Biochemistry of Carbohydrates: Part I

Biochemistry
of Carbohydrates
Part I
Dr. Kevin Ahern

Biochemistry of Carbohydrates
Glycolysis
• The Breakdown of Glucose
Glycolysis
• Primary Energy Source of Cells

Glycolysis

• Central Metabolic Pathway
Glycolysis

• All Reactions Occur in Cytoplasm
ATP ADP
Glycolysis
Phase 1
ATP ADP ATP Investment
• Two Phases
ATP ADP
Glycolysis
Phase 1
• Two Phases
2 NAD+ 2 NADH
2 ADP 2 ATP
Phase 2
Energy Production
2 ADP 2 ATP
ATP ADP
Glycolysis
Phase 1
• Two Phases
• Produces 2 Pyruvates, 2 ATP, 2 NADH
2 NAD+ 2 NADH
2 ADP 2 ATP
Phase 2
Energy Production
2 ADP 2 ATP
Glycolysis
• Glucose
Glycolysis
• Glucose
• Stored in Polymers (Amylose/Amylopectin/Glycogen)

Glycolysis
• Glucose

• Readily Released
Glycolysis
• Glucose

• Travels Easily in Blood
Glycolysis
• Glucose

• Travels Easily in Blood
• Made from Simple Precursors (Gluconeogenesis)
Glycolysis
• Phase 1
Hexokinase
+ H+
Glucose Glucose-6-Phosphate (G6P)

Glycolysis
• Phase 1
Hexokinase
+ H+

Glycolysis
• Phase 1
Hexokinase
+ H+

Glycolysis
• Phase 1
• Regulated Step of Glycolysis
Hexokinase
+ H+

Glycolysis
• Phase 1
• Regulated Step of Glycolysis

• ΔG°’ = -16.7 kJ/mol
Hexokinase
+ H+

ATP
Glycolysis Glucose
• Hexokinase
Hexokinase
ATP
Glycolysis Glucose
• Hexokinase
• Found in Virtually All Cells
Hexokinase
ATP
Glycolysis Glucose
• Hexokinase

• Not Specific to Glucose
Hexokinase
ATP
Glycolysis Glucose
• Hexokinase

• Glucokinase - Higher Km
Hexokinase
ATP
Glycolysis Glucose
• Hexokinase

• Glucokinase - Higher Km
• Inhibited by G6P Product
Hexokinase
Glycolysis
• Phase 1
Phosphoglucoisomerase
(G6P Isomerase)
Glucose-6-Phosphate (G6P) Fructose-6-Phosphate (F6P)

Glycolysis
• Phase 1
Phosphoglucoisomerase
(G6P Isomerase)
Glucose-6-Phosphate (G6P) Fructose-6-Phosphate (F6P)
Readily Reversible Reaction ΔG°’ = + 1.7 kJ/mol

Glycolysis
• Phase 1
Phosphofructokinase
(PFK-1)
+ H+
Fructose-6-Phosphate (F6P) Fructose-1,6-Bisphosphate (F1,6BP)

Glycolysis
• Phase 1
Phosphofructokinase
(PFK-1)
+ H+

Glycolysis
• Phase 1
Phosphofructokinase
+ H+

Glycolysis
• Phase 1
• Important Regulatory Enzyme of Glycolysis
Phosphofructokinase
+ H+

Glycolysis
• Phase 1
• Important Regulatory Enzyme of Glycolysis

• ΔG°’ = -14.2 kJ/mol
Phosphofructokinase
+ H+

Glycolysis
• Phosphofructokinase
Glycolysis
• AMP and Fructose 2,6 Bisphosphate Activate

Glycolysis

• ATP Inhibits
Glycolysis

• ATP Inhibits
• Two Binding Sites for ATP
Glycolysis
• Phase I
Glyceraldehyde-3-Phosphate
(GA3P)
Aldolase
Dihydroxyacetone
Fructose 1,6 Bisphosphate (F1,6 BP) Phosphate (DHAP
Glycolysis
• Phase I
• ΔG°’ = +23.9 kJ/mol
(GA3P)
Aldolase
Dihydroxyacetone
Fructose 1,6 Bisphosphate (F1,6 BP) Phosphate (DHAP
Glycolysis
• Aldolase Reaction
F1,6BP <=> GA3P + DHAP

Glycolysis

• Energy Barrier
{
ΔG = 23.9 + RTln [GA3P][DHAP]
[F1,6BP]
}
Glycolysis

• Energy Barrier
• “Pushing”
{
[F1,6BP]
}
{[F1,6BP]}
Glycolysis

• Energy Barrier
• “Pushing”
• “Pulling”
{
[F1,6BP]
}
{[F1,6BP]}
{[F1,6BP]}
Glycolysis
• Phase 2
Triose Phosphate Isomerase
Dihydroxyacetone Phosphate (DHAP) Glyceraldehyde-3-Phosphate (GA3P)

Glycolysis
• Phase 2
• Readily Reversible Reaction

Glycolysis
• Phase 2

• ΔG°’ = 7.6 kJ/mol

Glycolysis
• Phase 2

• ΔG°’ = 7.6 kJ/mol
• Diffusion-limited Enzyme

Glycolysis
• Phase 2

• ΔG°’ = 7.6 kJ/mol
• Diffusion-limited Enzyme
• Perfect Enzyme

Glycolysis
• Phase 2
Glycolysis
• Phase 2
Dehydrogenase (GA3PDH)
Glyceraldehyde-3-Phosphate (GA3P) 1,3 Bisphosphoglycerate (1,3 BPG)

Glycolysis
• Phase 2
• Only Oxidation of Glycolysis
Dehydrogenase (GA3PDH)

Glycolysis
• Phase 2
Aldehyde Dehydrogenase (GA3PDH) Ester

Glycolysis
• Phase 2

• ΔG°’ = 6.3 kJ/mol
Aldehyde Dehydrogenase (GA3PDH) Ester

Glycolysis
• Phase 2
Phosphoglycerate
Kinase
1,3 Bisphosphoglycerate (1,3 BPG) 3 Phosphoglycerate (3-PG)

Glycolysis
• Phase 2
• Substrate Level Phosphorylation
Phosphoglycerate
Kinase

Glycolysis
• Phase 2

• ΔG°’ = -18.9 kJ/mol
Phosphoglycerate
Kinase

Glycolysis
Glycolysis
Three means of making ATP

Glycolysis

1. Substrate level phosphorylation -‐ high energy molecule adds phosphate to
ADP
Glycolysis

ADP
2. Oxidative phosphorylation -‐ oxidative energy (electron movement) used in
mitochondria to generate ATP
Glycolysis

ADP
2. Oxidative phosphorylation -‐ oxidative energy (electron movement) used in
mitochondria to generate ATP
3. Photophosphorylation -‐ light energy captured in chloroplasts of plants to
make ATP
Glycolysis
• Phase 2
Phosphoglycerate Mutase
3 Phosphoglycerate (3-PG) 2 Phosphoglycerate (2-PG)

Glycolysis
• Phase 2
• Minor Source of 2,3 BPG

Glycolysis
• Phase 2
• Minor Source of 2,3 BPG

• ΔG°’ = 4.4 kJ/mol

Glycolysis
• 2,3 BPG and Glycolysis
Phosphoglycerate Kinase Phosphoglycerate Mutase

1,3 BPG 3-PG 2-PG
ADP ATP
Bi
sp te
ho
sp e ra
Pi ogly Pi Pi
Mu hog
tas lyc p h ase
e era o s at 2,3 BPG
te p h ph
s s
2,3 BPG Bi Pho
3
2,
Released at a Low Level in All Cells
Released Freely in Erythrocytes
and Placental Cells
Glycolysis
• 2,3 BPG and Glycolysis
• 2,3 BPG Binds to Hemoglobin and Favors O2 Release
Phosphoglycerate Kinase Phosphoglycerate Mutase

1,3 BPG 3-PG 2-PG
ADP ATP
Bi
sp te
ho
sp e ra
Pi ogly Pi Pi
Mu hog
tas lyc p h ase
e era o s at 2,3 BPG
te p h ph
s s
2,3 BPG Bi Pho
3
2,
Released at a Low Level in All Cells
Released Freely in Erythrocytes
and Placental Cells
Glycolysis
• Phase 2
Enolase
2 Phosphoglycerate (2-PG) Phosphoenolpyruvate (PEP)

Glycolysis
• Phase 2
• ΔG°’ = 1.8 kJ/mol
Enolase
2 Phosphoglycerate (2-PG) Phosphoenolpyruvate (PEP)

Glycolysis
• Phase 2
Pyruvate Kinase
Phosphoenolpyruvate (PEP) Pyruvate (Pyr)

Glycolysis
• Phase 2
Pyruvate Kinase

Glycolysis
• Phase 2

• “Big Bang” of Glycolysis
Pyruvate Kinase

Glycolysis
• Phase 2

• ΔG°’ = -31.7 kJ/mol
Pyruvate Kinase

Glycolysis
• Phase 2

• ΔG°’ = -31.7 kJ/mol
• Essentially Irreversible
Pyruvate Kinase

Glycolysis
• Pyruvate Kinase
Glycolysis
• Pyruvate Kinase
• Third Regulated Enzyme of Glycolysis

Glycolysis
• Pyruvate Kinase

• Inhibited by ATP, Alanine
Glycolysis
• Pyruvate Kinase

• Activated by F1,6BP
Glycolysis
• Pyruvate Kinase

• Inactivated by Phosphorylation
Glycolysis
• Pyruvate Kinase

• Inactivated by Phosphorylation
• Regulation Important for Gluconeogenesis
Glycolysis
• Pyruvate Kinase
Glycolysis
• Summary
Glycolysis
• Summary
Glucose + 2 ADP + 2Pi + 2 NAD+

Glycolysis
• Summary
Yields
Glycolysis
• Summary
Yields
2 Pyruvate + 2 ATP + 2 NADH + 2 H+ + 2 H2O

Metabolic Melody
The Sound of Glucose 
(to the tune of "A Few of My Favorite Things”)
Copyright © Kevin Ahern 
Metabolic Melody
Aldehyde sugars are always aldoses and 

If there's a ketone we call them ketoses 
Some will form structures in circular rings 
Saccharides do some incredible things
Onto a glucose we add a 'P' to it 
ATP energy ought to renew it 
Quick rearranging creates F6P 
Without requiring input energy
 
At a high rate
Add a phosphate
With PFK
F1,6BP is made up this way
So we can run and play
 
Aldolase breaks it and then it releases 
DHAP and a few G3Pieces 
These both turn in to 1,3 BPG 
Adding electrons onto NAD
Aldehyde sugars are always aldoses and  Phosphate plus ADP makes ATP 
If there's a ketone we call them ketoses  While giving cells what they need - en-er-gy 
Some will form structures in circular rings  Making triphosphate's a situa-shun 
Saccharides do some incredible things Of substrate level phosphoryla-shun
Onto a glucose we add a 'P' to it   
ATP energy ought to renew it  3-B-P-G
Quick rearranging creates F6P  2-B-P-G
Without requiring input energy Lose a water
  PEP gets a high energy state
At a high rate Just to make py-ru-vate
Add a phosphate  
With PFK So all the glucose gets broken and bent 
F1,6BP is made up this way If there's no oxygen cells must ferment 
So we can run and play Pyruvate / lactate our cells hit the wall 
  Some lucky yeast get to make ethanol
Aldolase breaks it and then it releases  This is the end of your glucose's song 
DHAP and a few G3Pieces  Unless you goof up and get it all wrong 
These both turn in to 1,3 BPG  Break it, don't make it to yield ATP 
Adding electrons onto NAD You'll save your cells from fu-til-i-ty
Metabolic Melody
Things You Should Remember
(to the tune of “In My Life”)
Copyright © Kevin Ahern
Metabolic Melody
There are things you should remember

When you’re stud-y-ing for this exam
All the pathways since September
And the mol-e-cules comprising them

Though that is an awful lot of information

I hope that you can retain it all
If you do you will avoid a grade deflation
When you-uuu study right, you will recall

Now in all your preparation

There is soooome-thing you should regard
How your brain stores information
So transcribe your notes onto a card
There are things you should remember I assure you it will up your recollection
When you’re stud-y-ing for this exam Of enzymes and com-plex Haworth rings
All the pathways since September It will drive performance to perfection
And the mol-e-cules comprising them Simply from the act of writing things

Though that is an awful lot of information I assure you it will up your recollection
I hope that you can retain it all Of enzymes and com-plex Haworth rings
If you do you will avoid a grade deflation It will drive performance to perfection
When you-uuu study right, you will recall Simply from the act of writing things

Now in all your preparation So go-ooo forward now and write down things
There is soooome-thing you should regard
How your brain stores information
So transcribe your notes onto a card

Biochemistry of Carbohydrates: Part I

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Biochemistry of Carbohydrates: Part I

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Biochemistry

Dr. Kevin Ahern

• Primary Energy Source of Cells

• Primary Energy Source of Cells

• Primary Energy Source of Cells

• Stored in Polymers (Amylose/Amylopectin/Glycogen)

• Stored in Polymers (Amylose/Amylopectin/Glycogen)

• Stored in Polymers (Amylose/Amylopectin/Glycogen)

• Stored in Polymers (Amylose/Amylopectin/Glycogen)

Glucose Glucose-6-Phosphate (G6P)

Glucose Glucose-6-Phosphate (G6P)

Glucose Glucose-6-Phosphate (G6P)

• Regulated Step of Glycolysis

Glucose Glucose-6-Phosphate (G6P)

• Regulated Step of Glycolysis

Glucose Glucose-6-Phosphate (G6P)

• Found in Virtually All Cells

• Found in Virtually All Cells

• Found in Virtually All Cells

• Found in Virtually All Cells

Glucose-6-Phosphate (G6P) Fructose-6-Phosphate (F6P)

Glucose-6-Phosphate (G6P) Fructose-6-Phosphate (F6P)

Readily Reversible Reaction ΔG°’ = + 1.7 kJ/mol

Fructose-6-Phosphate (F6P) Fructose-1,6-Bisphosphate (F1,6BP)

Fructose-6-Phosphate (F6P) Fructose-1,6-Bisphosphate (F1,6BP)

Fructose-6-Phosphate (F6P) Fructose-1,6-Bisphosphate (F1,6BP)

• Important Regulatory Enzyme of Glycolysis

Fructose-6-Phosphate (F6P) Fructose-1,6-Bisphosphate (F1,6BP)

• Important Regulatory Enzyme of Glycolysis

Fructose-6-Phosphate (F6P) Fructose-1,6-Bisphosphate (F1,6BP)

• AMP and Fructose 2,6 Bisphosphate Activate

• AMP and Fructose 2,6 Bisphosphate Activate

• AMP and Fructose 2,6 Bisphosphate Activate

• ΔG°’ = +23.9 kJ/mol

F1,6BP <=> GA3P + DHAP

F1,6BP <=> GA3P + DHAP

F1,6BP <=> GA3P + DHAP

F1,6BP <=> GA3P + DHAP

Triose Phosphate Isomerase

Dihydroxyacetone Phosphate (DHAP) Glyceraldehyde-3-Phosphate (GA3P)

• Readily Reversible Reaction

Triose Phosphate Isomerase

Dihydroxyacetone Phosphate (DHAP) Glyceraldehyde-3-Phosphate (GA3P)

• Readily Reversible Reaction

Triose Phosphate Isomerase

Dihydroxyacetone Phosphate (DHAP) Glyceraldehyde-3-Phosphate (GA3P)

• Readily Reversible Reaction

Triose Phosphate Isomerase

Dihydroxyacetone Phosphate (DHAP) Glyceraldehyde-3-Phosphate (GA3P)

• Readily Reversible Reaction

Triose Phosphate Isomerase

Dihydroxyacetone Phosphate (DHAP) Glyceraldehyde-3-Phosphate (GA3P)

Glyceraldehyde-3-Phosphate (GA3P) 1,3 Bisphosphoglycerate (1,3 BPG)

• Only Oxidation of Glycolysis

Glyceraldehyde-3-Phosphate (GA3P) 1,3 Bisphosphoglycerate (1,3 BPG)

• Only Oxidation of Glycolysis

Glyceraldehyde-3-Phosphate (GA3P) 1,3 Bisphosphoglycerate (1,3 BPG)

• Only Oxidation of Glycolysis

Glyceraldehyde-3-Phosphate (GA3P) 1,3 Bisphosphoglycerate (1,3 BPG)

1,3 Bisphosphoglycerate (1,3 BPG) 3 Phosphoglycerate (3-PG)

• Substrate Level Phosphorylation

1,3 Bisphosphoglycerate (1,3 BPG) 3 Phosphoglycerate (3-PG)

• Substrate Level Phosphorylation

Aldehyde sugars are always aldoses and 