Carbohydrates

1. Types of Carbohydrates
2. Classification of Monosaccharides
3. D and L Notations from Fischer Projections
4. Structures of Some Important Monosaccharides
5. Cyclic Structures of Monosaccharides

Compiled by: Dwika Riandari, M.Si

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Objectives
Explain why carbohydrates are important
Define what a carbohydrate molecule is
Recognise and classify carbohydrate molecules
Define
stereochemistry
and
explain
its
importance in the structures of carbohydrates

Dwika Riandari, M.Si_SMAK Bogor

Why Carbohydrates ?

Dwika Riandari, M.Si_SMAK Bogor

Importance of
Carbohydrates
Most

organisms that live in air obtain energy

from the oxidation of carbohydrates
Glucose is most common simple carbohydrate
used as fuel
Important to consider structure of carbohydrates
Differences in molecular structure are often small
but critical to their function

Dwika Riandari, S.Si_SMAK Bogor

Carbohydrates
Most abundant organic compounds in
nature
A major source of energy from our diet
Composed of the elements C, H and O
Also called saccharides, which means
sugars
Produced by photosynthesis in plants

Dwika Riandari, S.Si_SMAK Bogor

Properties
Differences in structures of sugars are
responsible for variations in properties
Physical

Chemical

Crystalline form; solubility; rotatory power

Reactions (oxidations, reductions, condensations)

Physiological

Nutritive value (human, bacterial); sweetness;

absorption

Dwika Riandari, S.Si_SMAK Bogor

Types of
Carbohydrates

Monosaccharides are the simplest carbohydrates

Empirical formula = CH2O

Disaccharides consist of two monosaccharides

Polysaccharides contain many monosaccharides

Dwika Riandari, S.Si_SMAK Bogor

Classification of
carbohydrates

Monosaccharides (monoses or glycoses)

Trioses, tetroses, pentoses, hexoses

Oligosaccharides
Di, tri, tetra, penta, up to 9 or 10
Most important are the disaccharides

Polysaccharides or glycans
Homopolysaccharides
Heteropolysaccharides
Complex carbohydrates

Dwika Riandari, S.Si_SMAK Bogor

Monosaccharide = unbranched chain of 3-8 C

atoms; one is carbonyl, others attached to -OH
Aldoses

monosaccharides with an aldehyde group (1st carbon)

Ketoses

monosaccharides with a ketone group (2nd carbon)

CH2OH
CHO
HO

H
CH2OH

Aldose

CHO
HO
H

HO

OH

OH

CH2OH

OH

Dwika Riandari, S.Si_SMAK Bogor

Aldose

CH2OH
OH

Ketose

Monosaccharides

Monosaccharides are also classified according to

the number of carbon atoms
A triose has three carbons; a tetrose has four
carbons; a pentose has five carbons; and a hexose
has six carbons.
CH2OH
CHO

HO

CHO

HO

CH2OH
triose
aldotriose

O
HO

OH

OH

CH2OH

OH

tetrose
Dwika Riandari, S.Si_SMAK Bogor
aldotetrose

CH2OH
OH
hexose
ketohexose

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Monosaccharide Nomenclature
C

Ketone

Aldehyde

Examples

Tetrose

Tetrulose

Erythrose,Threose

Pentose

Pentulose

Ribulose,Ribose

Hexose

Hexulose

Fructose,Glucose

Heptose

Heptulose

Sedoheptose, Sedoheptulose

Dwika Riandari, S.Si_SMAK Bogor

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Learning Check
Which classification fits this sugar?

Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Dihydroxyacetone
Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Galactose
Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Glyceraldehyde
Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

D-Threose

Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Dwika Riandari, S.Si_SMAK Bogor

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Which classification fits this sugar?

Ketoheptose

Sedoheptulose

Dwika Riandari, S.Si_SMAK Bogor

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Monosaccharides (Daldoses)

Dwika Riandari, S.Si_SMAK Bogor

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Sugars that are most common in

nature are indicated by boxes

The name mannose isDwika

derived
from Bogor
the Biblical word manna.23
Riandari, S.Si_SMAK

Dwika Riandari, S.Si_SMAK Bogor

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Fischer Projections
Using

these rules the distinguishing

features of the 3D structure of
stereoisomers
can
easily
and
accurately
represented
with
2D
drawings
Fischer projection named after Emil
Fischer who established the molecular
structures of many sugars

Dwika Riandari, S.Si_SMAK Bogor

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Fischer Projections

Used to represent carbohydrates (chiral carbons)

Places the most oxidized group at the top

Uses horizontal lines for bonds that come forward

Uses vertical lines for bonds that go back

Dwika Riandari, S.Si_SMAK Bogor

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D and L Notations

By convention, the letter L is assigned to the

structure with the OH on the left

The letter D is assigned to the structure with

OH on the right

Dwika Riandari, S.Si_SMAK Bogor

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D and L
Monosaccharides

The OH on the chiral atom farthest from the

carbonyl group is used to assign the D or L
configuration

D
D
Dwika Riandari, S.Si_SMAK Bogor

L
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Learning Check

Indicate whether each is the D or L isomer:

CH2OH

CHO
HO

HO

HO

H
CH2OH

CHO
H
HO

OH
H
CH2OH

O
HO

OH

OH
CH2OH

Ribose

Threose
Dwika Riandari, S.Si_SMAK Bogor

Fructose
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D-Glucose

Most common hexose

Found in fruits, corn

syrup, and honey

An aldohexose with
the formula C6H12O6

Known as blood sugar

in the body

Building block for

many disaccharides
and polysaccharides

Dwika Riandari, S.Si_SMAK Bogor

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Blood Glucose Level

In the body, glucose has a normal concentration of 70-90

mg/dL

Depends on time since last meal (rise after eat; decrease

as used or stored)

In a glucose tolerance test, blood glucose is measured for

several hours after ingesting glucose

Dwika Riandari, S.Si_SMAK Bogor

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D-Fructose

Ketohexose C6H12O6

Differ from glucose at C1 and C2

(location of carbonyl)

The sweetest carbohydrate (2x

sucrose)

CH2OH
C O
HO C H

Found in fruit juices and honey

Formed from hydrolysis of sucrose

H C OH

Converts to glucose in the body

H C OH
CH2OH

Dwika Riandari, S.Si_SMAK Bogor

D-Fructose 32

D-Galactose

Aldohexose

Differ from D-glucose at C4

Not found in the free form

CHO
H C OH

in nature

HO C H

Obtained from lactose, a

HO C H

disaccharide (milk products)

H C OH
CH2OH
D-Galactose

Dwika Riandari, S.Si_SMAK Bogor

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Hemiacetal Review

What is a hemiacetal?
How is a hemiacetal formed?
OH

O
+

H
CH3

CH3

CH3OH

OCH3

What if the alcohol and carbonyl are attached?

H
O

C
HO

HO

H+

O
C

H
HOCH2

O
C

CH2OH

H
HOCH2

H
O

C
=
C Dwika Riandari, S.Si_SMAK Bogor
H
H

H+

H
O

O
C

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H

Hexose hemiacetals

Favor formation of 5- or 6-membered rings

Hydroxyl group on C5 reacts with the aldehyde or ketone

The Haworth structure can be written from the Fischer projection

The cyclic structure of a D-isomer has the last CH2OH group located
above the ring

The OH group on the left (C3) is drawn up

Dwika
Riandari,
S.Si_SMAK
Bogordrawn down
The OH groups on the
right
(C2,
C4) are

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Rules for drawing

Haworth projections

draw either a six or 5-membered ring

including oxygen as one atom
O

most aldohexoses are six-membered

aldotetroses, aldopentoses, ketohexoses
are 5-membered

Dwika Riandari, S.Si_SMAK Bogor

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Rules for drawing

Haworth projections

next number the ring clockwise starting next

to the oxygen
5
O

4
3

4
3

if the substituent is to the right in the Fisher

projection, it will be drawn down in the
Haworth projection (Down-Right Rule)

Dwika Riandari, S.Si_SMAK Bogor

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Conversion of Fischers to
Haworths

Dwika Riandari, S.Si_SMAK Bogor

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 and Anomers for DGlucose

Anomers are isomers which differ in placement of

hydroxyl on C1
The OH is drawn down for the -anomer, and up
for the -anomer
CH2OH

CH2OH

OH

OH

OH

OH

OH
OH

OH

-D-Glucose

OH

-D-Glucose
Dwika Riandari, S.Si_SMAK Bogor

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Mutarotation

In solution, -D-glucose is in equilibrium with -D-glucose

Mutarotation involves the conversion of the cyclic anomers

into the open chain

At any time, there is only a small amount of open chain

Dwika Riandari, S.Si_SMAK Bogor

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Cyclic Structure of
Fructose

As a ketohexose, fructose forms a cyclic structure

when the OH on C5 reacts with the ketone on C2
Result is 5-atom ring
Anomeric carbon is C2

CH2OH
C O
HO C H

CH2OH
O

H C OH
H C OH
CH2OH
D-Fructose

CH2OH
OH
OH

OH

-D-Fructose

Dwika Riandari, S.Si_SMAK Bogor

CH2OH
O

OH

OH
OH
CH2OH

-D-Fructose

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Learning Check
Write the cyclic form of -D-galactose:
H

O
C

H C OH
HO C H
HO C H
H C OH
CH2OH

-D-galactose

Dwika Riandari, S.Si_SMAK Bogor

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Reactions of
monosaccharides

Carbonyl reactions:

Osazone formation
Cyanohydrin reaction
Reduction
Oxidation
Action of base
Action of acid
Ring chain tautomerism

Alcohol reactions

Glycoside formation
Ether formation
Ester formation

Dwika Riandari, S.Si_SMAK Bogor

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Formation of
osazones

once used for the identification of sugars

consists of reacting the monosaccharide with
phenylhydrazine
a crystalline compound with a sharp melting point
will be obtained
D-fructose and D-mannose give the same
osazone as D-glucose
seldom used for identification; we now use HPLC
or mass spectrometry

Dwika Riandari, S.Si_SMAK Bogor

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Dwika Riandari, S.Si_SMAK Bogor

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Oxidation reactions

Aldoses may be oxidized to 3 types of acids

Aldonic acids: aldehyde group is converted to a

carboxyl group ( glucose gluconic acid)
Uronic acids: aldehyde is left intact and primary
alcohol at the other end is oxidized to COOH

Glucose --- glucuronic acid

Galactose --- galacturonic acid

Saccharic acids (glycaric acids) oxidation at both

ends of monosaccharide)

Glucose ---- saccharic acid

Galactose --- mucic acid
Mannose --- mannaric acid
Dwika Riandari, S.Si_SMAK Bogor

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Dwika Riandari, S.Si_SMAK Bogor

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Fehlings reaction to determine glucose levels in blood.

D-Glucose
Dwika Riandari, S.Si_SMAK Bogor

D-Gluconate
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Fehlings reaction

Dwika Riandari, S.Si_SMAK Bogor

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Fehling solution

Fehling solution (Attention: very corrosive)

is a solution to test for aldehydes, aldoses and
fructose in urine developed by Fehling (1850).
(More reducing substances react with F.S.
leaving a brick red precipitation).

The deep blue solution is made by mixing 1 drop

of Fehling solution 1 ("Fehling 1") and 1 drop
Fehling solution 2 ("Fehling 2").
"Fehling 1": 0,7 g blue copper sulfate dissolved in
10 ml water.
"Fehling 2": 3,4 g potassium sodium tartrate and
1.0 g NaOH in 10 ml water.
Dwika Riandari, S.Si_SMAK Bogor

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Tollens reaction

Ag+ ions react with OH- of aqueous ammonia to

produce a brown precipitate of AgOH which is
dissolved on addition of an excess of aqueous
ammonia under the formation of [Ag(NH3)2]+. The
silver diamine complex is reduced by glucose to
metallic silver. Glucose
is oxidized to gluconic acid.
Dwika Riandari, S.Si_SMAK Bogor
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Tollens reaction

Dwika Riandari, S.Si_SMAK Bogor

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 Reducing sugar ?
The Fehling and Tollens test are important in
carbohydrate for proof of structure.
The test is spesific for reducing sugar.
Fructose is also capable of reducing Fehling and
Tollens solution, and is thus classified a reducing
sugar. Under basic condition fructose is converted
into glucose.

Dwika Riandari, S.Si_SMAK Bogor

53

Sugars Can Be
Reducing
Agents
Reducing Sugars - A sugar that will reduce
inorganic ions such as Cu++ (Fehlings
reagent).

All monosaccharides whether an aldose or

a ketose are reducing sugars.

Most disaccharides are reducing sugars;

sucrose is a notable exception.
Dwika Riandari, S.Si_SMAK Bogor

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Glycosidic binds are

between two sugars
They can either be in the or configuration and
can be linked through the 1-2, 1-4 or 1-6 linkage

Dwika Riandari, S.Si_SMAK Bogor

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Disaccharides
Disaccharidesarelinkedbyaglycosidicbondat
theanomericcarbonofoneunitandaOHgroup
oftheother.Threeimportantdisaccharidesare
maltose,lactose,andsucrose.

Dwika Riandari, S.Si_SMAK Bogor

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Non-reducing sugar

Reducing sugar

Reducing sugar
Dwika Riandari, S.Si_SMAK Bogor

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Maltose:
Maltoseisnamedaftermalt,thejuicefromsproutedbarleyandothercereal
grains.
MaltoseconsistsoftwomoleculesofDglucopyranosejoinedbya1,4
glycosidicbondbetweencarbon1(theanomericcarbon)ofoneunitandcarbon
4oftheotherunit.Maltoseisareducingsugar
IllustratedisMaltosenamedsobecausetheanomericcabonoftheglucoseon
therightisbeta.Thealphalinkagebetweenthetwosugarsisimpliedinthe
namemaltose.

Dwika Riandari, S.Si_SMAK Bogor

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Lactose:
Lactoseisthemainsugarpresentinmilk.Itmakesupabout5
8%ofhumanmilk,46%cowsmilk.ItconsistsofD
galactopyranosebondedbya1,4glycosidicbondtoacarbon4
ofDglucopyranose.Lactoseisalsoareducingsugar.

Theenzymeneededtodigestthisbetaglycosidicbondislacking
inmanypeopleand,also,tendstodisappearwithage.This
Dwika Riandari, S.Si_SMAK Bogor
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leadstosocalledlactoseintolerance.

Sucrose:
Sucroseortablesugaristhemostabundantdisaccharideinthe
naturalworld.Commercially,itisobtainedfromthejuiceofsugar
caneandsugarbeets.
Insucrose,carbon1ofDglucopyranoseisjoinedtocarbon2of
Dfructofuranosebyan1,2glycosidicbond.
Note:glucoseisasixmemberedring(pyranose)whereasfructose
isafivememberedring.Becausebothoftheanomericcarbonsof
themonosaccharidesareinvolvedintheglycosidicbond,sucroseis
anonreducingsugar.

Dwika Riandari, S.Si_SMAK Bogor

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