KARBOHIDR

AT

Week 2
Anna Safitri
POLISAKARIDA
• Energy Storage
• Starch: a-amylose and amylopectin
• Glygogen
• Structural
• Cellulose and Chitin
• Glycosaminoglycans
• Proteoglycans
Pati/starch
• Pati merupakan homopolimer glukosa dengan ikatan alfa-glikosidik.
• Berbagai macam pati tidak sama sifatnya, tergantung dari panjang
rantai C-nya, serta apakah lurus atau bercabang rantai molekulnya.
• Pati terdiri dari dua fraksi yang dapat dipisahkan dengan air panas.
• Fraksi terlarut disebut amilosa (20%) dan fraksi tidak terlarut disebut
amilopektin (80%).
• Amilosa mempunyai struktur lurus sedang amilopektin mempunyai
cabang.
 • AMILOSA

CH 2 OH 6 CH OH CH 2 OH CH 2 OH CH 2 OH
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
am ylo se
Amylose is a glucose polymer with a-(14) linkages.
The end of the polysaccharide with an anomeric C1 not
involved in a glycosidic bond is called the reducing end.
 CH 2OH CH 2 OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH 2OH CH 2OH 6 CH 2 CH 2OH CH 2OH

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

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 occur.
Perbedaan amilosa dan amilopektin
• Amilosa Amilopektin
• -Polimer rantai lurus -Polimer bercabang
• -Lebih mudah larut dalam air -Tidak larut dalam air
• -Larut dalam air panas, -Larut dalam air
panas,
• tidak membentuk gel/pasta -membentuk gel/pasta
• -Penyusun pati 20% -Penyusun pati 80%
• -Dengan tes iodine, biru -Dengan tes iodine,
merah-ungu
GLIKOGEN
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.
Glikogen

• Glikogen merupakan “pati hewan”, banyak

terdapat pada hati dan otot bersifat larut dalam
air, serta bila bereaksi dengan iodin akan
berwarna merah.
• Glikogen juga telah berhasil diisolasi dari benih
jagung (sweet corn).
• Glikogen disimpan dalam hati hewan sebagai
cadangan energi yang sewaktu-waktu dapat
diubah menjadi glukosa.
 CH 2 OH CH 2 OH
O O
glycogen
H H H H
H H
OH H OH H 1
O
OH
O
H OH H OH

CH 2 OH CH 2 OH 6 CH 2 CH 2 OH CH 2 OH
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

CH 2OH CH 2 OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH 2OH CH 2OH 6 CH 2 CH 2OH CH 2OH

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
• Branches in amylopectin every 12-30 residues

• Branches in glycogen every 8-12 residues

 Storage Polysaccharides

EOC Problem 20: How long can a game bird fly using its
muscle glycogen? To solve this assume you have 1 gram
of muscle tissue.
Glycogen and Starch…almost all α 1,4

Glycogen and
Amylopectin have
α 16 branches
Two cartoons of Amylopectin
SELULOSA
CH 2 OH 6 CH OH CH 2 OH CH 2 OH CH 2 OH
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
c e llu lo s e

a major constituent of plant cell walls, consists of long linear

chains of glucose with b(1®4) linkages.
Cellulose is the most abundant natural polymer on earth
• Selulosa merupakan serat-serat panjang yang
bersama-sama hemiselulosa, pektin, dan protein
membentuk struktur jaringan yang memperkuat
dinding sel tanaman.
• Turunan selulosa yang dikenal dengan carboxymethyl
cellulose (CMC) sering dipakai dalam industri
makanan untuk mendapatkan tekstur yang baik.
Misalnya pada pembuatan es krim, pemakaian CMC
akan memperbaiki tekstur dan kristal laktosa yang
terbentuk akan lebih halus.
KITIN
• Chitin - exoskeletons of crustaceans, insects and spiders, and cell walls
of fungi

• similar to cellulose, but C-2s are N-acetyl

Chitin – What are the modifications from cellulose?
KITIN
Agarose
HETEROPOLISAKARIDA
 Glycosaminoglycans (GAGs)

Glycosaminoglycans are polymers of repeating disaccharides

(heteropolisakarida)
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 groups.
GAGs are located primarily on the surface of cells or in the
extracellular matrix (ECM) but are also found in secretory
vesicles in some types of cells.
Jenis-jenis Glycosaminoglycans (GAGs)
 HYALURONATE
 CHONDROTIN SULFATE
 HEPARAN DAN HEPARIN SULFATE
 DERMATAN SULFATE
 KERATIN SULFATE
Hyaluronate is a glycosaminoglycan with a repeating
disaccharide consisting of 2 glucose derivatives, D-
glucuronate (glucuronic acid) & N-acetyl-glucosamine.
The glycosidic linkages are b(1®3) & b(1®4).
It is unique among the GAGs in that it does not contain
any sulfate
Hyaluronate is the largest polysaccharides produced by
vertebrate cells.
Molecular weight : 100,000–10,000,000
N-acetyl glucosamine
DERMATAN SULFATE

may function in coagulation, wound repair, fibrosis, and

infection;
KERATAN SULFATE

usually associated with protein forming

proteoglycans
HEPARIN DAN HEPARAN SULFATE

heparans have less overall sulfate than heparins

JUMLAH SULFAT DI HEPARIN >>> HEPARAN
Proteoglycans are glycosaminoglycans that are covalently
linked to specific core proteins.
The linkage of GAGs to the protein core, in most but not all
proteoglycans, involves a specific tetrasaccharide linker (link
modules) composed of a glucuronic acid (GlcA) residue, two
galactose (Gal) residues, and a xylose (Xyl) residue forming a
structure such as: GAG(n)–GlcA–Gal–Gal–Xyl–Ser–protein.
The tetrasaccharide linker is coupled to the protein core
through an O-glycosidic bond to a Ser or Thr residue in
the protein
Peptidoglycan Has Interpeptide Bridges
Syndecan – Human Membrane Core
Protein

Heparan is the same as

Heparin with a few less
sulfonates.
S-domains have 4 Functions
EOC Problem 23 has a good question about how heparin
(which is not heparin) binds to antithrombin and
demonstrates why clinical plastic and glassware is often
coated with heparin.
Extracellular Matrix Proteolgycan

Atomic Force
Microscopy
Carbohydrate Linkages to Protein
Gram Negative Bacterial Lipopolysaccharide
UJI-UJI PADA KARBOHIDRAT
• UJI KUALITATIF
UJI MOLISCH
UJI SALIWANOFF
UJI BARFOED
UJI BENEDICT
UJI IODIN/STARCH TEST
UJI MOLISCH
– Prinsip reaksi ini adalah dehidrasi senyawa karbohidrat oleh asam sulfat pekat.
– Dehidrasi heksosa menghasilkan senyawa hidroksi metil furfural, sedangkan
dehidrasi pentosa menghasilkan senyawa fulfural.

– Uji positif jika timbul cincin merah ungu yang merupakan kondensasi antara
furfural atau hidroksimetil furfural dengan alpha-naftol dalam pereaksi
molish.
UJI SALIWANOFF
• merupakan uji spesifik untuk karbohidrat yang
mengandung gugus keton atau disebut juga
ketosa
– Jika dipanaskan karbohidrat yang
mengandung gugus keton akan menghasikan
warna merah pada larutannya.
UJI SALIWANOFF
UJI BARFOED

• Digunakan untuk menunjukkan adanya monosakarida dalam

sampel
– Uji positif ditunjukkan dengan terbentuknya endapan
merah orange
UJI IODINE
• – Digunakan untuk menunjukkan adanya polisakarida
– Amilum dengan iodine dapat membentuk kompleks biru
– Amilopektin dengan iodin akan memberi warna merah ungu
– sedangkan dengan glikogen dan dekstrin akan membentuk warna
merah coklat
 Sugar derivatives
• Sugar alcohols: mild reduction of sugars
• Deoxy sugars: constituents of DNA, etc.
• Sugar esters: phosphate esters like ATP are
important
• Amino sugars contain an amino group in place of
a hydroxyl group
• Acetals, ketals and glycosides: basis for oligo-
and poly-saccharides
Sugar Alcohol

• Also called polyhydricalcohols,

polyalcohols, alditols or glycitols
 Have the general formula HOCH2(CHOH)nCH2OH
 Unlike sugars, which tend to exist as rings, sugar alcohols do not
Sugar alcohol
DEOXY SUGAR
• are sugar derivatives that are lacking
-OH hydroxyl group at the 2'-Carbon of the sugar cyclic ring,
hence "deoxy,"
de- being a prefix meaning "to remove," and "oxy" representing
"oxygen."
SUGAR ESTER

• ester of a sugar with an organic or inorganic

acid, for example, D-glucose 6-phosphate.
Amino Sugars
A sugar that contains an -NH2 group in place of an -OH group.
• Only three amino sugars are common in nature
• N-Acetyl-D-glucosamine is a derivative of D-glucosamine.
CHO CHO CHO CHO O
H NH2 H2 N 2 H H NH2 H NHCCH3
HO H HO H HO H HO H
4
H OH H OH HO H H OH
H OH H OH H OH H OH
CH2 OH CH2 OH CH2 OH CH2 OH
D-Glucosamine D-Mannosamine D-Galactosamine N-Acetyl-D-
glucosamine
Acetals, ketals and glycosides

Hemi-acetal acetal

Hemi-acetal Acetal
A glycoside
Modified Sugars
 ENANTIOMER PROPERTIES
• The physical properties of D and L enantiomers are
generally the same.
• D and L enantiomers rotate polarized light in equal, but
opposite directions.
• The enantiomer that rotates
ENANTIOMER polarized light(continued)
PROPERTIES to the left is the levorotatory
or (-) enantiomer.
• The enantiomer that rotates it to the right is the dextrorotatory or (+)
enantiomer.

• The D and L designations do not represent dextrorotatory and

levorotatory.

• The property of rotating the plane of polarized light is called optical

activity, and the molecules with this property are said to be optically
active.

• Measurements of optical activity are useful for differentiating between

enantiomers.
• InENANTIOMER PROPERTIES
some instances, only (continued)
the D or L enantiomers are found in
nature.
• If both D and L forms are found in nature, they are rarely
found together in the same biological system.

• For example:
• Carbohydrates and amino acids are chiral.
• Humans can only metabolize the D-isomers of
monosaccharides.
• Most animals are only able to utilize the L-isomers of
amino acids to synthesize proteins.
 • Besarnya sudut putar (α) atau sudut rotasi
bergantung pd jenis senyawa, suhu, λ cahaya
yg terpolarisasi, dan banyaknya molekul yg
dilalui cahaya.
• Rotasi spesifik : rotasi yg dihasilkan oleh 1,00
gram senyawa dalam 1,00 mL larutan dalam
suatu sel sepanjang 1,00 dm pada T dan λ yg
ditentukan
• Rumus Rotasi spesifik suatu senyawa pada
suhu 20 C adalah

[α] 20D = α
l xc
[α] 20D = rotasi spesifik memakai cahaya D
natrium pada suhu 20 C
α = sudut rotasi yg diamati pada polarimeter
l = panjang sel dalam dm
c = konsentrasi larutan dlm gram/mL
Rotasi spesifik beberapa gula
• D fruktosa : - 92,4
• D galaktosa : + 80,2
• L arabinose : + 104,5
• D manosa : + 14,2
• D xilosa : + 18,8

Perhatikan D tdk selalu +, dan L tdk selalu -

MUTAROTATION OF GLUCOSE
• When -D-(+)-glucose is dissolved in water, the specific rotation
of the sample decreases from a value of +112 to a value of
+53.
• The specific rotation of 112 corresponds to -D-(+)-glucose.
• The specific rotation of +53 corresponds to an equilibrium
mixture of -D-(+)-glucose and -D-(+)-glucose.
• A change in the optical rotation of freshly prepared solutions of
sugars is called mutarotation
Mutarotation
• Mutarotation: The change in specific rotation that occurs when an 
or  form of a carbohydrate is converted to an equilibrium mixture of
the two.
[] after % Present at
Monosaccharide [] Mutarotation Equilibrium
-D-glucose +112.0 +52.7 36
-D-glucose +18.7 +52.7 64

-D-galactose +150.7 +80.2 28

-D-galactose + 52.8 +80.2 72

CH2 OH CH2 OH
HO O HO O
HO HO
OH ( )
OH HO
-D-Glucopyranose OH ( )
25 -D-Glucopyranose
[] D + 18.7 25
[] D +112
• The forms of glucose involved in mutarotation are the
open chain form and two cyclic forms, which are in
equilibrium

CH2OH CH2OH CH2OH

HO HO HO
O OH O
HO HO HO
H
OH
HO HO HO

OH O
-D-glucose Open-chain form -D-glucose
m.p. 146C,  = +112 m.p. 150C,
 = +19
• If either cyclic compound is dissolved in water,
the specific rotation changes to +53.
• The specific rotation decreases from +112 to
+53 when -D-(+)-glucose is dissolved in
water and increases from +19 to +53 when
-D-(+)-glucose is dissolved in water.
• The mutarotation of glucose is acid-catalyzed
and proceeds rapidly at a pH of 7.