14. Succinyl-CoA

15. Fatty Acid Metabolism

19. Phospholipase A 1 Phospholipase A 2 Phospholipase A 1

20. FADH 2

21. Glycerol = GAP + NADH - ATP If: GAP = 2 ATP + NADH + Acetyl-CoA Then: glycerol = Acetyl-CoA + 2 NADH + ATP If: Acetyl-CoA = 3 NADH + FADH 2 + GTP Then: glycerol = 5 NADH + GTP + ATP + FADH 2 If: NADH = 3 ATP, FADH 2 = 2 ATP and GTP = ATP Then: glycerol = 19 ATP

22. 1 NADH is converted to FADH 2 : 1 less ATP

24. Fatty acid + CoA + ATP ---> Fatty acyl-CoA + AMP + PP i AMP + ATP ---> 2 ADP ADP + P i ---> ATP You essentially consume 2 ATP to activate FFAs

31. Claisen cleavage reaction: reverse of citrate synthase

32. Thiolase

34. For a saturated fatty acid with n carbon atoms (even number) You make n/2 Acetyl-CoA, which enter TCA cycle to yield n-2/2 NADH n-2/2 FADH 2  -oxidation yields 3n/2 NADH n/2 FADH 2 n/2 ATP 3ATP per NADH 2ATP per FADH 2 Cn:0 yields (n-2/2 + 3n/2)3ATP + (n-2/2 + n/2)2ATP + n/2 ATP - 2ATP Lost in activation

35. What about unsaturated fatty acids?

36. For every double bond an odd number of carbons away from carbonyl: 3 round  -oxidation Attempt 4th round Doesn’t work

37. Ready for another round of oxidation: however no FADH 2 produced. This ultimately costs 2 ATP in the end.

38. For every double bond an even number of carbons away from carbonyl: Neither dehydrogenase nor isomerase recognize ∆4 unsaturated fatty acids as a substrate. 5 rounds  -oxidation

39. Just reduce the double bond Resume oxidation with the cost of 1 NADPH which ultimately costs one NADH and 3 ATP in the end.

40. What about fatty acids with odd number carbons Last round produces propionyl-CoA instead of Acetyl-CoA

41. One extra ATP is consumed to convert propionyl-CoA to succinyl- CoA For odd chain fatty acids You make n-3 Acetyl-CoA and one propionyl-CoA Succinyl-CoA enters TCA cycle This is can be used as an anapleurotic rxn or the succinyl-CoA can be converted to malate. In the latter case.....

42. Conversion of succinyl-CoA to malate makes 1 ATP, 1 FADH 2

43. Malate pyruvate +1 NADPH 4 NADH + 1 FADH 2 + ATP Malic enzyme - decarboxylating

44. One extra ATP is consumed to convert propionyl-CoA to succinyl- CoA So.....for odd chain fatty acids You make n-3 Acetyl-CoA and one propionyl-CoA One ATP and one FADH 2 are made to convert succinyl-CoA into malate One NADPH is made converting malate into pyruvate Pyruvate = 4 NADH, 1 ATP and 1 FADH 2 So….propionyl-CoA = 2 FADH 2 + 4 NADH + 1ATP + NADPH Cn(odd):0 yields (n-3/2 + 3n-3/2 + 4)3ATP + (n-3/2 + n-3/2 + 2)2ATP + (n-3/2 + 1) ATP - 2ATP + NADPH

46. The glyoxosome is a special peroxisome in germinating seeds that uses Acetyl-CoA from triacylglycerol to make glucose

47.  -oxidation: in the ER

48.  -oxidation: peroxisome

49. Ketone Bodies Liver Muscle

51. Lipid Biosynthesis Reversing fatty acid catabolism. What steps are different?

52. Starts with malonyl-CoA instead of acetyl-CoA

58. Cost = (n-2)ATP + 2(n-2)NADPH

59. Fatty Acid Synthase Ketoacyl-ACP Synthase Malonyl-CoA-ACP transferase Ketoacyl-ACP reductase Hydroxyacyl-ACP dehydratase Enoyl-ACP reductase Acetyl-CoA-ACP transacetylase ACP = acyl carrier protein

62. Fatty acid biosynthesis occurs in cytosol Acetyl-CoA is made in the mitochondrion

64. Fatty acid desaturases are oxidases

69. Much of the fatty acids release by adipocytes is taken up by tissues and coverted to energy. This is triggered by low glucose by glucagon or epinephrine Much is reconverted into triacylglycerol by the liver and released

70. Glucagon tells the liver to stop glycolysis and make glucose How then do you get glycerol?

71. Glucocorticoids stimulate fatty acid release from adipose tissue

77. What cofactor would you use?

81. What cofactor?

82. Desaturase In plants and yeast there is hydroxylation instead of desaturation

84. Heme generated tyrosine radical abstracts this proton

87. How is the radical generated in the first place?

94. Flavin monooxygenase

110. Dihydrocholesterol 1  25-dihydroxycholecalciferol Cholecalciferol Vitamin D 3