CARBOHYDRATES

BIOCHEMISTRY
OVERVIEW
• Carbohydrates are the most abundant macromolecule
in the nature, since they are produced massively by
photosynthetic organisms.
• Although dietary carbohydrates are indeed sources of
energy, not all carbohydrates are edible. Furthermore,
carbohydrates also provide other functions in biochemical
systems such as structure, transport, cell recognition,
and protection.
 DEFINITION OF CARBOHYDRATES
• Historically, carbohydrates are so called
because the earliest known carbohydrates
contain carbon as well as hydrogen and
oxygen in the ratio of 2:1 just like water. They
follow the general formula Cn(H2O)m. For
example, the formula for glucose is C6H12O6
which can also be written as C6(H2O)6.
DEFINITION OF CARBOHYDRATES
• As more carbohydrates are discovered, it was found
out that some carbohydrates do not follow the
general formula. For example, deoxyribose (a
carbohydrate found in DNA) has a formula of
C5H10O4. It did not fit the general formula of a
hydrate of carbon, yet it is a carbohydrate. Also, such
compounds such as acetic acid, CH3COOH may fit
the general formula since it can be written as
C2(H2O)2, but is not a carbohydrate.
CLASSIFICATION OF CARBOHYDRATES
• Carbohydrates are classified according to the number of
saccharide (sugar) units. The term saccharide is derived
from the Latin word “saccharum” which means “sweet”.
CLASSIFICATION OF CARBOHYDRATES
• Monosaccharides – contains one saccharide unit; simplest
sugar unit.

GLUCOSE FRUCTOSE GALACTOSE

CLASSIFICATION OF CARBOHYDRATES
• Disaccharides – contains two saccharide units.

sucrose (table sugar) = glucose + fructose

lactose (milk sugar) = glucose + galactose
maltose (malt sugar) = glucose + glucose
CLASSIFICATION OF CARBOHYDRATES
• Polysaccharides – made up of polymers or chains of many
saccharide units
• Example : starch = polymer of glucose
 CLASSIFICATION OF MONOSACCHARIDES

According to the number of carbon atoms present

• Triose – contains 3 C atoms
• Tetrose - contains 4 C atoms
• Pentose - contains 5 C atoms
• Hexose - contains 6 C atoms
CLASSIFICATION OF MONOSACCHARIDES

According to the type of carbonyl group present

• Aldoses – monosaccharides that contain CHO
(aldehyde) in Carbon 1.

• Ketoses – monosaccharides that contain C=O

(ketone) in Carbon 2.
ISOMERISM IN MONOSACCHARIDES

Isomers are molecules having the same

molecular formula, that is they contain the same
elements present and the same number of atoms
for each element. However, their arrangement,
connectivity and orientation in space may be
different thus, resulting to different molecules.
 TYPES OF MONOSACCHARIDES ISOMERS

1. Constitutional Isomers – the same molecular formula but

different connectivity, different functional groups, and different
order of the bonding atoms.
TYPES OF MONOSACCHARIDES ISOMERS

Both sugars have the same

molecular formula, C6H12O6.
However, since they have
different functional groups,
and the atoms are bonded
differently, D-glucose and D-
fructose are constitutional
isomers.
 TYPES OF MONOSACCHARIDES ISOMERS

2. Stereoisomers - isomers that have the same structural

formula but differ in the orientation of atoms around the
molecule, usually in their stereogenic (chiral) carbons.
• Monosaccharides have often at least 1 and often 2 or
more stereogenic carbon.
• A stereogenic (chiral) carbon is an sp3-hybridized
(tetrahedral) carbon with four different groups around
it.
TYPES OF MONOSACCHARIDES ISOMERS

A compound containing
stereogenic carbon is a
chiral compound. It
demonstrates handedness,
a property characterized by
mirror images are not
superimposable with each
other.
 TYPES OF STEREOISOMERS
Enantiomers - stereoisomers whose molecules are non-
superimposable mirror images of each other.
• Enantiomers can be designated as:
– D – the –OH of the penultimate carbon is directed to the
right.
– L – the –OH of the penultimate carbon is directed to the left.
TYPES OF STEREOISOMERS
 TYPES OF STEREOISOMERS
• Both molecules have the same order of connectivity of the atoms and they
differ only in the orientation of the H and OH groups. Thus, the two
molecules are stereoisomers.

• The two molecules are mirror images of each other wherein the H and OH
groups are interchanged in the stereogenic carbons of both molecules.
The mirror images are nonsuperimposable since if the two molecules will
be overlapped, the H and OH groups will not coincide. Thus, the
molecules are enantiomers.

• To distinguish the enantiomers from each other, the glucose whose OH of

its penultimate carbon is at the right, is named as D-glucose. The glucose
whose OH of its penultimate carbon is at the left is named as L-glucose.
 TYPES OF STEREOISOMERS
Diastereomers – stereoisomers which are not mirror images of each other
• Both molecules have the same order of connectivity of the atoms and
they differ only in the orientation of the H and OH groups around the
stereogenic carbons. Thus, the two molecules are stereoisomers.
• The two sugars are not mirror images of each other since not all the H
and OH groups are interchanged. Thus, the sugars are diastereomers.
TYPES OF STEREOISOMERS
 TYPES OF STEREOISOMERS
Epimers – diastereomers that differ in the position of only one –OH group.

The two monosaccharides are stereoisomers which are not mirror images
of each other. Thus, they are diastereomers. Specifically, they are also
epimers because they differ only in the position of one OH group
(enclosed in box).
TYPES OF STEREOISOMERS
 CYLCLIC STRUCTURES OF MONOSACCHARIDES
Recall in organic chemistry that alcohols react with carbonyl
groups of aldehydes and ketones to form hemiacetals and
hemiketals, respectively.
 CYLCLIC STRUCTURES OF MONOSACCHARIDES

In the same manner, the carbonyl of an aldose

containing at least 5 carbons or of a ketose
containing at least 6 carbons can react with an
intramolecular hydroxyl group to form cyclic
hemiacetal and hemiketal, respectively. The
oxygen atom from the reacting hydroxyl group
becomes a member of the five- or six-membered
ring structures.
CYLCLIC STRUCTURES OF MONOSACCHARIDES

HEMIACETALS
CYLCLIC STRUCTURES OF MONOSACCHARIDES

HEMIKETAL
 CYLCLIC STRUCTURES OF MONOSACCHARIDES

- Six-membered ring of a monosaccharide is called a

pyranose. Aldohexoses form pyranoses.

- Five-membered ring of a monosaccharide is called a

furanose. Ketohexoses and aldopentoses form
furanoses
 ANOMERS

- Notice in the cyclic structure of glucose and fructose above that the
carbonyl carbon becomes a new stereogenic (chiral) center. Since it is
already a chiral carbon, the carbonyl carbon can assume 2 possible
conformations. Take for example the cyclic structures of D-glucose below:
 ANOMERS
This new stereogenic center formed is now known as the anomeric
carbon. Two cyclic monosaccharides that differ only at the position
of –OH at the anomeric carbon are known as anomers.

- There are 2 types of anomers, α and β. An α anomer has the –OH

of the anomeric carbon in opposite direction as the terminal –
CH2OH. A β anomer has the –OH of the anomeric carbon in
similar direction as the terminal –CH2OH.
ANOMERS
 NOMENCLATURE OF CYLCIC MONOSACCHARIDES
When a monosaccharide cyclizes, it assumes a different name. It follows the format:
type of anomer (α or β) – type of enantiomer (D or L) – name of
monosaccharide removed with –se + type of ring

- This is a β anomer of glucose since the–OH of

the anomeric carbon is similar of direction to
the terminal –CH2OH.

- -The name is β-D-glucopyranose.

D-GLUCOSE
NOMENCLATURE OF CYLCIC MONOSACCHARIDES

α -D-fructofuranose

D-FRUCTOSE
NOMENCLATURE OF CYLCIC MONOSACCHARIDES

D-GALACTOSE
NOMENCLATURE OF CYLCIC MONOSACCHARIDES

α -D-galactopyranose

D-GALACTOSE
 Haworth Projection: Representation of the Cyclic
Structure of Monosaccharides
- Haworth Projection is a 2-D representation of the cyclic conformation of the
monosaccharide.
- - In a Haworth projection, the terminal –CH2OH determines the type of
enantiomerism of the monosaccharide. For D monosaccharides, the terminal –
CH2OH is directed upwards. For L monosaccharides, the terminal –CH2OH is
directed downward.
- - All –OH directed to the right in a Fischer projection of monosaccharides is
drawn directed downwards in a Haworth projection. All –OH directed to the left
in a Fischer projection of monosaccharides is drawn directed upwards in a
Haworth projection.
- - An α anomer has the –OH of the anomeric carbon in opposite direction as the
terminal –CH2OH. A β anomer has the –OH of the anomeric carbon in similar
direction as the terminal –CH2OH.
Haworth Projection: Representation of the Cyclic
Structure of Monosaccharides
Haworth Projection: Representation of the Cyclic
Structure of Monosaccharides
Haworth Projection: Representation of the Cyclic
Structure of Monosaccharides
Haworth Projection: Representation of the Cyclic
Structure of Monosaccharides
Haworth Projection: Representation of the Cyclic
Structure of Monosaccharides

The –OH of carbons 2 and 4 are directed to

the right of the Fischer projection of D-
glucose, so both of them should be directed
downwards in the Haworth Projection.

- The –OH of carbon 3 is directed to the left

of the Fischer projection of D-glucose, so it
should be directed upwards in the Haworth
Projection.
MONOSACCHARIDES OF PHYSIOLOGIC
IMPORTANCE
MONOSACCHARIDES OF PHYSIOLOGIC
IMPORTANCE
 SUGAR ACIDS – monosaccharides with a carboxyl
group at one end or both ends of its chain .

• Sugar acids can be formed through OXIDATION PROCESS .

• OXIDATION PROCESS is important because it provides the

energy required for basal metabolic processes in the skeletal
muscles.
 SUGAR ACIDS

Common carbohydrates that undergo oxidation are those that contains an

aldehyde functional group on its structure.
SUGAR ACIDS

Aldoses may undergo oxidation since

they have aldehydic group and
alcoholic group. There are 2 possible
sites for oxidation in an aldose.
SUGAR ACIDS
Aldoses may undergo oxidation since
they have aldehydic group and
alcoholic group. There are 2 possible
sites for oxidation in an aldose.

Oxidation of aldoses yields 3

different sugar acids:
1. Aldonic acid
2. Aldaric acid
3. Alduronic acid (Uronic acid)
SUGAR ACIDS
- The type of sugar acid produced is
determined by the type of oxidizing
agent involved in the reaction.

OXIDIZING AGENT- is a substance

that has the ability to oxidize other
substances — in other words to
accept their electrons.
 SUGAR ACIDS
Aldonic Acid - Oxidation occurs at the aldehyde portion of an aldose.

- The aldehyde group is converted into a carboxylic acid.

- Produced by weak oxidizing agents (e.g. Fehling’s reagent, Benedict’s

reagent and Tollen’s reagent).

- Note that the weak oxidizing agents are always basic (pH above 7).
SUGAR ACIDS
- The aldonic acid that is
produced is named by
replacing the suffix –ose in
the original name of aldose
with the suffix -onic acid
(e.g. galactose-galactonic
acid).
SUGAR ACIDS
IMPORTANCE OF ALDONIC ACID

Benedict’s solution can be used to test for

glucose in urine, a symptom for diabetes. The
glucose content of urine can be determined by
dipping a plastic strip treated with Benedict’s
solution and comparing the color change of
the strip to a color chart that indicates glucose
concentration. The disadvantage of this test is
that it may also give a positive result to other
reducing sugars that may be present in the
sample.
 SUGAR ACIDS
Aldaric Acid - Oxidation occurs at the aldehyde portion and primary
alcohol portion of an aldose.

- Both aldehyde and primary alcohol groups are converted into

carboxylic acid.

- Oxidation is due to strong oxidizing agents

SUGAR ACIDS
- The aldaric acid that is
produced is named by
replacing the suffix –ose in
the original name of aldose
with the suffix -aric acid
(e.g. galactose-galactaric
acid).
 SUGAR ACIDS

IMPORTANCE OF ALDARIC ACID

Mucic acid (galactaric acid) is the only aldaric acid that is insoluble in
cold water. Thus, conversion of galactose to mucic acid using hot
concentrated HNO3 can be used to identify galactose.
 SUGAR ACIDS

Alduronic acid (Uronic acid) - Oxidation occurs at the

primary alcohol portion of an aldose.

- The primary alcohol group is converted into carboxylic acid.

- Oxidation of this type is only possible in biological systems in

the presence of enzymes.
SUGAR ACIDS
- The alduronic acid that is
produced is named by
replacing the suffix –ose in
the original name of aldose
with the suffix -uronic acid
(e.g. galactose-galacturonic
acid)
 SUGAR ACIDS

IMPORTANCE OF ALDURONIC
ACID

- Uronic acids like α–D–glucuronic acid is used by the body to detoxify

foreign phenols and alcohols; in the liver, these compounds are
converted to glycosides of glucuronic acid and excreted in the urine.

- α-D-Glucuronic acid is widely distributed in the plant and animal

world. In humans, it is an important component of the acidic
polysaccharides of connective tissues.
 SUGAR ALCOHOLS (ALDITOLS)

- Reduction converts the aldehyde of an aldose or the ketone of a ketose

into a primary alcohol and a secondary alcohol, respectively.

- The reducing agents that can be used include NaBH4 and H2 in the
presence of a transition metal catalyst like Palladium (Pd) or Platinum
(Pt).
SUGAR ALCOHOLS (ALDITOLS)

The alditol that is produced is

named by replacing the suffix –
ose in the original name of aldose
with the suffix –itol (e.g.
galactose-galactitol).
SUGAR ALCOHOLS (ALDITOLS)

The alditol that is produced is

named by replacing the suffix –
ose in the original name of aldose
with the suffix –itol (e.g.
galactose-galactitol).
SUGAR ALCOHOLS (ALDITOLS)

D-ribose
SUGAR ALCOHOLS (ALDITOLS)

D-xylose
 SUGAR ALCOHOLS (ALDITOLS)
Common alditols and their functions:

1. Xylitol – component of sugar free gum

2. Glucitol or sorbitol is found in the plant world in many berries and
in cherries, plums, pears, apples, seaweed, and algae. It is also used as a
sweetening agent. Accumulation of sorbitol in the eye is a major factor in
the formation of cataracts.
3. Mannitol is now used in the treatment of malignant brain tumors. It
is injected directly into the brain’s main arteries to lower the blood-brain
barrier and allow chemotherapeutic agents to be administered
intravenously.
 AMINO SUGARS
- If one of the hydroxyl groups of a monosaccharide is replaced with an
amino group (NH2), an amino sugar is produced.

- The amino sugar is named by replacing the suffix –e in the original

name of a monosaccharide with the suffix –amine (e.g.
galactosegalactosamine).

- There are 3 naturally occurring amino sugars. In all three, the amino
group replaces the hydroxyl group at carbon 2
 AMINO SUGARS

- If one of the hydroxyl groups of a monosaccharide is replaced with an

amino group (NH2), an amino sugar is produced.

- The amino sugar is named by replacing the suffix –e in the original

name of a monosaccharide with the suffix –amine (e.g.
galactosegalactosamine).
AMINO SUGARS
 AMINO SUGARS

- There are 3 naturally occurring amino sugars. In all three, the amino
group replaces the hydroxyl group at carbon 2.