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104 Cards in this Set
- Front
- Back
The Citric Acid Cycle is aka what? |
Tricarboxylic Acid Cycle (TCA) or the (Hans) Krebs cycle
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The CAC is involved in what kind of metabolism?
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Aerobic catabolism
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What does the CAC follow?
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Glycolysis
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How much energy did glycolysis capture from glucose? Where does the rest go?
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Only about 5% of the total energy in glucose is captured in glycolysis. The leftover energy resides in pyruvate.
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? goes into the CAC from glycolysis and it requires ? conditions.
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Pyruvate goes into the CAC from glyc. and it reqs AEROBIC conditions.
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In stage one of the CAC one molecule of what is removed?
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CO2
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How does pyruvate enter into the CAC cycle?
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It is transported from the cytosol into the mitochondria via the pyruvate carrier. Then it is activated by a 3-enzyme complex to become Acetyl-CoA.
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What is the ^G'" of stage 1 of the CAC?
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-33.4 ( Very Exergonic)
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After activation by the 3-enzyme complex, how many of pyruvates carbons are in acetyl CoA?
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Two of pyruvate's 3 carbons end up in Acetyl-CoA.
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How many enzymes are involved in stage 1 of the CAC?
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Three
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How many cofactors are involved in stage 1 of the CAC?
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5 cofactors are involved:
1. TPP (from thiamine) 2. FAD (from riboflavin) 3. Coenzyme A (CoA, from pantothenate) 4. NAD (from niacin) 5. Lipoate The first 4 are B vitamins. Lipoate is not a vitamin because we synthesize it ourselves. |
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A deficiency in what vitamins interferes with the CAC cycle?
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The B vitamins which include : Thiamine, Riboflavin, Panthothenate, and Niacin. These must be taken into the body from outside sources.
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Where does the CAC take place in the cell?
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In eukaryotes it occurs in the mitochondria and in prokaryotes it occurs in the cytosol.
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Coenzyme A is a ? : A ? ? compound.
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It is a thioester : A high-energy compound.
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How does Coenzyme-A combine with other molecules?
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It combines by the Mercapto- group.
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Lipoate is aka?
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Lipoic acid
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Lipoate can be observed in what form?
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It can be in either an oxidized or reduced form.
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What does lipoate have the ability to do?
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It can bind an acetyl group in one part of the complex and move it to another part of the complex.
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What is Arsenite?
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It is much more dangerous than arsenAte to a cell. It attaches to lipoate and once bound you cannot get rid of it. Once this occurs you can no longer bind Acetyl CoA. This causes a shutdown of the Kreb's Cycle.
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How many enzymes, cofactors, and regulatory proteins are involved in the pyruvate dehydrogenase complex?
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5 Cofactors. 3 enzymes. 2 Regulatory proteins.
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What is the Pyruvate dehydrogenase complex important for?
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It plays a role in substrate channeling. So when the 3 enzymes involved are involved in rxns the product from one rxn becomes the reactant from the next, etc.
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Briefly explain the transition from pyruvate to acetyl CoA? (ie. What goes in and what comes out of cycle?)
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Co-enzyme A and NAD+ enter into the cycle.
Acetyl Co-A (Co-enzyme bound to an acetyl group) and NADH (with energy captured) come out. |
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What is the problem with the oxidative decarboxylation of pyruvate?
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A LACK OF THE VITAMIN THIAMINE in the diet can result in problems with this rxn (esp. in the brain, where aerobic oxidation is very important). It slows down the rxn.
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What is a term that refers to a lack of the vitamin thiamine?
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beriberi
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What is the net loss or gain of C in the CAC?
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No net loss or gain of C. Two in and two out.
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What energy do you get from the CAC?
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You get 3 NADH, 1 FADH2, and 1 GTP or ATP.
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How does oxaloacetate relate to step 1 of the CAC?
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It is an intermediate in the matrix of the mitochondria.
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What is "spun-off" in the rxn between Acetyl-CoA and Oxaloacetate in step 1 of the CAC?
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Co-enzyme A
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What is the ^G'" of the 1st step of the CAC? For what reason is this important?
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-32.2. It is very exergonic and is important in moving the process along.
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What is the net loss or gain of step 2 of the CAC?
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There is no net loss or gain.
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What is the ^G'" of the 2nd step of the CAC? What does this infer about this step?
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+13.3. It is an endergonic process, so energy is required. It proceeds because it is coupled to step 1 and step 3 which are both exergonic. When this is taken into consideration it indicates that the ^G is probably actually around 0.
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What is effectively reversed in step 2 of the CAC?
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The H and OH of the citrate molecule (reactant) reverse in the isocitrate molecule (product).
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What is formed in the 3rd step of the CAC? (energy-wise)
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NADPH
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What is one NADPH approximately equivalent to?
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It is basically equivalent to 1 NADH equivalent in energy.
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What is the ^G'" of the 3rd step of the CAC?
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It is -20.9; this step is exergonic even though it synthesizes NADPH.
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Besides NADPH, what else is released in the 3rd step of the CAC?
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CO2
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What drives rxn 4 of the CAC to move forward?
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The alpha-ketoglutarate complex catalyzes it. It is composed of 3 enzymes and 5 cofactors.
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What re-enters in step 4 of the CAC?
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CoA
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What is formed in the 4th step of the CAC?
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NADH is formed.
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Besides NADH what else is formed in the 4th step of the CAC?
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CO2
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What is the ^G'" of the 4th step of the CAC?
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-33.5
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The ^G'" of step five of CAC? What can be said about this?
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-2.9kj/mol. It is slightly exergonic but it is practically a wash.
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What does step 5 of the CAC form?
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It forms either ATP or GTP.
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What is released in step 5 of the CAC?
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Co-A is released again.
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Why is Co-A considered a cofactor in CAC?
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It is considered a co-factor because it keeps entering and releasing from the CAC cycle.
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In step 5 of the CAC, Succinyl-CoA becomes Succinate. What can be said about this?
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Step 5 involves a higher energy compound going to a lower energy compound. Or "It is an endergonic hydrolysis of thioester bond coupled to formation of GTP or ATP (which is exergonic)"
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What is energy transferred to in step 6 of the CAC?
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It is transferred to FADH2. FAD is reduced to FADH2 and captures energy.
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What is the ^G'" of step 6 of the CAC?
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0 kj/mol
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Succinate becomes fumarate in step 6 of the CAC. What can be said about this?
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Again, a higher energy compound becomes a lower energy compound. The energy is captured in FADH2.
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What does step 7 of the CAC illustrate?
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It illustrates stereospecificity in both the recognition of substrate and the formation of product.
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Explain how step 7 of the CAC illustrates stereospecificity.
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It recognizes Fumarate (trans) but does not recognize Maleate (cis) as a substrate. It also forms L-malate as a product but D-malate is never formed.
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What is the ^G'" of step 8 of the CAC?
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+29.7kj/mol
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The standard ^G'" of step 8 of the CAC is is very endergonic. Explain how the CAC cycle is still able to proceed?
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The oxaloacetate concentration inside of the cell is actually quite low. This actually causes the ^G to be less endergonic. This along with the fact that it is coupled with the next reaction in the cycle (which is step one and is very exergonic) allows it to proceed.
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What is energy transferred to in step 8 of the CAC?
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NADH
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In the reaction; 2 pyruvate -> 2 Acetyl CoA; what is formed? Explain.
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2 NADH are directly formed but ultimately 5 ATP are formed. Every molecule of NADH and FADH2 can be converted into ATP energy (and they will be).
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Give the conversion ratios of energy transformation from NADH and FADH2 to ATP.
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2 NADH becomes about 5 ATP. 2 FADH2 becomes about 3 ATP.
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What is the energy in ultimate ATPs produced by glycolysis?
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2
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What is the energy in the form of NADH that is formed from glycolysis? How many ATPs does this produce ultimatlely?
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2 NADH. It yields about 3-5 ATP.
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How many G/ATP are produced by the CAC? How many ATPs does this ultimately produce?
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2 G/ATP. This results in 2 ATPs.
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How many NADH are produced in the CAC? How many ATPs does this result in ultimately?
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6 NADH. This results in about 15 ATP.
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How many FADH2 are produced in the CAC? How many ATPs does this ultimately produce?
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2 FADH2. This leads to 3 ATP ultimately.
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How many ATP equivalent do you get in total from the combined metabolism of Glycolysis and the CAC?
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You get about 30-32.
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? metabolism of glucose yields about 5 times as much ATP as ?. (30-32 vs. 5-7)
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Aerobic metabolism yields more than anaerobic.
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The CAC also plays a role in anabolism. What does this indicate?
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It indicates that the CAC generates compounds. It is not just for the purpose of getting energy out.
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Metabolic pathways have much overlap between different cycles. Give an example of how this is illustrated in the CAC.
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Bypass number 1 from gluconeogenesis is involved in the CAC. This is the reaction that involves pyruvate and oxaloacetate that bypasses step 10 of glycolysis.
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Alpha-ketoglutarate (an intermediate in the CAC) is involved in a side reaction that produces glutamate. What does this rxn go on to be involved in?
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It is involved in the metabolism of a.a.s.
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What is an Amphibolic pathway? Give an example.
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It is a pathway that displays catabolic and anabolic roles. An example is the CAC.
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What is an Anaplerotic reaction?
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It is a rxn that replenishes intermediates when they are removed to become precursors of other molecules.
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How many Anaplerotic reactions are involved in the CAC?
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There are 4 anaplerotic reactions. You are not required to memorize them but it is key to know that :
1. Malate is from Pyruvate 2. OAA is from Pyruvate or PEP (These 2 key notes basically summarize all 4 reactions, see slide # 26) |
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What is typically occuring during the 4 anaplerotic rxns of the CAC? What is an example of this?
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Typically a 4 C molecule receives a Bicarbonate group to make a 5 C molecule. Biotin is an example of this.
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What is Biotin?
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It is a B vitamin. So it is attained from diet. It is also a cofactor for several CAC anaplerotic reactions. It transfers CO2 from HCO3- to other molecules.
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How many anabolic side reactions is the CAC involved in?
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five
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What are the 4 methods of regulation?
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1. By substrate
2. By product 3. Allosteric 4. Covalent |
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How is substrate concentration related to the regulation of a reaction?
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The higher the [substrate] the higher the more exergonic the reaction will be. Will cause a more negative ^G.
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How is product concentration related to the regulation of a reaction?
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The higher the [product] the more endergonic a reaction will be. Will cause a more positive ^G.
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How is a reaction regulated allosterically?
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It involves some molecule acting on an enzyme.
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How is a reaction regulated covalently?
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It involves the addition or removal of a component by enzyme to either speed up or slow down the reaction.
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Which steps (rxns) of the CAC are allosterically regulated?
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The Lead-in reaction, plus steps 1, 3, and 4.
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What are the allosteric inhibitors of the reaction that leads into CAC?
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1. Acetyl-CoA (This is a PRODUCT of the CAC and feeds back)
2. ATP and NADH (these are ENERGY products that inhibit once there is a sufficient amount) |
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What are the "allosteric activators" or the reaction that leads into the CAC?
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1. CoA and NAD+ (These are considered SUBSTRATES that activate the rxn)
2. AMP, and NAD+ (These signify LOW ENERGY) 3. Ca++ (specifically in muscle tissue) |
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What are the allosteric inhibitors of step 1 of the CAC?
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1. Citrate, Succ. CoA (A PRODUCT INH)
2. NADH, and ATP (ENERGY INH.s) |
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What are the "allosteric activators" of step 1 of the CAC?
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ADP (A LOW ENERGY ACTIVATOR)
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What are the allosteric inhibitors of step 3 of the CAC?
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ATP (AN ENERGY INH.)
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What are the allosteric activators of step 3 of the CAC?
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1. ADP (A LOW ENERGY ACTIVATOR)
2. Ca++ |
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What are the allosteric inhibitors of step 4 of the CAC?
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1. Succinyl CoA (A PRODUCT INHIBITOR)
2. NADH (AN ENERGY INHIBITOR) |
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What are the allosteric activators of the 4th rxn of the CAC?
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Ca++
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What does increased substrate concentration do to a reaction?
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It moves the reaction forward.
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What does increased product do to a reaction?
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It slows a rxn down.
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What do increased energy molecules do to a reaction?
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They slow it down.
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What does decreased energy do to a reaction?
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It moves the reaction forward.
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It is important to remember what CAC is ultimately doing. What is that?
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It is turning energy from pyruvate into ATP and NADH which is usable by a cell.
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The regulation of the feed-in step by pyruvate dehydrogenase is an example of what?
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It is an example of COVALENT modification.
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What does the regulation of the feed-in step by covalent modification involve? |
3-enzymes, 5-cofactors, 2-regulatory molecules
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What are the two regulatory molecules that are involved in covalent modification of the feed-in step (Pyruvate Dehydrogenase) of the CAC?
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1. Kinase
2. Phosphatase |
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Which form of pyruvate dehydrogenase is active?
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When it is dephosphorylated it is active. Phosphorylated is inactive.
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What activates Pyruvate dehydrogenase?
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Phosphatase. It dephosphorylates the enzyme, making it active.
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What inactivates Pyruvate dehydrogenase?
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Kinase. It phosphorylates it; making it inactive.
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What activates Kinase?
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ATP activates kinase. Kinase then goes on to inactivate pyruvate dehydrogenase by phosphorylating it.
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Pyruvate dehydrogenase is similar to ? ? and the opposite of ? ?.
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It is similar to Glycogen synthase and the opposite of Glycogen phosphorylase.
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What methods of regulation are involved in CAC regulation?
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Allosteric and Covalent
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What is the Glyoxylate Cycle?
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It converts Fatty Acids and Amino Acids into Carbohydrates. This occurs in PLANTS ONLY because WE CAN NOT CONVERT FAs INTO CARBS. However, we can convert carbs into FAs.
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What is the ultimate product of the Glycoxylate cycle?
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Succinate
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What begins the glyoxylate cycle?
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Glyoxylate
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What is added into the Glycoxylate cycle?
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Acetyl-CoA is added into the cycle twice.
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