Carbohydrates

Carbohydrates are the most abundant class of compounds in the biological world, making up more than 50% of the dry weight of the earths biomass. Carbohydrates are important constituents of all living organisms, and have a variety of different functions. The most abundant carbohydrate in nature is D-glucose. Cells of organisms oxidize D-glucose in the first of a series of processes that provide them with energy. When animals have more D-glucose than they need for energy, they convert excess D-glucose into a polymer called glycogen. When an animal needs energy glycogen is broken into individual D-glucose molecules. Plants convert excess D-glucose into a polymer known as starch. The major structural component of plants, cellulose is another polymer of D-glucose. Chitin, a carbohydrate similar to cellulose, makes up the exoskeletons of crustaceans, insects and other arthropods. Animals obtain glucose by eating plants (or other food that contains D-glucose). Plants form glucose by photosynthesis. The terms carbohydrate (hydrate of carbon, Cn(H2O)n), saccharide and sugar are used interchangeably. Saccharide comes from the word sugar in Greek (sakcharon) and Latin (saccharum). There are two classes of carbohydrates simple carbohydrates and complex carbohydrates. Simple carbohydrates are monosaccharides (single sugars), whereas complex carbohydrates contain two or more sugar subunits linked together. Disaccharides are complex carbohydrates with two sugar subunits linked together. Monosaccharides A monosaccharide can be a polyhydroxy aldehyde or a polyhydroxy ketone. Polyhydroxy aldehydes are called aldoses (ose is the suffix for a sugar), while polyhydroxy ketones are called ketoses. Monosaccharides with three carbons are called trioses, those with four carbons tetroses, five carbons pentoses and six carbons hexoses. A six carbon polyhydroxy aldehyde such as D-glucose is an aldohexose, whereas a six carbon polyhydroxy ketone, such as D-fructose is a ketohexose. The smallest aldose, and the only one whose name does not end in ose is glyceraldehyde, an aldotriose. Glyceraldehyde has a chiral carbon and exists as a pair of enantiomers. We usually show the stereochemistry of sugars using Fisher projections. Emil Fischer studied carbohydrates in the late 19th century and he named the dextrorotatory stereoisomer of glyceraldehyde, D-glyceraldehyde. D-Glyceraldehyde turned out to be (R)-(+)-glyceraldehyde.
O H H OH CH2OH O HO H H CH2OH

D-glyceraldehyde (R)-(+)-glyceraldehyde

L-glyceraldehyde (S)-(-)-glyceraldehyde

D and L notations are often used to describe the configurations of carbohydrates and amino acids, so we need to understand what they signify. In Fisher projects, the carbonyl is always placed at the top or in the case of ketoses as close to the top as possible. From the structure of galactose below you can see that it has four chiral carbons. If the OH group attached to the bottom-most chiral centre (the second carbon up from the bottom) is on the right, the compound is a D-sugar. If the OH group is on the left the compound is an L-sugar. Almost all sugars found in nature are D-sugars. Notice that the mirror image of a D-sugar is an L-sugar.
O H HO HO H H OH H H OH CH2OH O HO H H HO H H OH OH H CH2OH

D-galactose

L-galactose mirror image of D-galactose

D and L, like R and S, indicate the configuration of a chiral centre, but they do not indicate whether the compound rotates the plane of polarized light to the right (+) or to the left (-).

Figure 1. Configurations of D-aldoses Aldotriose

H H O OH CH2OH

D-Glyceraldehyde or (R)-2,3-dihydroxypropanal Aldotetroses

H H H O OH OH CH2OH H HO H O H OH CH2OH

D-Erythrose Aldopentoses
H H H H O OH OH OH CH2OH H HO H H O H OH OH CH2OH H H HO H O OH H OH CH2OH

D-Threose
H HO HO H O H H OH CH2OH

D-Ribose Aldohexoses
H H H H H O OH OH OH OH CH2OH H HO H H H O H OH OH OH CH2OH H H HO H H

D-Arabinose
O OH H OH OH CH2OH H HO HO H H O H H OH OH CH2OH H H H HO H

D-Xylose
O OH OH H OH CH2OH H HO H HO H O H OH H OH CH2OH H H HO HO H O OH H H OH CH2OH

D-Lyxose
H HO HO HO H O H H H OH CH2OH

D-Allose D-Altrose

D-Glucose

D-Mannose

D-Gulose

D-Idose

D-Galactose

D-Talose

Diastereomers that differ in configuration at one chiral centre are called epimers. D-ribose and D-arabinose are C-2 epimers. D-glucose, D-mannose and D-galactose are the most common aldohexoses in biological systems. An easy way to learn their structures is to memorize the structure of D-glucose and then remember that D-mannose is a C-2 epimer and D-galactose is a C-4 epimer. Sugars such as D-glucose and D-galactose are diastereomers because they are stereoisomers that are not enantiomers. Configurations of the Ketoses Naturally occurring ketoses have the ketone group at carbon-2. A ketose has one fewer chiral carbons than does an aldose with the same number of carbon atoms. Therefore, a ketose has only half as many stereoisomers as an aldose with the same number of carbon atoms.

Figure 2. Configurations of D-ketoses Ketotriose

CH2OH O CH2OH

1,3-Dihydroxypropanone Ketotetrose
CH2OH O H OH CH2OH

D-Erythrulose Ketopentoses
CH2OH O H H OH OH CH2OH HO H CH2OH O H OH CH2OH

D-Ribulose Ketohexoses
CH2OH O H H H OH OH OH CH2OH HO H H CH2OH O H OH OH CH2OH H HO H CH2OH O OH H OH CH2OH

D-Xylulose
CH2OH O HO HO H H H OH CH2OH

D-Psicose

D-Fructose

D-Sorbose

D-Tagatose

Hemiacetal Formation D-Glucose exists in three different forms. There is an open chain form which we have just described and two cyclic forms -D-glucose and -D-glucose. The three forms have different physical properties and different specific rotations. The C-5 alcohol group reacts intramolecularly with the aldehyde group forming a six-membered ring hemiacetal. The aldehyde carbon has become a chiral centre in the hemiacetal. If the OH group bonded to the new chiral centre is on the right, it is -D-glucose; if the OH group is on the left, it is -D-glucose. -D-glucose and -D-glucose are called anomers. Anomers are two sugars that differ in configuration at the hemiacetal carbon (the carbonyl carbon). This is called the anomeric carbon (Ano is Greek for upper anomers differ in configuration at the uppermost chiral center. Anomers, like epimers, are a particular kind of diastereomer. In solution, glucose rapidly establishes an equilibrium (catalyzed by acid or base) with the open chain aldehyde and the and anomer. If the stereochemistry of the hemiacetal (or hemiacetal in glycosides) carbon is S, the sugar is called the anomer and if it is R, the -anomer.

H HOH2C HO HO OH H O OH H HO H H

O HOH2C OH H OH OH CH2OH HO HO OH OH O H

-D-glucopyranose -anomer (63%)

open-chain aldehyde (0.002%)

-D-glucopyranose -anomer (37%)

When crystals of pure -D-glucose are dissolved in water, the specific rotation gradually changes from +112.2 to +52.7. When crystals of pure -D-glucose are dissolved in water, the specific rotation gradually changes from +18.7 to +52.7. This change in rotation occurs because, in water the hemiacetal opens to form the aldehyde, which can then recyclize to form both -D-glucose and -D-glucose. When equilibrium is reached, (63% -D-glucose, 37% -D-glucose and 0.002% aldehyde) the specific rotation is +52.7. A slow change in optical rotation to an equilibrium value is known as mutarotation. If an aldose can form a five- or a six-membered ring, it will exist predominately as a cyclic hemiacetal in solution. Whether a five- or six-membered ring is formed depends on their relative stabilities. Six-membered ring sugars are called pyranoses and five-membered ring sugars are called furanoses. These names come from the pyran and furan rings. Consequently, -Dglucose is called -D-glucopyranose; where pyranose indicates that the sugar exists as a six-membered ring hemiacetal. Fisher projections are not effective at showing cyclic sugars and so we use Haworth projections. In a Haworth projection of a D-pyranose, the six-membered ring is represented as being flat and is viewed edge on. The ring oxygen is always placed in the back right-hand corner of the ring, with the anomeric carbon (C1) on the right-hand side and the primary alcohol group drawn up from the left-hand corner (C5). Groups on the right in a Fisher projection are down in a Haworth projection. Groups on the left in a Fisher projection are up in a Haworth projection. The Haworth projection of a D-furanose is viewed edge on with the ring oxygen away from the viewer. The anomeric carbon is on the right-hand side and the primary alcohol group is drawn up from the back left-hand corner. -D-glucopyranose
O HO H HO H H CH2OH H OH H OH HO H H H CH2OH H OH OH

-D-ribofuranose
O

Fisher projections
CH2OH O OH OH OH OH OH OH CH2OH O OH

Haworth projections Groups on the right are down and on the left, up. Ketoses also exist predominantly in cyclic forms, D-fructose forms a five-membered ring hemiketal as a consequence of the C5 OH group reacting with the ketone. If the new chiral centre has the new OH group on the right in a Fisher projection, the compound is -D-fructose; if the OH group is on the left, the compound is -D-fructose. These sugars can also be called D-fructofuranose and -D-fructofuranose. Notice that in fructose the anomeric carbon is at C2 and not C1 as in the aldoses.

CH2OH O HO H H H OH OH CH2OH HO HO H H

CH2OH O H OH CH2OH HOH2C HO H H CH2OH OH H OH

O HO HO H H CH2OH CH2OH H OH

D-fructose

-D-fructofuranose

-D-fructofuranose

Remember the -anomer is S and -anomer is R D-Fructose can also form a six-membered ring by using the C6 OH group. The pyranose form predominates in the monosaccharide, while the furanose form predominates when the sugar is in a disaccharide. -D-fructofuranose
O HO HO H H CH2OH CH2OH H OH HO HO H H H2C CH2OH H OH OH

-D-fructopyranose
O

Fisher projections
CH2OH OH OH

O OH OH OH

OH

CH2OH

CH2OH

OH

Haworth projections Remember groups on the right are down and on the left, up. Haworth projections are useful because they allow us to see easily whether the OH groups on the ring are cis or trans to each other. As five-membered rings are close to planar, furanoses are represented well by Haworth projections. However Haworth projections do not show the chair conformations that are important for the six-membered pyranose rings.
CH2OH CH2OH CH2OH O OH OH HO CH2OH OH H H O H OH OH CH2OH HO H H O H OH OH CH2OH HO OH OH CH2OH OH O

-D-fructofuranose (32%)

open-chain ketone of fructose

-D-fructopyranose (68%)

Stability of Glucose Drawing glucose in its chair conformation shows why it is the most common aldohexose in nature. To convert a Haworth projection into a chair conformation, start by placing the ring oxygen at the back right-hand corner and the primary alcohol group in the equatorial position (this is the largest of the substituents). Because the OH group bonded to C4 is trans to the primary alcohol group (this is easily seen in the Haworth projection), the C4 OH group is also in the equatorial position. The C3 OH group is trans to the C4 OH group, so the C3 OH group is also in the equatorial position. -D-glucopyranose
O HO H HO H H CH2OH H OH H OH OH OH OH CH2OH O OH HO HO HOH2C O OH

OH

Fisher projection

Haworth projection

chair conformation

As you move around the ring, you will find that all the OH substituents in -D-glucose are in equatorial positions. The axial positions are all occupied by hydrogens, which require little space and therefore experience little steric strain. No other aldohexose exists in such a strain-free conformation. This means that -D-glucose is the most stable of all the aldohexoses, So it is not surprising that it is the most prevalent aldohexose in nature. Why is there more -D-glucose than -D-glucose in an aqueous solution at equilibrium? The OH group bonded to the anomeric carbon is in the equatorial position in -D-glucose, whereas it is in the axial position in -D-glucose. Therefore, -D-glucose is more stable than -D-glucose, so -D-glucose predominates at equilibrium in an aqueous solution. If you remember that all the OH groups in -D-glucose are in equatorial positions, it is easy to draw the chair conformation of any other pyranose. For example, if you want to draw -D-mannose, you would put all the OH groups in equatorial positions except the OH groups at C2 (because mannose is a C2 epimer of glucose) and at C1 (because it is the -anomer). You would put these two OH groups in axial positions instead.
H H HO H H O OH H OH OH CH2OH HO HO HOH2C O OH OH H HO HO H H O H H OH OH CH2OH HO HO OH HOH2C OH

D-glucose

D-mannose

To draw an L-pyranose, draw the D-pyranose first, and then draw its mirror image. For example, to draw -L-gulose, first draw -D-gulose (gulose differs from glucose at C3 and C4, so the OH groups at these positions are in axial positions). Then draw the mirror image of -D-gulose to get -L-gulose.
OH HOH2C O OH OH OH HO HO OH O OH CH2OH

-D-gulose

-L-gulose

Glycoside formation Aldehydes react with an alcohol to form a hemiacetal and the hemiacetal can then react with another alcohol to form a acetal. Similarly the cyclic hemiacetal (or hemiketal) formed by a monosaccharide can react with an alcohol to form an acetal (or ketal). The acetal (or ketal) of a sugar is called a glycoside. Glycosides are named by replacing the e ending of the sugars name with ide. Thus the glycoside of glucose is a glucoside. If the pyranose or furanose name is used, the acetal is called a pyranoside or furanoside.
HOH2C HO HO OH HOH2C CH3OH OH HCl HO HO OH HOH2C O OCH3 HO HO OH OCH3 O

-D-Glucopyranose (cyclic hemiacetal)

Methyl -D-glucopyranoside (cyclic acetal, 33%)

Methyl -D-glucopyranoside (cyclic acetal, 66%)

Notice that the reaction of a single anomer with an alcohol leads to the formation of both the - and -glycosides. The mechanism explains why. The OH group bonded to the anomeric carbon becomes protonated in the acidic solution, and a nonbonding pair of electrons on the ring oxygen helps expel a molecule of water. The anomeric carbon in the resulting oxocarbenium ion is sp2 hybridized, so that part of the molecule is planar. (An oxocarbenium ion has a positive charge that is shared by a carbon and an oxygen.) When the alcohol comes in from the top of the plane, the -glycoside is formed; when the alcohol comes in from the bottom of the plane, the -glycoside is formed. Notice that the mechanism is the same as the mechanism for acetal formation.
attack from the top HOH2C HO HO O OH OH HOH2C HO HO O OH OH2 HOH2C HO HO O HOH2C OH H CH3OH HO HO O OH OCH3 H -H CH3OH HOH2C HO HO O OH OCH3 H -H

attack from the bottom

Surprisingly, D-glucose forms more of the -glycoside than the -glycoside. The reason for this is explained in the next section.
HOH2C O O OH OH OH

3-Oxo--ionol 9-O--D-glucopyranoside an important aroma precursor in chardonnay grapes The Anomeric Effect We have seen that -D-glucose is more stable than -D-glucose because there is more room for a substituent in the equatorial position. However, we just saw that when glucose reacts with an alcohol to form a glucoside, the major product is the -glucoside. This means that the -glucoside must be more stable than the -glucoside. The preference for the axial position by certain substituents bonded to the anomeric carbon is called the anomeric effect. What is responsible for the anomeric effect? One clue is that all the substituents that prefer the axial position have lone-pair electrons on the atom bonded to the ring. The lone-pair electrons of the anomeric substituent have repulsive interactions with the lone-pair electrons of the ring oxygen if the anomeric substituent is in the -position, but not if it is in the position.

HOH2C HO HO O OH O CH3

HOH2C HO HO O OH H3C O

Apparently the attractive interaction of the hydrogen of the anomeric OH group of D-glucose with the lone-pair electrons of the ring oxygen decreases the importance of the anomeric effect, making -D-glucose more stable than -D-glucose. However, when the hydrogen is replaced by an alkyl group, the anomeric effect decreases the stability of the -position, so -glycosides are more stable than -glycosides. Reducing sugars Like other aldehydes, aldoses are easily oxidized to yield the corresponding carboxylic acids, called aldonic acids. Aldoses react with Tollens reagent (Ag+ in aqueous ammonia), Fehlings reagent (Cu2+ in aqueous sodium tartrate), or Benedicts reagent (Cu2+ in aqueous sodium citrate) to yield the oxidized sugar and a reduced metallic species. All three reagents serve as simple chemical tests for what are called reducing sugars reducing because the sugar reduces the metal oxidizing reagent.
H H HO H H O OH H OH OH CH2OH H HO H H COOH OH H OH OH CH2OH

All aldoses are reducing sugars because they contain a aldehyde carbonyl group. Ketoses are only reducing if they can under-go keto-enol tautomerism to an aldehyde (e.g. fructose). Glycosides are nonreducing because the acetal group is not hydrolysed to an aldehyde under basic conditions. Fructose is a reducing sugar because it undergoes two base-catalysed keto-enol tautomerizations that result in conversion to an aldohexose. The wavy bonds indicate unknown stereochemistry.
CH2OH O HO H H H OH OH CH2OH NaOH / H2O keto-enol tautomerism H HO H H OH OH H OH OH CH2OH NaOH / H2O keto-enol tautomerism H H HO H H O OH H OH OH CH2OH

D-fructose

an enediol

An aldohexose

Disaccharides Disaccharides are dimers made up of two monosaccharide molecules. The monosaccharides may be either the same or different. The monosaccharides are joined by a glycoside linkage between the anomeric carbon of one monosaccharide and an OH group of the other. The most common glycoside linkage is between the 4-hydroxy group of one monosaccharide and the - or - position of the anomeric carbon. This kind of a link is called an -1,4- or -1,4-glycoside linkage (or bond), depending on the configuration at the anomeric carbon atom. Maltose, cellobiose, and lactose are disaccharides with -1,4- or -1,4-glycoside linkages. Maltose is the principal product of the acid- or enzyme-catalyzed hydrolysis of starch. It contains two D-glucose units, both in the pyranose form, joined by an -1,4-linkage. Maltose exists in both the - and -anomeric forms. One ring of maltose contains a carbonyl group that is still in a hemiacetal form. This carbonyl group can undergo the normal reactions of a carbonyl group of an aldose. Maltose, therefore, reduces Fehlings solution and Tollens reagent, so it is a reducing sugar. It undergoes mutarotation and can be oxidized to a carboxylic acid by bromine water.

OH HO HO O OH O HO H H OH HO HO

OH O OH O HO H H OH

O HO H HO OH

O HO H -Maltose 4-O-(-D-glucopyranosyl)--D-glucopyranoside

-Maltose 4-O-(-D-glucopyranosyl)--D-glucopyranoside

Cellobiose is a disaccharide that is obtained by the partial hydrolysis of cellulose. It contains two D-glucose units joined by a -1,4-glycoside bond, so it is isomeric with maltose. Like maltose, cellobiose exists as two anomers, is a reducing sugar and undergoes mutarotation. OH OH HO H OH OH O O HO H HO OH HO HO HO HO O O O O OH OH
H OH

-Cellobiose 4-O-(-D-glucopyranosyl)--D-glucopyranoside

OH -Cellobiose 4-O-(-D-glucopyranosyl)--D-glucopyranoside

Lactose, a disaccharide that occurs in both human and cows milk, contains a -1,4-glycoside bond. Unlike maltose and cellobiose, hydrolysis of lactose forms one equivalent of glucose and one equivalent of galactose. The two are both in their pyranose forms, and the -glycoside bond joins the anomeric carbon of galactose with C4 of glucose. Like maltose and cellobiose, lactose is a reducing sugar, undergoes mutarotation, and exists as two anomers. OH OH OH HO H OH OH OH O O H OH HO HO HO HO O O O O OH OH
H

-Lactose 4-O-(-D-galactopyranosyl)--D-glucopyranoside

OH

OH -Lactose 4-O-(-D-galactopyranosyl)--D-glucopyranoside

Sucrose (ordinary table sugar) is one of the most widespread carbohydrates in nature. It is obtained commercially from sugar beets and sugar cane. Hydrolysis of sucrose forms one equivalent of D-glucose and one equivalent of D-fructose. Sucrose is not a reducing sugar, so it cannot have a hemiacetal group. This means, in turn, that the pyranose form of glucose and the furanose form of fructose are joined by an acetal link between the two anomeric carbons.

OH HO HO O OH O H
1 2' 1'

OH

HO

OH

OH sucrose 2-O-(-D-glucopyranosyl)--D-fructofuranoside

Sucrose is dextrorotatory with []D = +66. Either acid- or enzyme-catalyzed hydrolysis of (+)-sucrose produces an interesting phenomenon. The dextrorotatory solution of pure (+)-sucrose becomes levorotatory during the hydrolysis reaction. This solution is called invert sugar because the sign of optical rotation inverts during its preparation. The reason the sugar inverts becomes apparent when we look at the optical rotations of glucose and fructose. The equilibrium mixture of fructose isomers has a negative optical rotation, []D = 92, while the equilibrium mixture of glucose isomers has a positive optical rotation, []D = 52. The optical rotation of fructose is so highly negative that the 1:1 mixture of fructose and glucose formed on complete hydrolysis of sucrose is also levorotatory; []D = 20. Based on the sign of their optical rotations, glucose is sometimes referred to as dextrose and fructose as levulose. Honeybees have enzymes called invertases that catalyze the hydrolysis of sucrose to fructose and glucose. Honey is largely a mixture of D-glucose, D-fructose, and sucrose. Polysaccharides Most carbohydrates in nature exist as high-molecular-weight polymers called polysaccharides. Polysaccharides are formed by joining hundreds and thousands of monosaccharides by means of glycoside bonds. The most common monosaccharide present in polysaccharides is D-glucose. Polysaccharides have two quite different roles in nature. Some polysaccharides serve as a means of storing chemical energy, while others serve as structural units. The remarkable fact is that the polysaccharides that function in these two ways both consist of 1,4-linked polyglucose. Their different roles are due to the fact that two D-glucopyranose molecules can be joined by either -1,4- or -1,4-glycoside bonds. Lets first learn how a -1,4-glycoside bond affects the properties of a 1,4-linked polyglucose. Straight chains are the most stable arrangement of D-glucopyranose molecules that are joined together by -1,4-glycoside bonds, as shown in Figure 3. Notice that every pyran ring in the straight chain is rotated by 180 relative to the previous one. This results in an almost fully extended polysaccharide chain. These extended chains pack tightly together because many hydrogen bonds form between the chains. As a result, these chains are strong and chemically relatively inert. Figure 3. Cellulose
OH O HO O OH H HO O A H OH O OH O HO O

O OH H OH A. The most stable arrangement of D-glucopyranose molecules joined by -1,4 bonds is a straight chain. Notice that every pyran ring in the chain is rotated 180 relative to the previous one.

B. The chains formed by D-glucopyranose molecules joined by -1,4 bonds pack tightly together because many hydrogen bonds form between adjacent chains. Cellulose is an example of a polysaccharide consisting of tightly packed extended chains of D-glucopyranose molecules joined by -1,4 glycoside bonds. Cellulose is the most abundant of all polysaccharides. It is the major constituent of cell membranes and other structural features of plants. Cotton fiber and filter paper are almost entirely cellulose, while wood is about 50% cellulose. Instead of linear chains, the chains of D-glucopyranose molecules joined by -1,4-glycoside bonds adopt a helical configuration, as shown in Figure 4. Figure 4. Starch
O HO H OH O H OH O

OH O HO

O HO

A. Two D-glucopyranose units joined by an -1,4-linkage.

B. A chain of D(+)-glucopyranose molecules joined by -1,4 glycoside bonds adopts a helical configuration. Starch is an example of a polysaccharide consisting of coiled chains of D-glucopyranose molecules joined by -1,4glycoside bonds. Starch is the major source of carbohydrates in the human diet. It is a mixture of about 20% amylose and 80% amylopectin. Amylose is a straight-chain polysaccharide made up entirely of D-glucopyranose molecules joined by 1,4-glycoside bonds. Amylopectin differs from amylose in that an occasional glucopyranose molecule in the polymer forms an additional glycoside bond at C6. Amylopectin, therefore, has a branched chain structure. It is estimated that branching occurs at one in every 20 to 25 glucopyranose molecules in the amylopectin chain.

Figure 5. Amylopectin

O HO

OH

O -1,4-linkage HO O OH

OH

-1,6-linkage HO HO O

H O HO

H O H OH O HO -1,4-linkage OH

OH HO -1,4-linkage

B HO O

Glycogen is another example of a polysaccharide consisting of coiled chains of D-glucopyranose molecules joined by 1,4-glycoside bonds. Glycogen is used to store carbohydrates in animals. Like amylopectin, glycogen is a branched polymer of glucopyranose molecules joined by -1,4- and -1,6-glycoside bonds. It is formed from D-(+)-glucose obtained by hydrolysis of starch in the food we eat. The amount of glucose obtained in this way is often more that the body needs, so the excess is converted to glycogen and stored in the body. Between meals and during fasting, the body hydrolyzes glycogen to glucose as it is needed. The extended linear chain of D-glucopyranose molecules joined by -1,4-glyocoside bonds is used in nature for cell membranes and the structural features of plants and trees. The coiled chain of D-glucopyranose molecules joined by -1,4glycoside bonds, on the other hand, is used in nature as an energy-storing polymer. Correlated with this difference in their functions is the widespread distribution of enzymes capable of hydrolyzing starch and glycogen and the very limited distribution of enzymes that hydrolyze cellulose. Cellulose is hydrolyzed in the gastrointestinal tract of herbivores, such as the cow, or in insects, such as termites, by a protozoan that synthesizes the enzyme cellulase, which hydrolyzes the -1,4g1ycoside bonds of cellulose. Humans do not have this enzyme, so we cannot use cellulose as a source of D-glucose.

Chitin is a polysaccharide that is structurally similar to cellulose. It is the major structural component of the shells of crustaceans (e.g., lobster, crabs and shrimps), the exoskeletons of insects and is a minor component of the cell wall of yeasts. Like cellulose, chitin has -1,4-glycosidic linkages. It differs from cellulose, in that it has an N-acetylamino group instead of an OH group at C2 of glucose.
OH O HO NH O H O HO O OH O NH O H O HO NH O H OH O O