0.40. Biochemistry of Carbohydrates
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1 0.40 Biochemistry of Carbohydrates
2 Biochemistry of Carbohydrates
3 ATP ADP Glycolysis The Breakdown of Glucose Primary Energy Source of Cells Central Metabolic Pathway All Reactions Occur in Cytoplasm Two Phases Produces 2 Pyruvates, 2 ATP, 2 NADH Regulation ATP ADP Phase 1 ATP Investment 2 NAD + 2 NADH 2 ADP 2 ATP Phase 2 Energy Production 2 ADP 2 ATP
4 Glucose Stored in Polymers (Amylose/Amylopectin/Glycogen) poison Readily Released Travels Easily in Blood Made from Simple Precursors (Gluconeogenesis)
5 Phase 1 Regulated Step of Glycolysis ΔG = kj/mol Hexokinase + H + Glucose Glucose-6-Phosphate (G6P)
6 ATP Glycolysis Hexokinase Glucose Found in Virtually All Cells Not Specific to Glucose Glucokinase - Higher Km Inhibited by G6P Product Hexokinase
7 Phase 1 Phosphoglucoisomerase )G6P Isomerase( Glucose-6-Phosphate (G6P( Fructose-6-Phosphate (F6P( Readily Reversible Reaction ΔG = kj/mol
8 Phase 1 Important Regulatory Enzyme of Glycolysis ΔG = kj/mol Phosphofructokinase (PFK-1) + H + Fructose-6-Phosphate (F6P( Fructose-1,6-Bisphosphate (F1,6BP(
9 Phosphofructokinase AMP and Fructose 2,6 Bisphosphate Activate ATP Inhibits Two Binding Sites for ATP
10 Phase I ΔG = kj/mol Aldolase Glyceraldehyde-3-Phosphate )GA3P( Fructose 1,6 Bisphosphate (F1,6 BP( Dihydroxyacetone Phosphate (DHAP
11 Aldolase Reaction Energy Barrier Pushing Pulling F1,6BP <=> GA3P + DHAP { } ΔG = RTln [GA3P][DHAP] [F1,6BP] ΔG = RTln {[GA3P][DHAP] } [F1,6BP] ΔG = RTln { } [GA3P][DHAP] [F1,6BP]
12 Phase 2 Readily Reversible Reaction ΔG = 7.6 kj/mol Diffusion-limited Enzyme Perfect Enzyme Triose Phosphate Isomerase Dihydroxyacetone Phosphate (DHAP( Glyceraldehyde-3-Phosphate (GA3P(
13 Phase 2
14 Phase 2 Only Oxidation of Glycolysis ΔG = 6.3 kj/mol Aldehyde Glyceraldehyde-3-Phosphate Dehydrogenase (GA3PDH) Ester Glyceraldehyde-3-Phosphate (GA3P) 1,3 Bisphosphoglycerate (1,3 BPG)
15 Phase 2 Substrate Level Phosphorylation ΔG = kj/mol Phosphoglycerate Kinase 1,3 Bisphosphoglycerate (1,3 BPG( 3 Phosphoglycerate (3-PG(
16 Three means of making ATP 1.Substrate level phosphorylation - high energy molecule adds phosphate to 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
17 Phase 2 Minor Source of 2,3 BPG ΔG = 4.4 kj/mol Phosphoglycerate Mutase 3 Phosphoglycerate (3-PG( 2 Phosphoglycerate (2-PG(
18 2,3 BPG and Glycolysis 2,3 BPG Binds to Hemoglobin and Favors O2 Release 1,3 BPG Phosphoglycerate Kinase 3-PG Phosphoglycerate Mutase 2-PG ADP ATP Pi Pi Pi 2,3 BPG 2,3 BPG Released Freely in Erythrocytes and Placental Cells Released at a Low Level in All Cells
19 Phase 2 ΔG = 1.8 kj/mol Enolase 2 Phosphoglycerate (2-PG( Phosphoenolpyruvate (PEP(
20 Phase 2 Substrate Level Phosphorylation ΔG = kj/mol Heat releases Essentially Irreversible Pyruvate Kinase Phosphoenolpyruvate (PEP( Pyruvate (Pyr(
21 Pyruvate Kinase Third Regulated Enzyme of Glycolysis Inhibited by ATP, Alanine Activated by F1,6BP Inactivated by Phosphorylation Regulation Important for Gluconeogenesis
22 Pyruvate Kinase
23 Summary Glucose + 2 ADP + 2Pi + 2 NAD + Yields 2 Pyruvate + 2 ATP + 2 NADH + 2 H H2O
24 Product of Process Glucose Glycolysis Fermentation in Yeast/Bacteria NAD + X NADH + H + GA3P 1,3 BPG O2 Helps to Make NAD + In Absence of Oxygen Pyruvate (PYR)
25 Fermentation in Yeast/Bacteria
26 Product of Process Glucose Glycolysis Fermentation in Animals NAD + X NADH + H + GA3P 1,3 BPG O2 Helps to Make NAD + Pyruvate (PYR)
27 Fermentation in Animals
28 Fates of Pyruvate Pyruvate Not an End Point Important for Amino Acids,Energy, Fermentation
29 Metabolism of Other Sugars - Galactose
30 Metabolism of Other Sugars - Galactose Reduced Quantities in Adults Leads to Lactose Intolerance Lactase Lactose Galactose Glucose
31 Metabolism of Other Sugars - Fructose Fructokinase F1P Fructose Fructoaldolase DHAP + Glyceraldehyde Fructose-1-Phosphate (F1P) Glyceraldehyde-3-Phosphate To Glycolysis
32 Fructose Regulatory Enzyme Bypassed Glycolysis Metabolism of Other Sugars - Fructose Regulatory Enzyme Bypassed F1P DHAP + GA3P Excess Pyruvate?
33 Gluconeogenesis Synthesis of Glucose Important for Regulating Blood Glucose Reactions in Cytoplasm, Mitochondrion, Endoplasmic Reticulum In the Body - Liver and Kidney
34 Gluconeogenesis Synthesis of Glucose Four Reactions in Gluconeogenesis Replace Three Reactions in Glycolysis All Other Reactions are Simply the Reverse of Glycolysis Reactions Two Pyruvates Needed for Each Glucose
35 Gluconeogenesis Synthesis of Glucose G6Pase (Hexokinase) F1,6BPase )PFK) PEPCK Pyruvate Carboxylase (Pyruvate Kinase)
36
37 Gluconeogenesis Reactions of Gluconeogenesis Run as Reverse of Glycolysis Reactions Glucose 11. Glucose-6-Phosphatase 1. Hexokinase G6P 10. Phosphoglucoisomerase 2. Phosphoglucoisomerase F6P 9. F1,6 Bisphosphatase 3. PFK1 F1,6BP 8. Aldolase 4. Aldolase DHAP + G3P 7. Triose Phosphate Isomerase 5. Triose Phosphate Isomerase GA3P 6.. GA3PDH 6. GA3PDH 1,3 BPG 5. Phosphoglycerate Kinase 7. Phosphoglycerate Kinase 3-PG 4. Phosphoglycerate Mutase 8. Phosphoglycerate Mutase 2-PG 3.. Enolase 9. Enolase PEP 2.. PEPCK 10. Pyruvate Kinase 1. Pyruvate Carboxylase Pyr
38 Gluconeogenesis Reactions of Gluconeogenesis Reaction #1 Step 1 of Bypassing Pyruvate Kinase Occurs in Mitochondrion
39 Gluconeogenesis Reactions of Gluconeogenesis Reaction #1 Step 1 of Bypassing Pyruvate Kinase Occurs in Mitochondrion Pyruvate Carboxylase Pyruvate )Pyr( Oxaloacetate )OAA(
40 Gluconeogenesis Reactions of Gluconeogenesis CO2 Biotin Carrying CO2
41 Gluconeogenesis Reactions of Gluconeogenesis Reaction #2 Occurs in cytoplasm Second Triphosphate Necessary Phosphoenolpyruvate Carboxykinase (PEPCK) Oxaloacetate ) OAA( Phosphoenolpyruvate (PEP(
42 Gluconeogenesis Reactions of Gluconeogenesis Reaction # 9 of Gluconeogenesis Not the Reversal of the PFK Reaction Energy Realized by Not Regenerating ATP Glycolysis Enzyme Required ATP Fructose 1,6 Bisphosphatase ) FBPase( Fructose 1,6 Bisphosphate )F1,6BP( Fructose 6 Phosphate )F6P(
43 Gluconeogenesis Reactions of Gluconeogenesis Reaction # 11 of Gluconeogenesis Not the Reversal of the Hexokinase Reaction Energy Reserved by Not Regenerating ATP Occurs in Endoplasmic Reticulum Glycolysis Enzyme Required ATP Glucose-6-Phosphatase (G6Pase) Glucose 6 Phosphate )G6P( Glucose
44 Gluconeogenesis and Glycolysis Regulation Glycolysis Glucose + 2 ADP + 2Pi + 2 NAD+ Yields 2 Pyruvate + 2ATP + 2 NADH + 2 H H2O Gluconeogenesis 2 Pyruvate + 2 NADH + 4 ATP + 2 GTP Yields Glucose + 2 NAD ADP + 2 GDP + 6 Pi Gluconeogenesis Requires More Energy Than Glycolysis Generates Futile Cycle Results if Both Running Simultaneously ATP/GTP Burned, Nothing but Heat Produced
45 Gluconeogenesis and Glycolysis Regulation
46 Gluconeogenesis and Glycolysis Regulation Gluconeogenesis Glycolysis
47 Gluconeogenesis and Glycolysis Reciprocal Regulation Regulation Low Energy High Energy Other Glycolysis Hexokinase - G6P (-) PFK - AMP (+), ATP (-), F2,6BP (++) Pyruvate Kinase - Alanine (-), ATP (-), F1,6BP (+) Gluconeogenesis FBPase - Citrate (+), AMP (-), F2,6BP (- -) PEPCK - ADP (-) Pyruvate Carboxylase - ADP (-), Acetyl-CoA (+) F2,6BP is Made Upon Insulin Stimulation - Favors Glycolysis F2,6BP is Broken Down Upon Glucagon Stimulation - Favors Gluconeogenesis
48 Gluconeogenesis and Glycolysis Regulation
49 Cori Cycle
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