1. Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Chapter 14 Lecture Outline Prepared by Jennifer N. Robertson-Honecker West Virginia University

2. Carbohydrates Introduction Carbohydrates, called sugars and starches, are polyhydroxy aldehydes or ketones, or compounds that can be hydrolyzed to them. Carbohydrates can be classified as mono- saccharides, disaccharides, and polysaccharides. They are synthesized in green plants through photosynthesis, a process that uses the energy from the sun to convert carbon dioxide and water into glucose and oxygen. In the body, they are used for bursts of energy needed during exercise in the form of glucose. 2

3. Carbohydrates Introduction 3

4. Monosaccharides Monosaccharides, the simplest carbohydrates, generally have 3 to 6 C atoms in a chain with a carbonyl group and many –OH groups. Monosaccharides with a carbonyl group at C1 are called aldoses and those with carbonyl group at C2 are called ketoses. 4

5. Monosaccharides The simplest aldose is glyceraldehyde. The simplest ketose is dihydroxyacetone. They are constitutional isomers of each other, sharing the formula C 3 H 6 O 3. 5

6. Monosaccharides A monosaccharide is characterized by the number of C atoms in its chain: A triose has 3 C’s. A tetrose has 4 C’s. A pentose has 5 C’s. A hexose has 6 C’s. These terms are then combined with the words aldose and ketose: Glyceraldehyde is an aldotriose. Dihydroxyacetone is a ketotriose. 6

7. Monosaccharides Monosaccharides are sweet tasting, but their relative sweetness varies a great deal. They are polar compounds with high melting points. The presence of so many polar functional groups capable of hydrogen bonding makes the monosaccharides very water-soluble. 7

8. Monosaccharides Fischer Projection Formula All carbohydrates except dihydoxyacetone have one or more chirality centers. Glyceraldehyde, the simplest aldose, has one chirality center, and has two possible enantiomers. 8

9. Monosaccharides Fischer Projection Formula The prefix D is used when the –OH group is drawn on the right side of the carbon chain. The prefix L is used when the –OH group is drawn on the left side of the carbon chain. The wedged and dashed lines can be re-drawn in a Fischer projection formula: 9

10. Monosaccharides With More than One Chirality Center Glucose has four chirality centers and is drawn as: 10

11. Monosaccharides With More than One Chirality Center The configuration of the chirality center farthest from the carbonyl group determines whether a monosaccharide is D or L. 11

12. Monosaccharides With More than One Chirality Center All naturally occurring sugars are D sugars. 12

13. Monosaccharides Common Monosaccharides Glucose (dextrose) is blood sugar and the most abundant monosaccharide. Normal blood glucose levels are 70-110 mg/dL. Insulin regulates blood glucose levels by stimulating the uptake of glucose into tissues or its conversion to glycogen. Patients with diabetes produce insufficient insulin to adequately regulate blood sugar levels, so they must monitor their diet and/or inject insulin daily. 13

14. Monosaccharides Common Monosaccharides 14

15. Monosaccharides Common Monosaccharides Galactose is one of the components of the disaccharide lactose. Patients with galactosemia lack an enzyme needed to metabolize galactose, which accumulates and causes cataracts and cirrhosis. Fructose is one of the components of the disaccharide sucrose. It is a ketohexose found in honey and almost twice as sweet as table sugar with the same number of calories per gram. 15

16. The Cyclic Forms of Monosaccharides The hydroxyl and carbonyl groups can react together to form a ring. 16

17. The Cyclic Forms of Monosaccharides The first step in cyclization is to rotate glucose 90 o. 17

18. The Cyclic Forms of Monosaccharides Next, the chain must be twisted around, forming a six-membered ring: 18

19. The Cyclic Forms of Monosaccharides Cyclization yields two isomers, since the OH can be located above or below the ring, an  anomer and a  anomer. These rings are called Haworth projections. 19

20. The Cyclic Forms of Monosaccharides 20

21. The Cyclic Forms of Monosaccharides Example Draw the αisomer of the cyclic form of D -galactose. 21 Sample Problem 14.3

22. The Cyclic Forms of Monosaccharides Step [1] Place the O atom in the upper right corner of a hexagon, and add the CH 2 OH group above the ring to the left of the O atom. 22

23. The Cyclic Forms of Monosaccharides Step [2] Draw the new chirality center on the first C clockwise from the O atom. 23

24. The Cyclic Forms of Monosaccharides Step [3] Add the other substituents to the remaining carbons, clockwise around the ring. 24

25. The Cyclic Forms of Monosaccharides The Cyclic Forms of Fructose Ketohexoses like fructose form five-membered rings with two isomers. 25

26. 26 The Cyclic Forms of Monosaccharides The Cyclic Forms of Fructose

27. Reactions of Monosaccharides Reduction of the Aldehyde Carbonyl Group The carbonyl group of an aldose is reduced to an alcohol using H 2 with Pd. 27

28. Reactions of Monosaccharides Oxidation of the Aldehyde Carbonyl Group The aldehyde group is easily oxidized to a carboxylic acid using Benedict’s reagent. 28

29. Disaccharides Disaccharides are carbohydrates composed of two monosaccharides. A disaccharide is formed when a hydroxyl group of one monosaccharide reacts with a hydroxyl group of a second monosaccharide 29

30. Disaccharides When this reaction occurs between two monosaccharides, the bond that joins the two rings is called a glycosidic linkage. 30

31. Disaccharides The glycosidic linkage joining the two rings can be alpha (  or beta ( . If the bond is alpha (  ): 31

32. Disaccharides If the bond is beta (  ): Hydrolysis cleaves the C—O glycosidic linkage and forms two monosaccharides. 32

33. Disaccharides Hydrolysis of maltose yields 2 glucose molecules. 33

34. Focus on Health & Medicine Lactose Intolerance Lactose is the disaccharide in milk; it consists of 1 galactose ring and 1 glucose ring joined by a 1  4-  -glycosidic bond. 34

35. Focus on Health & Medicine Lactose Intolerance The disaccharide bond is cleaved by the enzyme lactase in the body. Individuals who are lactose intolerant no longer produce this enzyme. Without the enzyme, lactose cannot be digested, causing abdominal cramps and diarrhea. 35

36. Focus on Health & Medicine Sucrose and Artificial Sweeteners Sucrose (table sugar) is a disaccharide consisting of 1 glucose ring and 1 fructose ring. Sucrose is very sweet, but contains many calories. To reduce caloric intake, many artificial sweeteners have been developed. 36

37. Focus on Health & Medicine Sucrose and Artificial Sweeteners Aspartame (sold as Equal) is hydrolyzed into phenylalanine, which cannot be processed by those individuals with the condition phenylketonuria. 37

38. Focus on Health & Medicine Sucrose and Artificial Sweeteners Saccharine (sold as Sweet’n Low) was used extensively during World War I. 38

39. Focus on Health & Medicine Sucrose and Artificial Sweeteners Sucralose (sold as Splenda) has a very similar structure to sucrose. 39

40. Polysaccharides Cellulose Polysaccharides contain three or more mono- saccharides joined together. Cellulose is an unbranched polymer made up of repeating glucose units joined by 1  4-  -glycosidic linkages. Cellulose is found in the cell walls of all plants, where it gives support and rigidity to wood, plant stems, and grass. Humans do not posses the enzyme to hydrolyze cellulose (  -glycosidase) and cannot digest it. 40

41. Polysaccharides Cellulose Cellulose makes up the insoluble fiber in our diets, which is important in adding bulk to waste to help eliminate it more easily. 41

42. Polysaccharides Starch Starch is a polymer made up of repeating glucose units joined by alpha glycosodic linkages. Starch is present in corn, rice, wheat, and potatoes. The first main type of starch is amylose: 42

43. Polysaccharides Starch The second type of starch is amylopectin: 43

44. Polysaccharides Starch Amylose is an unbranched polymer linked by 1  4-  -glycosidic linkages. Amylopectin is a branched polymer linked by 1  4-  and 1  6-  -glycosidic linkages. Both starch molecules can be digested by humans using the enzyme amylase. 44

45. Polysaccharides Glycogen Glycogen is the major form of polysaccharide storage in animals, similar in structure to amylopectin. It is stored mainly in the liver and in muscle cells. When glucose is needed for energy, glucose units are hydrolyzed from the ends of the glycogen polymer. Because glycogen is highly branched, there are many ends available for hydrolysis. 45