BIOCHEMISTRY

Carbohydrat
es
 Carbohydrates
Carbohydrate: a polyhydroxyaldehyde or
polyhydroxyketone, or a substance that gives these
compounds on hydrolysis

Monosaccharide: a carbohydrate that cannot be

hydrolyzed to a simpler carbohydrate
Building blocks of all carbohydrates
They have the general formula CnH2nOn, where n varies
from 3 to 8
Aldose: a monosaccharide containing an aldehyde
group
Ketose: a monosaccharide containing a ketone group
 Monosaccharides
Monosaccharides are
classified by their number
of carbon atoms

Trioses are simplest

carbohydrate
monosaccharides

Glyceraldehyde contains a
stereocenter and exists as
a pair of enantiomers

Mirror-image stereoisomers
are called enantiomers
Structure and Chemistry of
Monsaccharides
 Fischer Projections
Fischer projection:
bonds are written in a
two dimensional
representation showing
the configuration of
tetrahedral stereocenters
horizontal lines
represent bonds
projecting forward
vertical lines represent
bonds projecting to the
rear
the carbon atom at the
intersection of the
horizontal and vertical
lines is not shown
The Ketoses
 D,L Monosaccharides
According to the conventions proposed by Fischer
D-monosaccharide: a monosaccharide that,
when written as a Fischer projection, has the -OH
on its penultimate carbon on the right
L-monosaccharide: a monosaccharide that,
when written as a Fischer projection, has the -OH
on its penultimate carbon on the left
D,L do not specify the sign of rotation of plane-
polarized light

D-sugars predominate in nature

 Stereoisomerism
Stereoisomers: have the same molecular formula and
the same structure but differ in the arrangement of
atoms in space (configuration)

Enantiomers: stereoisomers that are non

-superimposable mirror images

Diastereomers: stereoisomers that are not mirror

images

Two sugars that differ in configuration at only one chiral

center are epimers
Stereoisomers of Aldotetroses
D- and L-Fructose, an enantiomeric pair.
 Cyclic monsaccharide
structures and anomeric
forms
Properties of D-glucose not accounted
for by open chain structures:

Glucose fails to undergo certain

reactions typical of aldehydes

Glucose exists in 2 isomeric forms

which undergo mutarotation from
112 to 52.7
 What Happens if a Sugar
Forms a Cyclic Molecule?
Cyclization of sugars takes place due to interaction
between functional groups on distant carbons, C1 to
C5, to make a cyclic hemiacetal

Cyclization using C2 to C5 results in hemiketal

formation.

In both cases, the carbonyl carbon is new chiral center

and becomes an anomeric carbon

Mutarotation is the interconversion of two distinct

stereoisomeric modifications of a compound yielding
an equilibrium mixture with a final rotation
Monosaccharides Exist in Cyclic,
Anomeric Forms
Simple sugars can
cyclize in two ways,
forming either
furanose or pyranose
structures.
Simple sugars can
cyclize in two ways,
forming either furanose
or pyranose structures.
 Cyclic Structure

Monosaccharides have -OH and C=O groups

in the same molecule and exist almost
entirely as five- and six-membered cyclic
hemiacetals

anomeric carbon: the new stereocenter

resulting from cyclic hemiacetal formation
anomers: carbohydrates that differ in
configuration only at their anomeric carbons
 Haworth Projections

Haworth projections
five- and six-membered hemiacetals are
represented as planar pentagons or hexagons,
as the case may be, viewed through the edge
most commonly written with the anomeric
carbon on the right and the hemiacetal
oxygen to the back right
the designation -means that -OH on the
anomeric carbon is cis to the terminal -CH2OH;
- means that it is trans
 Haworth Projections
A six-membered hemiacetal ring is
shown by the infix -pyran- (pyranose)
A five-membered hemiacetal ring is
shown by the infix -furan- (furanose)
Five-membered rings are so close to
being planar that Haworth projections are
adequate to represent furanoses
For pyranoses, the six-membered ring is
more accurately represented as a strain-
free chair conformation
(a) Chair and boat conformations of a pyranose sugar.
(b) Two possible chair conformations of -D-glucose. Note the axial and
equatorial substituents.
 Monosaccharides Can Be
Converted to Several Derivative
Forms
A variety of chemical and enzymatic
reactions produce derivatives of the
simple sugars
Some of the most common are:
Sugar acids
Sugar alcohols
Deoxy sugars
Sugar esters
Amino sugars
Acetals, ketals, and glycosides
 Oxidation reactions
The carbonyl group of a monosaccharide
can be oxidized to a carboxylic acid group
by a variety of oxidizing agents
aldose aldonic acid (mild oxidizing
agent)
aldose aldaric acid (strong oxidizing
agent) O
O
aldose alduronic acid
C C OH
Oxidation of D-glucose to
sugar acids
 More Monosaccharide
Derivatives

Sugar alcohols are formed by 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 polysaccharides
 Sugar Alcohols

Structures of some sugar alcohols.

 Deoxy Sugars
Deoxy sugars are monosaccharides with one or more
hydroxyl groups replaced by hydrogens
2-Deoxy-D-ribose is a constituent of DNA
Rhamnose is a component of ouabain, a toxic cardiac
glycoside
Fucose is a component of some cell walls
 Sugar Esters
Phosphate esters of glucose, fructose, and
other monosaccharides are important
metabolic intermediates
The ribose moiety of nucleotides such as
ATP and GTP is phosphorylated at the 5-
position.
 Phosphoric esters are particularly
important in the metabolism of
sugars to provide energy
phosphoric esters are frequently formed
by transfer of a phosphate group from
ATP
 Amino Sugars
Sugars with an amino group at C-2 are amino sugars.
They are found in many oligosaccharides and polysaccharides.
 Glycosidic Bond Formation
Glycoside: a carbohydrate in which
the -OH of the anomeric carbon is
replaced by OR

those derived from furanoses are

furanosides; those derived from
pyranoses are pyranosides
glycosidic bond: the bond from the
anomeric carbon to the -OR group
This is the basis for the formation of
polysaccharides/oligosaccharides
The anomeric forms of methyl-
D-glucoside.
 Different Disaccharides of -D-
Glucose
Glycosidic
linkages can
take various
forms; the
anomeric
carbon of one
sugar to any of
the -OH groups
of another
sugar to form
a/an - or -
 Maltose
two units of D-glucose
joined by an -(14)
-glycosidic bond
formed from the
hydrolysis of starch
differs from cellobiose
by the conformation of
the glycosidic linkage
Cellobiose
two units of D-glucose
joined by a -(14)
-glycosidic bond
disaccharide unit of
cellulose
 Disaccharides
Lactose
made up of D-galactose and one unit of
D-glucose joined by a -(14)-
glycosidic bond
Galactose is a C-4 epimer of glucose
found in milk
free anomeric C
 Disaccharides
Sucrose
Table sugar; obtained from the juice of
sugar cane and sugar beet
One unit of D-glucose and one unit of D-
fructose joined by an -(1 2)-glycosidic
bond
 C H2OH
Sucrose
O HO C H2
O O

OH C H2OH
HO
C H2OH
OH
O
OH OH
OH
OH

OH O
HOC H2
O
C H2OH
HOC H2
O O
HO
C H2OH

HO OH
C H2OH OH
OH
OH
O
OH
 S

Raffinose

Stachyose
 Structure and Chemistry of
Polysaccharides
Nomenclature for polysaccharides is based
on their composition and structure
Homopolysaccharide a polysaccharide
that contains only one kind of
monosaccharide
Heteropolysaccharide a polysaccharide
made of several monosaccharides
Starch and glycogen are storage molecules
Chitin and cellulose are structural molecules
Cell surface polysaccharides are recognition
molecules
 Starch
Starch is used for energy storage in plants
a polymer of -D-glucose units

amylose: continuous, unbranched chains of up to 4000 -

D-glucose units joined by -(14)-glycosidic bonds

amylopectin: a highly branched polymer consisting of 24-

30 units of D-glucose joined by -(14)-glycosidic bonds
and branches created by -(16)-glycosidic bonds

Most starch is 10-30% amylose and 70-90% amylopectin

Amylose and Amylopectin
Suspensions of amylose in
water adopt a helical
conformation. Iodine (I2)
can fit into the hydrophobic
middle of the amylose helix
to give a blue color that is
characteristic and
diagnostic for starch.
 Hydrolysis of Starch

amylases catalyze hydrolysis of -(14)-glycosidic

bonds

-amylase is an exoglycosidase and cleaves -(14)

linkages from the nonreducing end of the polymer

-amylase is an endoglycosidase and hydrolyzes -

(14)glycosidic linkages anywhere along the chain to
produce glucose and maltose

debranching enzymes catalyze the hydrolysis of

-(16)-glycosidic bonds
 Glycogen

The glucose storage device in animals

Glycogen constitutes up to 10% of liver mass and 1-2% of

muscle mass

Glycogen is stored energy for the organism

Only difference from amylopectin: even more highly

branched

Alpha(1,6) branches every 8-12 residues

Like amylopectin, glycogen gives a red-violet color with

iodine
 Dextrans

anches can be (1,2), (1,3), or (1,4)

 Roles for Dextrans

Dextrans formed by bacteria are

components of dental plaque
Dextrans in plaque presumably provide
protection for oral bacteria
Cross-linked dextrans are used as
"Sephadex" gels in column
chromatography
These gels, used to separate
biomolecules on the basis of size, are up
to 98% water!
 Cellulose

the major structural component of plants, especially

wood and plant fibers
found in the cell walls of nearly all plants
It is the most abundant natural polymer in the world
The wood and bark of trees are insoluble, highly
organized structures formed from cellulose and
lignin
Cotton is almost pure cellulose
Cotton acetates, made from the action of acetic
anhydride on cellulose, are used in dresses, lingerie,
and other clothing
 Structure of Cellulose

a linear polymer of approximately 2800

D-glucose units per molecule joined by
-(14)-glycosidic bonds
fully extended conformation with
alternating 180flips of glucose units
extensive intra- and intermolecular
hydrogen bonding between chains
Polymeric Structure of Cellulose
The structure of
cellulose, showing the
hydrogen bonds
(blue) between the
sheets, which
strengthen the
structure.

Intrachain H-bonds in
red; interchain H-
bonds in green.
 How Do Ruminant Animals Digest
Cellulose?

Giraffes, cattle, deer, and camels

are ruminant animals that are able
to metabolize cellulose, thanks to
bacterial cellulase in the rumen, a
large first compartment in the
stomach of a ruminant.
 Chitin
Chitin: the major structural component of the
exoskeletons of invertebrates, such as insects
and crustaceans; also occurs in cell walls of
algae, fungi, and yeasts
composed of units of N-acetyl--D-glucosamine
joined by -(14)-glycosidic bonds
 Pectin
Plant celll walls
consist largely of
cellulose
They also contain
pectin which
functions as an
intercellular
cementing material
Pectin is a polymer
of D-galacturonic
acid joined by -
(14)-glycosidic
bonds
Pectin
 Glycosaminoglycans
Glycosaminoglycans: polysaccharides based on a
repeating disaccharide where one of the monomers
is an amino sugar and the other has a negative
charge due to a sulfate or carboxylate group
Glycosaminoglycans are constituents of
proteoglycans

Heparin: natural anticoagulant

Hyaluronic acid: a component of the vitreous humor of
the eye and the lubricating fluid of joints
Chondroitin sulfate and keratan sulfate: components
of tendons, cartillage and other connective tissues
Dermatan sulfate is a component of the extracellular
matrix of skin
 Heparin
D-glucuronic acid-2-sulfate- -(14) - N-sulfo-
D-glucosamine-6-sulfate

Hyaluronic acid
D-glucuronic acid - -(13) - N-acetyl-D-
glucosamine

Chondroitin-4-sulfate
D-glucuronic acid - -(13)- N-acetyl-D-
galactosamine-4-sulfate

Keratan sulfate
D-galactose - -(14)- N-acetyl-D-glucosamine-6-
sulfate
Glycosaminoglycans Linear Chains of
Repeating Disaccharides
 Glycoproteins
Glycoproteins contain carbohydrate units
covalently bonded to a polypeptide chain

antibodies are glycoproteins

Oligosaccharide portion of glycoproteins act as
antigenic determinants
Among the first antigenic determinants discovered
were the blood group substances
In the ABO system, individuals are classified
according to four blood types: A, B, AB, and O
At the cellular level, the biochemical basis for this
classification is a group of relatively small
membrane-bound carbohydrates
Structures of Blood-Group
Antigenic Determinants
 Bacterial cell
walls:
prokaryotic
cell walls are
constructed on
the framework
of the
repeating unit
NAM-NAG
joined by -
(14)-
glycosidic
 Structure of Gram-positive Peptidoglycan

The crosslink between

tetrapeptides in Gram-
positive cell walls is a
pentaglycine bridge.
 Structure of Gram-negative Peptidoglycan

Note the direct crosslinks

between tetrapeptide
units

In Gram-negative cell
walls, the linkage
between tetrapeptide
segments involves a
direct amide bond.