Chapter 9 Catabolic Pathways Fermentation: Partial degradation of sugars that occurs without the use of oxygen.

Cellular respiration: Oxygen is consumed as a reactant along with the organic fuel. C6H12O2 + 602 6CO2 +6H2O + Energy (ATP +heat) Redox Reactions Oxidation: The loss of electrons from one substance. (Na+) Reduction: addition of electrons to another substance. (Cl-) Adding electrons is called reduction; negatively charged electrons added to an atom reduce the amount of positive charge of that atom.

Stepwise Energy Harvest via NAD+ and the Electron Transport Chain NAD+ functions as an oxidizing agent during respiration. Nicotinamide is a nitrogenous base, although not one that is present in DNA or RNA. H-C-OH + NAD+ Dehydrogenase C-OH + NADH + H+ Respiration uses an electron transport chain to break the fall of electrons to oxygen into several energy releasing steps. It also releases energy in the form of ATP and the rest is heat. The transport chain consists of a number of molecules, mostly proteins, built into the inner membrane of a mitochondrion. Food NADH electron transport chain oxygen. The Stages of Cellular Respiration Respiration is a cumulative function of three metabolic steps: 1. Glycolysis 2. The Citric Acid Cycle (Kerbs Cycle) 3. Oxidative Phosphorylation: Electron Transport and Chemiosmosis Glycolysis, occurs in the cytosol, and begins the degradation process by breaking glucose into two molecules of a compound called pyruvate. The citric acid cycle, which takes place in the mitochondrial matrix, completes the breakdown of glucose by oxidizing a derivative of pyruvate to carbon dioxide. Thus, the carbon dioxide produced in cellular respiration represents fragments of oxidized organic molecules.

During some steps of Glycolysis and the citric acid cycle are redox reactions in which dehydrogenase enzymes transfer electrons from substrates to NAD+, forming NADH. The third stage, the electron transport chain accepts electrons from the breakdown products of the first two stages (most often via NADH) and passes these electrons from one molecule to another. At the end of the chain electrons are combined with molecular oxygen and hydrogen ions forming water. The energy released at each step of the reaction is stored in a form the mitochondrion can use to make ATP. This mode of ATP synthesis is called oxidative phosphorylation because it is powered by the redox reactions of the electron transport chain. Electron transport + chemiosmosis = oxidative phosphorylation. (Happens in mitochondrion) Oxidative phosphorylation account for 90% of the ATP generated by respiration. A smaller amount of ATP is formed directly in a few reactions of Glycolysis and the citric acid cycle by a mechanism called substrate-level phosphorylation. Substrate-level phosphorylation: Some ATP is made by direct enzymatic transfer of a phosphate group from an organic substrate to ADP. Substrate molecule refers to an organic molecule generated during the catabolism of glucose. Glycolysis harvests chemical energy by oxidizing glucose to pyruvate. (Glycolysis) Glucose, a six-carbon sugar, is split into two three-carbon sugars. These smaller sugars are then oxidized and their remaining atoms are rearranged to form two molecules of pyruvate. (Pyruvate is the ionized form of pyruvic acid.) Glycolysis produces: Glucose 2 pyruvate + 2H2O 4ATP formed 2ATP used 2 ATP 2 NAD+ + 4e + 4H 2NADH + 2H The Citric Acid Cycle completes the energy-yielding oxidation of organic molecules. Upon entering the mitochondrion via active transport, pyruvate is first converted to a compound called acetyl coenzyme A, or acetyl CoA. This step is the junction between Glycolysis and the citric acid cycle. It is accomplished by a multi-enzyme complex that catalyzes three reactions. 1. Pyruvates carboxyl group (-COO-), which is already fully oxidized and thus has little chemical energy, is removed and given off as a molecule of CO2. (This is the first step in which CO2 is released during respiration.) 2. The remaining two-carbon fragment is oxidized, forming a compound named acetate. An enzyme transfers the extracted electrons to NAD+, storing energy in the form of NADH.

3. Finally, coenzyme A is attached to the acetate by an unstable bond, making the acetyl group very reactive. The product of this acetyl CoA, is now ready to feed its acetyl group into the citric acid cycle for further oxidation. Citric Acid cycle yields 2ATP, 8NADH (including junction between Glycolysis and citric acid cycle), 2FADH2. During oxidative phosphorylation, chemiosmosis couples electron transport to ATP synthesis. The pathway of electron transport. Molecules of NADH and FADH2 account for most of the energy extracted from food. These electron escorts link Glycolysis and the citric acid cycle to the machinery of oxidative phosphorylation, which uses energy released by the electron transport chain to power ATP synthesis. Cytochrome: Proteins that contain a prosthetic group, called a heme group, that has an iron atom that accepts and donates electrons. Cytochromes consist of the rest of the electron transport chain after Ubiquinone. NADH makes more energy than FADH2 because it starts at complex 1 of the electron transport chain rather that complex 2. The electron transport chain makes no ATP directly. Its function is to ease the fall of electrons from food to oxygen, breaking a large free-energy drop into a series of smaller steps that release energy in manageable amounts. Chemiosmosis: The Energy-Coupling Mechanism Chemiosmosis turns the released energy into ATP. Inside the inner membrane of the mitochondrion are many copies of a protein complex called ATP synthase, the enzyme that actually makes ATP from ADP and inorganic phosphate. An Accounting of ATP Production by Cellular Respiration During respiration, most energy flows in this sequence: Glucose NADH electron transport chain proton motive force ATP Glycolysis produces 2 ATP by substrate-level phosphorylation. Citric Acid Cycle produces 2 ATP by substrate-level phosphorylation. Oxidative Phosphorylation produces about 32-34 ATP Maximum per glucose: About 36 or 38 ATP

There are three reasons why we cannot state an exact number of ATP molecules generated by the breakdown of on molecule of glucose.

1. Phosphorylation and the redox reactions are not directly coupled to each other, so the ratio of number of NADH molecules to number of ATP molecules is not a whole number. 2. The ATP yield varies slightly depending on the type of shuttle used to transport electrons from the cytosol into the mitochondrion. 3. The use of the proton-motive force generated by the redox reactions of respiration to drive other kinds of work. (eg. Proton-motive force powers the uptake of pyruvate from the cytosol.) 40% of the energy stored in glucose has been transferred to storage in ATP. The rest of stored energy sis lost as heat. This heat is used to maintain our relatively high body temperature and we dissipate the rest through sweating and other cooling mechanisms. We are relatively efficient compared to automobiles which convert only about 25% of the energy stored in gasoline to energy that moves the car. Fermentation enables some cells to produce ATP without the use of oxygen. Alcohol Fermentation, pyruvate is converted to ethanol in two steps. The first step releases carbon dioxide from the pyruvate, which is converted to acetaldehyde. In the second step, acetaldehyde is reduced by NADH to ethanol. This regenerates the supply of NAD+ needed for the continuation of Glycolysis. Many bacteria carry out alcohol fermentation under anaerobic conditions. Yeast carries out alcohol fermentation. Lactic Acid Fermentation, pyruvate is reduced directly by NADH to form lactate as an end product, with no release of CO2. Lactic acid fermentation by fungi and bacteria is used in the dairy industry to make cheese and yogurt. Human muscles cells make ATP by lactic acid fermentation when oxygen is scarce. The lactate that accumulates may cause muscle fatigue, but the lactate is carried by blood to the liver where it is converted back to pyruvate. Fermentation and Cellular Respiration Compared Respiration yields 19times more ATP per glucose molecule than does fermentation up to 38ATP for respiration, compared to 2 ATP produced by substrate-level phosphorylation in fermentation. Species that can use both aerobic and anaerobic conditions to make enough ATP to survive are called facultative anaerobes. 9.6 Glycolysis and the citric acid cycle connect to many other metabolic pathways. Deaminaton: The process by which amino acids can feed into Glycolysis or the citric acid cycle, their amino groups must be removed. The nitrogenous refuse is excreted from the animal in the form of ammonia, urea, or other waste products. Beta oxidation: breaks the fatty acids down to two-carbon fragments, which enter the citric acid cycle as acetyl CoA. Fats make excellent fuel. A gram of fat oxidized by respiration produces more than twice as much ATP as a gram of carbohydrate. Fat is much more reduced than carbohydrates, it has many CH2- units. The electrons present in a carbohydrate molecule are already somewhat oxidized, as some of them are bound to oxygen.

If a muscle cell has used up its supply of oxygen and ATP... AMP will accumulate, stimulating phosphofruktokinase, which increases the rate of Glycolysis. Since oxygen is not present, the cell will convert pyruvate to lactate in lactic acid fermentation, providing a supply of ATP.