Draw a plausible mechanism for the oxidation of dihydrolipoamide to lipoamide by the E, subunit (dihydrolipoamide dehydrogenase) of pyruvate dehydrogenase complex.
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- Extending the Mechanism of Methylmalonyl-CoA Mutase to Similar Reactions Based on the mechanism for the methylmalonyl-CoA mutase (see problem 14), write reasonable mechanisms for the following reactions shown.Based on your knowledge of the structure of NAD+ and an assumption that coenzyme dissociation is the rate limiting step of the alcohol dehydrogenase mechanism, hypothesize why a N249W mutation at the coenzyme binding site would increase the rate of catalysis.Draw a plausible mechanism for the oxidation of dihydrolipoamide to lipoamide by the E3 subunit (dihydrolipoamide dehydrogenase) of pyruvate dehydrogenase complex.
- Describe the common characteristic among the reactions catalyzed by pyruvate dehydrogenase (PDH), isocitrate dehydrogenase (ID), and alpha-ketoglutarate dehydrogenase (KD) based on reversibility.Briefly describe the dual role of lipoic acid in the pyruvate dehydrogenase complexDescribe in detail the structure of the pyruvate dehydrogenase complex.
- Because dichloroacetate inhibits the enzyme pyruvatedehydrogenase kinase, this compound has been used,with limited results, to treat lactic acidosis. The phosphorylation of the a-subunit of the pyruvate dehydrogenasecomponent of the pyruvate dehydrogenase complex bypyruvate dehydrogenase kinase causes complete loss ofenzymatic activity. Describe the theory behind the clinicaluse of dichloroacetate.Considering the evidence that led Krebs to propose a cyclic pathway for oxidation of pyruvate, discuss the type of experimental evidence that might have led to realization of the cyclic nature of the glyoxylate pathwayBriefly describe the biological rationale for each of the following allosteric phenomena: (a) activation of pyruvate carboxylase by acetyl-CoA; (b) activation of pyruvate dehydrogenase kinase by NADH; (c) inhibition of isocitrate dehydrogenase by NADH; (d) activation of isocitrate dehydrogenase by ADP; (e) inhibition of a-ketoglutarate dehydrogenase by succinyl-CoA; (f) activation of pyruvate dehydrogenase phosphatase by Ca2+.
- Draw a plausible mechanism for the oxidative decarboxylation of isocitrate by isocitrate dehydrogenase.Which one of the five steps of the pyruvate dehydrogenase complex reaction is most likely to be metabolically irreversible? Explain.For each of the central pathway intermediates given below, calculate how many ATP equivalents can be generated by complete oxidation of the compound to CO2: 1. Acetyl-CoA 2. Pyruvate 3. GAP (glyceraldehyde-3-phosphate) And please explain why.