Chem 109 C Fall 2014 Armen Zakarian ffice: Chemistry Bldn 2217
o Catabolism of carbohydrates: 10 reactions of glycolysis Chapter 25 C C 2 C 2 D-glucose α-d-glucopyranose aworth projection α-d-glucopyranose conformational drawing α-d-glucopyranose α-d-fructofuranose
o Glycolysis: reaction 1 ATP ADP, + - hexokinase α-d-glucopyranose glucose-6-phosphate Cofactor: Mg 2+ - P - P - ATP P - Ad - + - P - P - ADP Ad
o Glycolysis : reaction 2 - glucose-6-phosphate glucose phosphate isomerase - fructose-6-phosphate
o Glycolysis : reaction 2 Chapter 25
o Glycolysis : reaction 3 - ATP ADP, + phosphofructokinase - P - - fructose-6-phosphate fructose-1,6-diphosphate Cofactor: Mg 2+
o Glycolysis : reaction 4 - P - - aldolase - + P - - fructose-1,6-diphosphate D-glyceraldehyde- 3-phosphate dihydroxyacetonephosphate 2 C 2 P 3 C 2 P 3 N + (C 2 ) 4 -Lys C 2 P 3 N 2 (C 2 ) 4 -Lys C 2 P 3 N (C 2 ) 4 -Lys C 2 P 3 N + (C 2 ) 4 -Lys B :B C 2 P 3 - - P
o Glycolysis : reaction 4 - P - - aldolase - + P - - fructose-1,6-diphosphate D-glyceraldehyde- 3-phosphate dihydroxyacetonephosphate 2 C 2 P 3 C 2 P 3 N + (C 2 ) 4 -Lys C 2 P 3 N 2 (C 2 ) 4 -Lys C 2 P 3 N (C 2 ) 4 -Lys C 2 P 3 N + (C 2 ) 4 -Lys B :B C 2 P 3 - - P
o Glycolysis : reaction 4 - P - - aldolase - + P - - fructose-1,6-diphosphate D-glyceraldehyde- 3-phosphate dihydroxyacetonephosphate 2 C 2 P 3 C 2 P 3 N + (C 2 ) 4 -Lys C 2 P 3 N 2 (C 2 ) 4 -Lys C 2 P 3 N (C 2 ) 4 -Lys C 2 P 3 N + (C 2 ) 4 -Lys B :B C 2 P 3 - - P
o Glycolysis : reaction 4 - P - - aldolase - + P - - fructose-1,6-diphosphate D-glyceraldehyde- 3-phosphate dihydroxyacetonephosphate 2 C 2 P 3 C 2 P 3 N + (C 2 ) 4 -Lys C 2 P 3 N 2 (C 2 ) 4 -Lys C 2 P 3 N (C 2 ) 4 -Lys C 2 P 3 N + (C 2 ) 4 -Lys B :B C 2 P 3 - - P
o Glycolysis : reaction 5 P - - triosephosphate isomerase - dihydroxyacetonephosphate D-glyceraldehyde- 3-phosphate
o Glycolysis : reaction 5 P - - triosephosphate isomerase - dihydroxyacetonephosphate D-glyceraldehyde- 3-phosphate endiol rearrangement: P - - enediol intermediate
o Glycolysis : reaction 6 - -- D-glyceraldehyde- 3-phosphate, P 4 NAD, + glyceraldehyde- 3-phosphate dehydrogenase - P D-1,3-diphosphoglycerate
, NADP + P 3 glyceraldehyde-3-phosphate P 3 dehydrogenase + + + + - P 3 D-glyceraldehyde-3-phosphate D-1,3-diphosphoglycerate R substrate GAP S B - R S B R - B - B S NAD S R NAD + R C P - - product B R S P - - - S B R - P -
o Glycolysis : reaction 7 - ADP ATP - P phosphoglycerate kinase - -- D-1,3-diphosphoglycerate 3-phosphoglycerate Cofactor: Mg 2+
o Glycolysis : reaction 8 - - phosphoglycerate mutase - P - - 3-phosphoglycerate phosphoglycerate - - P - - 2,3-diphosphoglycerate
o Glycolysis : reaction 9 2 - P - - enolase - P - - phosphoglycerate phosphoenolpyruvate PRACTICE PRBLEM Provide a mechanism for the transformation shown above.
o Glycolysis : reaction 10 ADP ATP - P - - pyruvate kinase - phosphoenolpyruvate pyruvate Cofactor: Mg 2+
o Glycolysis : summary 2 ATP 2 ADP 5 reactions α-d-glucopyranose 2 - D-glyceraldehyde- 3-phosphate 4 ADP, 2 4 ATP, 2NAD 5 reactions 2 - pyruvate
o Glycolysis : fates of pyruvate NAD, + + C 2 NAD, + - (S)-lactic acid lactate dehydrogenase; anaerobic conditions - pyruvate pyruvate decarboxylase, TPP anaerobic, yeast alcohol dehydrogenase pyruvate dehydrogenase system; aerobic conditions acetyl-coa
o Glycolysis : fates of pyruvate NAD, + + C 2 NAD, + - (S)-lactic acid lactate dehydrogenase; anaerobic conditions - pyruvate pyruvate decarboxylase, TPP anaerobic, yeast alcohol dehydrogenase pyruvate dehydrogenase system; aerobic conditions acetyl-coa
o Glycolysis : fates of pyruvate NAD, + + C 2 NAD, + - (S)-lactic acid lactate dehydrogenase; anaerobic conditions - pyruvate pyruvate decarboxylase, TPP anaerobic, yeast alcohol dehydrogenase pyruvate dehydrogenase system; aerobic conditions acetyl-coa
o Glycolysis : fates of pyruvate NAD, + + C 2 NAD, + - (S)-lactic acid lactate dehydrogenase; anaerobic conditions - pyruvate pyruvate decarboxylase, TPP anaerobic, yeast alcohol dehydrogenase pyruvate dehydrogenase system; aerobic conditions acetyl-coa
o Glycolysis : fates of pyruvate NAD, + + C 2 NAD, + - (S)-lactic acid lactate dehydrogenase; anaerobic conditions - pyruvate pyruvate decarboxylase, TPP anaerobic, yeast alcohol dehydrogenase pyruvate dehydrogenase system; aerobic conditions acetyl-coa PRACTICE PRBLEM Provide a mechanism for the reduction of acetaldehyde to ethanol with NAD.
o Catabolism of proteins: amino acids acetyl-coa Chapter 25 - N + 3 phenylalanine hydroxylase - N + 3 tyrosine aminotransferase PLP - MECANISM? phenylalanine tyrosine p-hydroxyphenylpyruvate p-hydroxyphenylalanine dioxygenase - homogentisate - C C - + fumarate acetyl-coa
o Catabolism of proteins: amino acids acetyl-coa Chapter 25 - N + 3 phenylalanine hydroxylase - N + 3 tyrosine aminotransferase PLP - MECANISM? phenylalanine tyrosine p-hydroxyphenylpyruvate oxidation decarboxylation p-hydroxyphenylalanine dioxygenase - epinephrine (adrenaline) N 2 C 3 homogentisate - C C - + fumarate acetyl-coa
PRACTICE PRBLEM eptadecanoic, or margaric acid is a saturated fatty acid found in the fat and milkfat of ruminants. Its complete metabolism gives 7 equivalents of acetyl-coa and one equivalent of propionyl-coa. Metabolism of propionyl-coa includes two reactions giving succinyl-coa, which is a citric cycle intermediate. Identify the coenzyme required for each step. - C C - propionyl-coa methylmalonyl-coa succinyl-coa
PRACTICE PRBLEM What carbon atoms of glucose end up in ethanol under anaerobic conditions in yeast? Chapter 25
NAD 2.5 ATP FAD 2 1.5 ATP
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3
2 NAD, + 8 C - - C (S)-malate 7 C - - C 2 C - oxaloacetate acetyl-coa 1 CoAS citrate C - C - citric acid cycle C - 2 1. eliminate 2 2. add 2 isocitrate 3 Chapter 25 C - C - C - C - NAD, +, C 2 - C fumarate FAD 2 FAD 6 C - - C 5 C - 4 C - α-ketoglutarate, CoAS succinate succinyl-coa NAD, +, C 2 GTP, CoAS GDP, P 3