CARBOHYDRATES

Learning Outcomes:

At the end of the class, the students are able to:

• Give the chemical structure and classification of

simple and complex carbohydrates and their
derivatives; and
• Correlate the structure of carbohydrates with their
function and activity
Outline:

1. Carbohydrates – definition, sources, and functions

2. Classes of Carbohydrates – monosaccharides, oligosaccharides,
and polysaccharides
3. Monosaccharides
4. Fischer Projections and Haworth Structures
5. Chemical Properties of Monosaccharides
6. Disaccharides
7. Polysaccharides
 BIOMOLECULES

polymer
1) Carbohydrates
2) Lipids
3) Proteins
4) Nucleic Acids

monomer
 CARBOHYDRATES (CHO)
Did you know?
sugar = carbohydrates

Simple sugars are the monomers of carbohydrates.

- Literally hydrates of carbon

*Hydrate – substance that contains water or its constituent elements

- Also referred to as saccharides because of the sweet taste of many CHOs

*Latin, saccharam, meaning sugar
 CARBOHYDRATES (CHO)
- The single most abundant class of organic molecules found in nature
*Energy from the sun captured by green plants, algae, and some bacteria during
photosynthesis converts more than 250 billion kg of CO2 into carbohydrates every day on
Earth

Carbon Cycle: photosynthesis

6CO2 + 6H2O + energy ⇄ C6H12O6 + 6O2
respiration Glucose
 FUNCTIONS OF CARBOHYDRATES (CHO)
a) Storehouse of chemical energy (glucose, starch, glycogen)
b) Supportive structural components in plants and some animals (cellulose,
chitin)
c) Essential components in the mechanisms of genetic control of growth
and development of living cells (ribose, deoxyribose)
d) CHO “markers” on cell surfaces play key roles in cell-cell recognition
processes
e) Ligands and receptors in cellular communication (lectin)
CARBOHYDRATES (CHO)
ALDEHYDE KETONE
- Are polyhydroxyaldehydes or
polyhydroxyketones
- Are hydrates of carbon, molecules with several
carbon atoms that each bear a hydrogen and a
hydroxyl group (OH)
- When they are small, they are also known as
sugars and their names end in “-ose” like GLUCOSE FRUCTOSE

glucose, sucrose
- Basic formula is (CH2O)n where n = 3 or more;
can also be written as (C·H2O)n to show that
these substances are hydrates of carbon
SUCROSE
 CLASSES OF CARBOHYDRATES (CHO)
1) Monosaccharides (and their derivatives)
2) Oligosaccharides
3) Polysaccharides
4) Derived carbohydrates
 MONOSACCHARIDES
CnH2nOn (n = 3 to 8)

- The simple sugars; contain a single polyhdroxy aldehyde or

polyhydroxy ketone unit
- Cannot be degraded into simpler products by hydrolysis reactions
- Monomeric units that polymerize to form polysaccharides; can be
linked to each other molecules by glycosidic bonds
- Pure monosaccharides are water-soluble , white , crystalline solids
(e.g., glucose)
 OLIGOSACCHARIDES
- Those that contain more than one monosaccharide unit and which,
on degradation, yield 2 to 10 monosaccharide units
- Often found associated with proteins and lipids in complexes that
have both structural and regulatory functions within the human body
- Free oligosaccharides, other than the disaccharides, are seldom
encountered in biological systems

Examples:
Disaccharides (maltose) Tetrasaccharide (stachyose)
Trisaccharides (raffinose)
 POLYSACCHARIDES
- Consists of tens of thousands of monosaccharide units
- Colloidal in size (∼1 nm to ∼1 μm)

a) Homopolysaccharides – polymers of a single monosaccharide

(glycogen, cellulose, starch)

b) Heteropolysaccharides – contain more than one kind of

monosaccharide (hyaluronic acid, heparin, chondroitin sulfate)

c) “Hybrid” macromolecules – proteoglycans, glycoproteins, glycolipids

 Sample Problem:
Classify the following carbohydrates as mono-, di-, or polysaccharides:

a. When lactose, milk sugar, is hydrolyzed, two monosaccharide units

are produced.
Ans. A disaccharide contains two monosaccharide units.

b. Cellulose, a carbohydrate in cotton, yields thousands of

monosaccharide units when completely hydrolyzed.
Ans. A polysaccharide contains many monosaccharide units.
 MONOSACCHARIDES (CnH2nOn)
Can be named according to the number of carbon atoms they have:

Fischer
Projections

C3H6O3 C4H8O4 C5H10O5 C6H12O6 (ketose*) C6H12O6 (aldose*)

*While examples of heptoses (C7H14O7) and octoses (C8H16O8) occur in

nature, they are far less abundant than the smaller monosaccharides
*aldose – contains an aldehyde group *ketose – contains a ketone group
Image: https://www.chemistrysteps.com/carbohydrates-structure-and-classification/
 TRIOSES

- The parent member of the family

of monosaccharides
- From them emanates the other
members of the monosaccharide
family
- The final form of CHO into which
all CHOs, regardless of their
complexity, are degraded in the
body during CHO metabolism
(an aldotriose) (a ketotriose)
PENTOSES
4 Aldopentoses: D-lyxose 2 Ketopentoses: D-ribulose
D-xylose D-xylulose
D-arabinose
D-ribose

Physiological Function:
• Lyxose – a constituent of the heart muscle
• Ribulose – formed during metabolism of CHO
• Ribose and 2-deoxyribose – present as intermediates in metabolic
pathways and are important building blocks
of RNA and DNA
HEXOSES
- The most common of all the monosaccharides

3 Aldohexoses: D-mannose 1 ketohexose: D-fructose

D-glucose
D-galactose

1) D-mannose – found in certain bacteria, fungi, and plants

– converted to usable glucose in the body, but has no real
physiological significance
HEXOSES
2) D-glucose
– ripe fruits, particularly ripe grapes (20-30% by mass)
– also known as grape sugar, dextrose, blood sugar; found in blood at
concentrations as high as 0.1%
– the most abundant sugar in nature; the most important sugar in the
human diet
– building block of the disaccharides sucrose, lactose, and maltose, and
polysaccharides such as amylose, cellulose, and glycogen
– during the process of digestion, all ingested CHOs are ultimately
degraded to glucose. It is the raw material for CHO metabolism that
produces energy for the body processes. For this reason, patients who
are unable to ingest CHOs but must maintain an adequate blood level of
glucose are given glucose by injection directly into the bloodstream (IV).
HEXOSES
3) D-galactose
- A hydrolysis product of or obtained from lactose (with glucose), which is found
in milk and milk products; seldom encountered as a free monosaccharide
- Not used as such in the body; must first be converted to glucose by specific
enzymes
- Also called “brain sugar” because it is a component of glycoproteins found in
brain and nervous tissues; N-acetyl-β-D-galactosamine are components of the
blood group antigens, which are chemical markers that distinguish various
types of blood groups
- When milk is used as food for infants, the lactose is broken down to produce
galactose and glucose. The galactose in turn is then converted to the usable D-
glucose. Galactosemia is a result of genetic deficiency in the infant – the gene
responsible for this particular enzyme that converts D-galactose to D-glucose.
Such infants cannot metabolize galactose and it builds up in the blood and
tissue.
HEXOSES

4) D-fructose
- Also known as levulose (from levorotatory) and fruit sugar
- Found in high concentrations in fruit juices and in honey
- Sweetest of all the CHOs, almost twice as sweet as sucrose (table sugar)
- Obtained as one of the hydrolysis products of sucrose
- It is very easily converted to glucose in the liver and intestine for use in
the body
- A High-fructose corn syrup (HFCS) mixture containing about 50% fructose
and 50% glucose is used in soft drinks and many foods, such as baked
goods.
 MONOSACCHARIDES (CnH2nOn)
Aldose – contains an aldehyde group Ketose – contains a ketone group
Ex. Glyceraldehyde (simplest, 3 Cs) Ex. Dihydroxyacetone (simplest; 3 Cs)
Presence of ketone group is usually indicated by using “-ul” or
the ending “-ulose” in naming the sugar (tetrulose, pentulose)
General Formula:

Image: https://www.toppr.com/ask/en-np/question/what-is-the-difference-between-an-aldose-and-a-ketose/ Image: https://www.youtube.com/watch?v=wFYsufJ9XMM&list=PLybg94GvOJ9Fazvaf8unWl9J2soXCAvy4&index=6

 MONOSACCHARIDES (CnH2nOn)
D (dextro) and L (levo) configurations: Looking at the chiral carbon (carbon farthest
away from the carbonyl group)

D – if the hydroxyl group is on the right side; L - if the hydroxyl points left

Image: https://www.youtube.com/watch?v=wFYsufJ9XMM&list=PLybg94GvOJ9Fazvaf8unWl9J2soXCAvy4&index=6
The D-aldoses with
three to six carbon
atoms. The arrows
indicate stereochemical
relationships (not
biosynthetic pathways).
The configuration
around C2 (red)
distinguishes the
members of each pair of
monosaccharides. The L
counterparts of these
15 sugars are their
mirror images. The
biologically most
common aldoses are
boxed.
Source: Voet, Voet, Pratt. Fundamentals of Biochemistry Life at the
Molecular Level. 5th ed.
 Sample Problem:
Classify each of the following monosaccharides to indicate their
carbonyl group and number of carbon atoms. Identify also if it is a D or
L enantiomer?
Ans. It has a ketone Ans. It has an
group thus it is a aldehyde group thus
ketose. Because it is an aldose.
there are five Because there are six
carbon atoms, it is a carbon atoms, it is
ketopentose. The - an aldohexose. The -
OH is on the right OH is on the right
side, thus it is D. side, thus it is D.
Ribulose Galactose
CYCLIC STRUCTURES OF MONOSACCHARIDES

- Chains of five- or six-carbon

atoms exist as stable ring
structures called Haworth
structures
- They are produced from the
reaction of a carbonyl group
and a hydroxyl group in the
same molecule
HOW TO DRAW HAWORTH STURCTURES
HOW TO DRAW HAWORTH
STURCTURES

Forms hemiacetal
HOW TO DRAW HAWORTH
STURCTURES
 𝛂 and 𝛃 Anomers

- Since the new –OH at carbon 1 can be up or down, two isomers called
anomers are formed.
• When –OH on C1 is down: the isomer is the 𝛼 form of the sugar
• When –OH on C1 is up: the isomer is the 𝛽 form of the sugar

Importance of the structural differences:

• Cellulose (a polysaccharide of glucose) contains 𝛽 isomers of glucose
which cannot be digested by humans (e.g., paper or wood)
• Starch (a polysaccharide of 𝛼-glucose) can be digested by humans (e.g.,
pasta) à humans have 𝛼-amylase but not 𝛽-amylase
HAWORTH STURCTURE OF GALACTOSE (An Aldohexose)
HAWORTH STURCTURE OF FRUCTOSE (A Ketohexose)
 Sample Problem:
Draw the Haworth structure for 𝛽-D-mannose.

Answer
CHEMICAL PROPERTIES OF MONOSACCHARIDES

Oxidation of Reduction of
Monosaccharides Monosaccharides
OXIDATION OF
MONOSACCHARIDES
CARBOXYLIC ACID

- An aldehyde group with an adjacent

hydroxyl can be oxidized to a carboxylic
acid by an oxidizing agent such as
Benedict’s reagent
- The sugar acids are named by replacing
–ose with –onic acid
- A carbohydrate that reduces another
substance (e.g., Cu2+ to Cu+) is called a
reducing sugar (ex. all monosaccharides,
fructose, lactose, arabinose, maltose)
REDUCTION OF
MONOSACCHARIDES
ALCOHOL

- The reduction of the carbonyl group in monosaccharides produces sugar

alcohols, which are called alditols.
- The sugar alcohols are named by replacing –ose with –itol
- Sugar alcohols such as D-sorbitol, D-xylitol from D-xylose, and D-mannitol
from D-mannose are used as sweeteners in many sugar-free products such as
diet drinks and sugarless gum as well as products for people with diabetes
 Sample Problem:
Draw and name the oxidation product of D-altrose. Why is D-altrose a
reducing sugar?
Answer
 DISACCHARIDES
- A disaccharide is composed of two monosaccharides linked together
(e.g., maltose, lactose, and sucrose)
- The two monosaccharides combine in a dehydration reaction (the
hydroxyl group on C1 and one of the hydroxyl groups on a 2nd
monosaccharide) and they are joined by a bond called glycosidic bond.
 𝛼(1à4)-glycosidic bond means that the 1st sugar
MALTOSE (Reducing Disaccharide) is in 𝛼-configuration and its C1 is linked to C4 of
the 2nd sugar.
- Or malt sugar, obtained from starch
and is found in malt, germinating
grains, and corn syrup
- Consists of two molecules of glucose
joined together by 𝛼(1à4)-
glycosidic bond
- Used in cereals, candies, and the
brewing of beverages
- When maltose in barley and other
grains is hydrolyzed by yeast
enzymes, glucose is obtained, which
can undergo fermentation to give
ethanol
CELLOBIOSE (Reducing Disaccharide)

𝛽(1à4)-glycosidic bond means that the –OH on C1 of 𝛽-

D-glucose forms a glycosidic bond with the –OH on C4 of
- One of the major fragments the D-glucose molecule
isolated after extensive
hydrolysis of cellulose
- Differs from maltose only in that
the 2 glucose units are joined by
𝛽(1à4)-glycosidic linkage
 𝛽(1à4)-glycosidic bond means that the –OH on C1 of
LACTOSE (Reducing Disaccharide) 𝛽-D-galactose forms a glycosidic bond with the –OH on
C4 of the D-glucose molecule

- Or milk sugar, found in milk and milk

products
- Consists of 𝛽-galactose with a
𝛽(1à4)-glycosidic linkage to 𝛽-
glucose (or 𝛼-glucose)
- Makes up 6 to 8% of human milk
and about 4 to 5% of cow’s milk, and
it is used in products that attempt to
duplicate mother’s milk
- Lactose intolerance: unable to
hydrolyze lactose because they lack
the enzyme lactase
SUCROSE (Non-reducing Disaccharide)
𝛼,𝛽(1à2)-glycosidic bond is between C1 of glucose and C2 of
- Common table sugar and is fructose. It cannot form an open chain and cannot be oxidized
(non-reducing).
readily obtained from the
juice of the sugar cane
(20% by mass) and the
sugar beet (15% by mass).
- Consists of 𝛼-D-glucose
and a 𝛽-D-fructose
molecule joined by an
𝛼,𝛽(1à2)-glycosidic bond
- Both the raw and refined
forms of sugar are sucrose
 POLYSACCHARIDES
- A polysaccharide is a polymer of many monosaccharides joined together
- The most abundant of the CHOs in nature
- Reserve food substances (starch, glycogen)
- Structural materials (cellulose)
- Tasteless, insoluble in water, amorphous compounds with high molar
masses
- 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.
HOMOPOLYSACCHARIDES

Starch
- The chief caloric distributor in the diet; the reserve CHO for plants;
- A storage form of glucose in plants, found as insoluble granules in rice,
wheat, potatoes, beans, and cereals
- A mixture of two polymers which can be separated from each other by
physical/chemical means: amylose and amylopectin
Amylose
– water-soluble fraction; about 15-20% of starch; soluble in hot water
- consists of 250 to 4000 𝛼-D-glucose molecules connected by 𝛼(1à4)-
glycosidic bonds in continuous chain
- Sometimes called a straight-chain polymer; polymers of amylose are coiled in
helical fashion
- The coiled arrangement just has enough room in its core to accommodate an
iodine molecule thus starch gives off a characteristic blue color when treated
with iodine due to the formation of the amylose-I2 complex
Amylopectin
– the water-insoluble fraction; 80-85% of starch
- a branched-chain polysaccharide connected by 𝛼(1à4)-glycosidic bonds
- At about every 25 glucose units, there is a branch of glucose molecules
attached by an 𝛼(1à4)-glycosidic bond between C1 of the branch and C6 in
the main chain

- In our bodies, these complex CHOs are digested by the enzymes amylase (in
saliva) and maltase (in the intestine)
- The glucose obtained provides about 50% of our nutritional calories
Glycogen
– or animal starch; glucose storage molecule of animals; stored in the liver and
muscle cells
- Hydrolyzed in our cells at a rate that maintains the blood level of glucose and
provides energy between meals
- More highly branched than amylopectin; the glucose units are joined by
𝛼(1à4)-glycosidic bonds, and branches occurring about every 10 to 15
glucose units are attached by 𝛼(1à6)-glycosidic bonds
- After a meal, the liver cells take up the excess glucose from the blood and
convert it to glycogen for storage, thereby lowering the blood glucose
concentration
- Between meals, when the blood glucose level falls, the liver cells break
glycogen down to glucose, which is released into the bloodstream
Cellulose
– major structural material of wood and plants (e.g., cotton)
- Glucose molecules form a long unbranched chain similar to amylose but
linked by 𝛽(1à4)-glycosidic bonds
- do not form coils but are aligned in parallel rows that are held by hydrogen
bonds between hydroxyl groups in adjacent chains, making cellulose
insoluble in water
- The linear nature of chains allows close packing into fibers, making it difficult
for solvent molecules to pull the chains apart, thus cellulose is inert towards
most solvents
 Glycogen

Cellulose
– Humans have an enzyme called 𝛼-amylase in saliva and pancreatic juices that
hydrolyze the 𝛼(1à4)-glycosidic bonds of starches but not the 𝛽(1à4)-
glycosidic bonds of cellulose

- Humans cannot digest cellulose

- Animals (e.g., horses, cows, and goats) can obtain glucose from cellulose
because their digestive systems contain bacteria that provide enzymes such
as cellulase to hydrolyze 𝛽(1à4)-glycosidic bonds
MODIFIED SUGARS
-structures similar to glucose but have been oxidized to carboxylic acids or
replaced by an amine

1) Chitin
2) Carrageenan
3) Alginic acid

HETEROPOLYSACCHARIDES
- have peptides, lipids, and proteins attached to them
1) Hyaluronic acid
2) Chondroitin sulfate
3) Heparin