1. 20 20-1 © 2003 Thomson Learning, Inc. All rights reserved General, Organic, and Biochemistry, 7e Bettelheim, Brown, and March

2. 20 20-2 © 2003 Thomson Learning, Inc. All rights reserved Chapter 20 Lipids

3. 20 20-3 © 2003 Thomson Learning, Inc. All rights reserved Lipids Lipids: Lipids: a heterogeneous class of naturally occurring organic compounds classified together on the basis of common solubility properties insoluble in water, but soluble in organic solvents including diethyl ether, dichloromethane, and acetone Lipids include fatty acids, triacylglycerols, sphingolipids, phosphoacylglycerols, and glycolipids lipid-soluble vitamins prostaglandins, leukotrienes, and thromboxanes cholesterol, steroid hormones, and bile acids

4. 20 20-4 © 2003 Thomson Learning, Inc. All rights reserved Triglyceride Triglyceride: Triglyceride: an ester of glycerol with three fatty acids

5. 20 20-5 © 2003 Thomson Learning, Inc. All rights reserved Fatty Acids Fatty acid: Fatty acid: an unbranched-chain carboxylic acid derived from hydrolysis of animal fats, vegetable oils, or membrane phospholipids nearly all have an even number of carbon atoms, most between 12 and 20, in an unbranched chain the three most abundant are palmitic acid (16:0), stearic acid (18:0), and oleic acid (18:1) in most unsaturated fatty acids, the cis isomer predominates; the trans isomer is rare unsaturated fatty acids have lower melting points than their saturated counterparts; the greater the degree of unsaturation, the lower the melting point

6. 20 20-6 © 2003 Thomson Learning, Inc. All rights reserved Fatty Acids

7. 20 20-7 © 2003 Thomson Learning, Inc. All rights reserved Triglycerides Physical properties depend on the fatty acid components melting point increases as the number of carbons in the hydrocarbon chains increases and as the number of double bonds decreases oilstriglycerides rich in unsaturated fatty acids are generally liquid at room temperature and are called oils fatstriglycerides rich in saturated fatty acids are generally semisolids or solids at room temperature and are called fats

8. 20 20-8 © 2003 Thomson Learning, Inc. All rights reserved Triglycerides The lower melting points of triglycerides rich in unsaturated fatty acids are related to differences in their three-dimensional shape hydrocarbon chains of saturated fatty acids can lie parallel with strong London dispersion forces between their chains; they pack into well-ordered, compact crystalline forms and melt above room temperature because of the cis configuration of the double bonds in unsaturated fatty acids, their hydrocarbon chains have a less ordered structure and London dispersion forces between them are weaker; these triglycerides have melting points below room temperature

9. 20 20-9 © 2003 Thomson Learning, Inc. All rights reserved Hydrogenation Hardening: reduction of some or all of the carbon-carbon double bonds of an unsaturated triglyceride using H 2 /catalyst in practice, the degree of hardening is carefully controlled to produce fats of a desired consistency the resulting fats are sold for kitchen use (Crisco, Spry, Dexo, and others) margarine and other butter substitutes are produced by partial hydrogenation of polyunsaturated oils derived from corn, cottonseed, peanut, and soybean oils

10. 20 20-10 © 2003 Thomson Learning, Inc. All rights reserved Soaps saponification Natural soaps are prepared by boiling lard or other animal fat with NaOH, in a reaction called saponification (Latin, sapo, soap)

11. 20 20-11 © 2003 Thomson Learning, Inc. All rights reserved Soaps Soaps clean by acting as emulsifying agents their long hydrophobic hydrocarbon chains cluster so as to minimize their contact with water their polar hydrophilic carboxylate groups remain in contact with the surrounding water molecules driven by these two forces, soap molecules spontaneously cluster into micelles

12. 20 20-12 © 2003 Thomson Learning, Inc. All rights reserved Soaps hard watersoaps form water-insoluble salts when used in water containing Ca(II), Mg(II), and Fe(III) ions (hard water)

13. 20 20-13 © 2003 Thomson Learning, Inc. All rights reserved Complex Lipids Phospholipids contain an alcohol, two fatty acids, and a phosphate ester in glycerophospholipids, the alcohol is glycerol in sphingolipids, the alcohol is sphingosine Glycolipids complex lipids that contain a carbohydrate

14. 20 20-14 © 2003 Thomson Learning, Inc. All rights reserved Complex Lipids

15. 20 20-15 © 2003 Thomson Learning, Inc. All rights reserved Membranes Complex lipids form the membranes around cells and small structures within cells In aqueous solution, complex lipids spontaneously form into a lipid bilayer, with a back-to-back arrangement of lipid monolayers polar head groups are in contact with the aqueous environment nonpolar tails are buried within the bilayer the major force driving the formation of lipid bilayers is hydrophobic interaction the arrangement of hydrocarbon tails in the interior can be rigid (if rich in saturated fatty acids) or fluid (if rich in unsaturated fatty acids)

16. 20 20-16 © 2003 Thomson Learning, Inc. All rights reserved Fluid Mosaic Model

17. 20 20-17 © 2003 Thomson Learning, Inc. All rights reserved Glycerophospholipids Glycerophospholipids Glycerophospholipids are the second most abundant group of naturally occurring lipids they are also called phosphoglycerides found almost exclusively in plant and animal membranes, which typically consist of 40% -50% phosphoacylglycerols and 50% - 60% proteins the most abundant phosphoacylglycerols are derived from phosphatidic acid, a molecule in which glycerol is esterified with two molecules of fatty acid and one of phosphoric acid the three most abundant fatty acids in phosphatidic acids are palmitic (16:0), stearic (18:0), and oleic (18:1)

18. 20 20-18 © 2003 Thomson Learning, Inc. All rights reserved Glycerophospholipids A phosphatidic acid the fatty acid on carbon 2 is always unsaturated further esterification with a low-molecular-weight alcohol gives a glycerophospholipid

19. 20 20-19 © 2003 Thomson Learning, Inc. All rights reserved Glycerophospholipids

20. 20 20-20 © 2003 Thomson Learning, Inc. All rights reserved Glycerophospholipids a lecithina lecithin

21. 20 20-21 © 2003 Thomson Learning, Inc. All rights reserved Sphingolipids Found in the coatings of nerve axons (myelin) contain the long-chain aminoalcohol, sphingosine, from which this class of compounds in named

22. 20 20-22 © 2003 Thomson Learning, Inc. All rights reserved Glycolipids Glycolipid: Glycolipid: a complex lipid that contains a carbohydrate the carbohydrate is either glucose or galactose the cerebrosides are ceramide mono- or oligosaccharides

23. 20 20-23 © 2003 Thomson Learning, Inc. All rights reserved Steroids Steroids: Steroids: a group of plant and animal lipids that have this tetracyclic ring structure

24. 20 20-24 © 2003 Thomson Learning, Inc. All rights reserved Cholesterol Cholesterol is the most abundant steroid in the human body, and also the most important it is a component in plasma membranes in all animal cells it is the precursor of all steroid hormones and bile acids

25. 20 20-25 © 2003 Thomson Learning, Inc. All rights reserved Lipoproteins Cholesterol, along with fats, are transported by lipoproteins

26. 20 20-26 © 2003 Thomson Learning, Inc. All rights reserved Lipoproteins Schematic of a low-density lipoprotein

27. 20 20-27 © 2003 Thomson Learning, Inc. All rights reserved Cholesterol Transport transport of cholesterol from the liver starts with VLDL VLDL is carried in the serum as fat is removed, its density increases and it becomes LDL; LDL stays in the plasma for about 2.5 days LDL carries cholesterol to cells, where specific LDL receptors bind it after binding, LDL is taken into cells where enzymes liberate free cholesterol and cholesteryl esters

28. 20 20-28 © 2003 Thomson Learning, Inc. All rights reserved Cholesterol Transport high-density lipoproteins (HDL) transport cholesterol from peripheral tissues to the liver and also transfer cholesterol to LDL while in the serum, free cholesterol in HDL is converted to cholesteryl esters in the liver, HDL binds to the liver cell surface and transfers its cholesteryl esters to the cell these esters are used for the synthesis of steroid hormones and bile acids after LDL has delivered its cholesteryl esters to liver cells, it reenters circulation

29. 20 20-29 © 2003 Thomson Learning, Inc. All rights reserved Levels of LDL and HDL most of the cholesterol is carried by LDL normal plasma levels are 175 mg/100 mL if there are sufficient LDL receptors on the surface of cells, LDL is removed from circulation and its concentration drops the number of LDL receptors is controlled by a feedback mechanism when the concentration of cholesterol inside cells is high, the synthesis of LDL receptors is suppressed in the disease called hypercholesterolemia, there are not enough LDL receptors and plasma levels of cholesterol may be as high as 680 mg/100 mL

30. 20 20-30 © 2003 Thomson Learning, Inc. All rights reserved Levels of LDL and HDL these high levels of cholesterol can cause premature atherosclerosis and heart attacks in general, high LDL means high cholesterol content in the plasma because LDL cannot get into cells therefore, high LDL together with low HDL is a symptom of faulty cholesterol transport and a warning of possible atherosclerosis the serum cholesterol level controls cholesterol synthesis in the liver when serum cholesterol is high, its synthesis in the liver is low, and vice versa the commonly used statin drugs inhibit the synthesis of cholesterol by blocking HMG-CoA reductase

31. 20 20-31 © 2003 Thomson Learning, Inc. All rights reserved Steroid Hormones Androgens: Androgens: male sex hormones synthesized in the testes responsible for the development of male secondary sex characteristics

32. 20 20-32 © 2003 Thomson Learning, Inc. All rights reserved Steroid Hormones Among the synthetic anabolic steroids are

33. 20 20-33 © 2003 Thomson Learning, Inc. All rights reserved Steroid Hormones Estrogens: Estrogens: female sex hormones synthesized in the ovaries responsible for the development of female secondary sex characteristics and control of the menstrual cycle

34. 20 20-34 © 2003 Thomson Learning, Inc. All rights reserved Steroid Hormones Progesterone-like analogs are used in oral contraceptives

35. 20 20-35 © 2003 Thomson Learning, Inc. All rights reserved Steroid Hormones Glucorticoid hormones Glucorticoid hormones synthesized in the adrenal cortex regulate metabolism of carbohydrates decrease inflammation involved in the reaction to stress

36. 20 20-36 © 2003 Thomson Learning, Inc. All rights reserved Bile Salts Bile salts Bile salts, the oxidation products of cholesterol synthesized in the liver, stored in the gallbladder, and secreted into the intestine where they emulsify dietary fats and aid in their absorption and digestion

37. 20 20-37 © 2003 Thomson Learning, Inc. All rights reserved Prostaglandins Prostaglandins: Prostaglandins: a family of compounds that have the 20-carbon skeleton of prostanoic acid

38. 20 20-38 © 2003 Thomson Learning, Inc. All rights reserved Prostaglandins Prostaglandins are not stored in tissues as such, but are synthesized from membrane-bound 20- carbon polyunsaturated fatty acids in response to specific physiological triggers one such polyunsaturated fatty acid is arachidonic acid

39. 20 20-39 © 2003 Thomson Learning, Inc. All rights reserved Prostaglandins

40. 20 20-40 © 2003 Thomson Learning, Inc. All rights reserved COX Enzymes The COX enzyme occurs in two forms COX-1 catalyzes the normal physiological production of prostaglandins COX-2 is responsible for the production of prostaglandins in inflammation when a tissue is injured or damaged, special inflammatory cells invade the injured tissue and interact with resident cells, for example, smooth muscle cells this interaction activates COX-2 and prostaglandins are synthesized

41. 20 20-41 © 2003 Thomson Learning, Inc. All rights reserved Thromboxanes Thromboxanes are also derived from arachidonic acid thromboxane A 2 induces platelet aggregation and vasoconstriction aspirin and other NSAIDs inhibit the synthesis of thromboxanes by inhibiting the COX enzyme

42. 20 20-42 © 2003 Thomson Learning, Inc. All rights reserved Leukotrienes Leukotrienes are also synthesized from arachidonic acid they occur mainly in leukocytes they produce muscle contractions, especially in the lungs and thereby can cause asthma-like attacks in this regard, they are 100 times more potent than histamine several recently-developed anti-asthma drugs inhibit the synthesis of leukotrienes

43. 20 20-43 © 2003 Thomson Learning, Inc. All rights reserved End Chapter 20 Lipids