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CARBOHYDRATES

BIO149

Prof. Ureah Thea A. Sevilla

Biological Functions of Carbohydrates

Generally, carbohydrates are the immediate sources of

energy
Carboydrates form structural tissues in plants and in
microorganisms ( e.g. cellulose, lignin, murein)

Other functions:
intermediates in the biosynthesis of other basic
biochemical entities (fats and proteins)
associated with other entities such as glycosides,
vitamins and antibiotics)
participate in biological transport, cell-cell recognition,
activation of growth factors, modulation of the immune
system

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CARBOHYDRATES
Considered as the most abundant biomolecule in
nature.
Most of carbohydrates consist of carbon, hydrogen
and oxygen in a 1:2:1 ratio (CH2O)n.
Carbohydrates are polyhydroxyaldehydes and
polyhydroxyketones.
Generally polar molecules.

CARBOHYDRATES
Classification
Monosaccharides
Simple

sugars: Aldoses and Ketoses

Oligosaccharides
Di,

tri, tetra, penta, up to 9 or 10

Most important are the disaccharides

Polysaccharides or glycans
Homopolysaccharides
Heteropolysaccharides
Complex

carbohydrates

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Enantiomers and Epimers

H

H
H

OH

OH

CH2OH

HO

HO

OH

HO

HO

OH

OH

HO

OH

OH

CH2OH

these two aldotetroses are enantiomers.

They are stereoisomers that are mirror
images of each other

CH2OH

CH2OH

these two aldohexoses are C-4 epimers.

they differ only in the position of the
hydroxyl group on one asymmetric carbon
(carbon 4)

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Aldoses- polyhydroxyaldehydes
H

(H

OH)n

CH2OH
Aldose

H
C

OH

CH2OH
Aldotriose
n=1

OH

OH

CH2OH
Aldotetrose
n=2

OH

OH

OH

OH

OH

OH

OH

CH2OH
Aldopentose
n=3

CH2OH
Aldohexose
n=4

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Ketoses - polyhydroxyketones
CH2OH

(H

OH)n

CH2OH

CH2OH
Ketose

OH

CH2OH
Ketotriose
n=0

CH2OH

CH2OH

CH2OH

Ketotetrose
n=1

CH2OH

OH

OH

OH

CH2OH

Ketopentose
n=2

OH
C

OH

CH2OH
Ketohexose
n=3

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Structure of a simple aldose and a simple ketose

Linear form:
FISCHER FORMULA
Ring form:
HAWORTH FORMULA

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Haworth projection formula

Cyclic form of aldose and ketose:
Furanose five-membered ring
Pyranose six-membered ring

Hemiacetal formation

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Anomers

Cyclization creates a carbon with two possible

orientations of the hydroxyl around it. We refer to
this carbon as the anomeric carbon and the two
possible forms as anomers.
The two possible configurations of the hydroxyl
group are called and , which correspond to the
hydroxyl being in the "down" and "up" positions,
respectively, in standard projections.

Stable sugar conformation

OH
H

H
OH H

OH

HO

OH
H

OH

OH

HO
HO

H
H

O
H
OH OH

*More stable conformation: Chair conformation

Constituents of the ring that project above or below the plane
of the ring are axial and those that project parallel to the
plane are equatorial.
In the chair conformation, the orientation of the hydroxyl
group about the anomeric carbon of a-D-glucose is axial and
equatorial in b-D-glucose.

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Monosaccharides as Reducing Agents

Glucose and other sugars are capable of reducing Fe+3 or Cu+2

and are called reducing sugars. Fehlings test is a quantitative test
to detect presence of reducing sugar (in diagnosis of diabetes
mellitus).

OXIDATION OF
ALDOSES

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O-Glycosidic Bond Formation

Condensation Reaction

Oligosaccharides

Most common are the disaccharides:

Sucrose, maltose, and lactose
Sucrose

hydrolyzes to a moledule of glucose and a molecule

of fructose
Maltose hydrolyzes to 2 molecules of D-glucose
Lactose hydrolyzes to a molecule of galactose and a
molecule of glucose

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Disaccharides

Sucrose

-D-glucopyranosyl-(12)--D-fructofuranoside
also known as tablet sugar
commercially obtained from sugar cane or sugar beet
hydrolysis yield glucose and fructose (invert sugar)
( sucrose: +66.5o ; glucose +52.5o; fructose 92o)
used pharmaceutically to make syrups, troches

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Maltose

2-glucose molecules joined via (1,4) linkage

known as malt sugar
produced by the partial hydrolysis of starch (either
salivary amylase or pancreatic amylase)
used as a nutrient (malt extract; Hordeum vulgare);
as a sweetener and as a fermentative reagent

Lactose

Lactose is the major sugar in mammalian milk.

-D-galactose joined to -D-glucose via (1,4)
linkage
milk contains the a and b-anomers in a 2:3 ratio
-lactose is sweeter and more soluble than ordinary
- lactose

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Lactose

Infants produce lactase to

hydrolyze the disaccharide to
monosaccharides.
Some adults have low levels of
lactase. This leads to lactose
intolerance. The ingested lactose
is not absorbed in the small
intestine, but instead is fermented
by bacteria in the large intestine,
producing uncomfortable volumes
of CO2.

Reducing end of oligosaccharides

To describe disaccharides or oligosaccharides, the

end of a chain that has a free anomeric carbon is
called the reducing end.

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Oligosaccharides

Trisaccharide: raffinose (glucose, galactose and

fructose)
Tetrasaccharide: stachyose (2 galactoses, glucose
and fructose)
Pentasaccharide: verbascose (3 galactoses, glucose
and fructose)
Hexasaccharide: ajugose (4 galactoses, glucose
and fructose)

Honey also contains glucose and fructose along with

some volatile oils

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Polysaccharides

homoglycans (starch, cellulose, glycogen, inulin)

heteroglycans (gums, mucopolysaccharides)
characteristics:

polymers (MW from 200,000)

White and amorphous products (glassy)
not sweet
not reducing (do not give the typical aldose or ketose reactions)
form colloidal solutions or suspensions

Molecular Weights of Polysaccharides

Homopolysaccharides Glycans
What is the Molecular weight of the resulting
polysaccharide when 100 glucose units are linked
together?

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Starch

most common storage polysaccharide in plants

composed of 10 30% -amylose and 70-90%
amylopectin depending on the source
the chains are of varying length, having molecular
weights from several thousands to half a million

Amylose and amylopectin are the 2 forms of starch. Amylopectin

is a highly branched structure, with branches occurring every 12
to 30 residues

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Starch in Plant Cell

suspensions of amylose
in water adopt a helical
conformation
iodine (I2) can insert in
the middle of the amylose
helix to give a blue color
that is characteristic and
diagnostic for starch

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Glycogen

also known as animal starch

stored in muscle and liver
present in cells as granules (high MW)
contains both (1,4) links and (1,6) branches at
every 8 to 12 glucose unit
complete hydrolysis yields glucose
glycogen and iodine gives a brown color
hydrolyzed by both and -amylases and by
glycogen phosphorylase

Glycogen in Animal Cell

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Cellulose

Polymer of -D-glucose attached by (1,4) linkages

Yields glucose upon complete hydrolysis
Partial hydrolysis yields cellobiose
Most abundant of all carbohydrates

Cotton flax: 97-99% cellulose

Wood: ~ 50% cellulose

Gives no color with iodine

Held together with lignin in woody plant tissues

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Inter- and Intra-chain Hydrogen Bonding of

Glucose in Cellulose

Structure of cellulose

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(in starch)

(in cellulose)

Products obtained from cellulose

Microcrystalline cellulose : used as binder-disintegrant

in tablets
Methylcellulose: suspending agent and bulk laxative
Oxidized cellulose: hemostat
Sodium carboxymethyl cellulose: laxative
Cellulose acetate: rayon; photographic film; plastics
Cellulose acetate phthalate: enteric coating
Nitrocellulose: explosives; collodion (pyroxylin)

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Chitin

chitin is the second most abundant

carbohydrate polymer
present in the cell wall of fungi and in the
exoskeletons of crustaceans, insects and spiders
chitin is used commercially in coatings (extends
the shelf life of fruits and meats)

Exoskeleton of butterfly.
Exoskeleton of Cicada.
Chitin used to make strong,
flexible surgical threads that
decomposes after the wound or
incision heal.

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Molting and
shedding off of
exoskeleton of
Cicada

Linear structures of cellulose and chitin

(2 most abundant polysaccharides)

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Dextrans

products of the reaction of glucose and the enzyme

transglucosidase from Leuconostoc mesenteroides
contains (1,4), (1,6) and (1,3) linkages
MW: 40,000; 70,000; 75,000
used as plasma extenders (treatment of shock)
also used as molecular sieves to separate proteins
and other large molecules (gel filtration
chromatography)
components of dental plaques

Dextrins

produced by the partial hydrolysis of starch along

with maltose and glucose
dextrins are often referred to as either
amylodextrins, erythrodextrins or achrodextrins
used as mucilages (glues)
also used in infant formulas (prevent the curdling of
milk in babys stomach)

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Glycosaminoglycans

they are the polysaccharide chains of proteoglycans

they are linked to the protein core via a serine or
threonine (O-linked)
the chains are linear (unbranched)
the glycosaminoglycan chains are long (over 100
monosaccharides)
they are composed of repeating disaccharides

Glycosaminoglycans
Involved in a variety of extracellular functions; chondroitin
is found in tendons, cartilage and other connective tissues

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Glycosaminoglycans
A characteristic of glycosaminoglycans is the presence
of acidic functionalities (carboxylate and/or sulfates)

Hyaluronic acid derivatives

several products are used in the management of

osteoarthritis symptoms
Hyalagan

and Synvisc

others are used as ophthalmic surgical adjuncts in

cataract extractions, intraocular lens implantation,
corneal transplant and retinal attachment surgery
(Healon, Amvisc, AMO Vitrax)

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Glycosaminoglycans

Pectins

pectins are heteropolysaccharides found in the pulp

of fruits (citrus, apples)
on hydrolysis pectins yield galacturonic acid,
galactose, arabinose, methanol and acetic acid
pectins are composed of galactans and arabans
used as gelling agents (to make jellies)

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Gums

widely used in the food and pharmaceutical industry

used as: suspending agents, gelling agents, thickening
agents, emulsifiers, foam stabilizers, crystallization
inhibitors, adhesives, binding agents
agar, tragacanth, karaya, carrageenan, guar gum,
gum arabic (acacia), furcellaran, sodium alginate,
locust bean gum

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Iranian gum tragacanth showing the spiny shrub.

A ribbon of gum exuding from the exposed upper taproot.
Powdered gum tragacanth.

Gum tragacanth

Bacterial cell wall

provide strength and rigidity for the organism

consists of a polypeptide-polysaccharide known as
petidoglycan or murein
determines the Gram staining characteristic of the
bacteria

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Structure of
peptidoglycan

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Cell wall of Gram-positive bacteria

Gram-negative bacteria

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Cross-section of the cell

wall of a gram-negative
organism such as E.coli

Lipopolysaccharide (LPS) coats the

outer membrane of Gram-negative
bacteria.
the lipid portion of the LPS is embedded
in the outer membrane and is linked to
a complex polysaccharide

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Glycosylated proteins

Usually done as a post-translational process

Proteins can contain either O-linked
oligosaccharides or N-linked oligosaccharides

Serine or threonine O-linked saccharides

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Aspargine N-linked glycoproteins

Oligosaccharides and Polysaccharides

as Cell Markers

Oligosaccharides play a role in cell recognition/ cell

identity.
Oligosaccharides form the blood group antigens. In
some cells, these antigens are attached as O-linked
glycans to membrane proteins. Alternatively, the
oligosaccharide may be linked to a lipid molecule to
form a glycolipid. These oligosaccharides determine the
blood group types in humans. There are actually 14
genetically characterized blood group systems with
more than 100 different blood group antigens.

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Oligosaccharides and Polysaccharides

as Cell Markers

Oligosaccharides and Polysaccharides

as Cell Markers

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References:
Voet and Voet, Biochemistry 2nd ed. Wiley
Publication (2004).
Starr and Taggart (2004). Biology. The Unity
and Diversity of Life, 10th edition, Wadsworth
Group, Thomson Learning, Inc., California
Lehninger, Nelson and Cox (1993). Principles of
Biochemistry, 2nd edition, Worth Publishers,
New York

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