Chemistry 451
Exam II (100 pts; 10 pts each unless otherwise indicated)
- Describe the role of coupled reactions in metabolism, give an example of a coupled reaction in one of the biochemical pathways we have covered AND identify the high energy compound in the reaction. (Sound Familiar)? (9 pts)
- In coupled reactions, one exergonic reaction drives an endergonic reaction (3 pt).
- An example is provided by the two half reactions below (3 pt):
Reaction 1: F6P + Pi -> FBP D G >0
Reaction 2: ATP + H2O -> ADP + Pi D G <0
Sum D G <0
- ATP is the high energy compound in the above coupled reaction (3 pt).
- Identify Enzyme Inhibitors A and B as competitive, uncompetitive or mixed inhibitors: (6pts)
Inhibitor A is Competitive (Apparent Km increases; Vmax does not change


Inhibitor B is Mixed (Apparent Km and Vmax change)


- What role does compartmentalization play in metabolism? AND Name or describe a transporter involved in carbohydrate or lipid metabolism.
Compartmentalization plays an important regulatory role in carbohydrate metabolism by physically separating catabolic reactions (breaking down) from anabolic reactions (building up).
Examples include:
- Pyruvate/H+ symport transporter used to move pyruvate into the mitochondrial matrix
- Malate and aspartate transporters for moving oxaloacetate out of the mitochondria for gluconeogenesis
- Fatty acyl carnitine/carnitine antiporter for moving Fatty Acyl groups into the mitochondria for fatty acid oxidation.
- Identify each of the following pathways or processes and indicate if the process occurs in the cytoplasm or mitochondrion. (10 pts)
|
Process |
Name of Process/
Cellular Compartment |
- Synthesizes ATP from ADP. Is driven by the separation of charge across the inner mitochondrial membrane.
|
Name: Oxidative Phosphorylation
Compartment: Mitochondrion |
|
Transfers electrons in a series of redox reactions that produces a separation of charge across the inner mitochondrial membrane. Ultimately transfers electrons to O2 which is then reduced to H2O. |
Name: Electron Transport Chain
Compartment: Mitochondrion
|
- Chops 2 carbons off a fatty acid each time it goes around the cycle making the process look like a spiral. Each 2 carbon unit becomes acetyl CoA.
|
Name: Fatty Acid Oxidation
Compartment: Mitochondrion |
|
Accepts 2 carbons from acetyl CoA which combine with oxaloacetic acid to form citric acid. Generates CO2 and reduced coenzymes (NADH and FADH2). (Coenzymes carry electrons to the electron transport chain). Regenerates oxaloacetic acid. |
Name: Citric Acid Cycle; TCA or Kreb's cycle
Compartment: Mitochondrion |
|
Converts 1 mole of glucose to 2 moles of pyruvate |
Name: Glycolysis
Compartment: Cytosol
|
5. BRIEFLY describe (8 pts):
- The reaction catalyzed by the pyruvate dehydrogenase complex in carbohydrate metabolism:
Pyruvate + NAD+ + CoA
® CO2 + NADH + AcetylCoA
One advantage of a multienzyme complex
Reactions happen faster because of proximity of reactants
Fewer side reactions
Coordinated control
With reference to the picture below, explain how pyruvate dehydrogenase is regulated. (Graphs of enzyme activity would be cool)!
See Below
What effect would increasing expression of the PDH kinase gene have on carbohydrate metabolism? (In other words, if concentrations of PDH kinase protein increased, what effect would this have on carbohydrate metabolism?)
Assuming increased expression of PDH kinase resulted in enhanced phosphorylation of PDH, increased expression of PDH kinase would inactivate PDH and suppress entry of pyruvate into the TCA cycle.

- The O2 consumption curve of a dilute, well buffered suspension of mitochondria containing plenty of ADP and Pi looks like:
Explain why you would expect [ATP] to increase as O2 decreases (i.e., how is O2 consumption associated with ATP synthesis? Pictures and diagrams might be useful) (10 pts)

7. Referring to the figure in #6 above, sketch the curves you would predict when (10 pts):
i. Rotenone is added at T1; and succinate is added at T2
ii. CN- is added at T1; and succinate is added at T2
8. (12 pts) Draw graphs to illustrate allosteric effects of fructose-2,6-bisphosphate (F2,6P) on
a. Phosphofructokinase (F6P ® F1,6P)
- Fructobisphosphatase (F1,6P ® F6P)
- What role does F2,6P play in regulating glycolysis and gluconeogenesis? (use back of page)
- Name or draw the reactancts and products or name the four enzymes that catalyze the reactions that bypass the three exergonic steps of glycolysis: (8pts)
|
Glycolysis |
Gluconeogenesis |
|
Pyruvate Kinase |
- Pyruvate Carboxylase
(pyruvate + HCO3- + ATP® oxaloacetate + ADP + Pi)
2. PEPCK (oxaloacetate + GTP ® PEP + GDP + CO2 ) (pg. 454)
|
|
Phosphofructokinase |
- Fructose-1,6-bisphosphatase (FBPase)
Fructose 1,6 bisphosphate + H20 ® Fructose 6 phosphate + Pi |
|
Hexokinase |
Glucose-6-phosphatase
Glucose-6-phosphate + H20 ® Glucose + Pi
|
10. Fatty acid oxidation occurs in four reactions. In the Citric Acid Cycle below, identify three consecutive reactions that are similar to those seen in fatty acid oxidation (6 pts)

- Complete the following table with reference to the Citric Acid Cycle above (8 pts):
|
Enzyme |
Classification |
Is Reaction Irreversible? |
|
Citrate Synthase |
Transacetase or Transferase |
YES |
|
Aconitase |
Hydratase |
NO |
|
Isocitrate Dehydrogenase |
Oxidoreductase |
YES |
|
a -Ketoglutarate Dehydrogenase Complex |
Oxidoreductase |
YES |
|
Succinyl CoA Synthase |
Ligase |
NO |
|
Succinate Dehyrogenase |
Oxidoreductase |
NO |
|
Fumarase |
Hydratase |
NO |
|
Malate Dehydrogenase |
Oxidoreductase |
NO |
- Briefly answer the following (4 pts):
- Name at least one role of the pentose phosphate pathway in carbohydrate metabolism.
- Synthesis of Ribose-5-phosphate for nucleotide biosynthesis
- Synthesis of NADPH (used for reductive biosynthesis and regeneration of reduced glutathione
b. What enzyme catalyzes the rate limiting step in the pentose phosphate pathway?
Glucose-6-phosphate dehydrogenase reaction (recall poster on this topic)?
- Olean (Olestra) is a fat free "fat" used for producing fat free foods. Olean is a sugar (maybe fructose or glucose) with fatty acids esterified onto each of its numerous OH groups. Olean is "fat free" because none of the fatty acids are absorbed from the intestine into the blood. For this reason, diarrhea and gastric bloating can result if you eat too much of those fat free chips. Why are the fatty acids in Olean not absorbed? (4 pts)
Fatty acids in Olean are not absorbed because olean is not a substrate for pancreatic lipase. We do not have an enzyme to hydrolyze the ester bonds and liberate the fatty acids for absorption. Consequently, the fatty acids are not absorbed.