KARBOHIDRAT

* Reaksi monosakarida
* Ikatan glikosida
* Fungsi karbohidrat
 KARBOHIDRAT

Karbohidrat adalah golongan senyawa organik,

polihidroksi aldehid atau polihidroksi keton, atau
senyawa lainnya apabila dihidrolisa dapat
menghasilkan kedua senyawa tersebut.
Karbohidrat berasal dari kata karbon (C) dan
hidrat (H2O). Karena molekul karbohidrat selalu
mempunyai perbandingan antara hidrogen dan
oksigen = 2 : 1 . Oleh karena itu rumus umum
karbohidrat adalah C12 (H2O)11, tetapi tidak
semua senyawa yang mempunyai perbandingan
 H : O = 2 : 1 adalah senyawa karbohidrat.
Contoh asam asetat mempunyai rumus C2H4O2
bukan termasuk karbohidrat.

Penggolongan Senyawa Karbohidrat

Berdasarkan susunan molekulnya, karbohidrat
dapat digolongkan menjadi tiga golongan
sebagai berikut :
1. Monosakarida
2. Disakarida / oligosakarida
3. Polisakarida
Monosakarida

Adalah golongan senyawa karbohidrat, yang

paling sederhana, yang tidak dapat dipecah lagi
menjadi gula yang lebih sederhana.
Berdasarkan gugus fungsionilnya,
monosakarida dapat digolongkan menjadi dua
golongan, masing- masing adalah aldose dan
ketose.
Berdasarkan jumlah atom C nya, monosakarida
dapat digolongkan menjadi empat golongan :
masing- masing adalah : Triose
(mengandung 3 atom C), Tetrose
(mengandung 4 atom C), Pentose
(mengandung 5 atom C), dan heksose
(mengandung 6 atom C.adapun secara
skematis penggolongan senyawa
karbohidrat seperti gambar skema berikut
:
 Monosakarida

 Memiliki atom karbon 3 sampai 6

 Setiap atom karbon memiliki gugus
hidroksil, keton atau aldehida.
 Setiap molekul monosakarida memiliki
1 gugus keton atau 1 gugus aldehida
 Gugus aldehida selalu berada di atom C
pertama
 Gugus keton selalu berada di atom C kedua
 Monosakarida
Aldosa (mis: glukosa) memiliki Ketosas (mis: fruktosa) biasanya
gugus aldehida pada salah satu memiliki gugus keto pada atom
ujungnya. C2.

H O
C CH2OH

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH

D-glucose D-fructose
 Notasi D vs L

Notasi D & L dilakukan CH O CH O

karena adanya atom C H C OH HO C H

dengan konfigurasi CH2OH CH2OH
asimetris seperti pada
D-gliseraldehida L-gliseraldehida
gliseraldehida.
CH O CH O
Penampilan dalam
H C OH HO C H
bentuk gambar
bagian bawah disebut CH2OH CH2OH
Proyeksi Fischer. D-glyceraldehyde L-gliseraldehida
 Penamaan Gula

Untuk gula dengan

atom C asimetrik lebih O H O H
dari 1, notasi D atau L C C
ditentukan oleh atom H – C – OH HO – C – H
C asimetrik terjauh HO – C – H H – C – OH
dari gugus aldehida H – C – OH HO – C – H
atau keto. H – C – OH HO – C – H
Gula yang ditemui di CH2OH CH2OH
alam adalah dalam D-glukosa L-glukosa

bentuk isomer D.
Gula dalam bentuk D O H O H
merupakan bayangan C C
cermin dari gula dalam H – C –OH HO – C – H
bentuk L. HO – C –H H – C – OH
Kedua gula tersebut H – C – OH HO – C – H
memiliki nama yang H – C – OH HO – C – H
sama, misalnya D- CH2OH CH2OH
glukosa & L-glukosa.
D-glukosa L-glukosa

Stereoisomers lainnya memiliki names yang unik,

misalnya glukosa, manosa, galaktosa, dll.
Jumlah stereoisomer adalah 2n, dengan n adalah jumlah
pusat asimetrik.
Aldosa dengan 6-C memiliki 4 pusat asimetrik, oleh
karenanya memiliki 16 stereoisomer (8 gula berbentuk D
dan 8 gula berbentuk L).
Pembentukan hemiasetal & hemiketal

Aldehida dapat H H
bereaksi
dengan alkohol C O + R' OH R' O C OH

membentuk R R
hemiasetal. aldehida alkohol hemiasetal

Keton dapat R R
bereaksi C O + "R OH "R O C OH
dengan alkohol
R' R'
membentuk keton alkohol hemiketal
hemiketal.
 1
CHO
Pentosa dan
heksosa dapat H C OH
2
membentuk struktur HO C H D-glukosa
3
siklik melalui reaksi (bentuk linier)
H C OH
gugus keton atau 4
aldehida dengan H
5
C OH
gugus OH dari atom CH2OH
6
C asimetrik terjauh.
6 CH2OH 6 CH2OH
Glukosa membentuk
5 5
hemiasetal intra- H O H H O OH
molekular sebagai H H
4 H 1 4 H 1
OH OH
hasil reaksi aldehida H
OH OH OH
dari C1 & OH dari 3 2 3 2

atom C5, dinamakan H OH H OH

cincin piranosa. a-D-glukosa b-D-glukosa

Penampilan dalam bentuk gula siklik disebut proyeksi Haworth.

 CH2OH
1

2C O

HO C
3
H
HOH2C 6 O 1 CH2OH
H C OH HO
4 5 H 2

H C OH H 4 3 OH
5
OH H
6 CH2OH

D-fruktosa (linear) a-D-fruktofuranosa

Fruktosa dapat membentuk

 Cincin piranosa, melalui reaksi antara gugus keto
atom C2 dengan OH dari C6.
 Cincin furanosa, melalui reaksi antara gugus keto
atom C2 dengan OH dari C5.
 6 C H2OH 6 C H OH
2
5 5 O
H O H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
a-D-glukosa b -D-glukosa

Pembentukan cincin siklik glukosa menghasilkan pusat

asimetrik baru pada atom C1. Kedua stereoisomer disebut
anomer, a & b.
Proyeksi Haworth menunjukkan bentuk cincin dari gula
dengan perbedaan pada posisi OH di C1 anomerik :
 a (OH di bawah struktur cincin)
 b (OH di atas struktur cincin).
 H OH H OH
4 6 H O H O
HO 5 HO
HO 2 H HO OH
3 H OH 1 H OH
H OH H H

a-D-glukopiranosa b-D-glukopiranosa

Karena sifat ikatan karbon yang berbentuk

tetrahedral, gula piranosa membentuk konfigurasi
“kursi" atau “perahu", tergantung dari gulanya.
Penggambaran konfigurasi kursi dari
glukopiranosa di atas lebih tepat dibandingkan
dengan proyeksi Haworth.
Turunan gula
COOH CH O

CH2OH H C OH H C OH

H C OH HO C H HO C H

H C OH H C OH H C OH

H C OH H C OH H C OH

CH2OH CH2OH COOH

D-ribitol Asam D-glukonat Asam D-glukuronat

 Gula alkohol – tidak memiliki gugus aldehida atau ketone;

misalnya ribitol.
 Gula asam –gugus aldehida pada atom C1, atau OH pada
atom C6, dioksidasi membentuk asam karboksilat;
misalnya asam glukonat, asam glukuronat.
Oksidasi gula aldehida
H O
C CO O H
H C OH H C OH

HO C H
Oksidator
HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2 O H

D-glucose Asam D-glukonat

 Oksidasi gula aldehida
 Gula yang dapat dioksidasi adalah senyawa
pereduksi. Gula yang demikian disebut
sebagai gula pereduksi.
 Senyawa yang sering digunakan sebagai
pengoksidasi adalah ion Cu+2, yang
berwarna biru cerah, yang akan tereduksi
menjadi ion Cu+, yang berwarna merah
kusam. Hal ini menjadi dasar bagi pengujian
Benedict yang digunakan untuk
menentukan keberadaan glukosa dalam
urin, suatu pengujian bagi diagnosa
diabetes.
 Oksidasi gula aldehida
panas & alk . pH
Glukosa + Cu++
Gluconic acid + Cu2O (Cu2O is insol ppt)
glukosa oksidase
Glukosa + O2
Asam glukonat + H2O2
(H2O2 nya diukur)
heksokinase
Glukosa + ATP

Glukosa-6-P + ADP (G-6-Pnya diukur)

Turunan gula
CH2OH CH 2OH

H O H H O H
H H
OH H OH H

OH OH OH O OH
H NH 2 H N C CH 3
H
a-D-glukosamina a-D-N-asetilglukosamina

Gula amino - gugus amino menggantikan

gugus hidroksil. Sebagai contoh glukosamina.
Gugus amino dapat mengalami asetilasi,
seperti pada N-asetilglukosamina.
 Ikatan Glikosida
Gugus hidroksil anomerik dan gugus hidroksil gula atau
senyawa yang lain dapat membentuk ikatan yang disebut
ikatan glikosida dengan membebaskan air :
R-OH + HO-R'  R-O-R' + H2O
Misalnya methanol bereaksi dengan gugus OH anomerik dari
glukosa membentuk metil glukosida (metil-glukopiranosa).

H OH H OH
H O H2O H O
HO HO
HO H + CH3- OH HO H
H OH H OH
H OH H OCH3
a-D-glukopiranosa metanol Metil-a-D-glukopiranosa
 6 CH2OH 6 CH2OH

Disaccharides: H
5 O H H
5 O H
H H
Maltose, a cleavage 4 OH H 1 4
OH H 1

product of starch OH 3 2
O
3 2
OH

(e.g., amylose), is a H OH
maltose H OH

disaccharide with an
a(1 4) glycosidic 6 CH2OH

5
6 CH2OH

O 5 O OH
link between C1 - C4 H
H
H
H
OH of 2 glucoses. 4
OH H 1 O 4
OH H 1

H
It is the a anomer OH H
3 2 3 2

H OH H OH
(C1 O points down). cellobiose
Cellobiose, a product of cellulose breakdown, is the
otherwise equivalent b anomer (O on C1 points up).
The b(1 4) glycosidic linkage is represented as a
zig-zag, but one glucose is actually flipped over
Other disaccharides include:
 Sucrose, common table sugar, has a glycosidic
bond linking the anomeric hydroxyls of glucose &
fructose.
Because the configuration at the anomeric C of
glucose is a (O points down from ring), the linkage
is a(12).
The full name of sucrose is a-D-glucopyranosyl-
(12)-b-D-fructopyranose.)
 Lactose, milk sugar, is composed of galactose &
glucose, with b(14) linkage from the anomeric
OH of galactose. Its full name is b-D-
 Polysaccharides
CH2OH 6CH OH CH2OH CH2OH CH2OH
2
O 5 O H O H O H H O H
H H H H H
H H H H H
OH H 1 4 OH H 1 OH H OH H OH H
O O O O OH
OH 2
3
H OH H OH H OH H OH H OH
amylose

Plants store glucose as amylose or amylopectin,

glucose polymers collectively called starch. Glucose
storage in polymeric form minimizes osmotic effects.
Amylose is a glucose polymer with a(14) linkages.
It adopts a helical conformation.
The end of the polysaccharide with an anomeric C1
not involved in a glycosidic bond is called the
reducing end.
 CH2OH CH2OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH2OH CH2OH 6 CH2 CH2OH CH2OH

H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH
3 2
H OH H OH H OH H OH H OH

Amylopectin is a glucose polymer with mainly a(14)

linkages, but it also has branches formed by a(16)
linkages. Branches are generally longer than shown
above.
The branches produce a compact structure & provide
multiple chain ends at which enzymatic cleavage can
 CH2OH CH2OH
H O O
glycogen
H H H
H H
OH H OH H 1
O
OH
O
H OH H OH

CH2OH CH2OH 6 CH2 CH2OH CH2OH

H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH 2
3
H OH H OH H OH H OH H OH

Glycogen, the glucose storage polymer in animals,

is similar in structure to amylopectin. But glycogen
has more a(16) branches.
The highly branched structure permits rapid release
of glucose from glycogen stores, e.g., in muscle
during exercise. The ability to rapidly mobilize
glucose is more essential to animals than to plants.
 CH2OH 6CH OH CH2OH CH2OH CH2OH
2
O 5 O O H O H O OH
H H H
H H H H H
OH H 1 O 4 OH H 1 O OH H O OH H O OH H
OH H H H
H 2 H
3
H OH H OH H OH H OH H OH
cellulose
Cellulose, a major constituent of plant cell walls,
consists of long linear chains of glucose with
b(14) linkages.
Every other glucose is flipped over, due to the b
linkages.
This promotes intra-chain and inter-chain H-bonds
and
van der Waals interactions, that
cause cellulose chains to be
straight & rigid, and pack with a
crystalline arrangement in thick Schematic of arrangement of
cellulose chains in a microfibril.
 CH2OH 6CH OH CH2OH CH2OH CH2OH
2
O 5 O O H O H O OH
H H H
H H H H H
OH H 1 O 4 OH H 1 O OH H O OH H O OH H
OH H H H
H 2 H
3
H OH H OH H OH H OH H OH
cellulose

Multisubunit Cellulose Synthase complexes in the

plasma membrane spin out from the cell surface
microfibrils consisting of 36 parallel, interacting
cellulose chains.
These microfibrils are very strong.
The role of cellulose is to impart strength and rigidity
to plant cell walls, which can withstand high
hydrostatic pressure gradients. Osmotic swelling is
prevented.
Tabel : Beberapa Uji Karbohidrat

--------------------------------------------------------------------------------------------
Jenis KH : Molisch : Fehling/Benedict : Fermentasi
--------------------------------------------------------------------------------------------
Glukose : + : + : +
Galaktosa : + : + : -
Fruktosa : + : - : +
Laktosa : + : + : -
Sukrose : + : - : +
Maltosa : + : + : +
Pati : + : - : -
Glikogen : + : - : +
 CH 2OH
D-glucuronate 6
 H 5 O
6COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NHCOCH 3
3 2 O
H OH N-acetyl-D-glucosamine
hyaluronate

Glycosaminoglycans (mucopolysaccharides) are

polymers of repeating disaccharides.
Within the disaccharides, the sugars tend to be
modified, with acidic groups, amino groups, sulfated
hydroxyl and amino groups, etc.
Glycosaminoglycans tend to be negatively
charged, because of the prevalence of acidic
 CH 2OH
D-glucuronate 6
 H 5 O
6COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NHCOCH 3
3 2 O
H OH N-acetyl-D-glucosamine
hyaluronate

Hyaluronate is a glycosaminoglycan with a

repeating disaccharide consisting of 2 glucose
derivatives, glucuronate (glucuronic acid) & N-acetyl-
glucosamine.
The glycosidic linkages are b(13) & b(14).
 CH 2OH
D-glucuronate 6
 H 5 O
6COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NHCOCH 3
3 2 O
H OH N-acetyl-D-glucosamine
hyaluronate

Proteoglycans are glycosaminoglycans that are

covalently linked to specific core proteins.
Some proteoglycans of the extracellular matrix in
turn link non-covalently to hyaluronate via protein
domains called link modules.
 CH 2OH
D-glucuronate 6
 H 5 O
6COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NHCOCH 3
3 2 O
H OH N-acetyl-D-glucosamine
hyaluronate

For example, in cartilage multiple copies of the

aggrecan proteoglycan bind to an extended
hyaluronate backbone to form a large complex.
Versican, another proteoglycan that binds to
hyaluronate, is in the extracellular matrix of loose
connective tissues.
See web sites on aggrecan and aggrecan plus
 iduronate-2-sulfate N-sulfo-glucosamine-6-sulfate
H CH2OSO3

H O H O H
COO H
OH H O OH H
H O

H OSO3 H NHSO3
heparin or heparan sulfate - examples of residues

Heparan sulfate is initially synthesized on a

membrane-embedded core protein as a polymer of
alternating N-acetylglucosamine and
glucuronate residues.
Later, in segments of the polymer, glucuronate
residues may be converted to the sulfated sugar
iduronic acid, while N-acetylglucosamine residues
 PDB 1RID

Heparin, a soluble
glycosaminoglycan found in
granules of mast cells, has a
structure similar to that of heparan
sulfates, but is more highly
sulfated.
When released into the blood, it
inhibits clot formation by interacting heparin: (IDS-SGN)5
with the protein antithrombin. C O N S

Heparin has an extended helical

Charge repulsion by the many negatively charged
conformation.
groups may contribute to this conformation.
Heparin shown has 10 residues, alternating IDS
(iduronate-2-sulfate) & SGN (N-sulfo-glucosamine-6-
 heparan sulfate
core glycosaminoglycan
protein

transmembrane
a-helix
cytosol

Some cell surface heparan sulfate

glycosaminoglycans remain covalently linked to
core proteins embedded in the plasma membrane.
Proteins involved in signaling & adhesion at the
cell surface recognize and bind segments of
heparan sulfate chains having particular patterns
of sulfation.
 CH2OH C O
O O CH2 CH
Oligosaccharides H
that are covalently
H NH serine
OH H residue
attached to OH O H
proteins or to H HN C CH3
membrane lipids
b-D-N-acetylglucosamine
may be linear or
branched chains.
O-linked oligosaccharide chains of glycoproteins
vary in complexity.
They link to a protein via a glycosidic bond between
a sugar residue & a serine or threonine OH.
O-linked oligosaccharides have roles in
recognition, interaction, and enzyme regulation.
 CH2OH C O

H O O CH2 CH
H NH serine
OH H residue
OH O H
H HN C CH3

b-D-N-acetylglucosamine

N-acetylglucosamine (GlcNAc) is a common O-

linked glycosylation of protein serine or threonine
residues.
Many cellular proteins, including enzymes &
transcription factors, are regulated by reversible
GlcNAc attachment.
Often attachment of GlcNAc to a protein OH
 CH2OH O HN

H O HN C CH2 CH Asn
H
H C O
OH
H HN
OH
HC R X
H HN C CH3
C O
O
N-acetylglucosamine HN

Initial sugar in N-linked

HC R Ser or Thr
glycoprotein oligosaccharide C O

N-linked oligosaccharides of glycoproteins tend to

be complex and branched. First N-
acetylglucosamine is linked to a protein via the
side-chain N of an asparagine residue in a
 NAN NAN NAN

Gal Gal Gal

NAG NAG NAG

Man Man N-linked oligosaccharide

Man Key:
NAN = N-acetylneuraminate
NAG Gal = galactose
NAG = N-acetylglucosamine
NAG Fuc
Man = mannose
Fuc = fucose
Asn

Additional monosaccharides are added, and the N-

linked oligosaccharide chain is modified by removal
and addition of residues, to yield a characteristic
branched structure.
Many proteins secreted by cells have attached N-
linked oligosaccharide chains.
Genetic diseases have been attributed to deficiency
of particular enzymes involved in synthesizing or
modifying oligosaccharide chains of these
glycoproteins.
Such diseases, and gene knockout studies in mice,
have been used to define pathways of modification
of oligosaccharide chains of glycoproteins and
glycolipids.
Carbohydrate chains of plasma membrane
glycoproteins and glycolipids usually face the
outside of the cell.
Lectins are glycoproteins that recognize and
bind to specific oligosaccharides. A few
examples:
 Concanavalin A and wheat germ agglutinin
are plant lectins that have been useful
research tools.
 Mannan-binding lectin (MBL) is a
glycoprotein found in blood plasma.
It associates with cell surface carbohydrates
of disease-causing microorganisms, promoting
phagocytosis of these organisms as part of the
Selectins are integral selectin
lectin domain
proteins of mammalian
cell plasma membranes
with roles in cell-cell
recognition & binding. outside
transmembrane
A lectin-like domain is at a-helix
the end of an extracellular cytosol cytoskeleton
segment that extends out binding domain
from the cell surface.
A cleavage site just outside the transmembrane a-
helix provides a mechanism for regulated release of
some lectins from the cell surface.
A cytosolic domain participates in regulated
interaction with the actin cytoskeleton.
Pretest
1. Jelaskan perbedaan antara aldosa dan
ketosa
Pretest
2. Ubahlah rumus senyawa di bawah ini menjadi suatu
proyeksi Fischer!

CH2OH

C O

HO C H

H C OH

H C OH (b)

CH2OH
(a)
D-fructose
Pretest
3. (a) Jelaskan perbedaan kedua struktur dibawah ini
berdasarkan system D dan L!

(b) Pada system D dan L, D dan L merupakan

singkatan dari?
Pretest
4. Sebutkan dan jelaskan klasifikasi dari
karbohidrat
Pretest
5. Sebutkan dan jelaskan klasifikasi dari
monosakarida