Chapter 2

Carbohydrates

Carbohydrates are defined as polyhydroxyaldehydes or polyhydroxyketones; also called

saccharides which comes from the Latin word saccharum, “sugar”. In plants, energy from the Sun is used
to convert carbon dioxide and water into the carbohydrate glucose. Many of the glucose molecules are
made into long-chain polymers of starch that store energy. About 65% of the foods in our diet consist of
carbohydrates. Each day we utilize carbohydrates in foods such as bread, pasta, potatoes, and rice.
Other carbohydrates called disaccharides include sucrose (table sugar) and lactose in milk. During
digestion and cellular metabolism, carbohydrates are converted into glucose, which is oxidized further in
our cells to provide our bodies with energy and to provide the cells with carbon atoms for building
molecules of protein, lipids, and nucleic acids. In plants, a polymer of glucose called cellulose builds the
structural framework. Cellulose has other important uses, too. The wood in our furniture, the pages in
this book, and the cotton in our clothing are made of cellulose.

Carbohydrates such as table sugar, lactose in milk, and cellulose are all made of carbon,
hydrogen, and oxygen. Simple sugars, which have formulas of (CH2O)n, were once thought to be hydrates
of carbon, thus the name carbohydrate. In a series of reactions called photosynthesis, energy from the
sun is used to combine the carbon atoms from carbon dioxide (CO2) and the hydrogen and oxygen atoms
of water (H2O) into the carbohydrate glucose.

Figure 1. Photosynthesis. During photosynthesis, energy from the sun combines CO2 and H2O to form glucose
(C6H12O6) and O2. During respiration in the body, carbohydrates are oxidized to CO2 and H2O, while energy is
produced.

In the body, glucose is oxidized in a series of metabolic reactions known as respiration, which
releases chemical energy to do work in the cells. Carbon dioxide and water are produced and returned
to the atmosphere. The combination of photosynthesis and respiration is called the carbon cycle, in
which energy from the sun is stored in plants by photosynthesis and made available to us when the
carbohydrates in our diets are metabolized (Figure 1).

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Classification of carbohydrates (based on their hydrolysis products)

1. Monosaccharides - simplest carbohydrates, composed of 3 to 6 C atoms; general formula is (CH 2O)n.

The names of the CHO’s usually end in –ose:

aldose – a monosaccharide with an aldehyde group
ketose – a monosaccharide containing a ketone group

Erythrose, Erythrulose,
an aldose a ketose

A monosaccharide with three carbon atoms is a triose, one with four carbon atoms is a tetrose; a
pentose has five carbons, and a hexose contains six carbons. We can use both classification systems to
indicate the type of carbonyl group and the number of carbon atoms. An aldopentose is a five-carbon
monosaccharide that is an aldehyde; a ketohexose is a six-carbon monosaccharide that is a ketone.

Some examples:

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Figure 2. Aldoses and ketoses. The series of (a) D-aldoses and (b) D-ketoses having from three to six carbon atoms,
shown as projection formulas. The carbon atoms in red are chiral centers. ln all these D isomers the chiral carbon
most distant from the carbonyl carbon has the same configuration as the chiral carbon in D–glyceraldehyde. The
sugars’ name in boxes are the most common in nature.

Question:
Classify the following monosaccharides according to the carbonyl group and number of C atoms.
1. gulose
2. ribulose
3. mannose
4. erythulose

Stereoisomers and Stereochemistry

Stereoisomer
The prefixes D- and L- found in the complete name of a monosaccharide are used to identify one
of two possible isomeric forms called stereoisomers. By definition, each member of a pair of
stereoisomers must have the same molecular formula and the same bonding. How then do isomers of
the D-family differ from those of the L-family? D- and L-isomers differ in the spatial arrangements of
atoms in the molecule.

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 Stereochemistry is the study of the different spatial arrangements of atoms. A general example
of a pair of stereoisomers is shown in Figure 3. In this example the general molecule C-abcd is formed
from the bonding of a central carbon to four different groups: a, b, c, and d. This results in two molecules
rather than one. Each isomer is bonded together through the exact same bonding pattern, yet they are
not identical. If they were identical, they would be superimposable one upon the other; they are not.
They are therefore stereoisomers. These two stereoisomers have a mirror-image relationship that is
analogous to the mirror-image relationship of the left and right hands (Figure 3b).

Figure 3. (a) A pair of enantiomers for the general molecule C-abcd. (b) Mirror-image right and left hands.

Two stereoisomers that are nonsuperimposable mirror images of one another are called a pair
of enantiomers. Molecules that can exist in enantiomeric forms are called chiral molecules. The term
simply means that as a result of different three-dimensional arrangements of atoms, the molecule can
exist in two mirror image forms. For any pair of nonsuperimposable mirror-image forms (enantiomers),
one is always designated D- and the other L-.
A carbon atom that has four different groups bonded to it is called a chiral carbon atom. Any
molecule containing a chiral carbon can exist as a pair of enantiomers. Consider the simplest
carbohydrate, glyceraldehyde, which is shown in Figure 4. Note that the second carbon is bonded to
four different groups. It is therefore a chiral carbon. As a result, we can draw two enantiomers of
glyceraldehyde that are nonsuperimposable mirror images of one another. Larger biological molecules
typically have more than one chiral carbon.

Figure 4. (a) Structural formulas of D- and L- glyceraldehyde. The end of the molecule with the carbonyl group is
the most oxidized end. The D- or L-configuration of a monosaccharide is determined by the orientation of the
functional groups attached to the chiral carbon farthest from the oxidized end. In the D-enantiomer, the –OH is
to the right. In the L-enantiomer, the –OH is to the left. (b) A three-dimensional representation of D- and L
glyceraldehyde.

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Rotation of Polarizable Light
Stereoisomers can be distinguished from one another by their different optical properties. Each
member of a pair of stereoisomers will rotate plane-polarized light in different directions.
White light is a form of electromagnetic radiation that consists of many different wavelengths
(colors) vibrating in planes that are all perpendicular to the direction of the light beam (Figure 5). To
measure optical properties of enantiomers, scientists use special light sources to produce
monochromatic light, that is, light of a single wavelength. The monochromatic light is passed through a
polarizing material, like a Polaroid lens, so that only waves in one plane can pass through. The light that
emerges from the lens is plane-polarized light (Figure 5).
Applying these principles, scientists have developed the polarimeter to measure the ability of a
compound to change the angle of the plane of polarized light (Figure 5). The polarimeter allows the
determination of the specific rotation of a compound, that is, the measure of its ability to rotate plane-
polarized light.

Figure 5. Schematic drawing of a polarimeter.

Some compounds rotate plane-polarized light in a clockwise direction. These are said to be
dextrorotatory and are designated by a plus sign (+) before the specific rotation value.
Other substances rotate plane-polarized light in a counterclockwise direction. These are called
levorotatory and are indicated by a minus sign (–) before the specific rotation value.

The Relationship Between Molecular Structure and Optical Activity

In 1848, Louis Pasteur was the first to see a relationship between the structure of a compound
and the effect of that compound on plane-polarized light. In his studies of winemaking, Pasteur noticed
that salts of tartaric acid were formed as a by-product. It is a tribute to his extraordinary powers of
observation that he noticed that two types of crystals were formed and that they were mirror images of
one another. Using a magnifying glass and forceps, Pasteur separated the left-handed and right-handed
crystals into separate piles. When he measured the optical activity of each of the mirror-image forms
and of the original mixed sample, he obtained the following results:
 A solution of the original mixture of crystals was optically inactive.
 But both of the mirror-image crystals were optically active. In fact, the specific rotation
produced by each was identical in magnitude but was of opposite sign.
Although Pasteur’s work opened the door to understanding the relationship between structure
and optical activity, it was not until 1874 that the Dutch chemist Van’t Hoff and the French chemist LeBel
independently came up with a basis for the observed optical activity: tetrahedral carbon atoms bonded
to four different atoms or groups of atoms. Thus, two enantiomers, which are identical to one another in
all other chemical and physical properties, will rotate plane-polarized light to the same degree, but in
opposite directions (i.e. one is dextrorotatory, the other is levorotatory).

Chiral Sugars
The group on the chiral carbon farthest from the carbonyl group is used to determine the D or L
isomer. In each of the mirror images, it is important to understand that the groups on all the chiral
carbon atoms are reversed from one side to the other. For example, in L-ribose, the groups are all

8
written on the left side of the horizontal line. In the mirror image, D-ribose, the groups are all written on
the right side of the horizontal line.

Question:
1. Identify the following monosaccharides as D or L Isomer.
a. Xylose b. Arabinose

2. Give the number of chiral centers in the cyclic form (hemiacetal) of glucose?

3. Identify the chiral carbons in

a. b.

Important Monosaccharides
Most biologically active monosaccharides are the D- isomers.

1. D – glucose - most abundant hexose

- also known as dextrose, grape sugar, blood sugar,
- found in fruits, vegetables, corn syrup, and honey
- building block of the disaccharides sucrose, lactose, and maltose, and polysaccharides
such as amylose, cellulose, and glycogen.

2. D – galactose - does not occur free in nature

- obtained as a hydrolysis product of the disaccharide lactose
- prevalent monosaccharide in the cellular membranes of the brain and nervous
system, “brain sugar”
- also component of the blood group antigens

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3. D – fructose - sweetest of all carbohydrates, twice as sweet as glucose
- 200x sweeter than sucrose
- also called levulose and fruit sugar
- found in fruit juices, honey, corn syrup
- obtained as a hydrolysis product of the disaccharide sucrose.

4. D-ribose and deoxyribose

- ribose is the sugar found in ribonucleic acid (RNA), deoxyribose in deoxyribonucleic
acid (DNA).

Figure 6. Epimers. D–glucose and two of its epimers are shown as projection formulas. Each epimer
differs from D–glucose in the configuration at one chiral center (shaded).

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The Common Monosaccharides Have Haworth Structures and Chair Conformations
For simplicity, we have thus far represented the structures of aldoses and ketoses as straight-
chain molecules (Figure 6). ln fact, in aqueous solution, aldotetroses and all monosaccharides with five
or more carbon atoms in the backbone occur predominantly as cyclic (ring) structures in which the
carbonyl group has formed a covalent bond with the oxygen of a hydroxyl group along the chain. The
formation of these ring structures is the result of a general reaction between alcohols and aldehydes or
ketones to form derivatives called hemiacetals or hemiketals (Figure 7), which contain an additional
asymmetric carbon atom and thus can exist in two stereoisomeric forms. For example, D-glucose exists
in solution as an intramolecular hemiacetal in which the free hydroxyl group at C-5 has reacted with the
aldehydic C-1, rendering the latter carbon asymmetric and producing two stereoisomers, designated α
and β (Figure 8).

Figure 7. Formation of hemiacetal and hemiketal. An aldehyde or ketone can react with an alcohol in a
1:1 ratio to yield a hemiacetal or hemiketal, respectively, creating a new chiral center at the carbonyl
carbon. Substitution of a second alcohol molecule produces an acetal or ketal. When the second alcohol is
part of another sugar molecule, the bond produced is a glycosidic bond.

≡ ≡

α, -OH group is down β, -OH group is up

α, -OH group at C1 is β, -OH group at C1 is
on the right on the left

Figure 8. Formation of the two cyclic forms of D – glucose. Reaction between the aldehyde group at C–1 and the
hydroxyl group at C–5 forms a hemiacetal linkage, producing either of two stereoisomers, the α and β anomers,
which differ only in the stereochemistry around the hemiacetal carbon. The interconversion of α and β anomers is
called mutarotation.

NOTE: -OH group that is written to the right of the carbon in a Fischer projection has a downward direction in
a Haworth projection; -OH group that is written to the left in a Fischer projection has an upward direction in a
Haworth projection. Note also that the –CH2OH group in D sugars is always above the plane of the ring. 11
These six-membered ring compounds are called pyranoses because they resemble the six-membered
ring compound pyran (Figure 9). Aldoses or ketoses also exist in cyclic forms having five membered rings,
which, because they resemble the five membered ring compound furan, are called furanoses (Figure
10). Only aldoses having five or more carbon atoms can form pyranose rings. Isomeric forms of
monosaccharides that differ only in their configuration about the hemiacetal or hemiketal carbon atom
are called anomers. The hemiacetal (or carbonyl) carbon atom is called the anomeric carbon (recall that
epimers are two sugars that differ only in configuration around one carbon atom, e.g. glucose and
galactose).

α – D - glucopyranose β – D - glucopyranose

Figure 9. Conformational formulas of pyranoses. (α–D–glucopyranose and β–D–glucopyranose are anomers). As

can be seen, the –OH group below the plane of the ring in the Haworth structure remain in the same position in
the chair.
Haworth perspective formulas like those in Figure 8 are commonly used to show the
stereochemistry of ring forms of monosaccharides. However, the six membered pyranose ring is not
planar, as Haworth perspectives suggest, but tends to assume either of two "chair" conformations
(Figure 9).

Figure 10. D-fructose cyclization.

Mutarotation of Anomers (α and β–D–glucose)

Mutarotation is the process in which the ring structure (hemiacetal) of α- or β-D-glucose forms
an open chain and then closes again as the hemiacetal reforms. As the molecule opens and closes, the
hydroxyl (-OH) group shifts from the α to the β position and back again. Although the open chain is an
essential part of mutarotation, only a small amount is present at any given time. Eventually, an
equilibrium mixture is obtained that is 36% α-D-glucose and 64% β-D-glucose.

Figure 11. Mutarotation of D-glucose

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Oxidation Reactions of Monosaccharides
1. Oxidation of an aldehyde group yields aldonic acid e.g. D–gluconic acid.

2. Oxidation of a terminal –CH2OH group (but not the aldehyde group) yields uronic acid e.g. D–
glucuronic acid

D – glucuronic acid

3. Oxidation of both the aldehyde and terminal –CH2OH gives an aldaric acid e.g. D–glucaric acid

D – glucaric acid

Reduction Reaction of Monosaccharides

Reduction of the aldehyde and ketone groups of monosaccharides yields the sugar alcohols
(alditols). Reduction of D-glucose, for example, yields D-glucitol, also known as D-sorbitol (Figure 12).
Sugar alcohols are used commercially in processing foods and pharmaceuticals. Sorbitol, for example,
improves the shelf life of candy because it helps prevent moisture loss. Adding sorbitol syrup to
artificially sweetened canned fruit reduces the unpleasant aftertaste of the artificial sweetener
saccharin. Once consumed, sorbitol is converted into fructose in the liver.

Figure 12. Laboratory reduction of glucose to form D–glucitol (sorbitol).

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Biologically Important Disaccharides
Recall that disaccharides consist of two monosaccharides joined through an “oxygen bridge.” In
biological systems, monosaccharides exist in the cyclic form and, as we have seen, they are actually
hemiacetals or hemiketals (Figure 7). Recall that when a hemiacetal reacts with an alcohol, the product
is an acetal, and when a hemiketal reacts with an alcohol, the product is a ketal. In the case of
disaccharides, the alcohol comes from a second monosaccharide. The acetals or ketals formed are given
the general name glycosides, and the carbon-oxygen bonds are called glycosidic bonds.
Glycosidic bond formation is nonspecific; that is, it can occur between a hemiacetal or hemiketal
and any of the hydroxyl groups on the second monosaccharide. However, in biological systems, we
commonly see only particular disaccharides, such as maltose, lactose, or sucrose. These specific
disaccharides are produced in cells because the reactions are catalyzed by enzymes. Each enzyme
catalyzes the synthesis of one specific disaccharide, ensuring that one particular pair of hydroxyl groups
on the reacting monosaccharides participates in glycosidic bond formation.
The most typical glycosidic bond forms between the C–1 of one monosaccharide unit and the –
OH group on C–4 of the second monosaccharide. The resulting glycosidic bond is labeled as an α-1,4
bond or β-1,4 bond depending on the isomer that reacted.

α and β – 1, 4 glycosidic bonds in a disaccharide:

+
α-1,4

+
β-1,4

1. Maltose – malt sugar; present in fermenting grains.

– obtained from the hydrolysis of starch
– the two glucose units are linked by an α–1,4–glycosidic bond.
– a reducing sugar because mutarotation occurs at the anomeric carbon to give an
aldehyde group

(α–D–glucopyranosyl–(1→4)–α–D–glucopyranose)

2. Lactose – milk sugar

– found in milk and milk products
– consist of a β–1,4–glycosidic bond between β–D–galactose and β–D–glucose
– also a reducing sugar

(β–D–galactopyranosyl–(1→4)–β–D–glucopyranose)

Lactose is the principal sugar in the milk of most mammals. To be used by the body as an energy
source, lactose must be hydrolyzed to produce glucose and galactose. Glucose liberated by the
hydrolysis of lactose is used directly in the energy-harvesting reactions of glycolysis. However, a series of
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reactions is necessary to convert galactose into a phosphorylated form of glucose that can be used in
cellular metabolic reactions. In humans the genetic disease galactosemia is caused by the absence of
one or more of the enzymes needed for this conversion. A toxic compound formed from galactose
accumulates in people who suffer from galactosemia. If the condition is not treated, galactosemia leads
to severe mental retardation, cataracts, and early death. However, the effects of this disease can be
avoided entirely by providing galactosemic infants with a diet that does not contain galactose. Such a
diet, of course, cannot contain lactose and therefore must contain no milk or milk products.
Many adults, and some children, are unable to hydrolyze lactose because they do not make the
enzyme lactase. This condition, which affects 20% of the population of the United States, is known as
lactose intolerance. Undigested lactose remains in the intestinal tract and causes cramping and diarrhea
that can eventually lead to dehydration. Some of the lactose is metabolized by intestinal bacteria that
release organic acids and CO2 gas into the intestines, causing further discomfort. Lactose intolerance is
unpleasant, but its effects can be avoided by a diet that excludes milk and milk products. Alternatively,
the enzyme that hydrolyzes lactose is available in tablet form. When ingested with dairy products, it
breaks down the lactose, preventing symptoms.

3. Sucrose – table sugar

– obtained from sugar cane and sugar beets
– consists of an α,β–1,2–glycosidic bond between C-1 of α-D–glucose and C-2 of β–D–
fructose
– not a reducing sugar since the glycosidic bond ties up both anomeric C’s, so no
mutarotation

(α–D–glucopyranosyl-β–D–fructofuranoside)

Hydrolysis of Sucrose (also known as inversion)

OH

Sucrose is dextrorotatory, [α]20

D
= +66.5o but upon hydrolysis, the sign of the specific rotation
changes (inverts) from positive to negative , [α]20
D
= -39.0o. The product of the reaction is an equimolar
mixture of D–glucose and D–fructose, both of which undergo mutarotation. The hydrolyzate actually
contains an equilibrium mixture of α- and β–D-glucose, [α]D20 = +53.0o and α– and β–D-fructose, [α]D20 = -
92.0o. The specific rotations of the hydrolyzate is the sum of the specific rotation of each of the
component.
The term inversion is often applied to the hydrolysis of sucrose since it is the only case in which
the hydrolysis of a disaccharide effects a change in the sign of the specific rotation. An equimolar
mixture of D–glucose and D–fructose is called invert sugar.

Practical applications:
The inversion reaction has several practical applications. Since sucrose can exist in only one
molecular configuration, it is one of the most readily crystallizable sugars. Invert sugar has a much
greater tendency to remain in solution. In the manufacture of jelly and candy and in the canning of fruit,
crystallization of the sugar is undesirable. Therefore, conditions leading to the hydrolysis of sucrose are

15
employed in these processes. In addition, fructose is sweeter than sucrose and hydrolysis adds to the
sweetening effect.

4. Cellobiose – obtained by partial hydrolysis of cellulose

– the two glucose units are linked by a β–1,4–glycosidic bond
– also a reducing sugar

(β–D–glucopyranosyl–(1→4)–β–D–glucopyranose)

Question:
1. Give the Haworth and chair forms for the α and β anomers of:
a. D–galactose b. D–mannose c. D–talose

2. α–sophorose, a disaccharide which is a product of the caramelization of glucose, has two glucose
units linked by β–1,2 glycosidic linkage.
a. give the structure of α–sophorose (chair)
b. what is its systematic name?
c. is it a reducing (or non–reducing) sugar?
d. which of the following groups (hemiacetal, hemiketal, acetal, ketal) is present in α–
sophorose?

Polysaccharides
A polysaccharide is a polymer of many monosaccharides joined together. Four important
polysaccharides—amylose, amylopectin, cellulose, and glycogen—are all polymers of D-glucose that
differ only in the type of glycosidic bonds and the amount of branching in the molecule. Oligosaccharide
refers to carbohydrates with 3 to 10 monosaccharide units; found in glycoproteins and some glycolipids.
homopolysaccharides–consist of only one type of monosaccharide repeating units
heteropolysaccharides–consist of two or more types of monosaccharides

1. Starch – storage form of glucose in plants

– found as insoluble granules in rice, wheat, potatoes, beans, and cereals
– composed of two kinds of polysaccharides, amylose (20%) and amylopectin (80%)

Amylose is a straight chain polymer of D-glucose molecules (250–4000) connected by α-1,4-glycosidic

bonds. Amylose coils up into a helix that repeats every 6 glucose units (Figure 13).

Amylopectin is a branched-chain polysaccharide. Like amylose, the glucose molecules are connected
by α-1,4-glycosidic bonds. However, at about every 25 glucose units, there is a branch of glucose
molecules attached by an α-1,6-glycosidic bond between carbon 1 of the branch and carbon 6 in the
main chain .

2. Glycogen – or animal starch

– storage form of glucose in animals

Glycogen is a polymer of glucose that is stored in the liver and muscle of animals. It is
hydrolyzed in our cells at a rate that maintains the blood level of glucose and provides energy
between meals. When fasting or during periods of starvation, animals draw upon these glycogen
reserves (in liver and muscle) to obtain the glucose needed to maintain a proper state of metabolic
balance. The structure of glycogen is very similar to that of amylopectin found in plants, except that
glycogen is more highly branched. In glycogen, the glucose units are joined by α-1,4-glycosidic
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 bonds, and branches occurring about every 10–15 glucose units are attached by α-1,6-glycosidic
bonds.

α-1,4-glycosidic linkage

(a)

(b)
Figure 13. The structure of (a) amylose is a straight–chain polysaccharide of glucose units, and the structure of (b)
amylopectin is a branched chain of glucose.

3. Cellulose – major structural material of plant cells

– most abundant polysaccharide or most abundant organic molecule in the world
– cotton is almost pure cellulose; wood is about 50% cellulose
– glucose molecules form a long unbranched chain similar to that of amylose but the
glucose units are linked by β–1,4–glycosidic bonds.

Humans have enzymes called α -amylase in saliva and pancreatic juices that hydrolyze the α-1,4-
glycosidic bonds of starches, but not the β-1,4-glycosidic bonds of cellulose. Thus, humans cannot digest
cellulose. Animals such as termites, horses, cows, and goats can obtain glucose from cellulose because
their digestive systems contain bacteria that provide enzymes such as cellulase to hydrolyze β-1,4-
glycosidic bonds.

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Other structural homopolysaccharides
 alginic acid – structural polysaccharide of brown algae and kelp
– industrial uses are as thickener, emulsifier, stabilizer and as hydrophilic agents in
medical and cosmetic ointment bases
 carrageenan – structural polysaccharide in red seaweeds
– used in the preparation of chocolate drinks to hold cocoa particles in suspension
 chitin – structural polysaccharide in insect skeletons and shells of crabs and lobsters and also
in the cell walls of most fungi and many algae

Dietary Fiber
The term dietary fiber includes all plant material that is not digestible by humans, including
cellulose. Food sources of dietary fiber include whole grains, bran, fruits, and vegetables.
Fiber in the diet aids in the formation of bulk in the intestinal tract, which increases the
absorption of water along the tract. The uptake of water has a laxative effect by producing softer stools.
It also increases the rate at which digestive wastes move through the intestinal tract, which lessens the
time the intestine comes in contact with any ingested carcinogens. Some forms of diverticulitis
(inflammation of the colon) have been relieved by increasing the quantity of fiber in the diet.
The absorptive effects of fiber may also be beneficial in weight maintenance. Fiber increases the
bulk in the stomach and intestines without contributing to caloric intake. Fiber may also absorb some of
the carbohydrate and cholesterol from the diet, thus decreasing the quantity that diffuses through the
intestinal walls.

Monosaccharide Derivatives and Important Heteropolysaccharides

1. α–D–glucuronate
In liver cells, α-D-glucuronate is bonded to hydrophobic molecules, such as steroids, to increase
their solubility in water. When bonded to the modified sugar, steroids are more readily removed
from the body.

2. Amino sugars e.g. α–D–glucosamine and α–D-N–acetylglucosamine

Amino sugars are a second important group of monosaccharide derivatives. In amino sugars one of
the hydroxyl groups (usually on carbon-2) is replaced by an amino group. Often these are found in
complex oligosaccharides that are attached to cellular proteins and lipids. The most common amino
sugars, D-glucosamine and D-galactosamine, are often found in the N-acetyl form. N-acetylglucosamine
is a component of bacterial cell walls and N-acetylgalactosamine is a component of the A, B, O blood
group antigens.

3. Glycosaminoglycans e.g. chondroitin sulfate, hyaluronic acid, and heparin.

Heteropolysaccharides are often referred to as glycosaminoglycans. Their structures consist of a
repeating disaccharide in which one of the sugars is an amino sugar and at least one of them has a
negative charge due to a sulfate group or a carboxyl group.

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  heparin – a polymer of D–glucuronic acid and D–glucosamine
– an anticoagulant used in open heart surgery to prevent clotting of the blood
 hyaluronic acid–a polymer with alternating units of D–glucuronic acid and N–acetyl–D-glucosamine
– present in connective tissues
– abundant in the fluid of joints and in the vitreous humor of the eye
 chondroitin sulfate – major structural components of cartilage, bone, cornea and other
connective tissue structures in vertebrates

The structures of the repeat units of these polymers are shown below.

The amino sugar D-glucosamine is thought to stimulate the production of collagen. Collagen is
one of the main components of articular cartilage, which is the shock-absorbing cushion within the
joints. With aging, some of the D-glucosamine is lost, leading to a reduced cartilage layer and to the
onset and progression of arthritis. It has been suggested that ingestion of D-glucosamine can actually
“jump-start” production of cartilage and help repair eroded cartilage in arthritic joints.
It has also been suggested that chondroitin sulfate can protect existing cartilage from premature
breakdown. It absorbs large amounts of water, which is thought to facilitate diffusion of nutrients into
the cartilage, providing precursors for the synthesis of new cartilage. The increased fluid also acts as a
shock absorber.
Glucosamine sulfate and chondroitin sulfate are sold in large quantities as over–the–counter
drugs used to help replace frayed or otherwise damaged cartilage, especially in knees. Many people
when advised that they need knee surgery for damaged ligaments look for improvement first with a
two– or three– month regimen of these GAG’s.

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