release Chemical Energy? Coenzyme NAD is an electron carrier in redox reactions. Two forms: NAD+ (oxidized) NADH + H+ (reduced)

Figure 7.4 NAD Is an Energy Carrier in Redox Reactions (A)

7.1 How Does Glucose Oxidation Release Chemical Energy? A hydride ion (H–) is transferred, leaving a free H+ H– : a proton with two electrons

Figure 7.4 NAD Is an Energy Carrier in Redox Reactions (B)

7.1 How Does Glucose Oxidation Release Chemical Energy? Oxygen accepts electrons from NADH: exergonic—ΔG = –52.4 kcal/mole Oxidizing agent is molecular oxygen—O2

7.2 What Are the Aerobic Pathways of Glucose Metabolism? Glycolysis takes place in the cytosol. Involves 10 enzyme-catalyzed reactions Results in: 2 molecules of pyruvate 4 molecules ATP 2 molecules NADH

Figure 7.5 Glycolysis Converts Glucose into Pyruvate (Part 1) probably 4 parts?

Figure 7.5 Glycolysis Converts Glucose into Pyruvate (Part 2) probably 4 parts?

Figure 7.5 Glycolysis Converts Glucose into Pyruvate (Part 3) probably 4 parts?

Figure 7.5 Glycolysis Converts Glucose into Pyruvate (Part 4) probably 4 parts?

Figure 7.5 Glycolysis Converts Glucose into Pyruvate (Part 5) probably 4 parts?

Figure 7.5 Glycolysis Converts Glucose into Pyruvate (Part 6) probably 4 parts?

7.2 What Are the Aerobic Pathways of Glucose Metabolism? A kinase is an enzyme that catalyzes transfer of a phosphate group from ATP to another substrate. In the first half of glycolysis, the glucose molecule is split into two 3-carbon molecules (G3P).

7.2 What Are the Aerobic Pathways of Glucose Metabolism? Phosphorylation: addition of a phosphate group Enzyme-catalyzed transfer of a phosphate group to ADP is called substrate-level phosphorylation.

Figure 7.6 Changes in Free Energy During Glycolysis

7.2 What Are the Aerobic Pathways of Glucose Metabolism? Pyruvate Oxidation: Links glycolysis and the citric acid cycle Pyruvate is converted to acetyl CoA Takes place in the mitochondrial matrix

1st part – pyruvate oxidation Figure 7.8 Pyruvate Oxidation and the Citric Acid Cycle (Part 1) 1st part – pyruvate oxidation

7.2 What Are the Aerobic Pathways of Glucose Metabolism? Acetyl CoA is the starting point of the citric acid cycle: Coenzyme A is removed in the first reaction and can be reused The cycle is in steady state: the concentrations of the intermediates don’t change Outputs: CO2, reduced electron carriers, and ATP

Figure 7.8 Pyruvate Oxidation and the Citric Acid Cycle (Part 2)

Figure 7.7 The Citric Acid Cycle Releases Much More Free Energy Than Glycolysis Does

7.2 What Are the Aerobic Pathways of Glucose Metabolism? The electron carriers that are reduced during the citric acid cycle must be reoxidized to take part in the cycle again. Fermentation—if no O2 is present Oxidative phosphorylation—O2 is present

7.3 How Is Energy Harvested from Glucose in the Absence of Oxygen? Fermentation occurs in the cytosol. Pyruvate is reduced by NADH + H+ and NAD+ is regenerated.

7.3 How Is Energy Harvested from Glucose in the Absence of Oxygen? Lactic acid fermentation: Occurs in microorganisms, some muscle cells. Pyruvate is the electron acceptor.

Figure 7.9 Lactic Acid Fermentation

7.3 How Is Energy Harvested from Glucose in the Absence of Oxygen? Alcoholic fermentation: Yeasts and some plant cells Pyruvate is converted to acetaldehyde, CO2 is released Acetaldehyde is reduced by NADH + H+, producing NAD+ and ethyl alcohol

Figure 7.10 Alcoholic Fermentation

7.4 How Does the Oxidation of Glucose Form ATP? Oxidative phosphorylation: ATP is synthesized as electron carriers are reoxidized in the presence of O2. Two stages: Electron transport chain Chemiosmosis

7.4 How Does the Oxidation of Glucose Form ATP? Why does the electron transport chain have so many steps? Why not in one step?

7.4 How Does the Oxidation of Glucose Form ATP? Too much free energy would be released all at once—it could not be harvested by the cell. In a series of reactions, each releases a small amount of energy that can be captured by an endergonic reaction.

7.4 How Does the Oxidation of Glucose Form ATP? The electron transport chain: On the inner mitochondrial membrane 4 protein complexes: I, II, III, IV Cytochrome c Ubiquinone (Q)—a lipid

Figure 7.11 The Oxidation of NADH + H+ (Part 1)

Figure 7.11 The Oxidation of NADH + H+ (Part 2)

Figure 7.12 The Complete Electron Transport Chain

7.4 How Does the Oxidation of Glucose Form ATP? The electron transport chain results in the active transport of protons (H+) across the inner mitochondrial membrane. The transmembrane complexes act as proton pumps.

Figure 7.13 A Chemiosmotic Mechanism Produces ATP (Part 1)

Figure 7.13 A Chemiosmotic Mechanism Produces ATP (Part 2)

7.4 How Does the Oxidation of Glucose Form ATP? The proton pump results in a proton concentration gradient and an electric charge difference across the inner membrane: potential energy! Proton-motive force

7.4 How Does the Oxidation of Glucose Form ATP? The protons must pass through a protein channel—ATP synthase—to flow back into the mitochondrial matrix. Chemiosmosis is the coupling of the proton-motive force and ATP synthesis.

7.4 How Does the Oxidation of Glucose Form ATP? ATP synthase allows protons to diffuse back to the mitochondrial matrix, and uses the energy of that diffusion to make ATP from ADP and Pi.

Figure 7.14 Two Experiments Demonstrate the Chemiosmotic Mechanism (Part 1)

Figure 7.14 Two Experiments Demonstrate the Chemiosmotic Mechanism (Part 2)

7.4 How Does the Oxidation of Glucose Form ATP? ATP synthesis can be uncoupled: if a different H+ diffusion channel is inserted into the mitochondrial membrane, the energy of the diffusion is lost as heat. The protein thermogenin occurs in human infants and hibernating animals.

7.4 How Does the Oxidation of Glucose Form ATP? ATP synthase: F0 subunit—transmembrane F1 subunit—projects into the mitochondrial matrix, rotates to expose active sites for ATP synthesis

Glycolysis and fermentation: 2 ATP 7.5 Why Does Cellular Respiration Yield So Much More Energy Than Fermentation? Energy yields: Glycolysis and fermentation: 2 ATP Glycolysis and cellular respiration: 32 ATP Fermentation by-products have a lot of energy remaining.

Figure 7.15 Cellular Respiration Yields More Energy Than Glycolysis Does (Part 1)

Figure 7.15 Cellular Respiration Yields More Energy Than Glycolysis Does (Part 2)

7.6 How Are Metabolic Pathways Interrelated and Controlled? Metabolic pathways are interrelated. Interchange of molecules occurs between the pathways.

7.6 How Are Metabolic Pathways Interrelated and Controlled? Catabolic interconversions: Polysaccharides → hydrolyzed to glucose, enters glycolysis Lipids broken down to glycerol → DAP fatty acids → acetyl CoA Proteins → hydrolyzed to amino acids— feed into glycolysis or the citric acid cycle at various points

Figure 7.16 Relationships among the Major Metabolic Pathways of the Cell

7.6 How Are Metabolic Pathways Interrelated and Controlled? Anabolic interconversions: Most catabolic reactions are reversible Gluconeogenesis: glucose from citric acid cycle and glycolysis intermediates

Figure 7.17 Coupling Metabolic Pathways

7.6 How Are Metabolic Pathways Interrelated and Controlled? Metabolic homeostasis: concentrations of the biochemical molecules remain constant (e.g., glucose concentration in blood) Allosteric control of enzymes in catabolic pathways Negative and positive feedback controls

Figure 7.18 Regulation by Negative and Positive Feedback

Figure 7.19 Allosteric Regulation of Glycolysis and the Citric Acid Cycle (Part 1)

Figure 7.19 Allosteric Regulation of Glycolysis and the Citric Acid Cycle (Part 2)

7.6 How Are Metabolic Pathways Interrelated and Controlled? The main control point in glycolysis is phosphofructokinase—allosterically inhibited by ATP. The main control point in the citric acid cycle is isocitrate dehydrogenase— inhibited by NADH + H+ and ATP.

7.6 How Are Metabolic Pathways Interrelated and Controlled? Acetyl CoA—accumulation of citrate diverts acetyl CoA to fatty acid synthesis. Cell differentiation: Slow twitch muscle cells have many mitochondria that catabolize aerobically, providing a steady supply of ATP.