1. 1 Chapter 15 Lipids 15.1 Lipids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

2. 2 Lipids Lipids are  Biomolecules that contain fatty acids or a steroid nucleus.  Soluble in organic solvents but not in water.  Named for the Greek word lipos, which means “fat.”  Extracted from cells using organic solvents.

3. 3 Types of Lipids The types of lipids containing fatty acids are  Waxes.  Fats and oils (triacylglycerols).  Glycerophospholipids.  Prostaglandins.  Not steroids, as they do not contain fatty acids.

4. 4 Structures of Lipids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

5. 5 15.2 Fatty Acids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

6. 6 Fatty Acids Fatty acids  Are long-chain carboxylic acids.  Typically contain 12-18 carbon atoms.  Are insoluble in water.  Can be saturated or unsaturated. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

7. 7 Fatty Acid Formulas The formulas for fatty acids are written as  Condensed formulas.  Line-bond formulas.  For example caprylic acid with 8 carbon atoms. CH 3 —(CH 2 ) 6 —COOH CH 3 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —COOH

8. 8 Saturated fatty acids have  Single C–C bonds.  Molecules that fit closely together in a regular pattern.  Strong attractions between fatty acid chains.  High melting points that make them solids at room temperature. Saturated Fatty Acids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

9. 9 Some Saturated Fatty Acids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

10. 10 Unsaturated Fatty Acids Unsaturated fatty acids  Have one or more double C=C bond  Typically contain cis double bonds. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

11. 11 Properties of Unsaturated Fatty Acids Unsaturated fatty acids  Have “kinks” in the fatty acid chains.  Do not pack closely.  Have few attractions between chains.  Have low melting points.  Are liquids at room temperature. “kinks” in chain Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

12. 12 Unsaturated Fatty Acids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

13. 13 Comparing Melting Points of Some Fatty Acids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

14. 14 Learning Check Assign the melting points of –17°C, 13°C, and 69°C to the correct fatty acid. Explain. stearic acid (18 C) saturated oleic acid (18 C) one double bond linoleic acid (18 C) two double bonds

15. 15 Solution Stearic acid is saturated and would have a higher melting point than the unsaturated fatty acids. Because linoleic has two double bonds, it would have a lower mp than oleic acid, which has one double bond. stearic acid mp 69°C saturated oleic acid mp 13°C linoleic acid mp -17°C most unsaturated

16. 16 Prostaglandins Prostaglandins have  20 carbon atoms in their fatty acid chains.  An OH on carbon 11 and 15.  A trans double bond at carbon 13. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings C 11 C 15C 13

17. 17 Prostaglandins in the Body Prostaglandins are  Produced by injured tissues.  Involved in pain, fever, and inflammation.  Not produced when anti-inflammatory drugs such as aspirin inhibit their synthesis. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

18. 18 Omega-6 and Omega 3- Fatty Acids Fatty acids  In vegetable oils are mostly omega-6 with the first C=C at C6. linoleic acid CH 3 ─(CH 2 ) 4 ─CH=CH─CH 2 ─CH=CH─(CH 2 ) 7 ─COOH 6  In fish oils are mostly omega-3 with the first C=C at C3. linolenic acid CH 3 ─CH 2 ─(CH=CH─CH 2 ) 3 ─(CH 2 ) 6 ─COOH 3 Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

19. 19 Some Omega-6 and Omega-3 Fatty Acids

20. 20 Learning Check Write a fatty acid with 10 carbon atoms that is: A. saturated B. monounsaturated omega-3 C. monounsaturated omega-6

21. 21 Solution Write a fatty acid with 10 carbon atoms that is: A. saturated CH 3 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —COOH B. monounsaturated omega-3 CH 3 —CH 2 —CH=CH—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —COOH C. monounsaturated omega-6 CH 3 —CH 2 —CH 2 —CH 2 —CH 2 —CH=CH—CH 2 —CH 2 —COOH

22. 22 Waxes, Fats, and Oils Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

23. 23 Waxes Waxes are  Esters of saturated fatty acids and long-chain alcohols.  Coatings that prevent loss of water by leaves of plants. TABLE 17.2 Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

24. 24 Fats and Oils: Triacylglycerols Fats and oils are  Also called triacylglycerols.  Esters of glycerol.  Produced by esterification.  Formed when the hydroxyl groups of glycerol react with the carboxyl groups of fatty acids. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

25. 25 In a triacylglycerol,  Glycerol forms ester bonds with three fatty acids. Triacylglycerols Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

26. 26 Formation of a Triacylglycerol glycerol + three fatty acids triacylglycerol + 3H 2 O +

27. 27 Olive Oil Olive oil  Contains a high percentage of oleic acid, which is a monounsaturated fatty acid with one cis double bond. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

28. 28 Learning Check What are the fatty acids in the following triacylglycerol?

29. 29 Solution Stearic acid Oleic acid Myristic acid

30. 30 Melting Points of Fats and Oils A triacylglycerol that is a fat  Is solid at room temperature.  Is prevalent in meats, whole milk, butter, and cheese. A triacylglycerol that is an oil  Is liquid at room temperature.  Is prevalent in plants such as olive and safflower.

31. 31 Oils with Unsaturated Fatty Acids Oils  Have more unsaturated fats.  Have cis double bonds that cause “kinks” in the fatty acid chains.  Cannot pack triacylglycerol molecules as close together as in fats.  Have lower melting points than saturated fats.  Are liquids at room temperature.

32. 32 Diagram of Triacylglycerol with Unsaturated Fatty Acids Unsaturated fatty acid chains have kinks that do not allow close packing. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

33. 33 Saturated and Unsaturated Fatty Acids In Fats and Oils Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

34. 34 Chemical Properties of Triacylglycerols Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

35. 35 The chemical reactions of triacylglycerols are similar to those of alkenes and esters.  In hydrogenation, double bonds in unsaturated fatty acids react with H 2 in the presence of a Ni or Pt catalyst.  In hydrolysis, ester bonds are split by water in the presence of an acid, a base, or an enzyme. Chemical Properties of Triacylglycerols

36. 36 Hydrogenation of Oils The hydrogenation of oils  Adds hydrogen (H 2 ) to the carbon atoms of double bonds.  Converts double bonds to single bonds.  Increases the melting point.  Produces solids such as margarine and shortening. Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

37. 37 Hydrogenation Ni + 3H 2 glyceryl tripalmitoleate (tripalmitolean ) glyceryl tripalmitate (tripalmitin )

38. 38 What product(s) is obtained from the complete hydrogenation of glyceryl trioleate? 1. Glycerol and 3 oleic acids 2. Glyceryltristearate 3. Glycerol and 3 stearic acids Learning Check

39. 39 What product(s) is obtained from the complete hydrogenation of glyceryl trioleate? 2. Glyceryltristearate Solution

40. 40 Olestra, A Fat Substitute Olestra is  Used in foods as an artificial fat.  Sucrose linked by ester bonds to several long-chain fatty chains.  Not broken down in the intestinal tract. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

41. 41 Cis and Trans Fatty Acids Unsaturated fatty acids can be  Cis with bulky groups on same side of C=C. CH 3 ─ (CH 2 ) 5 (CH 2 ) 7 ─ COOH cis C=C H H  Trans have bulky groups on opposite sides of C=C. CH 3 ─ (CH 2 ) 5 H C=C trans H (CH 2 ) 7 ─ COOH

42. 42 Trans Fatty Acids and Hydrogenation Trans fatty acids  Are formed during hydrogenation when cis double bonds are converted to trans double bonds.  In the body behave like saturated fatty acids.  Are estimated to make up 2-4% of our total Calories.  Are reported in several studies reported to raise LDL-cholesterol and lower HDL-cholesterol.

43. 43 Learning Check (1) True or (2) False A. There are more unsaturated fats in vegetable oils. B. Vegetable oils have higher melting points than fats. C. Hydrogenation of oils converts some cis-double bonds to trans- double bonds. D. Animal fats have more saturated fats.

44. 44 Solution (1) True or (2) False A. T There are more unsaturated fats in vegetable oils. B. F Vegetable oils have higher melting points than fats. C. T Hydrogenation of oils converts some cis-double bonds to trans- double bonds. D. T Animal fats have more saturated fats.

45. 45 Hydrolysis In hydrolysis,  Triacylglycerols split into glycerol and three fatty acids.  An acid or enzyme catalyst is required. +3 + 3

46. 46 Saponification and Soap Saponification  Is the reaction of a fat with a strong base.  Splits triacylglycerols into glycerol and the salts of fatty acids.  Is the process of forming “soaps” (salts of fatty acids).  With KOH gives softer soaps.

47. 47 Saponification + 3NaOH 3+ “soap”

48. 48 What products are obtained from the complete hydrolysis of glyceryl trioleate? 1. Glycerol and 3 oleic acids 2. Glyceryl tristearate 3. Glycerol and 3 stearic acids Learning Check

49. 49 What products are obtained from the complete hydrolysis of glyceryl trioleate? 1. Glycerol and 3 oleic acids Solution

50. 50 Learning Check Write the product of the following reaction. + 3

51. 51 Solution

52. 52 Glycerophospholipids are  The most abundant lipids in cell membranes.  Composed of glycerol, two fatty acids, phosphate and an amino alcohol. Glycerol PO 4 Amino alcohol Glycerophospholipids Fatty acid

53. 53 Glycerophospholipids Are Polar A glycerophospholipid has  Two nonpolar fatty acid chains.  A phosphate group and a polar amino alcohol. CH 3 │ + + HO−CH 2 −CH 2 −N−CH 3 HO−CH 2 −CH 2 −NH 3 │ choline CH 3 ethanolamine + NH 3 │ Amino alcohols HO−CH 2 −CH−COO − serine

54. 54 Structure and Polarity of A Glycerophospholipid Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

55. 55 Lecithin and cephalin are glycerophospholipids  Abundant in brain and nerve tissues.  Found in egg yolk, wheat germ, and yeast. Lecithin and Cephalin Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

56. 56 Learning Check Identify each as a A. fatty acid B. triacylglycerol C. amino alcoholD. glycerophospholipid 1. glyceryl trioleate 2. cephalin 3. choline 4. palmitic acid

57. 57 Solution Identify each as a A. fatty acid B. triacylglycerol C. amino alcoholD. glycerophospholipid 1. glyceryl trioleate B. triacylglycerol 2. cephalin D. glycerophospholipid 3. cholineC. amino alcohol 4. palmitic acidA. fatty acid

58. 58 Learning Check Identify the components and type of glycerophospholipid O ║ CH 2 − O −C −(CH 2 ) 16 −CH 3 O ║ CH 2 − O −C −(CH 2 ) 16 −CH 3 + O NH 3 ║ │ CH 2 − O −P −O − CH 2 −CH−COO - │ O -

59. 59 Solution Identify the components and type of glycerophospholipid O ║ CH 2 − O −C −(CH 2 ) 16 −CH 3 O2 stearic acids ║ CH 2 − O −C −(CH 2 ) 16 −CH 3 + O NH 3 ║ │type = cephalin CH 2 − O −P −O − CH 2 −CH−COO - │ serine O - phosphate amino alcohol

60. 60 Sphingolipids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

61. 61 Sphingolipids  Are similar to phospholipids.  Contain sphingosine (a long-chain amino alcohol), a fatty acid, phosphate, and a small amino alcohol.  Have polar and nonpolar regions. sphingosine PO 4 amino alcohol fatty acid

62. 62 Sphingosine Sphingosine is a long-chain unsaturated amino alcohol. CH 3 −( CH 2 ) 12 − CH=CH − CH−OH │ CH−NH 2 │ CH 2 −OH sphingosine

63. 63 In sphingomyelin, a sphingolipid found in nerve cells  There is an amide bond between a fatty acid and sphingosine, an 18-carbon alcohol. Sphingolipids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

64. 64 Glycosphingolipids  Glycosphingolipids contain monosaccharides bonded to the –OH of sphingosine by a glycosidic bond. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

65. 65 Glycosphingolipids and Cerebrosides Glycosphingolipids  Are sphingolipids that contain monosaccharides.  Can be a cerebroside with galactose. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

66. 66 Gangliosides  Are similar to cerebrosides, but contain two or more monosaccharides.  Are important in neurons.  Act as receptor for hormones and viruses.  Can accumulate and cause genetic diseases.

67. 67 Gangliosides GM 2 is a ganglioside  That accumulates in Tay-Sachs disease. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

68. 68 Lipid Diseases (Lipidoses)  In many lipid diseases, the deficiency of an enzyme causes the accumulation of glycolipids. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings TABLE 17.3

69. 69 Learning Check Identify each as a 1) Fatty acid 2) Triacylglycerol 3) Amino alcohol4) Glycerophospholipid 5) Glycosphingolipid A. Glyceryl trioleate B. Cephalin C. Choline D. Galactocerebroside E. Palmitic acid

70. 70 Solution A. Glyceryl trioleate2) Triacylglycerol B. Cephalin 4) Glycerophospholipid C. Choline3) Amino alcohol D. Galactocerebroside5) Glycosphingolipid E. Palmitic acid1) Fatty acid

71. 71 Steroids: Cholesterol, Bile Salts, and Steroid Hormones Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

72. 72 Steroid Nucleus A steroid nucleus consists of  3 cyclohexane rings.  1 cyclopentane ring.  No fatty acids. steroid nucleus

73. 73 Cholesterol  Is the most abundant steroid in the body.  Has methyl CH 3 - groups, alkyl chain, and -OH attached to the steroid nucleus.

74. 74 Cholesterol in the Body Cholesterol in the body  Is obtained from meats, milk, and eggs.  Is synthesized in the liver.  Is needed for cell membranes, brain and nerve tissue, steroid hormones, and Vitamin D.  Clogs arteries when high levels form plaque. A normal, open artery. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings An artery clogged by cholesterol plaque

75. 75 Cholesterol in Foods Cholesterol is  Synthesized in the liver.  Obtained from foods.  Considered elevated if plasma cholesterol exceeds 200 mg/dL. TABLE 17.4 Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

76. 76 Learning Check Match the components of the cholesterol molecule with the following: ___ carbon chain___hydroxyl group ___ steroid nucleus___methyl group A C B D

77. 77 Solution Match the components of the cholesterol molecule with the following: D carbon chain A hydroxyl group C steroid nucleus B methyl group A C B D

78. 78 Bile Salts Bile salts  Are synthesized in the liver from cholesterol.  Are stored in the gallbladder.  Are secreted into the small intestine.  Have a polar and a nonpolar region  Mix with fats to break them part.  Emulsify fat particles to provide large surface area.

79. 79 Bile Salts Nonpolar region Polar region

80. 80 Lipoproteins Combine lipids with proteins and phospholipids. Are soluble in water because the surface consists of polar lipids. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

81. 81 Types of Lipoproteins Lipoproteins  Differ in density, composition, and function.  Include low-density lipoprotein (LDLs) and high- density lipoprotein (HDLs). TABLE 17.5 Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

82. 82 Transport of Lipoproteins in the Body Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

83. 83 Steroid Hormones Steroid hormones  Are chemical messengers in cells.  Are produced from cholesterol.  Include sex hormones such as androgens (testosterone) in males and estrogens (estradiol) in females. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

84. 84 Adrenal Corticosteroids Adrenal corticosteroids are steroid hormones that  Are produced by the adrenal glands located on the top of each kidney.  Include aldosterone, which regulates electrolytes and water balance by the kidneys.  Include cortisone, a glucocorticoid, which increases blood glucose level and stimulates the synthesis of glycogen in the liver.

85. 85 Adrenal Corticosteroids Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

86. 86 Anabolic Steroids Anabolic steroids  Are derivatives of testosterone.  Are used illegally to increase muscle mass.  Have side effects including fluid retention, hair growth, sleep disturbance, and liver damage. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

87. 87 Learning Check Identify each as a 1. fatty acid2. steroid 3. triacylglycerol 4. phospholipid 5. sphingolipid A. cholesterol B. glycerol, 2 fatty acids, phosphate, and choline C. glyceryl tristearate D. sphingosine, fatty acid, phosphate, and choline E. estradiol F. bile salts G. lipids in plasma membranes

88. 88 Solution A.cholesterol 2 steroid B.glycerol, 2 fatty acids, phosphate, and choline 4 phospholipid C.glyceryl tristearate 3 triacylglycerol D.sphingosine, fatty acid, phosphate, and choline 5 sphingolipid E.estradiol 2 steroid F.bile salts 2 steroid G.lipids in plasma membranes 4 phospholipid, 5 sphingolipid.

89. 89 Cell Membranes Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

90. 90 Cell Membranes Cell membranes  Separate cellular contents from the external environment.  Consist of a lipid bilayer made of two rows of phospholipids.  Have an inner portion made of the nonpolar tails of phospholipids with the polar heads at the outer and inner surfaces.

91. 91 Fluid Mosaic Model of Cell Membranes The lipid bilayer  Contains proteins, carbohydrates, and cholesterol.  Has unsaturated fatty acids that make cell membranes fluid-like rather than rigid.  Has proteins and carbohydrates on the surface that communicate with hormones and neurotransmitters.

92. 92 Fluid Mosaic Model Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

93. 93 Transport Through Cell Membranes The transport of substances through cell Membranes involves  Diffusion (passive transport), which moves particles from a higher to a lower concentration.  Facilitated transport, which uses protein channels to increase the rate of diffusion.  Active transport, which moves ions against a concentration gradient.

94. 94 Transport Pathways Through Cell Membranes Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

95. 95 Learning Check The transport of particles across a cell membrane from high concentration to low concentration is called 1. Facilitated transport 2. Diffusion 3. Active transport

96. 96 Solution The transport of particles across a cell membrane from high concentration to low concentration is called 2. Diffusion