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what are the enzymes of glycogen synthesis
UDP-glucose pyrophosphorylase
- activates glucosyl units
glycogen synthase
- extends glycogen chains
glycogen branching enzyme
- transfers 7- residue glycogen segments
glycogen synth. from G1P is thermodynamically...
unfavorable
Describe the actions of UDP- glucose pyrophosphorylase
activates glucosyl units
- uridine diphosphate glucose (UDPG)
UDPG is an activated compound
- can donate a glucosyl unit to a growing glycogen
chain
formation of UDPG has ′ΔG°′≈0
Subsequent exergonic hydrolysis of PPi by inorganic pyrophosphatase makes the overall reaction exergonic
what is the net ΔG°from UDP-Glucose Pyrophosphorylase action
-19.2
G1P +UTP <-> UDPG + PPi ~ 0
H2O + PPi -> 2Pi ~ -19.2
what is PPi
inorganic pyrophosphate
Describe glycogen synthase (GS)
extends glycogen chains by:
transfer of glucosyl unit of UDPG to C4-OH group on one glycogen's non-reducing ends to from an α(1→4) glyosidic bond
ΔG° = -13.4 kJ-mol
spontaneous
UDPG + glycogen -> UDP + glycogen
How is UTP replenished
using ATP as a substrate through a phosphoryl-transfer reaction
mediated by nucleoside diphosphate kinase
is UTP consumption energetically equivalent to ATP consumption
yes
can GS simply link 2 glucose residues together
no, it can only extend using already existing α(1→4)-linked glucan chain
in the first step of GS what is at work
glycogenin working as a glycosyltransferase
What does glycogenin do
attaches glucose residue donated by UDPG to OH on its tyr 194
extends glucose chain by up to 7 addition UDPH donated glucose residues
forms a glycogen primer, allowing GS to start by extending the primer
each glycogen molecule is associated with
1 molc. glycogenin
1 molc. GS
what does GS generate
transfers only α(1→4)linkages to yield α-amylose
what is the glycogen branching enzyme called
amylo-(1,4 ->1,6) - transglycosylase
distinct from glycogen debranching enzyme
glycogen branching enzyme does what
creates branches by transferring a 7-residue segment from chain end to C6-OH group of a glucose residue on same or other glycogen chain
each transferred segments must come from a chain of at least 11 residues
each branch point must be at least 4 residues from other branch points
why is the branching pattern of glycogen important
its optimized by evolution for the efficient storage and mobilization of glucose