What are macromolecules???

when

the small organic molecules are joined

together, "giant" molecules are produced.

these

giant molecules are known as

macromolecules.

Meaning that
Macromolecules are polymers.
Polymers

are large molecules of

many similar "units" linked together.
~ individual units = monomers.

Major macromolecules in cells

Biomolecules:
Carbohydrates
Proteins
Nucleic acids
Lipids

CARBOHYDRATES I

Lecture Contents

Monosaccharides

structure and classification

important monosaccharides

reactions of monosaccharides

monosaccharides derivatives

Objectives

after you have studied this chapter, you should be

able to answer these questions:
how are carbohydrates classified?
what are the most common monosaccharides
found in nature and what purpose do they serve?
what are optical isomers and why are they
important in living organisms?
what are the chemical reactions of
monosaccharides?

What is a Carbohydrate?

carbo - carbon & hydrate - water

contains elements: C, H & O
general formula: Cn(H2O)n
also known as saccharide or sugar
produced thru photosynthesis
functions: energy source, energy storing
mol., structural components, derivatives
in mol. biology

Definition
Carbohydrate

are usually defined

as polyhydroxy aldehydes and
ketones or substances that
hydrolize to yield polyhydroxy
aldehydes and ketones. They
exist primarily in their hemiacetal
or acetal forms

Classification of Saccharides:

Class

Monomer

Monosaccharide

Disaccharide

Trisaccharide

Oligosaccharide

2-10

Polysaccharide

> 10

glycoconjugates (e.g. proteoglycan, peptidoglycan,

glycoprotein, glycolipid)

The Monosaccharide

contains single
aldehyde/ketone group &
hydroxyl groups at each C:
polyhydroxyaldehyde/
polyhydroxyketone

classification:
chemical nature of carbonyl
grp aldehyde-aldose &
ketone-ketose
number of their C atoms
3C-triose, 4C-tetrose, 5Cpentose, 6C-hexose, 7Cheptose, 8C-octose

C3H6O3
tautomers

properties: cant be
hydrolyzed, soluble in
water, can form isomers

Common monosaccharides:

Glucose

common names include dextrose,

grape sugar, blood sugar

an aldohexose sugar

most important sugar in our diet

a source of energy and
metabolic intermediate for cells

most abundant organic compound

found in nature

level in blood can be as high as

0.1%

Galactose

also called brain sugar

found in dairy products(i.e. milk) &

in sugar beets

an aldohexose sugar

synthesized by the body, where it

forms part of glycolipids and
glycoproteins in several tissues
considered a nutritive sweetener
because it has food energy

less sweet than glucose and not very

water-soluble

Ribose

an aldopentose sugar

an important sugar used in

genetic material

not used as energy source but

an important backbone of
RNA
when C2-OH is removed,
deoxyribose is formed, which
is the backbone of DNA

Fructose

another common sugar

known also as levulose

a ketohexose sugar

sweetest of all sugars

found as sugar of the fruits

and also in honey

Stereoisomers
stereochemistry study of the spatial
arrangement of molecules
stereoisomers have:
same order and type of bonds
different spatial arrangements
different properties
many biologically important chemicals,
like sugars, exist as stereoisomers

Why isomers are important to life?

our entire biology is built on them
every biologically important molecule has one or
more isomers due to the necessary complexity of
those molecules, which require numerous
different types of atoms and will commonly
contain a mixture of single and double bonds
evolution, in almost all cases, has favoured the
use of one isomer for a given purpose over the
use of the others that exist (e.g. D-form of
sugars)

Monosaccharide Stereochemistry
Let us examine the molecular structure of
glyceraldehyde [C3H6O3], the parent compound of
aldoses as below:
It will indicate that:
the molecule is a chiral
molecule (i.e. C2 is a
stereogenic center)
in general, n-C aldoses
have 2x isomers (x refers
to chiral C present)

If we put a mirror in front of the molecule

mirror

a pair of nonsuperimposable molecules will be

produced.

Nonsuperimposable mirror images are like

your right and left hands

 nonsuperimposable molecules :

are different from each other (in

spatial arrangement of atoms)

contain a chiral* central C

(asymmetry)

are optically active

are known as enantiomers (or optical

isomers**)

* Chirality (or dissymmetry)

chiral

achiral

1
1
2
2
3

e.g. glyceraldehyde

e.g. dihydroxyacetone

** Optically active compounds (i.e. enantiomers)

rotate the plane of the polarized light

[D-, (+)]
[L-, (-)]

Enantiomers
one type of
configurational
stereoisomer
have identical physical
and chemical properties
EXCEPT:
interact with another
chiral molecule
differently
rotate the plane of planepolarized light by equal
amounts but in opposite
directions

a mixture that contains

equal quantities of
enantiomers
racemate/racemic mixture
& is optically inactive
can be separated by
biological or chemical
resolutions
for monosaccharides,
common enantiomers are
in D- form

ENANTIOMERS are stereoisomers that are mirror images of each

other
e.g.

D-glucose

mirror

L-glucose

Q1: How many stereoisomers?

D-threose

D-ribose

D-fructose

How many stereogenic centers are there in each sugars?

Diastereoisomers

one type of
configurational
stereoisomer
opposite of
enantiomers (i.e. not
mirror image
isomers)
have distinct
chemical and
physical properties

have the same

functional groups,
usually rather similar
to one another in their
reactions and
properties
two diastereoisomers
can usually be
separated from one
another by , e.g.,
recrystallization

DIASTEREOMERS are stereoisomers that are not enantiomers, or

not mirror images of each other
e.g.

L-glucose

mirror

D-galactose

The diastereoisomers of the D-aldoses

The
diastereoisomers
of the D-ketoses

EPIMER is a diastereomer that has a different configuration at

only one of several stereogenic centers
e.g.
C2 epimers

C4 epimers
D-glucose

D-galactose

D-mannose

EPIMER

D
I
A
S
T
E
R
E
O
M
E

ENANTIOMER

In summary

Q2: Give ONE example of a/an:

1. Enantiomer
2. Diastereomer (at one chiral center)
3. Epimer
AND explain why.

Monosaccharide Cyclic Structure

sugars

with 4C or more exist primarily in cyclic

forms
ring formation occurs in aqueous soln. when
CHO & -C=O grps react with OH grps present in
the sugar:
cyclic hemiacetal or hemiketal forms
an intramolecular cyclization process
furanose & pyranose structures
production of a new chiral center (i.e. anomeric C
atom & anomers)

Hemiacetal
formation

Hemiketal formation

ANOMER is a diastereomer of a saccharide (in the cyclic form)

that differs only in its configuration at the hemiacetal or
hemiketal carbon (i.e. anomeric carbon)
e.g. D-glucose

In carbohydrates, the anomeric carbon is the carbon bonded to two oxygens.

Monosaccharide Reactions
mutarotation
oxidation
reduction
isomerization
esterification
glycoside formation

Mutarotation

- & -forms readily interconverted when dissolved in

water
produces equilibrium mixture of both forms in both
furanose & pyranose ring structures
e.g. glucose: 38% of - & 62% - pyranose forms

Oxidation

in the presence of oxidizing agents (e.g. nitric acid, bromine

water, silver nitrate, Cu2+) & certain enzymes

common reactions:

oxidation of an aldehyde grp aldonic acid

oxidation of a terminal CH2OH grp (not the aldehyde grp)
uronic acid
oxidation of both aldehyde and CH2OH aldaric acid
-C=O in aldonic & uronic acids react with OH grp in same
mol. lactone

reducing sugars tests Tollens, Benedicts or Fehlings Tests

Reducing and nonreducing sugars e.g. lactose and sucrose

for oxidation to occur, cyclic form must first ring-open to produce reactive
aldehyde
any sugar with a hemiacetal (can become free form) will be a reducing sugar
glycosides with acetals (cannot become free form) are nonreducing sugars

ketoses can be reducing sugars because they can isomerise to aldoses

Oxidation of an aldose
oxidation at this site produces an aldonic acid

oxidation at this site produces

an uronic acid

oxidation at both these sites produces

an aldaric acid

Oxidation of monosaccharide with bromine water to

produce aldonic acid

Oxidation of monosaccharide with Nitric acid to produce

aldaric acid

e.g. oxidized forms of D-glucose:

further oxidized to
further oxidized to

Q3:
Write the open-chain structure for the aldaric acid
(mannaric acid) that would be obtained by nitric
acid oxidation of D-mannose.

Q4:
Would you expect mannaric acid to be optically
active?

Periodate oxidations: Oxidative Cleavage of Polyhydroxy

Compounds
Compounds with OH group on the adjacent atoms undergo oxidative
cleavage
when they are treated with aqueous periodic acid (HIO4).
The reaction breaks the C-C bonds carbonyl compounds (aldehydes,
ketones or
acids)

Periodate oxidation take place through a cyclic

intermediate

For every C-C bond broken, a C-O bond is formed at

each carbon

Oxidative cleavage also take place when H group is

adjacent to aldehyde/ketone group (but not acid or ester)

Reduction

carbonyl grp is reduced to alcohol by reducing agents

(e.g. NaBH4, LiAlH4, H2/Ni) to produce alditols

deoxy sugars when H replaces one or more

hydroxyl groups

Reaction of monosaccarides with

phenylhydrazine:Osazones

Osazone formation results in aloss of the chirallity center at C2

but does not effect other chirality centers, thus:

Q5: Does D-fructose yield the same

phenylosazone as D-glucose and Dmannose?

Isomerization

involved transition in intramolecular H atom & double bond thru

the formation of enediol intermediate
e.g.

interconversion of aldose-ketose (e.g. glucose to fructose)

epimerization (e.g. glucose to mannose)

e.g. isomerization of D-glucose

aldose-ketose
interconversion

epimerization

Esterification

OH reacts with acids (e.g. phosphoric acid,

sulphuric acid) to produce ester

produce phosphate, acyl & sulfate esters of

carbohydrate

Glycoside formation

in an acid-catalyzed reaction, anomeric C of a sugar (i.e.

hemiacetal/hemiketal) reversibly condenses with alcohols/sugar
to form glycoside (i.e. acetal/ketal) glycosidic bond

furanoside or pyranoside forms

sugar + sugar disaccharide/polysaccharide

sugar + other than sugar (i.e. aglycone) glycoside proper

aglycone

O-glycosidic
bond

How is a glycosidic bond

formed?

Hydrolysis of glycoside

Monosaccharide derivatives:
Derivative

e.g.

Phosphate sugars

Triose phosphate, ribose-5phosphate, glucose-6-phosphate

Deoxy sugars

2-deoxy-D-ribose, L-fucose

Acids and lactones

Ascorbic acid, D-galacturonic

acid

Alcoholic sugars

Glycerol, D-ribitol

Amino sugars

N-acetylneuraminic acid, Dacetyl glucosamine

Glycosides

Ouabain, amygdalin

Common
monosaccharide
derivatives of
biological
importance
(a) Phosphate sugars

(b) Deoxy sugars

(c) Acids and lactones

(d) Alcoholic sugars

(e) Amino sugars

(f) Glycosides

CARBOHYDRATES II

Lecture Contents

the disaccharides
sucrose, maltose, lactose, cellulose

the oligosaccharides
N-linked, O-linked

the polysaccharides
homopolysaccharides
heteropolysaccharides

Objectives

after you have studied this chapter, you should be able to

answer these questions:
what are the general structural features of oligosaccharides
and polysaccharides?
what structural properties of cellulose? what account for its
widespread occurrence in plants?
what are the most common homopolysaccharides and
heteropolysaccharides and what are their functions?
what structural properties distinguish proteoglycans from
glycoproteins?
what are the functions of proteoglycans and glycoproteins?

The Disaccharide

when 2 monosaccharides are joined together to form a

glycoside
glycosidic bond:
bond bet. one anomeric C of a monosaccharide with a
hydroxyl grp of another monosaccharide
cat. by an enzyme glycosidase via a condensation
reaction
various types: (12); (13); (14) (16) & ,
configurations
crystalline, water soluble, sweet tasting
e.g.: sucrose, lactose, maltose, cellobiose

How is a glycosidic bond formed?

Different types of glycosidic bond

Alpha, where the C1 OH
that is formed ends up
on the same side of the
ring as the -OH of C2

(16)

-linkages
(14)

(13)

Beta, where the C1 OH that is formed ends up

on the opposite side of the ring from the -OH of C2

(12)
(11)

-linkage

Common disaccharides:

sucrose

lactose

maltose

cellobiose

Sucrose

also known as table sugar

extracted from sugar cane,

sugar beet

made up of glucose and

fructose with (12)
glycosidic bond

a nonreducing sugar

common sweetener less

sweet than fructose

hydrolysis by
sucrase/invertase

-D-glucopyranosyl (12) -Dfructofuranoside

Lactose

also known as milk sugar

-makes up around 2-8% of
the solids in milk

made up of galactose and

glucose with (14)
glycosidic bond

-D-galactopyranosyl (14) -Dglucopyranose

a reducing sugar
hydrolysis by lactase
(lacking this enzyme can
cause lactose intolerance)

Maltose

-D-glucopyranosyl (14) -Dglucopyranose

also known as malt sugar

intermediate product of
starch hydrolysis

present in germinating
grain, in a small
proportion in corn syrup

made up of 2 molecules
of glucose with (14)
glycosidic bond

a reducing sugar

hydrolysis by maltase

Cellobiose

a degradation
product of cellulose

made up of 2
molecules of glucose
linked by (14)
glycosidic bond

-D-glucopyranosyl (14) -Dglucopyranose

a reducing sugar

does not freely exists

in nature

The Oligosaccharide
consists of between 2 - 20 monosaccharides
can be found linked to polypeptide/lipid in glycoprotein &
glycolipid
functions:
glycoprotein immune cell recognition, improve stability
of protein folding, sperm-egg interaction
glycolipid - provide energy, markers for cell recognition
2 types of glycans:
N-linked after N-glycosylation at Asn
O-linked after O-glycosylation at hydroxylysine,
hydroxyproline, Ser or Thr

Oligosaccharides linked to polypeptides forming glycoproteins

oligosaccharides

Asn

Ser

polypeptide
chain

N-linked

O-linked

The diversity of glycoproteins

Carbohydrat
e part

Lipid part

The Polysaccharide

store energy or as structural components

homopolysaccharide
formed from one type of monosaccharide
e.g.: starch, glycogen, cellulose, chitin

heteropolysaccharide
formed from 2/more types of
monosaccharide
e.g.: glycosaminoglycan, peptidoglycan

Homopolysaccharide

Starch

main food storage for plants

consists of:
-amylose linear glucose polymer linked by
(14) bonds
amylopectin glucose units are linked in a linear
way with (14) bonds; branching takes place with
(16) bonds occurring each 24 to 30 glucose units
degradation enzymes:

amylases
-glucosidase
starch phosphorylase
debranching enzyme

Amylose of starch

(a) The D-glucose residues of amylose linked through

(14) glycosidic bonds
(b) The amylose polymer forms a left-handed helix

Homopolysaccharide

Glycogen
main animal food storage
basic structure similar to amylopectin
but more branches, every 8-12 glucose
residues
more compact
degradation:
amylases
glycogen phosphorylase
glycogen debranching enzyme

Homopolysaccharide

Cellulose
main component of plant cell wall
linear polymer of glucose 15000 residues
linked by (14) linkage
H-bonded structure form parallel microfibril
strong & water resistant
cross-linked with matrix containing other
polysaccharides & lignin resistant to
pressure
degradation celullase

Homopolysaccharide

Chitin
main component of arthropods
exoskeleton as well as algae/fungi cell wall
similar to cellulose except:
every C2OH grp replaced by acetamide
polymer of N-acetyl-D-glucosamine
bonded by (14) linkage
3 types of microfibril: , ,
degradation: chitinase

Struture of chitin

Comparison between struture of cellulose and

chitin

Heteropolysaccharide

Glycosaminoglycan
or mucopolysaccharide
major structural importance in vertebrate
animals e.g. proteoglycan in connective
tissues, skin
polymers of repeating disaccharide units (i.e. Nacetylgalactosamine or N-acetylglucosamine or
one of their derivatives) with either sulfate or
carboxylate grps
5 main classes: hyaluronic acid, chondroitin
sulfate, dermatan sulfate, heparin/heparan sulfate
& keratan sulfate

Heteropolysaccharide

Peptidoglycan
cross-linked complex of polysaccharides and peptides found in the cell
walls of bacteria
protects bacteria from osmotic lysis
framework:

polysaccharide component linear chains of alternating (14)-linked

N-acetylglucosamine (NAG) & N-acetylmuramic acid (NAM)
peptide component D-amino acid containing tetrapeptide forms amide
linkage with NAMs lactic acid residue
neighbouring parallel peptidoglycan chains are covalently cross-linked
thru tetrapeptide side chains

Comparison between gram-(-) and gram-(+) bacteria

peptidoglycan framework
a. The peptidoglycan monomer

The peptidoglycan monomer of a

gram-(-) bacterium: e.g. Escherichia
coli

The peptidoglycan monomer of a

gram-(+) bacterium: e.g.
Staphylococcus aureus

b. The peptidoglycan
structure

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