Which reaction below in the glycolytic pathway has a highly unfavorable delta Gº¹ but a favorable delta G under physiological conditions? 1,3-Bisphosphoglycerate + ADP3-Phosphoglycerate + ATP O2-phosphoglyerate → phosphoenolpyruvate Ofructose-1,6-bisphosphate dihydroxyacetone phosphate + glyceraldehyde-3-phosphate fructose-6-phosphate → fructose-1,6-bisphosphate
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- Although phosphoesters are generally not energetic enough to donate the phosphate to make a high energy bond (e.g., a phosphoanhydride), the phosphate in PEP is used to convert ADP to ATP in the pyruvate kinase reaction. Carefully explain the ‘quirk’ of this reaction that makes it energetically feasible.The intermediates of glycolysis with a free energy of hydrolysis sufficient to couple conversion of ADP + phosphate to ATP (a substrate level phosphorylation) include (Choose all that apply) O phosphoenolpyruvate O 2-phosphoglycerate O 1,3-bisphosphoglycerate O glucose-6-phosphate. O fructose-6-phosphate. O fructose-1,6-bisphosphate. O dihydroxyacetone phosphateDraw the products of the reaction of xylulose-5-phosphate and erythrose-4-phosphate catalyzed by transketolase in the pentose phosphate pathway. Provide the structure in the protonation state found in physiological conditions. H H H OH FO HO-H H-OH H OPO3²- Q transketolase Draw glyceraldehyde-3- phosphate H H- H H H O OH OH OPO3²- Draw fructose-6- phosphate Q I I
- Indicate the general type of enzyme that mediates each glycolysis reaction depicted below. (e.g. Transferase, Oxidoreductase, Kinase, Hydrolase, Lyase, or Isomerase) iii. O H Glyceraldehyde-3-phosphate → 1,3-Bisphosphoglycerate H-C-OH + NAD CH₂O-P + P₁ H-O- -C-H Glucose →→ Glucose-6-phosphate H b 0 OH HO OH H-C- 0 -H HO- H ОН H-C-OH + NADH +H+ CH₂O P P ATP ADP 1 H (P-O- -C- H H HO OH 2-Phosphoglycerate → Phosphoenolpyruvate 0 OH H ОН -O~(P) + HOHThe reaction catalyzed by phosphorylase is readily reversible in vitro. At pH 6.8, the equilibrium ratio of orthophosphate to glucose 1-phosphate is 3.6. The value of ΔG°’ for this reaction is small because a glycosidic bond is replaced by a phosphoryl ester bond that has a nearly equal transfer potential. However, phosphorolysis proceeds far in the direction of glycogen breakdown in vivo. Suggest one means by which the reaction can be made irreversible in vivo.The oxidation of Gly-3-P to 1,3-bisphosphoglycerate proceeds with an unfavorable AG which equals 6.3 KJ/mol, yet the flow through this point in the glycolytic pathway proceeds smoothly. Why???
- Imagine a triglyceride comprised of (3) saturated C12 fatty acids. Calculate the number of ATP generated from the complete oxidation of one of these 12-carbon fatty acids to CO2 and water in the liver. Assume that each NADH = 2.5 ATP and each FADH2 = ETC generates 1.5 ATP. Any step that yields pyrophosphate as a product should be treated as an input (i.e. net loss) of (2) ATP.The phosphorylation and oxidative decarboxylation of oxaloacetate by inorganic phosphate (Pi) to make phosphoenolpyruvate and carbon dioxide is endergonic under intracellular conditions. It is characterized by this equation: Oxaloacetate + Pi ←→ Phosphoenolpyruvate + H2O + CO2 ΔG’ = +24.6 kJ/mol The synthesis of GTP from GDP and inorganic phosphate (Pi) in solution is endergonic under intracellular conditions, and it is characterized by this equation: GDP + Pi ←→ GTP + H2O ΔG’ = +30.5 kJ/mol Write a new net thermodynamically coupled reaction equation that describes the synthesis of phosphoenolpyruvate from oxaloacetate using the hydrolysis of GTP to power the reaction and calculate the new net ΔG’ of this reaction. Show all of your work.The coenzyme NAD+ is required for which glycolytic reaction shown below? Oglyceraldehyde-3-P→ 1,3-bisphosphoglycerate glucose glucose-6-P fructose-6-P→ fructose-1,6-BP 2-phosphoglycerate → phosphoenolpyruvate
- The oxidation of glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate, catalyzed by glyceraldehyde 3- phosphate dehydrogenase, proceeds with an unfavorable equilibrium constant ( K'eq= 0.08; ΔG′° = 6.3 kJ/mol), yet the flow through this point in the glycolytic pathway proceeds smoothly. How does the cell overcome the unfavorable equilibrium?phosphofructokinase is an allosteric enzyme that catalyzes the conversion of fructose 6-phosphate to fructose 1,6-bisphosphate and represents the key control point in mammalian glycolysis. The enzyme is a homotetramer that is inhibited by ATP binding, activated by AMP binding, negatively regulated by phosphorylation, and competitively inhibited by 2,5-anhydro-D-glucitol-1,6-diphosphate. (a) Would you expect a plot of the initial rate of fructose 1,6-bisphosphate formation as a function of substrate concentration to show a sigmoidal or hyperbolic curve? (b) How would each of the regulators above affect the dynamics of the T state to R state equilibrium of phosphofructokinase? Briefly explain your reasoning. (c) If it were possible to isolate phosphofructokinase monomers in an active form, how would you expect the kinetics in (a) to be affected? How would the rate of the reaction be affected by ATP, AMP, and 2,5-anhydro-D-glucitol-1,6-diphosphate? Briefly explain your answers.Decylic acid is a saturated fatty acid that occurs naturally in coconut oil and palm kernel oil. Calculate the net ATP yield when decylic acid undergoes complete B oxidation. The formula of decylic acid is shown below: (Given: The oxidation of one NADH yields 2.5 ATP; the oxidation of one FADH2 yields 1.5 ATP; and the oxidation of one acetyl CoA yields 10 ATP.) O 50 ATP O 52 ATP 66 ATP OH O 64 ATP