F

C 116- Biochemistry
CARBOHYDRATES

Submitted By: Submitted To:

NESTOR JOHN B. VALBAREZ WILMA A. BESANA, LPT

BSFi 2A Biochemistry instructor

Objectives:
1. To know what is Monosaccharides,
2. To understand the importance of Monosaccharide,
3. Give the 3 components of Monosaccharide.

Carbohydrates
Carbohydrates: What Are Monosaccharides?
Carbohydrates are the most abundant organic compounds in the plant world. They act as
storehouses of chemical energy (glucose, starch, glycogen); are components of supportive
structures in plants (cellulose), crustacean shells (chitin), and connective tissues in animals
(acidic polysaccharides); and are essential components of nucleic acids (D-ribose and 2-deoxy-
D-ribose). Carbohydrates account for approximately three-fourths of the dry weight of plants.
Animals (including humans) get their carbohydrates by eating plants, but they do not store much
of what they consume. In fact, less than 1% of the body weight of animals is made up of
carbohydrates.
The word carbohydrate means “hydrate of carbon” and derives from the formula Cn
1H2O2 m. Two examples of carbohydrates with this general molecular formula that can be
written alternatively as hydrates of carbon are
 Glucose (blood sugar): C6H12O6, which can be written as C6 1H2O2 6
 Sucrose (table sugar): C12H22O11, which can be written as C12 1H2O2 11
Not all carbohydrates, however, have this general formula. Some contain too few oxygen atoms
to fit it; some contain too many oxygens. Some also contain nitrogen. The term carbohydrate has
become so firmly rooted in the chemical nomenclature that, although not completely accurate, it
persists as the name for this class of compounds.
At the molecular level, most carbohydrates are polyhydroxyaldehydes,
polyhydroxyketones, or compounds that yield them after hydrolysis. The simpler members of the
carbohydrate family are often referred to as saccharides because of their sweet taste (Latin:
saccharum, “sugar”). Carbohydrates are classified as monosaccharides, oligosaccharides, or
polysaccharides depending on the number of simple sugars they contain.
A. Structure and Nomenclature
Monosaccharides have the general formula CnH2nOn, with one of the carbons being the
carbonyl group of either an aldehyde or a ketone. The most common monosaccharides have three
to nine carbon atoms. The suffix -ose indicates that a molecule is a carbohydrate, and the
prefixes tri-, tetr-, pent-, and so forth indicate the number of carbon atoms in the chain.
Monosaccharides containing an aldehyde group are classified as aldoses; those containing a
ketone group are classified as ketoses.
There are only two trioses: the aldotriose glyceraldehyde and the ketotriose
dihydroxyacetone Dihydroxyacetone (a ketotriose)

Often the designations aldo- and keto- are omitted, and these molecules are referred to
simply as trioses, tetroses, and the like.
B. Fischer Projection Formulas
Glyceraldehyde contains a stereocenter and therefore exists as a pair of enantiomers (Figure
20.1).
Chemists commonly use two-dimensional representations called Fischer projections to
show the configuration of carbohydrates. To draw a Fischer projection, draw a three-dimensional
representation of the molecule oriented so that the vertical bonds from the stereocenter are
directed away from you and the horizontal bonds from it are directed toward you (none of the
bonds to stereocenter are in the plane of the paper). Then write the molecule as a cross, with the
stereocenter indicated by the point at which the bonds cross.

The horizontal segments of this Fischer projection represent bonds directed toward you,
and the vertical segments represent bonds directed away from you. The only atom in the plane of
the paper is the stereocenter.
C. D- and L-Monosaccharides
Even though the R,S system is widely accepted today as a standard for designating
configuration, the configuration of carbohydrates is commonly designated using the D,L system
proposed by Emil Fischer in 1891. At that time, it was known that one enantiomer of
glyceraldehyde has a specific rotation (Section 15.4B) of 113.5°; the other has a specific rotation
of 213.5°. Fischer proposed that these enantiomers be designated D and L, but he had no
experimental way to determine which enantiomer has which specific rotation. Fischer, therefore,
did the only possible thing—he made an arbitrary assignment. He assigned the dextrorotatory
enantiomer the following configuration and named it D-glyceraldehyde. He named its
enantiomer L-glyceraldehyde. Fischer could have been wrong, but by a stroke of good fortune,
he wasn’t. In 1952, scientists proved that his assignment of the D,L-configuration to the
enantiomers of glyceraldehyde is correct.

D-glyceraldehyde and L-glyceraldehyde serve as reference points for the assignment of

relative configurations to all other aldoses and ketoses. The reference point is the penultimate
carbon—that is, the next-to-the-last carbon on the chain. A D-monosaccharide has the same
configuration at its penultimate carbon as D-glyceraldehyde (its iOH group is on the right) in a
Fischer projection; an L-monosaccharide has the same configuration at its penultimate carbon as
L-glyceraldehyde (its iOH group is on the left).
Tables 20.1 and 20.2 show names and Fischer projections for all D-aldo- and D-2-
ketotetroses, pentoses, and hexoses. Each name consists of three parts. The D specifies the
configuration at the stereocenter farthest from the carbonyl group. Prefixes such as rib-, arabin-,
and gluc- specify the configuration of all other stereocenters in the monosaccharide relative to
one another. The suffix -ose indicates that the compound is a carbohydrate.
The three most abundant hexoses in the biological world are D-glucose, D-galactose, and D-
fructose. The first two are D-aldohexoses; the third is a D-2-ketohexose. Glucose, by far the most
abundant of the three, is also known as dextrose because it is dextrorotatory. Other names for this
monosaccharide include grape sugar and blood sugar. Human blood normally contains 65–110
mg of glucose/100 mL of blood.
TABLE 20.1 Configurational Relationships among the Isomeric D-Aldotetroses, D-Aldopentoses, and D-
Aldohexoses

TABLE 20.2 Configurational Relationships among the D-2-Ketopentoses and D-2-Ketohexoses

D. Amino Sugars
Amino sugars contain an –NH2 group in place of an –OH group. Only three amino sugars are
common in nature: D-glucosamine, D-mannosamine, and D-galactosamine.

N- Acetyl-D-glucosamine, a derivative of D-glucosamine, is a component of many

polysaccharides, including connective tissue such as cartilage. It is also a component of chitin,
the hard, shell-like exoskeleton of lobsters, crabs, shrimp, and other shellfish. Several other
amino sugars are components of naturally occurring antibiotics.
E. Physical Properties of Monosaccharides
Monosaccharides are colorless, crystalline solids. Because hydrogen bonding is possible between
their polar –OH groups and water, all monosaccharides are very soluble in water. They are only
slightly soluble in ethanol and are insoluble in nonpolar solvents such as diethyl ether,
dichloromethane, and benzene.

What Are the Cyclic Structures of Monosaccharides?

 In Section 17.4C, we saw that aldehydes and ketones react with alcohols to form
hemiacetals. We also saw that cyclic hemiacetals form very readily when hydroxyl and carbonyl

groups are part of the same molecule and that their interaction produces a ring. For example, 4-
hydroxypentanal forms a five-membered cyclic hemiacetal. Note that 4-hydroxypentanal
contains one stereocenter and that hemiacetal formation generates a second stereocenter at
carbon 1.
Monosaccharides have hydroxyl and carbonyl groups in the same molecule. As a result,
they exist almost exclusively as five- and six-membered cyclic hemiacetals.
A. Haworth Projections
A common way of representing the cyclic structure of monosaccharides is the Haworth
projection, named after the English chemist Sir Walter N. Haworth (Nobel Prize for chemistry,
1937). In a Haworth projection, a five or six-membered cyclic hemiacetal is represented as a
planar pentagon or hexagon, respectively, lying roughly perpendicular to the plane of the paper.
Groups bonded to the carbons of the ring then lie either above or below the plane of the ring. The
new carbon stereocenter created in forming the cyclic structure is called an anomeric carbon.
Stereoisomers that differ in configuration only at the anomeric carbon are called anomers. The
anomeric carbon of an aldose is carbon 1; that of the most common ketoses is carbon 2.
Typically, Haworth projections are most commonly drawn with the anomeric carbon to the
right and the hemiacetal oxygen to the back (Figure 20.2).
In the terminology of carbohydrate chemistry, the designation β means that the –OH on the
anomeric carbon of the cyclic hemiacetal lies on the same side of the ring as the terminal –
CH2OH. Conversely, the designation a means that the –OH on the anomeric carbon of the cyclic
hemiacetal lies on the side of the ring opposite from the terminal –CH2OH.
A six-membered hemiacetal ring is indicated by -pyran-, and a five membered hemiacetal
ring is indicated by -furan-. The terms furanose and pyranose are used because
monosaccharide five- and six-membered rings correspond to the heterocyclic compounds furan

and pyran.
Because the α and β forms of glucose are six-membered cyclic hemiacetals, they are named α
-D-glucopyranose and β -D-glucopyranose, respectively. The designations -furan- and -pyran-
are not always used in monosaccharide names, however. Thus, the glucopyranoses, for example,
are often named simply α -D-glucose and β -D-glucose.
 You would do well to remember the configurations of the groups on the Haworth projections

of α-D-glucopyranose and β -D-glucopyranose as reference structures. Knowing how the open-

chain configuration of any other aldohexose differs from that of D-glucose, you can construct
Haworth projections for the aldohexose by referring to the Haworth projection of D-glucose.
Aldopentoses also form cyclic hemiacetals. The most prevalent forms of D-ribose and other
pentoses in the biological world are furanoses. Following are Haworth projections for α -D-
ribofuranose (α-D-ribose) and β -2-deoxyD-ribofuranose (β-2-Deoxy-D-ribose). The prefix 2-
deoxy indicates the absence of oxygen at carbon 2. Units of D-ribose and 2-deoxy-D-ribose in
nucleic acids and most other biological molecules are found almost exclusively in the β
configuration.
Fructose also forms five-membered cyclic hemiacetals. β-D-fructofuranose, for example, is
found in the disaccharide sucrose (Section 20.4A).
 B.
C

onformation Representations
A five-membered furanose ring is so close to being planar that Haworth projections provide
adequate representations of furanoses. For pyranoses, however, the six-membered ring is more
accurately represented as a chair conformation (Section 11.6B). Following are structural
formulas for α-D-glucopyranose and β-D-glucopyranose, both drawn as chair conformations.
Also shown is the open-chain or free aldehyde form with which the cyclic hemiacetal forms are
in equilibrium in aqueous solution. Notice that each group, including the anomeric –OH group,
on the chair conformation of β-D-glucopyranose is equatorial. Notice also that the –OH group on
the anomeric carbon is axial in α -D-glucopyranose. Because the –OH on the anomeric carbon of
β -D-glucopyranose is in the more stable equatorial position (Section 11.6B), the β anomer
predominates in aqueous solution.

At this point, let us compare the relative orientations of groups on the D-glucopyranose
ring in the Haworth projection and the chair conformation. The orientations of groups on carbons
1 through 5 of b-D-glucopyranose, for example, are up, down, up, down, and up in both
representations. Note that in b-D-glucopyranose, all groups other than hydrogen atoms are in the
stable equatiorial position.
C. Mutarotation
Mutarotation is the change in specific rotation that accompanies the equilibration of α and β
anomers in aqueous solution. For example, a solution prepared by dissolving crystalline α-D-
glucopyranose in water has a specific rotation of 1112°, which gradually decreases to an
equilibrium value of 152.7° as α-D-glucopyranose reaches equilibrium with β-D-glucopyranose.
A solution of β-D-glucopyranose also undergoes mutarotation, during which the specific rotation
changes from 118.7° to the same equilibrium value of 152.7°. The equilibrium mixture consists
of 64% β-D-glucopyranose and 36% α -D-glucopyranose, with only a trace (0.003%) of the
open-chain form. Mutarotation is common to all carbohydrates that exist in hemiacetal forms.