Part,Ioregonstate.edu/instruct/bb450/450material/... · • 2,3 BPG and Glycolysis •2,3 BPG Binds...

Biochemistry of Carbohydrates Part I

Dr. Kevin Ahern

Biochemistry of Carbohydrates

Glycolysis• The Breakdown of Glucose

• Primary Energy Source of Cells

• Primary Energy Source of Cells• Central Metabolic Pathway

• Primary Energy Source of Cells• Central Metabolic Pathway• All Reactions Occur in Cytoplasm

• Primary Energy Source of Cells• Central Metabolic Pathway• All Reactions Occur in Cytoplasm• Two Phases

Phase 1 ATP Investment

ATP ADP

• Primary Energy Source of Cells• Central Metabolic Pathway• All Reactions Occur in Cytoplasm• Two Phases

ATP ADP

Phase 2 Energy Production

2 ADP 2 ATP

2 NAD+ 2 NADH

• Primary Energy Source of Cells• Central Metabolic Pathway• All Reactions Occur in Cytoplasm• Two Phases• Produces 2 Pyruvates, 2 ATP, 2 NADH

ATP ADP

Phase 2 Energy Production

2 ADP 2 ATP

2 NAD+ 2 NADH

Glycolysis• Glucose

•Stored in Polymers (Amylose/Amylopectin/Glycogen)

•Stored in Polymers (Amylose/Amylopectin/Glycogen)•Readily Released

•Stored in Polymers (Amylose/Amylopectin/Glycogen)•Readily Released•Travels Easily in Blood

•Stored in Polymers (Amylose/Amylopectin/Glycogen)•Readily Released•Travels Easily in Blood•Made from Simple Precursors (Gluconeogenesis)

Glycolysis• Phase 1

Glucose Glucose-6-Phosphate (G6P)

Hexokinase

• Regulated Step of Glycolysis

Hexokinase

• Regulated Step of Glycolysis•ΔG°’ = -16.7 kJ/mol

Glycolysis• Hexokinase

Hexokinase

Glucose

Hexokinase

Glucose

• Found in Virtually All Cells

Hexokinase

Glucose

• Found in Virtually All Cells• Not Specific to Glucose

Hexokinase

Glucose

• Found in Virtually All Cells• Not Specific to Glucose• Glucokinase - Higher Km

Hexokinase

Glucose

• Found in Virtually All Cells• Not Specific to Glucose• Glucokinase - Higher Km• Inhibited by G6P Product

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

Phosphoglucoisomerase

(G6P Isomerase)

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

Phosphoglucoisomerase

(G6P Isomerase)

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

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

Phosphofructokinase

(PFK-1)

Phosphofructokinase

(PFK-1)

Phosphofructokinase

• Important Regulatory Enzyme of Glycolysis

Phosphofructokinase

• Important Regulatory Enzyme of Glycolysis•ΔG°’ = -14.2 kJ/mol

Glycolysis• Phosphofructokinase

• AMP and Fructose 2,6 Bisphosphate Activate

• AMP and Fructose 2,6 Bisphosphate Activate• ATP Inhibits

• AMP and Fructose 2,6 Bisphosphate Activate• ATP Inhibits• Two Binding Sites for ATP

Glycolysis• Phase I

Fructose 1,6 Bisphosphate (F1,6 BP)

Aldolase

Glyceraldehyde-3-Phosphate (GA3P)

Dihydroxyacetone Phosphate (DHAP

Glycolysis• Phase I

Fructose 1,6 Bisphosphate (F1,6 BP)

Aldolase

Glyceraldehyde-3-Phosphate (GA3P)

Dihydroxyacetone Phosphate (DHAP

•ΔG°’ = +23.9 kJ/mol

Glycolysis• Aldolase Reaction

F1,6BP <=> GA3P + DHAP

•Energy BarrierF1,6BP <=> GA3P + DHAP

ΔG = 23.9 + RTln [GA3P][DHAP]

[F1,6BP]{ }

•Energy Barrier• “Pushing”

[F1,6BP]{ }ΔG = 23.9 + RTln [GA3P][DHAP]

[F1,6BP]{ }

•Energy Barrier• “Pushing”• “Pulling”

[F1,6BP]{ }ΔG = 23.9 + RTln [GA3P][DHAP]

[F1,6BP]{ }

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

Triose Phosphate Isomerase

•Readily Reversible Reaction

•Readily Reversible Reaction•ΔG°’ = 7.6 kJ/mol

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

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

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

Glyceraldehyde-3-Phosphate Dehydrogenase (GA3PDH)

•Only Oxidation of Glycolysis

Glyceraldehyde-3-Phosphate Dehydrogenase (GA3PDH)

•Only Oxidation of Glycolysis

Glyceraldehyde-3-Phosphate Dehydrogenase (GA3PDH)Aldehyde Ester

•Only Oxidation of Glycolysis•ΔG°’ = 6.3 kJ/mol

Glyceraldehyde-3-Phosphate Dehydrogenase (GA3PDH)Aldehyde Ester

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

Phosphoglycerate Kinase

•Substrate Level Phosphorylation

•Substrate Level Phosphorylation•ΔG°’ = -18.9 kJ/mol

Glycolysis

Three means of making ATP

Glycolysis

Three means of making ATP1. Substrate level phosphorylation -‐ high energy molecule adds phosphate to ADP

Glycolysis

Three means of making ATP1. Substrate level phosphorylation -‐ high energy molecule adds phosphate to ADP2. Oxidative phosphorylation -‐ oxidative energy (electron movement) used in mitochondria to generate ATP

Glycolysis

Three means of making ATP1. Substrate level phosphorylation -‐ high energy molecule adds phosphate to ADP2. Oxidative phosphorylation -‐ oxidative energy (electron movement) used in mitochondria to generate ATP3. Photophosphorylation -‐ light energy captured in chloroplasts of plants to make ATP

Glycolysis

3 Phosphoglycerate (3-PG)

Phosphoglycerate Mutase

•Minor Source of 2,3 BPG

•Minor Source of 2,3 BPG•ΔG°’ = 4.4 kJ/mol

Glycolysis• 2,3 BPG and Glycolysis

2,3 BPG

3-PG 2-PG

2,3 BPG

Bisphosphoglycerate

Mutase

2,3 Bisphosp

hoglyerate

Phosphatase

1,3 BPG

Released Freely in Erythrocytes and Placental Cells

Released at a Low Level in All Cells

PiPi Pi

ADP ATP

Glycolysis• 2,3 BPG and Glycolysis

•2,3 BPG Binds to Hemoglobin and Favors O2 Release

2,3 BPG

3-PG 2-PG

2,3 BPG

Bisphosphoglycerate

Mutase

2,3 Bisphosp

hoglyerate

Phosphatase

1,3 BPG

Released Freely in Erythrocytes and Placental Cells

Released at a Low Level in All Cells

PiPi Pi

ADP ATP

Enolase

2 Phosphoglycerate (2-PG) Phosphoenolpyruvate (PEP)

•ΔG°’ = 1.8 kJ/mol

Enolase

2 Phosphoglycerate (2-PG) Phosphoenolpyruvate (PEP)

Pyruvate Kinase

Phosphoenolpyruvate (PEP) Pyruvate (Pyr)

•Substrate Level Phosphorylation

Pyruvate Kinase

•Substrate Level Phosphorylation• “Big Bang” of Glycolysis

Pyruvate Kinase

•Substrate Level Phosphorylation• “Big Bang” of Glycolysis•ΔG°’ = -31.7 kJ/mol

Pyruvate Kinase

•Substrate Level Phosphorylation• “Big Bang” of Glycolysis•ΔG°’ = -31.7 kJ/mol•Essentially Irreversible

Pyruvate Kinase

Glycolysis• Pyruvate Kinase

•Third Regulated Enzyme of Glycolysis

•Third Regulated Enzyme of Glycolysis• Inhibited by ATP, Alanine

•Third Regulated Enzyme of Glycolysis• Inhibited by ATP, Alanine•Activated by F1,6BP

•Third Regulated Enzyme of Glycolysis• Inhibited by ATP, Alanine•Activated by F1,6BP• Inactivated by Phosphorylation

•Third Regulated Enzyme of Glycolysis• Inhibited by ATP, Alanine•Activated by F1,6BP• Inactivated by Phosphorylation•Regulation Important for Gluconeogenesis

Glycolysis• Summary

Glucose + 2 ADP + 2Pi + 2 NAD+

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”)

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 rateAdd a phosphateWith PFKF1,6BP is made up this waySo we can run and playAldolase 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 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 rateAdd a phosphateWith PFKF1,6BP is made up this waySo we can run and playAldolase breaks it and then it releases DHAP and a few G3Pieces These both turn in to 1,3 BPG Adding electrons onto NAD

Phosphate plus ADP makes ATP While giving cells what they need - en-er-gy

Making triphosphate's a situa-shun Of substrate level phosphoryla-shun

3-B-P-G2-B-P-GLose a waterPEP gets a high energy stateJust to make py-ru-vateSo all the glucose gets broken and bent If there's no oxygen cells must ferment Pyruvate / lactate our cells hit the wall Some lucky yeast get to make ethanol

This is the end of your glucose's song Unless you goof up and get it all wrong

Break it, don't make it to yield ATP You'll save your cells from fu-til-i-ty

Metabolic Melody

Things You Should Remember (to the tune of “In My Life”)

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 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

I assure you it will up your recollection Of enzymes and com-plex Haworth rings

It will drive performance to perfection Simply from the act of writing things

I assure you it will up your recollection

Of enzymes and com-plex Haworth rings It will drive performance to perfection Simply from the act of writing things

So go-ooo forward now and write down things

Part,Ioregonstate.edu/instruct/bb450/450material/... · • 2,3 BPG and Glycolysis •2,3 BPG Binds...

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