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Lecture 9

Carbohydrates:
Polysaccharides and
Glycocojugates
Sugar acids
Oxidation of carbonyl group
generate aldonic acids while
C-6 oxidation results in
alduronic acids.
glucose  gluconate or
glucuronate D-gluconate cyclizes to D-glucono-δ-lactone

β-D-glucuronate
Number Monosaccharide or derivatives abbreviations

1 Ribose Rib
2 2-Deoxyribose dRib
3 Fructose Fru
4 Galactose Gal
5 Fucose (6-Deoxy-L-galactose) Fuc
6 Galactosamine GalN
7 N-Acetylgalactosamine GalNAc
8 Glucose Glc
9 Glucosamine GlcN
10 N-Acetylglucosamine GlcNAc
11 Glucuronic acid GlcUA/ GlcA
20 Iduronic acid IdoA
12 Mannose Man
13 Xylose Xyl
14 Ribose Rib
15 Ribulose Ribulo (or Rul)
16 Ribose 5-phosphate Rib5P
17 Muramic acid Mur
18 Neuraminic acid Neu
19 Rhamnose Rha
Reducing and non-reducing Oligosaccharides
Polysaccharides
1) homoglycans - homopolysaccharides composed on
one monosaccharide
2) Heteroglycans heteropolysaccharides made of more
than one type of monosaccharide

According to their biological role


•Storage Starch and glycogen
•Structural Chitin and cellulose
•Recognition Cell surface polysaccharides
Starch
• A plant storage polysaccharide
• Two forms: amylose and amylopectin
• Most starch is 10-30% amylose and 70-90% amylopectin
• Average amylose chain length 100 to 1000 residues polymerized by a-
1->4 links, one reducing end.
• Amylopectin is a branched polymer a-(1--> 6) branches of residues in
an a-(1 --> 4) linkage; overall between 300-6000 glucose residues,
with branches once every 25 residues; side chains are 15-25 residues
long. Many non-reducing ends and one reducing.
Amylose and Amylopectin
Starch
• Amylose is poorly soluble
in water, but forms
micellar suspensions
• In these suspensions,
amylose is helical
• Amylose reacts with iodine
to give dark blue complex.
While amylopectine gives a
red-violet color with
complex.
Starch hydrolysis
• α-amylase is an endoglycosidase (act on internal a-(1 --> 4)
glycosidic linkage). found in human saliva and also plants.
hydrolyzes the a (1--> 4) bond of amylose and amylopectin
randomly.
• β-amylase is an exoglycosidase (act on terminal a-(1 --> 4)
glycosidic linkage). Found in higher plants that hydrolyzes maltose
residues from non-reducing ends of amylopectin.
Amylase enzymes
Glycogen
• Glycogen is stored energy for animals
• Glycogen constitutes up to 10% of liver mass and 1-2%
of muscle mass
• Only difference from amylopictine: number of
branches residues. Alpha(1,6) branches every 8-12
residues containing as many as 50,000 glucose.
• Like amylopectin, glycogen gives a red-violet color with
iodine
glycogen
Cellulose
• Cellulose is the most abundant natural polymer on earth
• Cellulose is the principal strength and support of trees and plants
• Cellulose can also be soft and fuzzy - in cotton
• straight chain homoglycan of glucose with β-(1--> 4) linkages.
ranges in size from 300-15,000 glucose residues.
• β -linkages results extended conformation in which each glucose
residue is rotated 180° relative to its neighbors.
• Extensive H-bonding within and between cellulose chains. Makes
bundles or fibrils ---> rigid.
• Cellulose hydrolysis is catalysed by cellulase (β -glucosidase)
enzyme that is not present in human and other mammals. ruminant
(sheep and cows) have microorganisms in their rumen that produce
β -glucosidase, therefore they can obtain glucose from cellulose
rich grass and other plants.
Cellulose
Cellulose
•β-(1--> 4) linkages.

•Alternate residue rotation


180° relative to its neighbors

•Intrachain and Interchain H-


bonding allows multi-chain
interactions. Forms cable like
structures
Cellulose vs Amylose
amylose

cellulose

Glucose units rotated 180o relative to next residue


Chitin
• Exoskeletons of crustaceans, insects and spiders,
and cell walls of fungi CH2OH

• similar to cellulose, but instead of glucose uses OH O OH


N-acetyl glucosamine (C-2s are N-acetyl instead OH H
of –OH)
H H
• β-1->4 linked N-acetylglucosamine units H NH

• cellulose strands are parallel, chitins can be C O


parallell or antiparallel CH3
Chitin
Chitin vs Cellulose
Dextrans
• If you change the main linkages between glucose from
alpha(1,4) to alpha(1,6), you get a new family of
polysaccharides - dextrans
• Branches can be (1,2), (1,3), or (1,4)
• Dextrans formed by bacteria are components of dental
plaque
• Cross-linked dextrans are used as "Sephadex" gels in
column chromatography
Dextrans
Heteroglycans =
1) Proteoglycans
Glycoconjugates
• Complexes of polysaccharides called glycosaminoglycans and
core proteins.
• Found in extracellular matrix of connective tissues.
• Glycosaminoglycans are unbranched heteroglycans of repeating
disaccharide units. e.g. hyaluronic acid Found in cartilage and
synovial fluid = GlcNac + GlcA ß-(1-3)linkage.
• 1) Amino sugar, usually D-galactosamine or D-glucosamine with
acetyl group some times,
• 2) Alduronic acid such as glucuronic acid and iduronic acid.
*Specific hydroxyl and amino groups of many glycosaminoglycans
are sulphated. SO3- and COO- of alduronic acid make
glycosaminoglycans polyionic. highly hydrated
glycosaminoglycans
= GlcNac + GlcA
ß-(1-3)linkage

Every unit is composed


of uronic acid (D-GlcA
or L-IdoA) and amino
sugar (D-GalNAc or D-
GlcNH2). R, H or SO3- ;
R', H, COCH3 or SO3-.
Glycosaminoglycan Proteoglycans
chains covalently
bound by a
glycosidic linkage to
the OH oxygen of
ser residue
2) Peptidoglycans
Found in cell wall of bacteria = hetroglycan linked
cvalently to peptides
• The hetroglycan component Composed of
alternating residues of N-acetylglucosamine and N-
acetylmuramic acid joined by ß-(1--> 4) linkages.
• N-acetylmuramic is 9C sugar specific to bacteria =
lactate (3C) joined by ether linkage to C3 of
GlcNAc.
• The peptide component varies among bacteria
Peptidoglycans

*Compare between structures of heteroglycan component of the


peptidoglycans and chitin .
3) Glycoproteins
• Proteins with covalently oligosaccharides attached.
• Carbohydrate chains are from 1-30 residues in length. and
account 80% of total mass of the molecule.
• Extraordinteroarily groupe of proteins that could be
enzymes, hormones, structural proteins, transport proteins.
• Oligosacharide chaines exhibt great variability in
composition (unlike glycosaminoglycan)
• Found in eucaryotic cells.
• Can be attached to proteins with one of two configurations:
– O-linked - carbohydrate bonded to -OH of serine or threonine
– N-linked - carbohydrate (usually N-acetylglucosamine) linked to
asparagines.