KARBOHIDRAT

DIBAGI 3 GOLONGAN :
1. Monosakarida
* karbohidrat paling sederhana
* tidak dapat diuraikan dgn cara hidrolisis
* contoh :
aldosa
ketosa
Atom C3 (triosa)
gliserosa
dihidroksiaseton
C4(tetrosa)
eritrosa
eritrulosa
C5 (pentosa)
ribosa
ribulosa
C6 (heksosa)
glukosa
fruktosa

Glukosa

Beda bentuk L dgn D pd monosakarida

Bentuk cincin Piran dan Furan

Gugus Keton pada Monosakarida

2. Disakarida : terdiri dari 2 monosakarida

* Sukrosa : glukosa + fruktosa
* Laktosa : galaktosa + glukosa
* Maltosa : glukosa + glukosa
3. Oligosakarida : terdiri dari 3 6 monosakarida
4. Polisakarida : > 6 monosakarida
* Amilum ( tepung )
* Glikogen
polimer glukosa
* Dekstrin
* Selulosa

Sukrosa

Laktosa

Maltosa

Ikatan 1,4 Glikosidik pd Selobiosa

Beda Maltosa dgn Selobiosa

 Amilum :
* Mempunyai rantai lurus ( ikatan -1,4 glikosidik ) dan
rantai cabang ( ikatan -1,6 glikosidik )
* Terdapat pada tumbuh2an : biji2an ( padi/beras, gandum, jagung dll. ) dan umbi2an ( ketela, ubi, kentang )
* Terdiri dari amilosa dan amilopektin
Glikogen
* struktur spt amilum, rantai cabang lebih banyak
* terdapat di sel hati dan otot
Selulosa
* berupa rantai lurus ( ikatan -1,4 glikosidik )
* mamalia (manusia tidak mempunyai enzim selulase)
* terdapat pd dinding sel tanaman

Struktur Amilum

Struktur Glikogen

Ikatan 1,6 Glikosidik pd polisakarida

Struktur Glikogen dan Amilum

Struktur Selulosa

Epimers

Carbohydrates

19

Carbohydrates

20

Hemiacetal & hemiketal

formation
H

An aldehyde can
OH
C O + R'
react with an
alcohol to form
R
a hemiacetal.
aldehyde
alcohol
A ketone can
react with an
alcohol to form
a hemiketal.

H
R'

OH

hemiacetal

R
C

R
O

"R

OH

R'

ketone

"R

C
R'

alcohol

hemiketal

OH

Pentoses and
hexoses can cyclize
as the ketone or
aldehyde reacts
with a distal OH.
Glucose forms an
intra-molecular
hemiacetal, as the
C1 aldehyde & C5
OH react, to form a
6-member pyranose
ring, named after
pyran.

H
HO
H
H

2
3
4
5
6

CHO
C

OH

OH (linear form)

OH

D-glucose

CH2OH
6 CH2OH

6 CH2OH
5

H
4

OH

H
OH
3

OH

-D-glucose

OH

H
4

OH

H
OH
3

OH

OH

-D-glucose

These representations of the cyclic sugars are called

Haworth projections.

CH 2OH

CHO
H

OH

HO

OH

OH
CH 2OH

glucose

OH

HO

NaBH4
H

OH

OH
CH 2OH

glucitol

Glycoside Formation

Glycosides can be hydrolyzed in aqueous

acid
The alcohol obtained after hydrolysis of a
glycoside is called an aglycone

 Other Reactions of Monosaccharides

Enolization, Tautomerization and Isomerization
Monosaccharides dissolved in aqueous base will
isomerize by a series of keto-enol tautomerizations
A solution of D-glucose containing calcium hydroxide will
form several products, including D-fructose and Dmannose

A monosaccharide can be protected from keto-enol

tautomerization by conversion to a glycoside

 Formation of Ethers
The hydroxyl groups of carbohydrates can be

converted to ethers by the Williamson ether synthesis

Benzyl ethers are commonly used to protect or block
carbohydrate hydroxyl groups
Benzyl ethers can be easily removed by
hydrogenolysis

Exhaustive methylation of methyl glucoside can

be carried out using dimethylsulfate

Conversion to Esters
Carbohydrates react with acetic
anhydride in the presence of weak
base to convert all hydroxyl groups to
acetate esters

Conversion to Cyclic Acetals

Carbohydrates form cyclic acetals with
acetone selectively between cis-vicinal
hydroxyl groups
Cyclic acetals from reaction with
acetone are called acetonides

 Oxidation Reactions of Monosaccharides

Benedicts or Tollens Reagents: Reducing
Sugars
Aldoses and ketoses give positive tests when

treated with Tollens solution or Benedicts reagent

Tollens reagent [Ag(NH3)2OH] gives a silver mirror when
Ag+ is reduced to Ag0
Benedicts reagent (an alkaline solution of cupric citrate
complex) gives a brick red precipitate of Cu2O
In basic solution a ketose can be converted to an aldose
that can then react with Tollens or Benedictss reagent

 Carbohydrates with hemiacetal linkages are

reducing sugars because they react with Tollens

and Benedicts reagents
The hemiacetal form is in equilibrium with a
small amount of the aldehyde or ketone form,
which can react with Tollens and Benedicts
reagents
Carbohydrates with only acetal groups (glycosidic
linkages) do not react with these reagents and are
called non-reducing sugars
Acetals are not in equilibrium with the aldehyde
or ketone and so cannot react with these
reagents

Bromine Water:
The Synthesis of Aldonic Acids
Bromine in water selectively oxidizes the
aldehyde group of an aldose to the
corresponding carboxylic acid
An aldose becomes an aldonic acid

Nitric Acid Oxidation: Aldaric Acids

Dilute nitric acid oxidizes both the aldehyde
and primary hydroxyl groups of an aldose to
an aldaric acid

Periodate Oxidations: Oxidative Cleavage of

Polyhydroxy Compounds
Compounds with hydroxyl groups on adjacent
carbons undergo cleavage of carbon-carbon bonds
between the hydroxyl groups
The products are aldehydes, ketones or
carboxylic acids

With three or more contiguous hydroxyl groups,

the internal carbons become formic acid

Cleavage also takes place when a hydroxyl

group is adjacent to an aldehyde or ketone
group
An aldehyde is oxidized to formic acid; a
ketone is oxidized to carbon dioxide

No cleavage results if there are intervening

carbons that do not bear hydroxyl or carbonyl
groups

Reactions of Monosaccharides with

Phenylhydrazine: Osazones
An aldose or ketose will react with three
equivalents of phenylhydrazine to yield a
phenylosazone

Reaction of D-Glucose or D-Mannose with excess

phenylhydrazine yields the same phenylosazone.
Therefore, D-glucose and D-mannose differ in
configuration only at C2.
Compounds that differ in configuration at only one
stereogenic center are called epimers.

Synthesis and Degradation of Monosaccharides

Kiliani-Fischer Synthesis
The carbon chain of an aldose can be extended by:
Addition of cyanide to epimeric cyanohydrins
Hydrolysis to a mixture of epimeric aldonic acids
or aldonolactones
Reduction of the epimeric aldonic acids or
aldonolactones to the corresponding aldoses
For example, D-glyceraldehyde can be converted to
D-erythrose and D-threose by the Kiliani-Fischer
synthesis

 The Ruff Degradation

An aldose can be shortened by one carbon via:
Oxidation with bromine water to the aldonic acid
Oxidative decarboxylation with hydrogen
peroxide and ferric sulfate

Conversion of an aldose into its

epimer
CHO
H

OH

HO

OH

Br2/H2O

HO

CH2OH

HO

HO

OH

OH
CH2OH

D-Glucose

D-Gluconic acid

CHO
H

HO

H
H

OH
N

OH

HO

OH
CH2OH

COOH

COOH

Na/Hg H2O
pH 3-5

HO

HO

OH

OH
CH2OH

D-Mannose

Epimerization

OH

OH
CH2OH

D-Mannonic acid

HCl

lactonization

Conversion of a ketohexose into an

aldohexose
CH2OH
O
HO

OH

OH

NaBH4

HO

HO

or H2, Pt

HO

OH

OH

OH

Mannitol

controlled HO
oxidation by dil. H
nitric acid

HO

HO

H
O

HO

OH
CH2OH

OH
CH2OH

Na/Hg H2O
pH 3-5

HO

OH

OH

OH

OH
CH2OH

D-Gluconic acid
CHO

CHO
OH

HO

CH2OH

Glucocitol, or
Sorbitol

COOH

OH

CH2OH

CH2OH

COOH

OH

OH

D-Fructose

lactonization

CH2OH

HCl

CH2OH

CH2OH

HO

HO

HO

OH

OH
CH2OH

D-Mannose

OH
H

OH

OH
CH2OH

D-Glucose

Conversion of an aldohexose into

ketohexose
H

CHO
CH2OH
(CHOH)n
CH2OH

A ld o s e

3C6H5NHNH2

P h e n y lh y d r a z in e

CHO

NH C6H5
N

(CHOH)n
CH2OH

P h e n y lo s a z o n e

C6 H5

CHO
O

CH2OH

Zn/ Acetic acid

(CHOH)n

(CHOH)n

CH2 OH

CH2OH

O so ne

K e to se

Too much ..
Carbohydrate will be converted
into fat and stored under the
skin leading to weight gain!

TERIMAKASIH