BIOCHEMISTRY 1
2nd Lecture
CARBOHYDRATE
Structure and functions
Chemistry Education Department-UPI
Biochemistry
Why do we need carbohydrate?
To give us energy
Biochemistry
Cx(H2O)y
Hydrated carbon!
Carbohydrates (glycans) have the following
basic composition:
(CH2O)n
I
or H - C - OH
I
Biochemistry
Carbohydrates
Many carbohydrates are soluble in water.
The usual chemical test for the simpler
carbohydrates is heating with Benedicts
solution.
The formula for a carbohydrate is
(CH2O)n
The n represents the number of times the
CH2O unite is repeated.
Biochemistry
They are of major importance to both plants and
animals. More that half of all organic carbon
atoms in the world are in carbohydrate
molecules.
They are made by chlorophyll-containing plants
in the process of photosynthesis.
6CO2 + 6H2O C6H12O6 + 6O2
Our bodies use carbohydrates for energy and
also as a source of carbon atoms for the
synthesis of many other compounds.
Carbon Cycles
6CO2 + 6H2O
C6H12O6+ 6O2
CO2
C6H12O6+ 6O2
C6H12O6+ 6O2
6CO2 + 6H2O
Biochemistry
They are polyhydroxy aldehydes or ketones, or
compounds that yield polyhydroxy aldehydes or
ketones on hydrolysis.
They Are Split Into Three Groups Known As:
Monosaccharides (Monomers) Oligosaccharides Polysaccharides (Polymers) -
Biochemistry
Classification of carbohydrates
Monosaccharides (monoses or glycoses)
simple sugars with multiple OH groups. Based on number of carbons (3, 4, 5, 6),
a monosaccharide is a triose, tetrose, pentose or hexose.
Oligosaccharides
a few monosaccharides covalently linked.
di, tri, tetra, penta, up to 9 or 10
Most important are the disaccharides
Polysaccharides or glycans
polymers consisting of chains of monosaccharide or disaccharide units.
Homopolysaccharides
Heteropolysaccharides
Complex carbohydrates
Biochemistry
Monosaccharides
also known as simple sugars
classified by
1. the number of carbons and
2. whether aldoses or ketoses
most (99%) are straight chain compounds
D-glyceraldehyde is the simplest of the aldoses (aldotriose)
all other sugars have the ending ose (glucose, galactose,
ribose, lactose, etc)
Biochemistry
Aldose sugars
H
(H
OH)n
CH2OH
Aldose
H
C
OH
CH2OH
Aldotriose
n=1
OH
OH
CH2OH
OH
Aldotetrose
n=2
OH
OH
OH
OH
OH
OH
CH2OH
Aldopentose
n=3
CH2OH
Aldohexose
n=4
Biochemistry
Ketose sugars
CH2OH
(H
OH)n
CH2OH
C
CH2OH
CH2OH
Ketose
OH
CH2OH
Ketotriose
n=0
CH2OH
CH2OH
Ketotetrose
n=1
CH2OH
OH
OH
OH
CH2OH
Ketopentose
n=2
OH
C
OH
CH2OH
Ketohexose
n=3
Biochemistry
Structure of a simple aldose and ketose
Biochemistry
CONCEPTS OF ISOMERS
Two or more different compounds which contain the
same number and types of atoms and the same
molecular weights.
Projection formula (spatial arrangement to represent 3dimensional structure):
Biochemistry
D vs L Designation
D & L designations are based
on the configuration about the
single asymmetric C in
glyceraldehyde.
The lower representations are
Fischer Projections.
CHO
CHO
H
OH
HO
L-glyceraldehyde
CHO
H
OH
CH2OH
D-glyceraldehyde
CH2OH
CH2OH
D-glyceraldehyde
CHO
HO
CH2OH
L-glyceraldehyde
Biochemistry
Sugar Nomenclature
For sugars with more than one
chiral center, D or L refers to the
asymmetric C farthest from the
aldehyde or keto group.
Most naturally occurring sugars
are D isomers.
C
H C OH
HO C H
H C OH
H C OH
CH2OH
D-glucose
C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose
Biochemistry
Biochemistry
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)
Biochemistry
Sugar Properties
Differences in structures of sugars are responsible
for variations in properties
Physical
Crystalline form; solubility; rotatory power
Chemical
Reactions (oxidations, reductions, condensations)
Physiological
Nutritive value (human, bacterial); sweetness;
absorption
Biochemistry
Structural representation of sugars
Fisher projection: straight chain representation
Haworth projection: simple ring in perspective
Conformational representation: chair and boat
configurations
Biochemistry
Biochemistry
Biochemistry
Cyclic Structure of Monosaccharides
Hemiacetal Formation
anomer
anomer
The specific rotation of pure -D-glucose or -D-glucose
changes over time to reach an equilibrium (mutarotation)
Biochemistry
Hemiacetal & hemiketal formation
H
An aldehyde can
react with an
alcohol to form a
hemiacetal.
A ketone can react
with an alcohol to
form a hemiketal.
H
O
R'
OH
R'
OH
aldehyde
alcohol
hemiacetal
R
C
R
O
"R
OH
R'
ketone
"R
C
R'
alcohol
hemiketal
OH
Biochemistry
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 6member 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.
Biochemistry
On the same
side as
attacking OH, is
-anomer!
On the opposite
side as
attacking OH, is
-anomer!
Intramolecular hemiacetal formation results in two C(1)
stereoisomers called anomers.
Biochemistry
Ring Formation (Glucose)
These are all Glucose
Memorize this structure
Biochemistry
Biochemistry
Biochemistry
Biochemistry
Biochemistry
Reactions of monosaccharides
Carbonyl reactions:
Osazone formation
Cyanohydrin reaction
Reduction
Oxidation
Action of base
Action of acid
Ring chain tautomerism
Alcohol reactions
Glycoside formation
Ether formation
Ester formation
Biochemistry
Formation of osazones
once used for the identification of sugars
consists of reacting the monosaccharide with
phenylhydrazine
a crystalline compound with a sharp melting point
will be obtained
D-fructose and D-mannose give the same osazone
as D-glucose
seldom used for identification; we now use HPLC
or mass spectrometry
Biochemistry
Biochemistry
Disaccharide Synthesis
The reactions, the names of the sugars, and whether they
are mono- or disaccharides is what you should know (also,
Glycosidic linkage)
Biochemistry
Disaccharides:
Maltose, a cleavage
product of starch (e.g.,
amylose), is a
disaccharide with an (1
4) glycosidic link
between C1 - C4 OH of
2 glucoses.
It is the anomer (C1 O
points down).
6 CH 2OH
6 CH 2OH
H
OH
OH
H
1
maltose
OH
H
1
OH
cellobiose
H
OH
OH
2OH
OH
H
3
6 CH
H
OH
H
OH
3
OH
6 CH 2OH
OH
1
OH
Cellobiose, a product of cellulose breakdown, is the otherwise equivalent anomer
(O on C1 points up).
The (1 4) glycosidic linkage is represented as a zig-zag, but one glucose is
actually flipped over relative to the other.
Biochemistry
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
points down from ring), the linkage is (1 2).
(O
The full name of sucrose is -D-glucopyranosyl-(1 2)- -Dfructopyranose.)
Lactose, milk sugar, is composed of galactose & glucose, with
(1 4) linkage from the anomeric OH of galactose. Its full name
is -D-galactopyranosyl-(1 4)- -D-glucopyranose
Biochemistry
Sucrose
-D-glucopyranosido- -D-fructofuranoside
-D-fructofuranosido- -D-glucopyranoside
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
Biochemistry
Sugar cane
Sugar beet
Biochemistry
Polysaccharides or glycans
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
Biochemistry
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
Biochemistry
Amylose and amylopectin are the 2 forms of starch. Amylopectin
is a highly branched structure, with branches occurring every 12
to 30 residues
Biochemistry
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
Biochemistry
(in starch)
(in cellulose)
Biochemistry
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
Biochemistry
Structure of cellulose
Biochemistry
Linear structures of cellulose and chitin
(2 most abundant polysaccharides)
Biochemistry
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 red-violet color
hydrolyzed by both and -amylases and by
glycogen phosphorylase
Biochemistry
C H2OH
CH2OH
O
H
H
OH
OH
H
O
OH
CH2OH
H
OH
H
H
OH
OH
CH2OH
O
H
OH
OH
H
O
O
H
OH
H
H
OH
H
O
glycogen
H
1
O
6 CH2
H 5
H
4 OH
3
H
CH2OH
O
H
2
OH
H
1
O
CH2OH
O
H
4 OH
H
H
O
OH
O
H
OH
H
OH
OH
Glycogen, the glucose storage polymer in animals, is similar in structure to
amylopectin.
But glycogen has more (1 6) branches.
The highly branched structure permits rapid glucose release from glycogen stores,
e.g., in muscle during exercise.
The ability to rapidly mobilize glucose is more essential to animals than to plants.
Biochemistry
Starches
carbon and energy (glucose) storage molecules
more branching
Biochemistry
Oligosaccharides occur widely as components of antibiotics
derived from various sources
Biochemistry
Special monosaccharides: deoxy sugars
These are monosaccharides which lack one or
more hydroxyl groups on the molecule
one quite ubiquitous deoxy sugar is 2-deoxy
ribose which is the sugar found in DNA
6-deoxy-L-mannose (L-rhamnose) is used as a
fermentative reagent in bacteriology
Biochemistry
Starch/Glycogen
Biochemistry
Cellulose
Biochemistry
Biochemistry
Sugar derivatives
CHO
COOH
CH2OH
H
OH
OH
OH
CH2OH
D-ribitol
OH
HO
OH
OH
OH
OH
OH
HO
CH2OH
D-gluconic acid
COOH
D-glucuronic acid
sugar alcohol - lacks an aldehyde or ketone; e.g., ribitol.
sugar acid - the aldehyde at C1, or OH at C6, is oxidized to a
carboxylic acid; e.g., gluconic acid, glucuronic acid.
Biochemistry
Biochemistry
Sugar alcohols are very useful
intermediates
Mannitol is used as an osmotic diuretic
Glycerol is used as a humectant and can be nitrated to
nitroglycerin
Sorbitol can be dehydrated to tetrahydropyrans and
tetrahydrofuran compounds (sorbitans)
Sorbitans are converted to detergents known as spans and
tweens (used in emulsification procedures)
Biochemistry
Sugar derivatives
CH 2OH
CH 2OH
O
H
H
OH
H
OH
H
OH
OH
H
NH 2
H
O OH
OH
H
CH 3
-D-glucosamine
-D-N-acetylglucosamine
amino sugar - an amino group substitutes for a hydroxyl. An
example is glucosamine.
The amino group may be acetylated, as in N-acetylglucosamine.
TERIMA KASIH
Too much ..
Carbohydrate will be converted
into fat and stored under the
skin leading to weight gain!
