Glycolysis Rxn 1: enzyme & class Hexokinase Transferase

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Glycolysis
Rxn 1: enzyme & class
Hexokinase
Transferase
Glycolysis
Rxn 2: enzyme & class
Phosphoglucose isomerase
Isomerase
Glycolysis
Rxn 3: enzyme & class
Phospofructokinase (PFK-1)
Transferase
Glycolysis
Rxn 4: enzyme & class
Aldolase
Lyase
Glycolysis
Rxn 5: enzyme & class
Triose phosphate isomerase
Isomerase
Glycolysis
Rxn 6: enzyme & class
Glyceraldehyde-3-Phosphate dehydrogenase
Oxidoreductase
Glycolysis
Rxn 7: enzyme & class
Phosphoglycerate kinase
Transferase
Glycolysis
Rxn 8: enzyme & class
Phosphoglycerate mutase
Mutase
Glycolysis
Rxn 9: enzyme & class
Enolase
Lyase
Glycolysis
Rxn 10: enzyme & class
Pyruvate kinase
Transferase
Glycolysis
Rxn 1: reactant -> product & rxn type
Glucose -> Glucose-6-Phosphate
-Phosphorylation
Glycolysis
Rxn 2: reactant -> product & rxn type
Glucose-6-Phosphate -> Fructose-6Phosphate
-Aldose-Ketose interconversion
Glycolysis
Rxn 3: reactant -> product & rxn type
Fructose-6-Phosphate -> Fructose-1,6Bisphosphate
-Phosphorylation
Glycolysis
Rxn 4: reactant -> product & rxn type
Fructose-1,6-Bisphosphate ->
Dihydroxyacetone Phosphate (DHAP) + Glyceraldehyde-3-Phosphate
-Reverse aldol condensation
Glycolysis
Rxn 5: reactant -> product & rxn type
Dihydroxyacetone Phosphate (DHAP) ->
Glyceraldehyde-3-Phosphate
-Ketose-Aldose interconversion
Glycolysis
Rxn 6: reactant -> product & rxn type
Glyceraldehyde-3-Phosphate -> Glycerate1,3-Bisphosphate
-1) oxidation
-2) phosphorylation
Glycolysis
Rxn 7: reactant -> product & rxn type
Glycerate-1,3-Bisphosphate -> 3Phosphoglycerate
-Substrate level phosphorylation
Glycolysis
Rxn 8: reactant -> product & rxn type
3-Phosphoglycerate -> 2-Phosphoglycerate
-Isomerization
Glycolysis
Rxn 9: reactant -> product & rxn type
2-Phosphoglycerate ->
Phosphoenolpyruvate (PEP)
-Dehydration
Glycolysis
Rxn 10: reactant -> product & rxn type
Phosphoenolpyruvate (PEP) -> Pyruvate
-Substrate level phosphorylation
Glycolysis
Rxn 1: purpose
Starts destabilization by phosphorylating glucose to make it
glucose-6-P. Phosphorylation by hexokinase traps glucose within the cell for metabolism
and allows more glucose to enter the cell.
Glycolysis
Rxn 2: purpose
Conversion of secondary alcohol to a primary alcohol, making
molecule more symmetrical in preparation of splitting it into two 3-carbon pieces.
Glycolysis
Rxn 3: purpose
1. Phosphorylation such that both 3-carbon pieces will be retained
in the cell
2. Committing molecules to glycolysis so once initiated, molecule will finish glycolysis
(main regulation step)
Glycolysis
Rxn 4: purpose
To create two 3-carbon pieces
Glycolysis
Rxn 5: purpose
Conversion to glyceraldehyde-3-P makes both molecules DHAP
carbons
Glycolysis
Rxn 6: purpose
Making an energy rich molecule (glycerate-1,3-BP) for substrate
level phosphorylation
Glycolysis
Rxn 7: purpose
To make ATP
Glycolysis
Rxn 8: purpose
Moving phosphate from C3 to C2 helps set up for PEP formation
Glycolysis
Rxn 9: purpose
Production of energy rich PEP which sets up for substrate level
phosphorylation
Glycolysis
Rxn 10: purpose
1. To make pyruvate
2. To make ATP
Glycolysis
Energy investment rxns
Rxn 1: 1 ATP/glucose
Rxn 3: 1 ATP/glucose
Glycolysis
Energy payoff rxns Rxn 7: 2 ATP/glucose
Rxn 10: 2 ATP/glucose
Glycolysis
ATP net gain 2 ATP/glucose
Glycolysis
Irreversible rxns
Reactions 1, 3 and 10 are irreversible, therefore, they are the
regulated steps
Glycolysis
Rxn 1 regulation
Inhibitors:
1) Glc-6-P: product inhibition
2) ATP: high levels indicate that cellular energy is high
Glycolysis
Rxn 3 regulation: Activators 1) AMP: indicates low cellular energy
2) Frc-2,6-BP: allosteric regulator produced by a bifunctional enzyme (F-2,6-BPase/PFK2). Buildup of Frc-2,6-BP causes activation of Frc-2,6-BPase, which makes more Frc-6-P
for the rxn.
Glycolysis
Rxn 3 regulation: Inhibitors 1) ATP - high cellular energy
2) NADH - high cellular energy
3) Citrate - CAC intermediate
Glycolysis
Rxn 3 regulation: Hormonal control 1) glucagon
-"glucose is gone" indicates low blood glucose
-phosphorylates bifunctional enzyme
-Frc-2,6-BPase activates
-PFK-2 deactivates
-glycolysis is inhibited
2) insulin
-indicates high blood glucose
-dephosphorylates bifunctional enzyme
-Frc-2,6-BPase deactivates
-PFK-2 activates
-glycolysis is activated
Glycolysis
Rxn 10 regulation: Allosteric 1) ATP - Inhibits because indicates high cellular energy
2) Acetyl CoA - Inhibits because indicates high cellular energy and plentiful CAC
intermediates
3) Frc-1,6-BP - Activates because of feed forward activation
Glycolysis
Rxn 10 regulation: Hormonal Glucagon - Inhibits - Causes phosphorylation of pyruvate
kinase which leads to inhibition of enzyme
Gluconeogenesis
Bypass 1, Rxn 1:
Enzyme & Class
Pyruvate Carboxylase
Ligase
Gluconeogenesis
Bypass 1, Rxn 2:
Enzyme & Class
PEP Carboxykinase
Lyase
Gluconeogenesis
Bypass 2:
Enzyme & Class
Fructose-1,6-Bisphosphatase
Hydrolase
Gluconeogenesis
Bypass 3:
Enzyme & Class
Glucose-6-Phosphatase
Hydrolase
Gluconeogenesis
Bypass 1, Rxn 1:
Reactant -> product & rxn type
Pyruvate -> Oxaloacetate (OAA)
-Carboxylation
Gluconeogenesis
Bypass 1, Rxn 2:
Reactant -> product & rxn type
Oxaloacetate (OAA) -> PEP
-Decarboxylation and phosphorylation
Gluconeogenesis
Bypass 2:
Reactant -> product & rxn type
Fructose-1,6-Bisphosphate -> Fructose-6-Phosphate
-Dephosphorylation
Gluconeogenesis
Bypass 3:
Reactant -> product & rxn type
Glucose-6-Phosphate -> Glucose
-Dephosphorylation
Gluconeogenesis
Bypass 1, Rxn 1:
Regulation
Allosteric
1) ADP - Inhibits - Indicates low cellular energy
2) Acetyl CoA - Activates - Fatty acid degradation, starvation conditions
Gluconeogenesis
Bypass 1, Rxn 2:
Regulation
Allosteric
1) ADP - Inhibits - Indicates low cellular energy
Gluconeogenesis
Bypass 2:
Allosteric Regulation 1) AMP - Inhibits
2) Frc-2,6-BP - Inhibits
3) ATP - Activates
4) Citrate - Activates
Gluconeogenesis
Bypass 2:
Hormonal Regulation 1) Glucagon
-Bifunctional enzyme is phosphorylated
-Favors degradation of Frc-2,6-BP
-Gluconeogenesis is favored
2) Insulin
-Bifunctional enzyme is dephosphorylated
-Favors the production of Frc-2,6-BP
-Glycolysis is favored
Gluconeogenesis
Bypass 3:
Regulation
Yes but complex and not well understood
Glycogenesis
Rxn 1: enzyme and class
Hexokinase or Glucokinase
Transferase
Glycogenesis
Rxn 2: enzyme and class
Phosphoglucomutase
Mutase
Glycogenesis
Rxn 3: enzyme and class
UDP-Glucose Phosphorylase
Transferase
Glycogenesis
Rxn 4: enzyme and class
Glycogen Synthase
Lyase
Glycogenesis
Rxn 5: enzyme and class
Branching Enzyme
Transferase
Glycogenesis
Rxn 1: reactant -> product & rxn type
Glucose -> Glucose-6-Phosphate
-Phosphorylation
Glycogenesis
Rxn 2: reactant -> product & rxn type
Glucose-6-Phosphate -> Glucose-1Phosphate
-Isomerization
Glycogenesis
Rxn 3: reactant -> product & rxn type
Glucose-1-Phosphate -> UDP-Glucose
-UDP transfer
Glycogenesis
Rxn 4: reactant -> product & rxn type
Glycogenin Primer + UDP-Glucose ->
Glycogenin + growing glycogen chain
-Glycosylation
Glycogenesis
Rxn 5: reactant -> product & rxn type
Growing glycogen chain -> Branched
glycogen
-Transferase
Glycogenesis
Rxn 1: purpose
Starts destabilization of glucose by phosphorylating it.
Phosphorylation of glucose also traps it inside the cell and allows more glucose to enter
Glycogenesis
Rxn 2: purpose
Form a more reactive phosphosugar that will be used for
glycosylation reactions
Glycogenesis
Rxn 3: purpose
Further activation of glucose for glycosylation. UDP is a great
leaving group.
Glycogenesis
Rxn 4: purpose
Formation of alpha-1,4 linkage to new glucose, growing glycogen
chain
Glycogenesis
Rxn 5: purpose
To form a branched alpha-1,6 glycogen chain. Need a minimum of
4 alpha-1,4 linkages between each alpha-1,6 linkage
Glycogenesis
Rxn 1: regulation
1) Glc-6-P - product inhibition
2) ATP - Inhibition - indicates high cellular energy
Glycogenesis
Rxn 4: regulation (allosteric) 1) Glc-6-P - activator - plentiful precursors
Glycogenesis
Rxn 4: regulation (covalent) 1) glycogen synthase a - dephosphorylated = active
2) glycogen synthase b - phosphorylated = inactive
3) glycogen primer - Tyr-OH on glycogenin protein is autocatalytic. 4-8 glucoses are
added to Tyr-OH before glycogen synthase can act
Citric Acid Cycle
Rxn 1: enzyme & class
Citrate synthase
Transferase
Citric Acid Cycle
Rxn 2: enzyme & class
Aconitase
Isomerase
Citric Acid Cycle
Rxn 3: enzyme & class
Isocitrate dehydrogenase
Oxidoreductase
Citric Acid Cycle
Rxn 4: enzyme & class
alpha-Ketoglutarate Dehydrogenase
Oxidoreductase
Citric Acid Cycle
Rxn 5: enzyme & class
Succinyl CoA Synthase
Ligase
Citric Acid Cycle
Rxn 6: enzyme & class
Succinate Dehydrogenase
Oxidoreductase
Citric Acid Cycle
Rxn 7: enzyme & class
Fumarase
Lyase
Citric Acid Cycle
Rxn 8: enzyme & class
Malate Dehydrogenase
Oxidoreductase
Citric Acid Cycle
Rxn 1: reactant -> product & rxn type
Oxaloacetate (OAA) -> Citrate
-Aldol condensation
Citric Acid Cycle
Rxn 2: reactant -> product & rxn type
Citrate -> Isocitrate
-Stereospecific dehydration and rehydration
Citric Acid Cycle
Rxn 3: reactant -> product & rxn type
Isocitrate -> Oxalosuccinate -> alphaKetoglutarate
-Oxidative decarboxylation
Citric Acid Cycle
Rxn 4: reactant -> product & rxn type
alpha-Ketoglutarate -> Succinyl-CoA
-Oxidative decarboxylation
Citric Acid Cycle
Rxn 5: reactant -> product & rxn type
Succinyl CoA -> Succinate
-Substrate level phosphorylation
Citric Acid Cycle
Rxn 6: reactant -> product & rxn type
Succinate -> Fumarate
-Dehydrogenation
Citric Acid Cycle
Rxn 7: reactant -> product & rxn type
Fumarate -> Malate
-Stereospecific hydration
Citric Acid Cycle
Rxn 8: reactant -> product & rxn type
Malate -> Oxaloacetate (OAA)
-Dehydrogenation
Citric Acid Cycle
Irreversible steps
Reactions 1, 3, 4
Citric Acid Cycle
Rxn 1: Substrate Regulation 1) Acetyl CoA - Activator
2) Oxaloacetate - Activator
Citric Acid Cycle
Rxn 1: Product Regulation 1) Citrate - Product inhibition
Citric Acid Cycle
Rxn 1: Allosteric Regulation 1) Succinyl CoA - Inhibitor - (negative feedback inhibition)
2) ATP - inhibitor - because cellular energy is high
3) NADH - inhibitor - because cellular energy is high
Citric Acid Cycle
Rxn 3: Allosteric Regulation 1) ATP - inhibitor
2) NADH - inhibitor
3) ADP - activator
4) NAD+ - activator
5) Ca2+ - activator
Citric Acid Cycle
Rxn 4: Product Regulation 1) Succinyl CoA - Product inhibition
Citric Acid Cycle
Rxn 4: Allosteric Regulation 1) ATP - inhibitor
2) NADH - inhibitor
3) ADP - activator
4) NAD+ - activator
5) Ca2+ - activator
Citric Acid Cycle
Rxn 1: Purpose
Replenishing carbons lost as CO2 in last turn of the cycle
Citric Acid Cycle
Rxn 2: Purpose
Convert unreactive tertiary alcohol to a more reactive secondary
alcohol
Citric Acid Cycle
Rxn 3: Purpose
Converting secondary alcohol to a ketone
1. oxidize carbon to CO2
2. make NADH for ETC/OP
Citric Acid Cycle
Rxn 4: Purpose
1. Oxidize carbon to CO2
2. Make NADH
3. Make energy rich molecule
Citric Acid Cycle
Rxn 5: Purpose
1. Make GTP
2. Make symmetrical molecule
Citric Acid Cycle
Rxn 6: Purpose
1. Place a strategic CC double bond
2. Make FADH2
Citric Acid Cycle
Rxn 7: Purpose
Add OH that will be oxidized in next step to make OAA
Citric Acid Cycle
Rxn 8: Purpose
To make OAA
ETC/OP
Complex 1: molecules in & out
In: NADH
Out: CoQH2
ETC/OP
Complex 1: molecules in & out
In: FADH
Out: CoQH2
ETC/OP
Complex 1: molecules in & out
In: CoQH2
Out: reduced CytC
ETC/OP
Complex 1: molecules in & out
In: reduced CytC
Out: 1/2 O2 (final electron acceptor)
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