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Carbohydrates Classifications

 Most abundant organic compounds. 1. Monosaccharides

 Act as storehouses of chemical energy 2. Disaccharides
 Supportive components in plants 3. Oligosaccharides
 Essential components of nucleic acids 4. Polysaccharides
 “Hydrate of Carbon”
Saccharides are bonded by Glycosidic
Classification of Carbohydrates bond/linkage.

 Contains many OH (Hydroxyl group) 2 or Monosaccharides

more.
- Carbohydrates cannot be hydrolyzed to a
 Contains carbonyl group C=O.
simpler compound.
- General formula CnH2nOn
3 Carbon = Triose
- One of the Carbons being the carbonyl
4 Carbon = Threose
group of either Aldehyde or Ketone.
5 Carbon = Pentose
- Suffix “ose” indicates that a molecule is a
6 Carbon = Hexose
carbohydrate.
1. Polyhydroxyaldehyde – C=OH
Nomenclature | IUPAC way
- Location of Carbonyl group is in C1
1. Functional Group
2. Number of Carbons
3. + suffix -ose to indicate that it is a
carbohydrate.

Chirality: Handedness in molecules

Monosaccharides exist in left and right-handed

molecule.

Achiral (ASC) – Superimposable mirror images

2. Polyhyroxyketone – C=OC/C=OR
- Location of Carbonyl group is in C2
that coincides at all points. Exactly pitted, alike.
Chiral (CND) – Nonsuperimposable mirror
images where not all points coincide. Not exactly
pitted, unlike.

a). Chiral
b). Chiral
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How can you predict whether a given molecule is
or not a chiral? A molecule is not chiral if it has
a plane of symmetry. If left and right side is alike
Asymmetric centers (Chiral centers) – an
asymmetric center is an atom that is bonded to
four different groups.
Organic molecules, especially monosaccharides,
may contain more than one chiral center.
Fischer Projection
A two-dimensional representation for showing the
configuration of tetrahedral stereocenters.
 Horizontal lines represent bonds projecting
forward from the stereocenter
 Vertical lines represent bonds projecting to
the rear.
 Only the stereo centers are 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 (right side) (existing
sugar): the -OH on its penultimate carbon
(2nd to the last Carbon) is on the right in a
Fischer projection.
- L-monosaccharide (left side) (laboratory
made): the -OH on its penultimate carbon
is on the left in a Fischer projection.
Amino sugars
- Contain an -NH2 group in place of an -OH
group.
- Only three amino sugars are common in
nature.
Physical properties
 Monosaccharides are colorless, crystalline
solids.
 Water soluble
 Slightly soluble to ethanol and insoluble to
nonpolar solvents.
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 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
Anomers.
 The anomeric carbon of an aldose is C-1;
that of the most common ketose is C-2.
 In a Haworth projection, the hemiacetal
ring system is viewed “edged on” with the
oxygen ring atom at the upper right (six-
membered ring) or at the top (five-
membered ring).
 In the D form, CH2OH is positioned above
the ring. In the L form, which is not
usually encountered un biochemical
systems, the terminal CH2OH group is
positioned below the ring.
Fischer projections
D = R (OH)
L = L (OH)
Haworth projections
D = terminal carbon (up)
L = terminal carbon (down)
  or  configuration is determined by
the position of the -OH group on
carbon 1 relative to the CH2OH group
that determines D or L series. In 
configuration, both groups point in the
same direction; in  configuration, the
two groups in opposite direction.
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Haworth Projections Essential Monosaccharides

1. Glucose
-  means that the -OH on the anomeric
- Most abundant in nature.
carbon is on the same side of the ring as
- Other names: grape sugar, blood sugar,
the terminal CH2OH.
dextrose
-  means that the -OH on the anomeric
- 6-membered cyclic form
carbon is on the side of the ring opposite
- Important in human nutrition
from the terminal -CH2OH.
- Not all monosaccharides can’t form
2. Galactose
Haworth
- “Brain sugar” brain nerves=glycoproteins
- Pyranose – cyclic monosaccharides
- “Milk sugar”
containing a six-atom ring. (All
- Used to differentiate between blood types.
aldohexoses)
- Six-membered cyclic form.
- Furanose – cyclic monosaccharide
containing a five-atom ring. (All
3. Fructose
aldopentose; ketohexoses)
- Ketohexose
- Sweetest tasting of all sugars
Chair Conformation
- High dietary sugar due to sweetness
- Five-membered cyclic form
For pyranoses, the six-membered ring is more
accurately represented as a Strain-free chair
4. Ribose
conformation.
- Part of a variety of complex molecules
which include RNA, ATP, DNA
In both Haworth projections and Chair
- Five-membered cyclic form
conformations, the orientations of groups on
carbons 1-5 of the -D-glucopyranose are up, Disaccharides
down, up, down, and up and all are equatorial.
- Contains 2 sugar units
Axial = Straight lines - Two monosaccharides are joined by a
Equatorial = Slanting glycosidic linkage/bond between the
anomeric Carbon of one unit and an -OH
group of the other unit.
- 1st hemiacetal (removes H in Ch, exposing
O), 2nd sugar (alcohol – OH)

1. Maltose
- Glucose + Glucose
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- Structurally made of 2 D-glucose units,
one of which must be -D-glucose, linked
via an (1-4) glycosidic linkage.
- Can be easily digested by humans.
2. Lactose
- Made up of -D-galactose unit and a D-
glucose unit joined by a (1-4) glycosidic
linkage.
- Lactase hydrolyzes (1-4) glycosidic
linkages.
3. Sucrose
- The most abundant of all disaccharides and
found in plants.
- Also known as “Table sugar”
- Special because of -(1-2) glycosidic
bond
4. Cellobiose
- Contains two D-glucose monosaccharide
units, one of which must have a 
configuration, linked through a (1-4)
glycosidic linkage.
- Cannot be digested by humans.
Oligosaccharides
Types
- Carbohydrates that contain 3-10
monosaccharide units bonded to each other
via glycosidic linkages.
- Commonly found in onions, cabbage,
broccoli, and whole meat.
- Can distinguish blood types.
- The body doesn’t have enough enzymes to
break down Raffinose and Stachyose
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, whereas
monosaccharides are sweet and show
positive tests.
- Limited water solubility.
1. Starch
- Storage polysaccharide: Polysaccharide
that is a storage form for monosaccharides
and used as an energy source in cells.
- Glucose is the monomeric unit
- Storage polysaccharide in plants
- Amylose – unbranched. (1-4) glycosidic
bonds
- Amylopectin – branched. (1-4) and (1-
6)
2. Glycogen
- Storage polysaccharide in humans and
animals.
- Contains only glucose units.
- Branched chain polymer with (1-4)
glycosidic bonds in straight chains and
(1-6) in branches
- Contains up to 1,000,000 glucose units.
- Excess glucose in blood is stored in the
form of glycogen.
3. Cellulose
- Linear homopolysaccharide with (1-4)
glycosidic bond.
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- Humans do not have enzymes that
hydrolyze (1-4) linkages and so they
cannot digest cellulose.
4. Chitin
- Linear polymer with all (1-4) glycosidic
linkages.
- It has an N-acetyl amino derivative of
glucose.
5. Hyaluronic acid
- Alternating residues of N-acetyl- -D-
glucosamine and D-glucuronate.
- Highly viscous and serve as lubricants in
the fluid of joints as well as vitreous
humor of the eye.
- Glucosamine to Glucuronate = (1-4)
- Glucuronate to Glucosamine = (1-3)
6. Heparin
- Blood anticoagulant
- Acidic polysaccharide
Reactions and Qualitative Tests
 Carbohydrate oxidation provides
energy.
 Carbohydrate storage, in the form of
glycogen, provides a short-term energy
reserve
 Carbohydrate supply carbon atoms for
the synthesis of other biochemical
substances (proteins, lipids, and
nucleic acids)
 Carbohydrate form part of the
structural framework of DNA and
RNA molecules.
 Carbohydrates linked to lipids are
structural components of cell
membranes.
 carbohydrates linked to proteins
function in a variety of cell-cell and
cell-molecule recognition processes.
Classification of Carbohydrates
- empirical formula of simple carbohydrates
CnH2nOn or Cn (H 2O)n (hydrate of C) n is the
number of atoms
- Carbohydrate: polyhydroxy aldehyde,
ketone, or a compound that produces
such substances upon hydrolysis.
Monosaccharides
- Contain single polyhydroxy aldehyde or
ketone unit
- Cannot be broken down into simpler
substances by hydrolysis reactions.
- Contain 3-7 C atoms
- 5 – 6 carbon species are more common
- Pure monosaccharides – water soluble
white, crystalline solids.
The Eight Essential Monosaccharides
Structures of the eight monosaccharides essential
to humans. All are used for synthesis of the
glycoconjugate components of cell walls, and
glucose is also the body’s primary source of
energy.
Reaction of Monosaccharides
Five important reactions of monosaccharides:
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 Oxidation to acidic sugars
 Reduction to sugar alcohols
 Glycoside formation
 Phosphate ester formation
 Amino sugar formation
Glucose will be used as the monosaccharide
reactant
Other aldoses, as well as ketoses, undergo similar
reactions.
Oxidation to Produce Acidic Sugars
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.
Loss of Hydrogen
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.
Mild oxidizing agent(s):
- Tollens’ reagent
- Fehling’s reagent
- Benedict’s reagent
 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.
Monosaccharide oxidation can yield three
different types of acidic sugars. The oxidizing
agent used determines the product.
Reduction to Produce Sugar Alcohols
The carbonyl group in a monosaccharide (either
an aldose or a ketose) is reduced to a hydroxyl
group using hydrogen as the reducing agent.
Addition of Hydrogen.
- 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 gum.
Glycoside Formation
Glycoside: Acetal formed from a cyclic
monosaccharide by replacement of the hemiacetal
carbon -OH group with an -OR group
- “O bond”
- Glucoside produced from glucose
- Galactoside – glycoside produced from
galactose
Phosphate Ester formation
Hydroxyl groups of a monosaccharide can react
with inorganic oxyacid to form inorganic esters.
- Phosphate esters of various
monosaccharides are stable in aqueous
solution and play important roles in the
metabolism of carbohydrate.
- Phosphate groups (C1-C6) of
monosaccharides
Amino sugar formation
Amino sugar – formed when one of the hydroxyl
groups of a monosaccharide is replaced with an
amino group.
In naturally occurring amino sugars, the C2
hydroxyl group is replaced by an amino group.
Nitrogen at C2
Amino sugars and their N-acetyl derivatives are
important building blocks of polysaccharides such
as chitin and hyaluronic acid.
Three common natural amino acid sugars:
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- D-glucosamine - The biochemical basis for the various
- D-galactosamine blood types involves oligosaccharides
- D-mannosamine present on plasma membranes of red blood
cells.
Disaccharides
- The oligosaccharides responsible for blood
- Contain two monosaccharide units groups are D-galactose and its derivatives.
covalently bonded to each other
- Crystalline and water-soluble substance
- Common disaccharides – table sugar Biochemistry in Medicine
(sucrose) and milk sugar (lactose)
- Upon hydrolysis, they produce two
monosaccharide units.

Formation of Disaccharides

- One monosaccharide acts as a hemiacetal

and other as an alcohol
- Resulting ether bond is a glycosidic
linkage
- In the process of glycoside formation
resulting to glycosidic bond = covalently
bond. Polysaccharides

Oligosaccharides - Contain many monosaccharide units

- Contain 3-10 monosaccharide are seldom
encountered in biochemical systems
- Usually found associated with proteins and
lipids in complex molecules.
- Serve structural and regulatory functions
covalently bonded
- Number of monosaccharide units varies
from a few 100 units to 50,000 units
Qualitative Tests for Carbohydrates

Blood types and Oligosaccharides 1. Molisch Test

- Human blood is classified into four types.
(A, B, AB, and O)
- The basis for the difference is the type of
sugars (oligosaccharides) present
- Blood of one type cannot be given to a
recipient with blood of another type.
- A transfusion of wrong blood type can
cause the blood cells to form clumps, a
potentially fatal reaction.
- People with blood type O blood universal
donors, and those with type AB blood are
universal recipients.
- In the United States, type O blood is the
most common and type A the second most
common.
- Common tests for all carbohydrates larger
than tetroses. The test is on the basis that
pentoses and hexoses are dehydrated by
conc. Sulphuric acid to form furfural or
hydroxymethylfurfural, respectively.
These products condense with alpha-
naphthol to form purple condensation
product.
Positive = if there’s a purple ring at the junction of
two solutions
2. Fehling’s Test
- This forms the reduction test of
carbohydrates. Fehling’s solution contains
blue alkaline CuOH solution, heated with
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reducing sugars gets reduced to red
cuprous oxide and is precipitated. Hence,
formation of the yellow or brownish-red
colored precipitate helps in the detection of
reducing sugars in the test solution.
Positive = presence of brownish-red colored
(brick red) precipitate in the test solution.
3. Benedict’s test
- This test is used for the detection of starch
in the solution. The blue-black color is due
to the formation of starch-iodine complex.
Starch contains polymer of alpha-amylose
and amylopectin which forms a complex
with iodine to give a blue-black color.
Positive = if dark blue/black there’s a presence of
starch

- Is to test for one reducing sugar glucose.

- Starts out aqua-blue. The sample solution
turned into a dark blue color and indicated
the presence of starch. As it is heated in
the presence of reducing sugars, it turns
yellow to orange. The hotter the final color
of the reagent, the higher the concentration
of reducing sugar.

Positive = green/yellow: traces of reducing sugar

Orange: moderate, brick-red: large amount of
reducing sugar.

4. Barfoed’s test

- The reaction will be negative in the

presence of disaccharide sugars because
they are weaker reducing agents. This test
is specific for monosaccharides. Due to the
weakly acidic nature of Barfoed’s reagent,
it is reduced only by monosaccharides.

Positive = a red copper (II) oxide precipitate is

formed will indicate the presence of reducing
sugar.

5. Seliwanoff’s test

- Is a chemical test which distinguishes

between aldose and ketose sugars. This
test relies on the principle that, when
heated, ketoses are more rapidly
dehydrated than aldoses.

Positive = ketoses present, cherry red colored

complex formed.

6. Iodine test