CHE 120 - Introduction to Organic Chemistry - Textbook

Glucose is one of the carbohydrates you will learn about in this chapter as we begin the study of biochemistry—the chemistry of molecules found in living organisms. Later we will study the other three major types of macromolecules found in living organisms: lipids, proteins, and nucleic acids.

6.1 Carbohydrates

All carbohydrates consist of carbon, hydrogen, and oxygen atoms and are polyhydroxy aldehydes or ketones or are compounds that can be broken down to form such compounds. Examples of carbohydrates include starch, fiber, the sweet-tasting compounds called sugars, and structural materials such as cellulose. The term carbohydrate had its origin in a misinterpretation of the molecular formulas of many of these substances. For example, because its formula is C₆H₁₂O₆, glucose was once thought to be a “carbon hydrate” with the structure C₆·6H₂O.

Green plants are capable of synthesizing glucose (C₆H₁₂O₆) from carbon dioxide (CO₂) and water (H₂O) by using solar energy in the process known as photosynthesis:

6CO₂ + 6H₂O + 686 kcal → C₆H₁₂O₆ + 6O₂

(The 686 kcal come from solar energy.) Plants can use the glucose for energy or convert it to larger carbohydrates, such as starch or cellulose. Starch provides energy for later use, perhaps as nourishment for a plant’s seeds, while cellulose is the structural material of plants. We can gather and eat the parts of a plant that store energy—seeds, roots, tubers, and fruits—and use some of that energy ourselves. Carbohydrates are also needed for the synthesis of nucleic acids and many proteins and lipids.

Animals, including humans, cannot synthesize carbohydrates from carbon dioxide and water and are therefore dependent on the plant kingdom to provide these vital compounds. We use carbohydrates not only for food (about 60%–65% by mass of the average diet) but also for clothing (cotton, linen, rayon), shelter (wood), fuel (wood), and paper (wood).

The simplest carbohydrates—those that cannot be hydrolyzed to produce even smaller carbohydrates—are called monosaccharides. Two or more monosaccharides can link together to form chains that contain from two to several hundred or thousand monosaccharide units. Prefixes are used to indicate the number of such units in the chains. Disaccharide molecules have two monosaccharide units, trisaccharide molecules have three units, and so on. Chains with many monosaccharide units joined together are called polysaccharides. All these so-called higher saccharides can be hydrolyzed back to their constituent monosaccharides.

Answer

1. Trehalose is a disaccharide because it is hydrolyzed into two molecules of glucose (a monosaccharide).

6.2 Classes of Monosaccharides

The naturally occurring monosaccharides contain three to seven carbon atoms per molecule. Monosaccharides of specific sizes may be indicated by names composed of a stem denoting the number of carbon atoms and the suffix -ose. For example, the terms triose, tetrose, pentose, and hexose signify monosaccharides with, respectively, three, four, five, and six carbon atoms. Monosaccharides are also classified as aldoses or ketoses. Those monosaccharides that contain an aldehyde functional group are called aldoses; those containing a ketone functional group on the second carbon atom are ketoses. Combining these classification systems gives general names that indicate both the type of carbonyl group and the number of carbon atoms in a molecule. Thus, monosaccharides are described as aldotetroses, aldopentoses, ketopentoses, ketoheptoses, and so forth. Glucose and fructose are specific examples of an aldohexose and a ketohexose, respectively.

The simplest sugars are the trioses. The possible trioses are shown in part (a) of Figure 6.1 "Structures of the Trioses"; glyceraldehyde is an aldotriose, while dihydroxyacetone is a ketotriose. Notice that two structures are shown for glyceraldehyde. These structures are stereoisomers, isomers having the same structural formula but differing in the arrangement of atoms or groups of atoms in three-dimensional space. If you make models of the two stereoisomers of glyceraldehyde, you will find that you cannot place one model on top of the other and have each functional group point in the same direction. However, if you place one of the models in front of a mirror, the image in the mirror will be identical to the second stereoisomer in part (b) of Figure 6.1 "Structures of the Trioses". Molecules that are nonsuperimposable (nonidentical) mirror images of each other are a type of stereoisomer called enantiomers (Greek enantios, meaning “opposite”).

Figure 6.1 Structures of the Trioses

(a) D- and L-glyceraldehyde are mirror images of each other and represent a pair of enantiomers. (b) A ball-and-stick model of D-glyceraldehyde is reflected in a mirror. Note that the reflection has the same structure as L-glyceraldehyde.

A key characteristic of enantiomers is that they have a carbon atom to which four different groups are attached. Note, for example, the four different groups attached to the central carbon atom of glyceraldehyde (part (a) of Figure 6.1 "Structures of the Trioses"). A carbon atom that has four different groups attached is a chiral carbon. If a molecule contains one or more chiral carbons, it is likely to exist as two or more stereoisomers. Dihydroxyacetone does not contain a chiral carbon and thus does not exist as a pair of stereoisomers. Glyceraldehyde, however, has a chiral carbon and exists as a pair of enantiomers. Except for the direction in which each enantiomer rotates plane-polarized light, these two molecules have identical physical properties. One enantiomer has a specific rotation of +8.7°, while the other has a specific rotation of −8.7°.

H. Emil Fischer, a German chemist, developed the convention commonly used for writing two-dimensional representations of the monosaccharides, such as those in part (a) of Figure 6.1 "Structures of the Trioses". In these structural formulas, the aldehyde group is written at the top, and the hydrogen atoms and OH groups that are attached to each chiral carbon are written to the right or left. (If the monosaccharide is a ketose, the ketone functional group is the second carbon atom.) Vertical lines represent bonds pointing away from you, while horizontal lines represent bonds coming toward you. The formulas of chiral molecules represented in this manner are referred to as Fischer projections.

The two enantiomers of glyceraldehyde are especially important because monosaccharides with more than three carbon atoms can be considered as being derived from them. Thus, D- and L-glyceraldehyde provide reference points for designating and drawing all other monosaccharides. Sugars whose Fischer projections terminate in the same configuration as D-glyceraldehyde are designated as D sugars; those derived from L-glyceraldehyde are designated as L sugars.

Looking Closer: Polarized Light

A beam of ordinary light can be pictured as a bundle of waves; some move up and down, some sideways, and others at all other conceivable angles. When a beam of light has been polarized, however, the waves in the bundle all vibrate in a single plane. Light altered in this way is called plane-polarized light. Much of what chemists know about stereoisomers comes from studying the effects they have on plane-polarized light. In this illustration, the light on the left is not polarized, while that on the right is polarized.

Sunlight, in general, is not polarized; light from an ordinary light bulb or an ordinary flashlight is not polarized. One way to polarize ordinary light is to pass it through Polaroid sheets, special plastic sheets containing carefully oriented organic compounds that permit only light vibrating in a single plane to pass through. To the eye, polarized light doesn’t “look” any different from nonpolarized light. We can detect polarized light, however, by using a second sheet of polarizing material, as shown here.

In the photo on the left, two Polaroid sheets are aligned in the same direction; plane-polarized light from the first Polaroid sheet can pass through the second sheet. In the photo on the right, the top Polaroid sheet has been rotated 90° and now blocks the plane-polarized light that comes through the first Polaroid sheet.

Certain substances act on polarized light by rotating the plane of vibration. Such substances are said to be optically active. The extent of optical activity is measured by a polarimeter, an instrument that contains two polarizing lenses separated by a sample tube, as shown in the accompanying figure. With the sample tube empty, maximum light reaches the observer’s eye when the two lenses are aligned so that both pass light vibrating in the same plane. When an optically active substance is placed in the sample tube, that substance rotates the plane of polarization of the light passing through it, so that the polarized light emerging from the sample tube is vibrating in a different direction than when it entered the tube. To see the maximum amount of light when the sample is in place, the observer must rotate one lens to accommodate the change in the plane of polarization.

Figure 6.2 Diagram of a Polarimeter

Some optically active substances rotate the plane of polarized light to the right (clockwise) from the observer’s point of view. These compounds are said to be dextrorotatory; substances that rotate light to the left (counterclockwise) are levorotatory. To denote the direction of rotation, a positive sign (+) is given to dextrorotatory substances, and a negative sign (−) is given to levorotatory substances.

Answers

1.

a. aldose; hexose

b. ketose; pentose

c. aldose; triose

3.

a. aldose; D sugar

b. ketose; L sugar

6.3 Important Hexoses

Although a variety of monosaccharides are found in living organisms, three hexoses are particularly abundant: D-glucose, D-galactose, and D-fructose. Glucose and galactose are both aldohexoses, while fructose is a ketohexose.

Fructose

D-Fructose is the most abundant ketohexose. Note that from the third through the sixth carbon atoms, its structure is the same as that of glucose. It occurs, along with glucose and sucrose, in honey (which is 40% fructose) and sweet fruits. Fructose (from the Latin fructus, meaning “fruit”) is also referred to as levulose because it has a specific rotation that is strongly levorotatory (−92.4°). It is the sweetest sugar, being 1.7 times sweeter than sucrose, although many nonsugars are several hundred or several thousand times as sweet (Table 6.1 "The Relative Sweetness of Some Compounds (Sucrose = 100)").

Looking Closer: Artificial Sweeteners

Although sweetness is commonly associated with mono- and disaccharides, it is not a property found only in sugars. Several other kinds of organic compounds have been synthesized that are far superior as sweetening agents. These so-called high-intensity or artificial sweeteners are useful for people with diabetes or other medical conditions that require them to control their carbohydrate intake. The synthetic compounds are noncaloric or used in such small quantities that they do not add significantly to the caloric value of food.

The first artificial sweetener—saccharin—was discovered by accident in 1879. It is 300 times sweeter than sucrose, but it passes through the body unchanged and thus adds no calories to the diet. After its discovery, saccharin was used until it was banned in the early 1900s. However, during the sugar-short years of World War I, the ban was lifted and was not reinstated at the war’s end. One drawback to the use of saccharin is its bitter, metallic aftertaste. The initial solution to this problem was to combine saccharin with cyclamate, a second artificial sweetener discovered in 1937.

In the 1960s and 1970s, several clinical tests with laboratory animals implicated both cyclamate and saccharin as carcinogenic (cancer-causing) substances. The results from the cyclamate tests were completed first, and cyclamate was banned in the United States in 1969. Then a major study was released in Canada in 1977 indicating that saccharin increased the incidence of bladder cancer in rats. The US Food and Drug Administration (FDA) proposed a ban on saccharin that raised immediate public opposition because saccharin was the only artificial sweetener still available. In response, Congress passed the Saccharin Study and Labeling Act in 1977, permitting the use of saccharin as long as any product containing it was labeled with a consumer warning regarding the possible elevation of the risk of bladder cancer. Today this warning is no longer required; moreover, the FDA is currently reviewing the ban on cyclamate, as 75 additional studies and years of usage in other countries, such as Canada, have failed to show that it has any carcinogenic effect.

A third artificial sweetener, aspartame, was discovered in 1965. This white crystalline compound is about 180 times sweeter than sucrose and has no aftertaste. It was approved for use in 1981 and is used to sweeten a wide variety of foods because it blends well with other food flavors. Aspartame is not used in baked goods, however, because it is not heat stable.

In the body (or when heated), aspartame is initially hydrolyzed to three molecules: the amino acids aspartic acid and phenylalanine and an alcohol methanol. Repeated controversy regarding the safety of aspartame arises partly from the fact that the body metabolizes the released methanol to formaldehyde. It should be noted, though, that a glass of tomato juice has six times as much methanol as a similar amount of a diet soda containing aspartame. The only documented risk connected to aspartame use is for individuals with the genetic disease phenylketonuria (PKU); these individuals lack the enzyme needed to metabolize the phenylalanine released when aspartame is broken down by the body. Because of the danger to people with PKU, all products containing aspartame must carry a warning label.

Acesulfame K, discovered just two years after aspartame (1967), was approved for use in the United States in 1988. It is 200 times sweeter than sugar and, unlike aspartame, is heat stable. It has no lingering aftertaste.

One of the newest artificial sweeteners to gain FDA approval (April 1998) for use in the United States is sucralose, a white crystalline solid approximately 600 times sweeter than sucrose. Sucralose is synthesized from sucrose and has three chlorine atoms substituted for three OH groups. It is noncaloric because it passes through the body unchanged. It can be used in baking because it is heat stable.

All of the extensive clinical studies completed to date have indicated that these artificial sweeteners approved for use in the United States are safe for consumption by healthy individuals in moderate amounts.

Answers

1.

a. D-glucose

b. D-fructose

3.

a. aldohexose

b. aldohexose

c. ketohexose

6.4 Cyclic Structures of Monosaccharides

So far we have represented monosaccharides as linear molecules, but many of them also adopt cyclic structures. This conversion occurs because of the ability of aldehydes and ketones to react with alcohols:

In some cases, OH and carbonyl groups on the same molecule are able to react with one another in an intramolecular reaction. Thus, monosaccharides larger than tetroses exist mainly as cyclic compounds (Figure 6.3 "Cyclization of D-Glucose"). You might wonder why the aldehyde reacts with the OH group on the fifth carbon atom rather than the OH group on the second carbon atom next to it. Recall from Chapter 1 "Organic Chemistry Review / Hydrocarbons", Section 1.9 "Cycloalkanes", that cyclic alkanes containing five or six carbon atoms in the ring are the most stable. The same is true for monosaccharides that form cyclic structures: rings consisting of five or six carbon atoms are the most stable.

Figure 6.3 Cyclization of D-Glucose

D-Glucose can be represented with a Fischer projection (a) or three dimensionally (b). By reacting the OH group on the fifth carbon atom with the aldehyde group, the cyclic monosaccharide (c) is produced.

When a straight-chain monosaccharide forms a cyclic structure, the carbonyl oxygen atom may be pushed either up or down, giving rise to two stereoisomers, as shown in Figure 6.4 "Monosaccharides". The structure shown on the left side of Figure 6.4 "Monosaccharides", with the OH group on the first carbon atom projected downward, represent what is called the alpha (α) form. The structures on the right side, with the OH group on the first carbon atom pointed upward, is the beta (β) form. These two stereoisomers of a cyclic monosaccharide are known as anomers; they differ in structure around the anomeric carbon—that is, the carbon atom that was the carbonyl carbon atom in the straight-chain form.

Figure 6.4 Monosaccharides

In an aqueous solution, monosaccharides exist as an equilibrium mixture of three forms. The interconversion between the forms is known as mutarotation, which is shown for D-glucose (a) and D-fructose (b).

It is possible to obtain a sample of crystalline glucose in which all the molecules have the α structure or all have the β structure. The α form melts at 146°C and has a specific rotation of +112°, while the β form melts at 150°C and has a specific rotation of +18.7°. When the sample is dissolved in water, however, a mixture is soon produced containing both anomers as well as the straight-chain form, in dynamic equilibrium (part (a) of Figure 6.4 "Monosaccharides"). You can start with a pure crystalline sample of glucose consisting entirely of either anomer, but as soon as the molecules dissolve in water, they open to form the carbonyl group and then reclose to form either the α or the β anomer. The opening and closing repeats continuously in an ongoing interconversion between anomeric forms and is referred to as mutarotation (Latin mutare, meaning “to change”). At equilibrium, the mixture consists of about 36% α-D-glucose, 64% β-D-glucose, and less than 0.02% of the open-chain aldehyde form. The observed rotation of this solution is +52.7°.

Even though only a small percentage of the molecules are in the open-chain aldehyde form at any time, the solution will nevertheless exhibit the characteristic reactions of an aldehyde. As the small amount of free aldehyde is used up in a reaction, there is a shift in the equilibrium to yield more aldehyde. Thus, all the molecules may eventually react, even though very little free aldehyde is present at a time.

In Figure 6.3 "Cyclization of D-Glucose" and Figure 6.4 "Monosaccharides", and elsewhere in this book, the cyclic forms of sugars are depicted using a convention first suggested by Walter N. Haworth, an English chemist. The molecules are drawn as planar hexagons with a darkened edge representing the side facing toward the viewer. The structure is simplified to show only the functional groups attached to the carbon atoms. Any group written to the right in a Fischer projection appears below the plane of the ring in a Haworth projection, and any group written to the left in a Fischer projection appears above the plane in a Haworth projection.

The difference between the α and the β forms of sugars may seem trivial, but such structural differences are often crucial in biochemical reactions. This explains why we can get energy from the starch in potatoes and other plants but not from cellulose, even though both starch and cellulose are polysaccharides composed of glucose molecules linked together. We will examine the effects of these differences more closely in Section 6.7 "Polysaccharides" and when we discuss enzyme specificity in Chapter 9 "Proteins, and Enzymes", Section 9.2 "Enzymes".

Answers

1.

3.

6.5 Properties of Monosaccharides

Monosaccharides such as glucose and fructose are crystalline solids at room temperature, but they are quite soluble in water, each molecule having several OH groups that readily engage in hydrogen bonding. The chemical behavior of these monosaccharides is likewise determined by their functional groups.

An important reaction of monosaccharides is the oxidation of the aldehyde group, one of the most easily oxidized organic functional groups. Aldehyde oxidation can be accomplished with any mild oxidizing agent, such as Tollens’ reagent or Benedict’s reagent. (For more information about aldehyde oxidation, see Chapter 2 "Alcohols, Phenols, Thiols, Ethers", Section 2.5 "Reactions of Alcohols".) With the latter, complexed copper(II) ions are reduced to copper(I) ions that form a brick-red precipitate [copper(I) oxide; Figure 6.5 "Benedict’s Test"].

Any carbohydrate capable of reducing either Tollens’ or Benedict’s reagents without first undergoing hydrolysis is said to be a reducing sugar. Because both the Tollens’ and Benedict’s reagents are basic solutions, ketoses (such as fructose) also give positive tests due to an equilibrium that exists between ketoses and aldoses in a reaction known as tautomerism.

Figure 6.5 Benedict’s Test

Benedict’s test was performed on three carbohydrates, depicted from left to right: fructose, glucose, and sucrose. The solution containing sucrose remains blue because sucrose is a nonreducing sugar.

These reactions have been used as simple and rapid diagnostic tests for the presence of glucose in blood or urine. For example, Clinitest tablets, which are used to test for sugar in the urine, contain copper(II) ions and are based on Benedict’s test. A green color indicates very little sugar, whereas a brick-red color indicates sugar in excess of 2 g/100 mL of urine.

Answers

1. All three will give a positive Benedict’s test because they are all monosaccharides.

3.

6.6 Disaccharides

In Section 6.4 "Cyclic Structures of Monosaccharides", you learned that monosaccharides can form cyclic structures by the reaction of the carbonyl group with an OH group. These cyclic molecules can in turn react with another alcohol. Disaccharides (C₁₂H₂₂O₁₁) are sugars composed of two monosaccharide units that are joined by a carbon–oxygen-carbon linkage known as a glycosidic linkage. This linkage is formed from the reaction of the anomeric carbon of one cyclic monosaccharide with the OH group of a second monosaccharide.

The disaccharides differ from one another in their monosaccharide constituents and in the specific type of glycosidic linkage connecting them. There are three common disaccharides: maltose, lactose, and sucrose. All three are white crystalline solids at room temperature and are soluble in water. We’ll consider each sugar in more detail.

Maltose

Maltose occurs to a limited extent in sprouting grain. It is formed most often by the partial hydrolysis of starch and glycogen. In the manufacture of beer, maltose is liberated by the action of malt (germinating barley) on starch; for this reason, it is often referred to as malt sugar. Maltose is about 30% as sweet as sucrose. The human body is unable to metabolize maltose or any other disaccharide directly from the diet because the molecules are too large to pass through the cell membranes of the intestinal wall. Therefore, an ingested disaccharide must first be broken down by hydrolysis into its two constituent monosaccharide units. In the body, such hydrolysis reactions are catalyzed by enzymes such as maltase. The same reactions can be carried out in the laboratory with dilute acid as a catalyst, although in that case the rate is much slower, and high temperatures are required. Whether it occurs in the body or a glass beaker, the hydrolysis of maltose produces two molecules of D-glucose.

$$\text{maltose }\stackrel{{\text{H}}^{\text{+}}\text{ or maltase}}{\to }\text{ 2 D-glucose}$$

Maltose is a reducing sugar. Thus, its two glucose molecules must be linked in such a way as to leave one anomeric carbon that can open to form an aldehyde group. The glucose units in maltose are joined in a head-to-tail fashion through an α-linkage from the first carbon atom of one glucose molecule to the fourth carbon atom of the second glucose molecule (that is, an α-1,4-glycosidic linkage; see Figure 6.6 "An Equilibrium Mixture of Maltose Isomers"). The bond from the anomeric carbon of the first monosaccharide unit is directed downward, which is why this is known as an α-glycosidic linkage. The OH group on the anomeric carbon of the second glucose can be in either the α or the β position, as shown in Figure 6.6 "An Equilibrium Mixture of Maltose Isomers".

Figure 6.6 An Equilibrium Mixture of Maltose Isomers

Lactose

Lactose is known as milk sugar because it occurs in the milk of humans, cows, and other mammals. In fact, the natural synthesis of lactose occurs only in mammary tissue, whereas most other carbohydrates are plant products. Human milk contains about 7.5% lactose, and cow’s milk contains about 4.5%. This sugar is one of the lowest ranking in terms of sweetness, being about one-sixth as sweet as sucrose (see Table 6.1 "The Relative Sweetness of Some Compounds (Sucrose = 100)" in Section 6.3 "Important Hexoses"). Lactose is produced commercially from whey, a by-product in the manufacture of cheese. It is important as an infant food and in the production of penicillin.

Lactose is a reducing sugar composed of one molecule of D-galactose and one molecule of D-glucose joined by a β-1,4-glycosidic bond (the bond from the anomeric carbon of the first monosaccharide unit being directed upward). The two monosaccharides are obtained from lactose by acid hydrolysis or the catalytic action of the enzyme lactase:

Many adults and some children suffer from a deficiency of lactase. These individuals are said to be lactose intolerant because they cannot digest the lactose found in milk. A more serious problem is the genetic disease galactosemia, which results from the absence of an enzyme needed to convert galactose to glucose. Certain bacteria can metabolize lactose, forming lactic acid as one of the products. This reaction is responsible for the “souring” of milk.

Example 3

For this trisaccharide, indicate whether each glycosidic linkage is α or β.

Solution

The glycosidic linkage between sugars 1 and 2 is β because the bond is directed up from the anomeric carbon. The glycosidic linkage between sugars 2 and 3 is α because the bond is directed down from the anomeric carbon.

Skill-Building Exercise

1. For this trisaccharide, indicate whether each glycosidic linkage is α or β.

   

To Your Health: Lactose Intolerance and Galactosemia

Lactose makes up about 40% of an infant’s diet during the first year of life. Infants and small children have one form of the enzyme lactase in their small intestines and can digest the sugar easily; however, adults usually have a less active form of the enzyme, and about 70% of the world’s adult population has some deficiency in its production. As a result, many adults experience a reduction in the ability to hydrolyze lactose to galactose and glucose in their small intestine. For some people the inability to synthesize sufficient enzyme increases with age. Up to 20% of the US population suffers some degree of lactose intolerance.

In people with lactose intolerance, some of the unhydrolyzed lactose passes into the colon, where it tends to draw water from the interstitial fluid into the intestinal lumen by osmosis. At the same time, intestinal bacteria may act on the lactose to produce organic acids and gases. The buildup of water and bacterial decay products leads to abdominal distention, cramps, and diarrhea, which are symptoms of the condition.

The symptoms disappear if milk or other sources of lactose are excluded from the diet or consumed only sparingly. Alternatively, many food stores now carry special brands of milk that have been pretreated with lactase to hydrolyze the lactose. Cooking or fermenting milk causes at least partial hydrolysis of the lactose, so some people with lactose intolerance are still able to enjoy cheese, yogurt, or cooked foods containing milk. The most common treatment for lactose intolerance, however, is the use of lactase preparations (e.g., Lactaid), which are available in liquid and tablet form at drugstores and grocery stores. These are taken orally with dairy foods—or may be added to them directly—to assist in their digestion.

Galactosemia is a condition in which one of the enzymes needed to convert galactose to glucose is missing. Consequently, the blood galactose level is markedly elevated, and galactose is found in the urine. An infant with galactosemia experiences a lack of appetite, weight loss, diarrhea, and jaundice. The disease may result in impaired liver function, cataracts, mental retardation, and even death. If galactosemia is recognized in early infancy, its effects can be prevented by the exclusion of milk and all other sources of galactose from the diet. As a child with galactosemia grows older, he or she usually develops an alternate pathway for metabolizing galactose, so the need to restrict milk is not permanent. The incidence of galactosemia in the United States is 1 in every 65,000 newborn babies.

Sucrose

Sucrose, probably the largest-selling pure organic compound in the world, is known as beet sugar, cane sugar, table sugar, or simply sugar. Most of the sucrose sold commercially is obtained from sugar cane and sugar beets (whose juices are 14%–20% sucrose) by evaporation of the water and recrystallization. The dark brown liquid that remains after the recrystallization of sugar is sold as molasses.

The sucrose molecule is unique among the common disaccharides in having an α-1,β-2-glycosidic (head-to-head) linkage. Because this glycosidic linkage is formed by the OH group on the anomeric carbon of α-D-glucose and the OH group on the anomeric carbon of β-D-fructose, it ties up the anomeric carbons of both glucose and fructose.

This linkage gives sucrose certain properties that are quite different from those of maltose and lactose. As long as the sucrose molecule remains intact, neither monosaccharide “uncyclizes” to form an open-chain structure. Thus, sucrose is incapable of mutarotation and exists in only one form both in the solid state and in solution. In addition, sucrose does not undergo reactions that are typical of aldehydes and ketones. Therefore, sucrose is a nonreducing sugar.

The hydrolysis of sucrose in dilute acid or through the action of the enzyme sucrase (also known as invertase) gives an equimolar mixture of glucose and fructose. This 1:1 mixture is referred to as invert sugar because it rotates plane-polarized light in the opposite direction than sucrose. The hydrolysis reaction has several practical applications. Sucrose readily recrystallizes from a solution, but invert sugar has a much greater tendency to remain in solution. In the manufacture of jelly and candy and in the canning of fruit, the recrystallization of sugar is undesirable. Therefore, conditions leading to the hydrolysis of sucrose are employed in these processes. Moreover, because fructose is sweeter than sucrose, the hydrolysis adds to the sweetening effect. Bees carry out this reaction when they make honey.

The average American consumes more than 100 lb of sucrose every year. About two-thirds of this amount is ingested in soft drinks, presweetened cereals, and other highly processed foods. The widespread use of sucrose is a contributing factor to obesity and tooth decay. Carbohydrates such as sucrose, are converted to fat when the caloric intake exceeds the body’s requirements, and sucrose causes tooth decay by promoting the formation of plaque that sticks to teeth.

Answers

1.

a. lactose

b. sucrose

3.

a.

b.

5.

3a: nonreducing; 3b: reducing

7.

a. galactose and glucose

b. α-glycosidic linkage

c.

6.7 Polysaccharides

The polysaccharides are the most abundant carbohydrates in nature and serve a variety of functions, such as energy storage or as components of plant cell walls. Polysaccharides are very large polymers composed of tens to thousands of monosaccharides joined together by glycosidic linkages. The three most abundant polysaccharides are starch, glycogen, and cellulose. These three are referred to as homopolymers because each yields only one type of monosaccharide (glucose) after complete hydrolysis. Heteropolymers may contain sugar acids, amino sugars, or noncarbohydrate substances in addition to monosaccharides. Heteropolymers are common in nature (gums, pectins, and other substances) but will not be discussed further in this textbook. The polysaccharides are nonreducing carbohydrates, are not sweet tasting, and do not undergo mutarotation.

Starch

Starch is the most important source of carbohydrates in the human diet and accounts for more than 50% of our carbohydrate intake. It occurs in plants in the form of granules, and these are particularly abundant in seeds (especially the cereal grains) and tubers, where they serve as a storage form of carbohydrates. The breakdown of starch to glucose nourishes the plant during periods of reduced photosynthetic activity. We often think of potatoes as a “starchy” food, yet other plants contain a much greater percentage of starch (potatoes 15%, wheat 55%, corn 65%, and rice 75%). Commercial starch is a white powder.

Starch is a mixture of two polymers: amylose and amylopectin. Natural starches consist of about 10%–30% amylase and 70%–90% amylopectin. Amylose is a linear polysaccharide composed entirely of D-glucose units joined by the α-1,4-glycosidic linkages we saw in maltose (part (a) of Figure 6.7 "Amylose"). Experimental evidence indicates that amylose is not a straight chain of glucose units but instead is coiled like a spring, with six glucose monomers per turn (part (b) of Figure 6.7 "Amylose"). When coiled in this fashion, amylose has just enough room in its core to accommodate an iodine molecule. The characteristic blue-violet color that appears when starch is treated with iodine is due to the formation of the amylose-iodine complex. This color test is sensitive enough to detect even minute amounts of starch in solution.

Figure 6.7 Amylose

(a) Amylose is a linear chain of α-D-glucose units joined together by α-1,4-glycosidic bonds. (b) Because of hydrogen bonding, amylose acquires a spiral structure that contains six glucose units per turn.

Amylopectin is a branched-chain polysaccharide composed of glucose units linked primarily by α-1,4-glycosidic bonds but with occasional α-1,6-glycosidic bonds, which are responsible for the branching. A molecule of amylopectin may contain many thousands of glucose units with branch points occurring about every 25–30 units (Figure 6.8 "Representation of the Branching in Amylopectin and Glycogen"). The helical structure of amylopectin is disrupted by the branching of the chain, so instead of the deep blue-violet color amylose gives with iodine, amylopectin produces a less intense reddish brown.

Figure 6.8 Representation of the Branching in Amylopectin and Glycogen

Both amylopectin and glycogen contain branch points that are linked through α-1,6-linkages. These branch points occur more often in glycogen.

Dextrins are glucose polysaccharides of intermediate size. The shine and stiffness imparted to clothing by starch are due to the presence of dextrins formed when clothing is ironed. Because of their characteristic stickiness with wetting, dextrins are used as adhesives on stamps, envelopes, and labels; as binders to hold pills and tablets together; and as pastes. Dextrins are more easily digested than starch and are therefore used extensively in the commercial preparation of infant foods.

The complete hydrolysis of starch yields, in successive stages, glucose:

starch → dextrins → maltose → glucose

In the human body, several enzymes known collectively as amylases degrade starch sequentially into usable glucose units.

Cellulose

Cellulose, a fibrous carbohydrate found in all plants, is the structural component of plant cell walls. Because the earth is covered with vegetation, cellulose is the most abundant of all carbohydrates, accounting for over 50% of all the carbon found in the vegetable kingdom. Cotton fibrils and filter paper are almost entirely cellulose (about 95%), wood is about 50% cellulose, and the dry weight of leaves is about 10%–20% cellulose. The largest use of cellulose is in the manufacture of paper and paper products. Although the use of noncellulose synthetic fibers is increasing, rayon (made from cellulose) and cotton still account for over 70% of textile production.

Like amylose, cellulose is a linear polymer of glucose. It differs, however, in that the glucose units are joined by β-1,4-glycosidic linkages, producing a more extended structure than amylose (part (a) of Figure 6.9 "Cellulose"). This extreme linearity allows a great deal of hydrogen bonding between OH groups on adjacent chains, causing them to pack closely into fibers (part (b) of Figure 6.9 "Cellulose"). As a result, cellulose exhibits little interaction with water or any other solvent. Cotton and wood, for example, are completely insoluble in water and have considerable mechanical strength. Because cellulose does not have a helical structure, it does not bind to iodine to form a colored product.

Figure 6.9 Cellulose

(a) There is extensive hydrogen bonding in the structure of cellulose. (b) In this electron micrograph of the cell wall of an alga, the wall consists of successive layers of cellulose fibers in parallel arrangement.

Cellulose yields D-glucose after complete acid hydrolysis, yet humans are unable to metabolize cellulose as a source of glucose. Our digestive juices lack enzymes that can hydrolyze the β-glycosidic linkages found in cellulose, so although we can eat potatoes, we cannot eat grass. However, certain microorganisms can digest cellulose because they make the enzyme cellulase, which catalyzes the hydrolysis of cellulose. The presence of these microorganisms in the digestive tracts of herbivorous animals (such as cows, horses, and sheep) allows these animals to degrade the cellulose from plant material into glucose for energy. Termites also contain cellulase-secreting microorganisms and thus can subsist on a wood diet. This example once again demonstrates the extreme stereospecificity of biochemical processes.

Answers

1.

a. glucose

b. glucose

c. glucose

3. Amylose and cellulose are both linear polymers of glucose units, but the glycosidic linkages between the glucose units differ. The linkages in amylose are α-1,4-glycosidic linkages, while the linkages in cellulose they are β-1,4-glycosidic linkages.

6.8 End-of-Unit Material

Answers

1.

3.

5. Lactose, D-ribose, and D-glyceraldehyde would give a positive Benedict’s test.

7. To be a reducing sugar, a disaccharide must contain an anomeric carbon atom that can open up to form an aldehyde functional group, as shown in this disaccharide (answers will vary).

9.

a. The carbohydrate is being oxidized; Tollens’ or Benedict’s reagent could be used.

b. To form the compound shown, an aldehyde must react with methanol (CH₃OH) and an acid catalyst.

11. galactose and fructose

13.

15. Sucralose would be expected to have the sweetest taste because its relative sweetness is the highest. Lactose would have the least sweet taste because it has the lowest relative sweetness.

17. Intestinal bacteria can act on the lactose present in the intestine to produce organic acids and gases. The buildup of water and bacterial decay products leads to cramps and diarrhea.