U01.01.090 Rate-determining enzymes of metabolic processes

 

Learning Objectives

  • Identify the rate-limiting step for each major metabolic pathway.
  • Predict how allosteric effectors (AMP, ATP, Citrate) shift metabolic flux.
  • Understand the hormonal regulation (Insulin vs. Glucagon) of fuel storage and mobilization.

1. Carbohydrate Metabolism

The balance between energy production and storage is tightly controlled by adenine nucleotides and hormonal signals.

Process Rate-Limiting Enzyme Key Regulators
Glycolysis PFK-1 (+) AMP, F-2,6-BP
(-) ATP, Citrate
Gluconeogenesis Fructose-1,6-bisphosphatase 1 (-) AMP, F-2,6-BP
TCA Cycle Isocitrate dehydrogenase (+) ADP; (-) ATP, NADH
Glycogenesis Glycogen synthase (+) G6P, Insulin
(-) Glucagon, Epinephrine
Glycogenolysis Glycogen phosphorylase (+) Epinephrine, AMP
(-) Insulin, ATP

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2. Lipid and Nucleotide Metabolism

Metabolism of fats and nucleotides is regulated to ensure precursor availability and prevent futile cycling.

Process Rate-Limiting Enzyme Key Regulators
Fatty Acid Synthesis Acetyl-CoA carboxylase (ACC) (+) Insulin, Citrate
(-) Glucagon, Palmitoyl-CoA
Fatty Acid Oxidation Carnitine acyltransferase I (-) Malonyl-CoA
Cholesterol Synthesis HMG-CoA reductase (+) Insulin, Thyroxine
(-) Glucagon, Cholesterol
Urea Cycle CPS I (+) N-acetylglutamate

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Clinical Correlate: Statins

Statins are competitive inhibitors of HMG-CoA reductase. By inhibiting this rate-limiting step, they reduce endogenous cholesterol production and upregulate LDL receptor expression on hepatocytes.

Mnemonic

Ketogenesis: HMG-CoA Synthase… “Hey My God! I’m starving!”

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