Carbohydrates

Structure & Functions

Lec Module 4

Far Eastern University

IAS – Dept. of Mathematics
Biochemistry Cluster
 Outline
• Introduction to Carbohydrates
• Classification of Carbohydrates
• Structure Drawing
• Carbohydrate Derivatives
• Biologically Relevant Carbohydrates
Introduction to Carbohydrates
• Most abundant organic compounds.
• Act as storehouses of chemical energy.
• Supportive components in plants.
• Essential components of nucleic acids
• “Hydrate of Carbon”
 Introduction to Carbohydrates

• “Hydrate of Carbon”

Glyceraldehyde Dihydroxyacetone
Classification of Carbohydrates

ALDOSES

ALDOSES
Classification of Carbohydrates

KETOSES
 Classification of Carbohydrates
⮚A polyhydroxyaldehyde or polyhydroxyketone, or a substance that
gives these compounds on hydrolysis.

⮚Classifications:
1. Monosaccharides
2. Disaccharides
3. Oligosaccharides
4. Polysaccharides
 Monosaccharides

⮚Carbohydrates that cannot be hydrolyzed

to a simpler compound.
⮚General formula: CnH2nOn
⮚One of the Carbons being the
carbonyl group of either an Aldehyde
or Ketone.
⮚Suffix “ose” indicates that a molecule is a
carbohydrate.
 Monosaccharides
Physical Properties

• Monosaccharides are colorless, crystalline solids.

• Water soluble
• Slightly soluble to Ethanol and insoluble to nonpolar solvents such as diethyl
ether, dichloromethane and benzene.
 Nomenclature of Monosaccharides
Aldoses: Monosaccharides containing the aldehyde group (-CHO).
Ketoses: Containing the ketone group (-C=O).
Prefixes: “tri-, tetr-, pent-” indicates the number of Carbon atoms in the chain.
Monosaccharides
Structure Drawing
 Chirality: Handedness in Molecules

Superimposable mirror images

are images that coincide at all
points when the images are
laid upon each other.
Review
Nonsuperimposable mirror
images are images where not
all points coincide when the
images are laid upon each A person’s left and right hands are not
superimposable upon each other.
other.
 Chirality

Examples of simple molecules that are chiral. (a) The mirror image forms of the molecule
bromochloroiodomethane are nonsuperimposable. (b) The mirror image forms of the molecule
glyceraldehyde are nonsuperimposable.
 Chirality

• Chiral – Nonsuperimposable on its

mirror image.
• Achiral – Superimposable on its mirror
image.
• If a molecule (or object) has a mirror
plane or an inversion center, it cannot
be chiral.
Chirality
How can you predict whether a
given molecule is or is not
chiral?

A molecule is not chiral if it has a

plane of symmetry.
 Chirality
Chiral or Achiral?
• Brandy snifter

achiral
 Chirality
Chiral or Achiral?
• Baseball glove

chiral
 Chirality
Chiral or Achiral?
• cis-1,3-dimethylcyclopentane

achiral

mirror plane
 Chirality
Chiral or Achiral?
⮚trans-1,3-dimethylcyclopentane

chiral
Chirality

Asymmetric centers
• An asymmetric center is an atom that is bonded to
four different groups.
Chirality

Isomers with more than asymmetric center

Organic molecules, especially monosaccharides,

may contain more than one chiral center.
Fischer Projection
⮚A two-dimensional representation for
showing the configuration of tetrahedral
stereocenters.
o Horizontal lines represent bonds projecting
Fischer- forward from the stereocenter.
o Vertical lines represent bonds projecting to the

Projection: rear.
o Only the stereo center is in the plane.
 L- and D-Monosaccharides:

⮚In 1891, Emil Fischer made the

arbitrary assignments of D- and L- to
the enantiomers of glyceraldehyde.
• D-monosaccharide: The -OH on its
penultimate carbon is on the right in a
Fischer projection.
• L-monosaccharide: The -OH on its
penultimate carbon is on the left in a
Fischer projection.
 Cyclic Structure
• Aldehydes and ketones react with alcohols to form hemiacetals.
• Cyclic hemiacetals form readily when hydroxyl and carbonyl groups are
part of the same molecule and their interaction can form a five- or six-
membered ring.
 Haworth Projections
• A five- or six-membered cyclic hemiacetal is
represented as a planar ring.

• The new carbon stereocenter created in

forming the cyclic structure is called the
Anomeric carbon.

• Stereoisomers that differ in configuration

only at the anomeric carbon are called Glyceraldehyde Dihydroxyacetone
Anomers.

• The anomeric carbon of an aldose is C-1;

that of the most common ketose is C-2.
 Haworth Projections

• Terminologies:
• Pyranose - Cyclic
monosaccharide containing
a six-atom ring

• Furanose - Cyclic
monosaccharide containing
a five-atom ring
 Haworth Projections
Aldopentoses also form cyclic hemiacetals.

The most prevalent forms of D-ribose and other pentoses in the biological world are
furanoses.
Haworth Projections

• In a Haworth projection, the hemiacetal ring

system is viewed “edge on” with the oxygen
ring atom at the upper right (six-membered
Haworth ring) or at the top (five-membered ring).

Projection: • In the D form, CH2OH is positioned above

the ring. In the L form, which is not usually
encountered in biochemical systems, the
terminal CH2OH group is positioned below
the ring.
 Haworth Projections
⮚
 Converting Fischer to Haworth
1. Draw a Haworth’s “stem”

2. Number your atoms 1 through 5 starting from

the anomeric carbon and going clockwise

3. If your sugar was D, then the carbon #6 is

going to be looking “up” (down for the L sugar)

4. The “right” groups on carbons 2, 3, and 4 in

the Fischer projection go onto the “bottom”
positions in Haworth

5. The “left” groups on carbons 2, 3, and 4 in the

Fischer projection go onto the “up” positions
in Haworth
Haworth Projections
 Haworth Projections
• D-Fructose also forms a 5-membered cyclic hemiacetal.
Haworth Projections
2 Forms of Glucose:
 Chair Conformation
• For pyranoses, the six-membered ring is more accurately represented as a
Strain-free chair conformation.
 Chair Conformation
• In both Haworth projections and chair conformations, the orientations of
groups on carbons 1- 5 of b-D-glucopyranose are up, down, up, down, and up
and all are equatorial.
 Converting Haworth to Chair

The trick is to remember that just

like the Haworth projections, the
chair conformations also have the
well-defined “up” and “down”
positions!

Example. Haworth projection and chair conformation of glucopyranose

Carbohydrate Derivatives
 Amino sugars:
⮚Contain an -NH2 group in place of an -OH group.
⮚Only three amino sugars are common in nature:
 Alcohol Sugars from Reduction of Carbohydrates:

The carbonyl group in a monosaccharide

(either an aldose or a ketose) is reduced
to a hydroxyl group using hydrogen as
the reducing agent
The product is the corresponding
polyhydroxy alcohol called sugar
alcohol or alditol
Sorbitol - Used as a moisturizing
agent in foods and cosmetics and
as a sweetening agent in chewing Common reagents: H2/Pd; NaBH4/H2O
gum
 Acidic Sugars from Oxidation of Carbohydrates:

The redox chemistry of monosaccharides is closely linked to the alcohol and

aldehyde functional groups

Oxidation can yield three different types of acidic sugars depending on the type of
oxidizing agent used
• Aldonic acid - Formed when weak oxidizing agents such as Tollens and
Benedict’s solutions oxidize the aldehyde end
• Reducing sugar: Carbohydrate that gives a positive test with Tollens and
Benedict’s solutions
 Acidic Sugars from Oxidation of Carbohydrates:
Recall:

Example:

Mild oxidizing agent(s):

• Tollens’ reagent (Ag+), Fehling’s
reagent (Cu2+ in aqueous sodium
tartrate), and Benedict’s
reagent (Cu2+ in aqueous sodium
citrate)
 Acidic Sugars from Oxidation of Carbohydrates:

• Strong oxidizing agents can oxidize both ends of a

monosaccharide at the same time (the carbonyl group and the
terminal primary alcohol group) to produce a dicarboxylic acid
➢ Such polyhydroxy dicarboxylic acids are known as aldaric acids
• In biochemical systems, enzymes can oxidize the primary alcohol
end of an aldose such as glucose, without oxidation of the
aldehyde group, to produce an alduronic acid
 Acidic Sugars from Oxidation of Carbohydrates:
Monosaccharide oxidation can yield three different types of acidic sugars.
The oxidizing agent used determines the product.
Strong oxidizing agent Weak oxidizing agent Enzymes

Product: aldaric acid Product: aldonic acid Product: alduronic acid

Biologically Relevant
Carbohydrates
Monosaccharides

1. Glucose
• Most abundant in nature.
• Other names:
• Grape sugar
• Blood sugar
• Dextrose
• 6-membered cyclic form
• Important in human nutrition
Monosaccharides

2. Galactose
• “Brain sugar”
• “Milk sugar”
• Used to differentiate between blood
types.
• Six-membered cyclic form
Monosaccharides

3. Mannose
• Aldohexose
• Found in many fruits
• Important in the glycosylation of proteins
in the body.
• Six-membered cyclic form
Monosaccharides

4. Fructose
• Ketohexose
• Sweetest tasting of all sugars
• High dietary sugar due to sweetness
• Five-membered cyclic form
Monosaccharides

5. Ribose
• Part of a variety of complex
molecules which include:
• RNA
• ATP
• DNA
• Five-membered cyclic form
 Disaccharides

• Contain 2 sugar units

• Two monosaccharides are

joined by a glycosidic bond
between the anomeric carbon
of one unit and an –OH group
of the other unit.
 Disaccharides
1. Maltose
• Structurally made of 2 D-glucose units, one of which must be α-D-glucose,
linked via an α(1→4) glycosidic linkage.
• Can be easily digested by humans.
 Disaccharides
2. Lactose
• Made up of β-D-galactose unit and a D-glucose unit joined by a β(1 → 4)
glycosidic linkage.
• Lactase hydrolyzes β(1 → 4) glycosidic linkages.
 Disaccharides
3. Sucrose
• The most abundant of all
disaccharides and found in
plants.

• Also known as the “Table

sugar”.
 Disaccharides
4. Cellobiose
• Contains two D-glucose monosaccharide units, one of which must have a β
configuration, linked through a β(1🡪 4) glycosidic linkage.
• Cannot be digested by humans.
 Oligosaccharides
• Carbohydrates that contain 3–10 monosaccharide units bonded to each other via
glycosidic linkages.
• Commonly found in onions, cabbage, broccoli, and whole wheat.
• Can distinguish blood types.
Oligosaccharides
 Polysaccharides
• Polymers of many
monosaccharide units bonded
with glycosidic linkages.

• Polysaccharides are not sweet

and do not show positive tests
with Tollen’s and Benedict’s
solutions,

• Limited water solubility.

 Polysaccharides
1. Starch
⮚
Polysaccharides
 Polysaccharides
2. Glycogen
⮚
 Polysaccharides
3. Cellulose
• Linear homopolysaccharide with β(1 → 4) glycosidic bond.
• Humans do not have enzymes that hydrolyze β(1 → 4) linkages and so they
cannot digest cellulose.
 Polysaccharides
4. Chitin
• Linear polymer with all β(1→4) glycosidic linkages.
• It has an N-acetyl amino derivative of glucose.
 Polysaccharides
5. Hyaluronic acid
• Alternating residues of N-acetyl- β-D-glucosamine and D-glucuronate.
• Highly viscous and serve as lubricants in the fluid of joints as well as vitreous
humor of the eye.
 Polysaccharides:
6. Heparin

• Blood anticoagulant
• Acidic polysaccharide
Summary of Carbohydrates
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