Carbohydrates

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Carbohydrates contain only the elements carbon, hydrogen and oxygen. The group includes
monomers, dimers and polymers, as shown in this diagram:

Carbohydrates are compounds of carbon, hydrogen and oxygen.

General formula of carbohydrates is Cx(H2O)y, or, CxH2yOy.

Carbohydrates are also known as sugars.

The most common simple carbohydrates have either:

5 carbon atoms (pentoses)
or 6 carbon atoms (hexoses).

Examples of Carbohydrates
Carbohydrate
Monosaccharides
(simple sugars)

Disaccharides
(double sugars)

Polysaccharides

Name
glucose
fructose
galactose

Formula
C6H12O6
C6H12O6
C6H12O6

Source
fruits
fruits, honey
not naturally occurring

sucrose (glucose + fructose)

lactose (glucose + galactose)
maltose (glucose + glucose)

C12H22O11
C12H22O11
C12H22O11

sugar cane, sugar beet

milk
germinating grain

starch

-(C6H10O5)-n

glycogen

-(C6H10O5)-n

cellulose

-(C6H10O5)-n

energy store in plants

energy store in animals
(liver and muscles)
plant fibre

Aldehydes and ketones Group

are simple compounds which contain a carbonyl group - a carbon-oxygen

double bond.

In aldehydes, the carbonyl group has a hydrogen atom attached to it

together with either

a second hydrogen atom

or, more commonly, a hydrocarbon group which might be an alkyl group or

one containing a benzene ring.

In ketones, the carbonyl group has two hydrocarbon groups attached. Again,
these can be either alkyl groups or ones containing benzene rings. Again, we'll
concentrated on those containing alkyl groups just to keep things simple.
Notice that ketones never have a hydrogen atom attached to the carbonyl group.

When the closed-ring (cyclic) structure of a monosaccharide opens to form a chain,

the result may be either:
an aldehyde (alkanal)

or

a ketone (alkanone)

||

||

R-

-H

Sugars that are aldehydes are known as

aldoses.

R-

- R'

Sugars that are ketones are known as

ketoses.

A monosaccharide containing 5 carbon atoms is known as a pentose. The open-chain form is

therefore either:

an aldopentose if it is an aldehyde (alkanal)

or a ketopentose if it is a ketone (alkanone)

A monosaccharide containing 6 carbon atoms is known as a hexose. The open-chain form is

therefore either:

an aldohexose if it is an aldehyde (alkanal)

or a ketohexose if it is a ketone (alkanone)

Ketoses
Aldoses
Aldotriose
Ketotriose
Dihydroxyacetone
D-Glyceraldehyde
Aldopentoses
ketopentoses

D-Ribulose
D-Ribose

ketohexoses

D-Fructose

Aldohexoses

D-Glucose

Monosaccharides (simple sugars)

D-Galactose

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These all have the formula (CH 2O)n, where n can be 3-7. The most common and important
monosaccharide is glucose, which is a six-carbon or hexose sugar, so has the formula C6H12O6.

A monosaccharide is made up of one sugar

(mono means 1).
Monosaccharides contain the hydroxy (alcohol, OH) functional group.
There are 3 types of monosaccharide : triose sugar,pentose sugar, hexose sugar

Triose
A triose is a monosaccharide containing three carbon atoms. There are only two trioses, an
aldotriose (glyceraldehyde) and a ketotriose (dihydroxyacetone). Trioses are important in
respiration. Namely, lactic acid and pyruvic acid are derived from aldotriose and ketotriose,
respectively.
The structure of triose is:

The D-aldotriose is D-Glyceraldehyde

The ketotriose is dihydroxyacetone:

Pentose
A pentose is a monosaccharide with five carbon atoms.[1] Pentoses are organized into two
groups. Aldopentoses have an aldehyde functional group at position 1. Ketopentoses have a
ketone functional group in position 2 or 3.
The structure of pentose ring (ribose & deoxyribose) is:

Ribose

Ribose and its related compound, deoxyribose, are the building blocks of the backbone chains
in nucleic acids, better known as DNA and RNA. Ribose is used in RNA and deoxyribose is
used in DNA. The deoxy- designation refers to the lack of an alcohol, -OH, group as will be
shown in detail further down.
Ribose and deoxyribose are classified as monosaccharides, aldoses, pentoses, and are reducing
sugars.

Ring Structure for Ribose:

The chair form of ribose follows a similar pattern as that for glucose with one exception. Since
ribose has an aldehyde functional group, the ring closure occurs at carbon # 1, which is the
same as glucose. See the graphic on the left.The exception is that ribose is a pentose, five
carbons. Therefore a five membered ring is formed. The -OH on carbon #4 is converted into the
ether linkage to close the ring with carbon #1. This makes a 5 member ring - four carbons and
one oxygen.

Click for larger image

Compare Ribose and Deoxyribose Structures:

The presence or absence of the -OH group on carbon (#2) is an important distinction between
ribose and deoxyribose. Ribose has an alcohol at carbon # 2, while deoxyribose does not have
the alcohol group. See red -OH and H in the structures on the left.
The Beta position is defined as the -OH being on the same side of the ring as the C # 6. In the
ring structure this results in a upward projection.
The Alpha position is defined as the -OH being on the opposite side of the ring as the C # 6.
In the ring structure this results in a downward projection.
The alpha and beta label is not applied to any other carbon - only the anomeric carbon, in this
case # 1.

Hexose
A hexose is a monosaccharide with six carbon atoms, having the chemical formula C6H12O6.
Hexoses are classified by functional group, with aldohexoses having an aldehyde at position 1,
and ketohexoses having a ketone at position 2.
Glucose, fructose and galactose are all examples of hexoses, simple sugars containing 6 carbon atoms.

Name
Formula

glucose
C6H12O6

galactose
C6H12O6

Structure

The structure of hexose ring (glucose) is:

-glucose (used to make starch and glycogen)

or more simply

-glucose (used to make cellulose)

fructose
C6H12O6

Monosaccharide

Glucose

Fructose

aldohexose

ketohexose

Closed-ring (cyclic)
Structure

Open-chain Structure

Classification

Disaccharides (double sugars)

Disaccharides are formed when two monosaccharides are joined together by a glycosidic bond. The
reaction involves the formation of a molecule of water (H 2O):

This shows two glucose molecules joining together to form the disaccharide maltose. Because this bond
is between carbon 1 of one molecule and carbon 4 of the other molecule it is called a 1-4 glycosidic bond.
Bonds between other carbon atoms are possible, leading to different shapes, and branched chains.

This kind of reaction, where H2O is formed, is called a condensation reaction. The reverse process, when
bonds are broken by the addition of water (e.g. in digestion), is called a hydrolysis reaction.

polymerisation reactions are condensations

In
general:

breakdown reactions are hydrolyses

There are three common disaccharides:

Maltose (or malt sugar) is glucose 1-4 glucose. It is formed on digestion of starch by amylase,
because this enzyme breaks starch down into two-glucose units. Brewing beer starts with malt,
which is a maltose solution made from germinated barley. Maltose is the structure shown above.

Sucrose (or cane sugar) is glucose 1-2 fructose. It is common in plants because it is less reactive
than glucose, and it is their main transport sugar. It is the common table sugar that you put in your
tea.

Lactose (or milk sugar) is galactose 1-4 glucose. It is found only in mammalian milk, and is the
main source of energy for infant mammals.

Polysaccharides

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Polysaccharides are long chains of many monosaccharides joined together by glycosidic bonds. There
are three important polysaccharides:

Starch is the plant storage polysaccharide. It is insoluble and forms starch granules inside many
plant cells. Being insoluble means starch does not change the water potential of cells, so does
not cause the cells to take up water by osmosis (more on osmosis later). It is not a pure
substance, but is a mixture of amylose and amylopectin.

Amylose is simply poly-(1-4) glucose, so is a straight

chain. In fact the chain is floppy, and it tends to coil up
into a helix.

Amylopectin is poly(1-4) glucose with about 4% (1-6)

branches. This gives it a more open molecular structure
than amylose. Because it has more ends, it can be
broken

more

quickly

than

amylose

by

amylase

enzymes.

Both amylose and amylopectin are broken down by the enzyme amylase into maltose, though at different rates.

Glycogen is similar in structure to amylopectin. It is

poly (1-4) glucose with 9% (1-6) branches. It is
made by animals as their storage polysaccharide,
and is found mainly in muscle and liver. Because it
is so highly branched, it can be mobilised (broken
down to glucose for energy) very quickly.

Cellulose is only found in plants, where it is the main component of cell walls. It is poly (1-4)
glucose, but with a different isomer of glucose. Starch and glycogen contain a-glucose, in which
the hydroxyl group on carbon 1 sticks down from the ring, while cellulose contains b-glucose, in
which the hydroxyl group on carbon 1 sticks up. This means that in a chain alternate glucose
molecules are inverted.

This apparently tiny difference makes a huge difference in structure and properties. While the 1-4
glucose polymer in starch coils up to form granules, the 14 glucose polymer in cellulose forms straight
chains. Hundreds of these chains are linked together by hydrogen bonds to form cellulose microfibrils.
These microfibrils are very strong and rigid, and give strength to plant cells, and therefore to young plants
and also to materials such as paper, cotton and sellotape.

The b-glycosidic bond cannot be broken by amylase, but requires a specific cellulase enzyme. The only
organisms that possess a cellulase enzyme are bacteria, so herbivorous animals, like cows and termites
whose diet is mainly cellulose, have mutualistic bacteria in their guts so that they can digest cellulose.
Humans cannot digest cellulose, and it is referred to as fibre.

Other polysaccharides that you may come across include:

Chitin (poly glucose amine), found in fungal cell walls and the exoskeletons of insects.
Pectin (poly galactose uronate), found in plant cell walls.
Agar (poly galactose sulphate), found in algae and used to make agar plates.
Murein (a sugar-peptide polymer), found in bacterial cell walls.

Lignin (a complex polymer), found in the walls of xylem cells, is the main component of wood.

Reducing and Non-reducing Sugars

Key Concepts

Sugars exist in solution as an equilibrium mixture of open-chain and closedring (or cyclic) structures.

In the open-chain form, the carbon atom that contains the C=O bond is called
the carbonyl carbon.

In the closed-ring (cyclic) structure, the carbonyl carbon is the one which is
attached to the O of the ring and an OH group.

Sugars that can be oxidised by mild oxidising agents are called reducing
sugars because the oxidising agent is reduced in the reaction.

A non-reducing sugar is not oxidised by mild oxidising agents.

All common monosaccharides are reducing sugars.

The disaccharides maltose and lactose are reducing sugars.

The disaccharide sucrose is a non-reducing sugar.

Common oxidising agents used to test for the presence of a reducing sugar
are:

a. Benedict's Solution
b. Fehling's Solution
c. Tollen's Reagent

Testing for the Presence of a Reducing Sugar

The common oxidising agents used to test for the presence of a reducing sugar:
Oxidising Reagent

Benedict's
Solution

Fehling's
Solution

Tollen's Reagent

Composition

copper sulfate in
alkaline citrate

copper sulfate in
alkaline tartrate

silver nitrate in
aqueous ammonia

Colour of Solution

deep blue

deep blue

colourless

Colour After Reaction

with a Reducing Sugar

brick red
precipitate
Cu2O(s)

brick red
precipitate
Cu2O(s)

silver mirror forms

Ag(s)

Species Being
Reduced
(the oxidant)
Species Being
Oxidised
(the reductant)

Cu2+

Cu2+
+ e ---> Cu+

Cu2+

reducing sugar
oxidised to
carboxylate

Cu2+
+ e ---> Cu+

reducing sugar
oxidised to
carboxylate

Ag+
Ag+ + e ---> Ag(s)
reducing sugar
oxidised to
carboxylate

Oxidation of Monosaccharides
Oxidation of Aldoses
Glucose and galactose are both examples of aldoses.
1. Oxidation Using Benedict's or Fehling's Solution:
O
||
R- C -H

O
+ 2Cu2+ + 5OHdeep blue

aldose
2. Oxidation Using Tollen's Reagent

||
R - C - Ocarboxylate

+ Cu2O(s)
brick red

+ 3H2O

||
R- C -H

+ 2Ag(NH3)2+ + 3OHcolourless

aldose

||
R - C - O-

+ 2Ag(s)
silver mirror

+ 4NH3(g) + 2H2O

carboxylate

Oxidation of Ketoses
Fructose is an example of a ketose.

1 Oxidation Using Benedict's or Fehling's Solution:

OH
O

||
R- C -CH2OH

R- C -COO-

+ 2Cu2+ + 5OHdeep blue

+ Cu2O(s)
+ 3H2O
brick red

|
H

ketose
hydroxy carboxylate

2. Oxidation Using Tollen's Reagent

OH
|

O
||
R- C -CH2OH

+ 2Ag(NH3)2+ +
3OHcolourless

ketose

R- C -COO|
H

+ 2Ag(s)
silver
mirror

+ 4NH3(g) +
2H2O

hydroxy
carboxylate

Structure and Oxidation of Disaccharides

Sugar

sucrose

maltose

lactose

Cyclic
Structu
re

Glycosi
dic Link
through

2 carbonyl carbons

1 carbonyl carbon

1 carbonyl carbon

Openchain
structu
re

no

yes

yes

+Bened
ict's
Solutio
n

no reaction

forms brick red solid

forms brick red solid

+Fehlin
g's
Solutio
n

no reaction

forms brick red solid

forms brick red solid

+Tollen'
s
Reagen
t

no reaction

forms silver mirror

forms silver mirror

Type

non-reducing sugar

reducing sugar

reducing sugar