25-Glycogen+Synthesis
Glycogen Synthesis Overview
Glycogen is synthesized from UDP-glucose.
UDP-glucose Formation
UDP-glucose as a glucose donor:
Synthesized by UDP-glucose pyrophosphorylase from glucose 1-phosphate and UTP.
Hydrolysis of pyrophosphate product during this reaction is crucial for its irreversibility.
Key Enzymatic Steps in Glycogen Synthesis
Glycogen Synthase:
Transfers a glucose moiety from UDP-glucose to the C-4 terminal residue of a glycogen chain.
Forms an α-1,4-glycosidic bond during the process.
Oligosaccharide Primer Requirement:
Glycogen synthase requires a primer, an oligosaccharide of glucose residues.
Glycogenin (a homo-dimer enzyme) synthesizes this primer, generating an oligosaccharide of glucose 8 residues long.
Primer and Branching in Glycogen
Branching Enzyme Role:
Glycogen synthase can synthesize only α-1,4-linkages.
Branching enzyme cleaves an α-1,4-linkage, taking a block of about 7 glucoses and forming an α-1,6-linkage.
Branch points must be separated by at least 4 glucose residues.
Energy Efficiency of Glycogen
Incorporating one glucose into glycogen requires only two ATP molecules.
Complete oxidation of glucose derived from glycogen yields 30 ATP molecules.
Regulation:
Glycogen synthase is usually inactive in the phosphorylated b form and active in the unphosphorylated a form.
Key regulatory process involves conversion from b form T state to active b form R state via binding of glucose 6-phosphate.
Reciprocal Regulation of Glycogen Metabolism
Glycogen synthase kinase phosphorylates and inhibits glycogen synthase.
Glucagon (in the liver) and epinephrine (in muscle and liver) stimulate glycogen breakdown and inhibit glycogen synthesis.
Protein kinase A (PKA) phosphorylates glycogen synthase leading to inhibition of glycogen synthesis.
Insulin's Role in Glycogen Synthesis
In muscle, insulin activates protein kinases that inactivate glycogen synthase kinase, promoting glycogen synthesis.
Protein Phosphatase 1 (PP1) promotes insulin's effects by dephosphorylating and activating glycogen synthase.
Insulin receptor acts as a tyrosine kinase that phosphorylates insulin receptor substrate.
Insulin also increases number of glucose transporters (GLUT4) in plasma membrane, facilitating glycogen synthesis.
Protein Phosphatase 1 (PP1) Mechanism
PP1 shifts glycogen metabolism from degradation to synthesis by:
Removing phosphoryl groups from phosphorylase kinase and glycogen phosphorylase, inhibiting degradation.
Converting glycogen synthase b (less active) to a form (more active).
Regulatory Subunits of PP1:
Composed of a catalytic subunit (PP1) and two regulatory subunits.
G subunit (GL in liver and GM in muscle) helps localize PP1 to glycogen substrates.
Phosphorylation leads to dissociation of PP1 from glycogen, reducing activity in muscle.
Regulation by Blood Glucose Levels
High blood glucose levels inhibit glycogen degradation while stimulating synthesis.
Conversion of glycogen phosphorylase a from R state to T state leads to activating PP1, promoting glycogen synthesis.
The lag between decreased degradation and increased synthesis is due to small proportion of phosphorylase molecules associated with PP1.
Role of Glucagon and Insulin
Pancreatic Regulation:
Insulin stimulates beta cells' glucose uptake, promoting hyperglycemia.
Glucagon stimulates gluconeogenesis and glycogenolysis in liver, releasing glucose to plasma during hypoglycemia.
Insulin and glucagon play critical roles in maintaining normal blood glucose levels.