Basic Concepts in Biomolecules

Learning Outcomes
• Explain how molecular structures and intermolecular
interactions influence the properties of biomolecules.
• Describe the major structural features, properties and
functions of carbohydrates.
• Describe the structures, properties and functions of
fatty acids and biomolecules derived from lipids.
• Describe how the structure and conformation of a
protein determines its function.
• Describe the structures of nucleic acids and the flow of
genetic information.
 The Molecules of Life
• All functional groups we have studied so far, are found in the
biologically active organic molecules called biomolecules.
• These are constantly synthesized and destroyed by every living
organism on Earth.

• The study of detailed understanding of the reactions that occur

in living organism is called BIOCHEMISTRY.
• The most abundant biomolecules present in living system are
classified into four major categories:
1. Carbohydrates
2. Lipids
3. Proteins
4. Nucleic acids
 The Four Classes of Biomolecules
• Carbohydrates are the main source of metabolic energy for all the
organism’s activities from locomotion to the building of other
molecules.
• Lipids are family of compounds that includes fats, waxes, steroids
and some vitamins. The functions of lipids range from energy
source to membrane formation. These are characterized by their
insolubility in water.
• Proteins are made up of amino acids. They act as catalysts,
structural support, protection, transport agents, chemical
messengers and cell recognition factors.
• Nucleic acids are the constituents of our genes. They are involved
in gene replication and translation of genetic message to proteins.
CARBOHYDRATES
 CARBOHYDRATES
Sugars, starch, cellulose are the best known members of this group
Carbohydrates have three elements, carbon, hydrogen and oxygen
arranged primarily into three groups :
General formula of carbohydrates is Cx(H2O)y which gives them the
name carbohydrates

Examples
C6H12O6 or C6(H2O)6 they appear to be hydrates of carbon
C12H22O11 or C12(H2O)11

Modern definition of carbohydrates:

They are polyhydroxyketones or polyhydroxyaldehydes.
 Nomenclature of Carbohydrates
• In chemical and biochemical discussions carbohydrates are more
frequently referred to as saccharides, or sugars (Latin sacharum,
“sugar”)
• But not all carbohydrates are sweet.
• The suffix ‘ose’ is a general way of naming the carbohydrates.
• Aldose meaning polyhydroxyaldehyde
• Ketose meaning polyhydroxyketone
• The number of carbon atoms are indicated by tri-, tetr-, pent-,
• Apart from this general way of naming, they can be named in the
IUPAC system also.
• Eg:
H O
C CH2OH
Aldose Ketose
H C OH C O
Triose Triose
CH2OH CH2OH
Aldotriose Ketotriose
2,3-dihydroxypropanal 1,3-dihydroxypropanone
 Examples
Examples

Common name: Glyceraldehyde Dihydroxyacetone

(polyhydroxyaldehyde) (polyhydroxyketone)

An aldose HO O H2CH
C 2OH
OH A ketose
C
A triose CH AAtriose
ketose
An aldose
AnAaldotriose
H C OH CC O O AAketotriose
triose
triose HCCHOH
2OH CH2OH
H2C OH
H2C OH
2,3-dihydroxypropanal 1,3-dihydroxypropanone

C3H6O
C3H6O3

Functional isomers
Functional isomers
 1:28 PM Page 922

Chemical Representation
• The chemical structures of carbohydrates are
22 commonly represented by wedge-and-dash
Carbohydrates

structures
polyhydroxy ketones or by 22.17).
(Section Fischer projections.
The chemical structures of carbohydrates are
commonly represented by wedge-and-dash structures or by Fischer projections.
Notice
• Notice that
that both both D -glucose and D -fructose
D-glucose and D-fructose have the molecular formula C6H 12O6 ,
consistent with the general formula C6(H 2O)6 that made early chemists think that
have
those molecular
compounds were hydratesformulae
of carbon. C6H12O6
HC O HC O CH2OH CH2OH
H C OH H OH C O C O
HO C H HO H HO C H HO H
at horizontal
iewer and H C OH H OH H C OH H OH
y from the
ons. H C OH H OH H C OH H OH
CH2OH CH2OH CH2OH CH2OH
wedge-and-dash Fischer projection wedge-and-dash Fischer projection
structure structure
D-glucose D-fructose
a polyhydroxy aldehyde a polyhydroxy ketone

The most abundant carbohydrate in nature is D-glucose. Living cells oxidize

 O H H2C OH
C
C O
H C OH
HO C H HO C H
H C OH H C OH
H C OH More examples H C OH
H C OH H C OH
H H
Glucose Fructose
An aldohexose A ketohexose
2,3,4,5,6-pentahydroxyhexanal
1,3,4,5,6-pentahydroxy-2-hexanone
H O H2C OH
C
C O
H C OH
H C OH
H C OH
H C OH
H C OH
H2C OH H2C OH
Ribose Ribulose
An aldopentose An ketopentose
2,3,4,5- 1,3,4,5-tetrahydroxy-2-
tetrahydroxypentanal pentanone
 Classification of Carbohydrates
• Simple carbohydrates are termed monosaccharides
(single sugars), whereas complex carbohydrates
contain two or more sugar subunits linked together
• Disaccharides are complex carbohydrates with two
sugar units linked together
• Oligosaccharides have 3-10 sugar units linked
together
• Polysaccharides have more than 10 sugar units
linked together
 Classification of Carbohydrates
• A monosaccharide can be a polyhydroxyaldehyde or a
polyhydroxyketone
– polyhydroxyaldehyde is called an aldose
– polyhydroxyketone is called a ketose
• Monosaccharides are also classified according to the
number of carbons they contain
– three carbons = triose; four carbons = tetraose;
five carbons = pentose; six carbons = hexose;
seven carbons = heptose; ... etc
– eg. six-carbon polyhydroxyaldehyde (eg. D-glucose) is
an aldohexose; six-carbon polyhydroxyketose (eg. D-
fructose) is a ketohexose
 Classification of Carbohydrates
• The smallest aldose (the only one whose name does
not end in –ose) is glyceraldehyde, an aldotriose
∗ CHO CHO CHO
HO
OH HO H H OH
CH2OH HOH2C
glyceraldehyde
2,3-dihydroxypropanal (R)-(+)-glyceraldehyde (S)-(-)-glyceraldehyde

CHO CHO
H OH HO H
CH2OH CH2OH

(R)-(+)-glyceraldehyde (S)-(-)-glyceraldehyde

• Fischer arbitrarily assigned the configuration on the left to the

dextrorotatory isomer of glyceraldehye (D-glyceraldehyde)
• D-glyceraldehyde = D-(R)(+)-glyceraldehyde, and
L-glyceraldehyde = L-(S)-(−)-glyceraldehyde
 D- and L- notation
2003 1:28 PM Page 924

• D- and L- notations are used to describe the

configurations of carbohydrates and amino acids
• In Fischer projections of monosaccharides, the
ER 22
carbonyl group is always placed on top (for aldoses)
Carbohydrates

oramino
as acids
The near
notations to the top as possible (for ketoses)
D and L are used to describe the configurations of carbohydrates and
(Section 23.2), so it is important to learn what D and L signify. In Fischer
• Ifprojections
the OH group attached to the bottom-most chiral
of monosaccharides, the carbonyl group is always placed on top (in the
case of aldoses) or as close to the top as possible (in the case of ketoses). From its
centre is
structure, you on the
can see that right,
galactose the
has fourcompound
asymmetric carbonsis a
(C-2, -sugar;
DC-3, C-4, andif it
C-5). If the OH group attached to the bottom-most asymmetric carbon (the carbon that
isis on the
second fromleft, it isisan
the bottom) L-sugar
on the right, then the compound is a D-sugar. If the OH
group is on the left, then the compound is an L-sugar. Almost all sugars found in nature
• Almost
are D-sugars.allNotice
sugars
that the found inofnature
mirror image a D-sugar isare D-sugars
an L-sugar.

carbonyl group HC O HC O
placed on top H OH HO H
HO H H OH
HO H H OH
H OH HO H
CH2OH the OH group CH2OH
D-galactose is on the right L-galactose
mirror image of D-galactose

otation Like R and S, D and L indicate the configuration of an asymmetric carbon, but they
 at the mirror image of a D-sugar is an L-sugar.

D- and L- notation
• D- and L-notations, like (R)- and (S)-notations, only
indicate the configuration of the chiral centre
– the notations do not indicate whether the compound
rotates the plane-polarised light to the right (+) or to the
left (−)
like R and –S,do not confuse
indicate D- and L- with d- and l-
the configuration of a chiral centre, but they do not
the compound– d- = (+) and
rotates l- = (−)
plane-polarized light to the right (+) or to the left (-).
• For example, D-glyceraldehyde is dextrorotatory (d)-
mple, D-glyceraldehyde
but D-lactic is dextrorotatory
acid (d) but
is laevorotatory (l)-D-lactic acid is levorotatory
 Configuration of the Aldoses
• Aldotetroses have two chiral centres, and have four
stereoisomers (2n = 22 = 4)
• Two of the stereoisomers are D-sugars and two are
L-sugars

• Stereoisomers that are mirror images of each other

are called enantiomers
All colour figures, schemes and tables are copied from Bruice P. Y., Organic Chemistry, Prentice Hall, 8th. Ed
Stereoisomers
roduction to •Medicinal thatoxford
Chemistry G. Patrick are NOT mirror
University images
press 5th Ed 2013 of each
other are called diastereomers
 Configuration of the Aldoses
• Epimers are diastereomers that differ in
configuration
mers that differ at only at
in configuration one asymmetric
only centrecenter are called E
on asymmetric

ations of the D-aldoses

Aldoses
Aldoses
R configuration

• Highest numbered chiral centre of all D-sugars have the same configuration as
D-(R)-(+)-glyceraldehyde
 D-Glucose L-Glucose

Aldotriose
Aldoses
CHO

HCOH Aldotriose

CH2OH
D-Glyceraldehyde

CHO CHO

HCOH HOCH
Aldotetroses
Aldotetroses
HCOH HCOH

CH2OH CH2OH
D-Erythrose D-Threose

CHO CHO CHO CHO

HCOH HOCH HCOH HOCH Aldopentoses

HCOH HCOH HOCH HOCH Aldopentoses

HCOH HCOH HCOH HCOH

CH2OH CH2OH CH2OH CH2OH

D-Ribose (Rib) D-Arabinose (Ara) D-Xylose (Xyl) D-Lyxose (Lyx)

CHO CHO CHO CHO CHO CHO CHO CHO

HCOH HOCH HCOH HOCH HCOH HOCH HCOH HOCH

Aldohexoses
HCOH HCOH HOCH HOCH HCOH HCOH HOCH HOCH Aldohexoses
HCOH HCOH HCOH HCOH HOCH HOCH HOCH HOCH

HCOH HCOH HCOH HCOH HCOH HCOH HCOH HCOH

CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH

D-Allose D-Altrose D-Glucose D-Mannose D-Gulose D-Idose D-Galactose D-Talose
(Glc) (Man) (Gal)

Figure 11-1 The stereochemical relationships, shown in distinguishes the members of each pair. The L- counterparts of
Biochemistry,
Fischer projection,Voet
amongand
the DVoet, p246,
-aldoses ISBN:
with three 0-471-61769-5.
to six carbon these Configuration
15 sugars are their at C2 images.
mirror distinguishes members
The biologically most of each pair.
atoms. The arrows indicate stereochemical relationships (not common aldoses are boxed.
biosynthetic reactions). The configuration about C2 (red)
• http://www.bioinfo.org.cn/book/biochemistry/chapt11/bio1.htm
• Chiral centres marked in magenta.
 nose
tainin

Ketoses
CH2OH rings
C O

CH2OH
Dihydroxyacetone

CH2OH The c
C O memb
and fr
HCOH

CH2OH a.
D-Erythrulose
Th
need
rende
CH2OH CH2OH sultin
the h
C O C O
anom
HCOH HOCH the a
ring
HCOH HCOH

CH2OH CH2OH
D-Ribulose D-Xylulose

CH2OH CH2OH CH2OH CH2OH

C O C O C O C O

HCOH HOCH HCOH HOCH

HCOH HCOH HOCH HOCH

HCOH HCOH HCOH HCOH

CH2OH CH2OH CH2OH CH2OH

D-Psicose D-Fructose D-Sorbose D-Tagatose
Biochemistry, Voet and Voet, p247, ISBN: 0-471-61769-5.
http://www.bioinfo.org.cn/book/biochemistry/chapt11/bio1.htm Figure 11-2 The stereochemical relationships among the
D-ketoses with three to six carbon atoms. The configuration
about C3 (red) distinguishes the members of each pair. The Figur
 Cyclic Structures of Monosaccharides
I22-919_958r2 29-03-2003 1:28 PM Page 935

• Aldehydes and ketones react with alcohols to form hemiacetals

H H
O
R1 OH
OH R2 O
R1 R 2 of Monosaccharides: He
Section 22.10 Cyclic Structure
alcohol aldehyde hemiacetal
the left, the hemiacetal is b -D-glucose. The mechanism for cyclic hemiacetal forma-
•tionSince
is the both functional
same as groups
the mechanism are present
for hemiacetal in thebetween
formation same molecule,
individual alde-
hyde and alcohol molecules (Section 18.7).
intramolecular reactions can occur, giving rise to two cyclic forms
anomeric carbon

H C OH HC O HO C H
H OH H OH H OH
HO H O HO H HO H O
H OH H OH H OH
H H OH H
CH2OH CH2OH CH2OH
-D-glucose -D-glucose
36% 0.02% 64%
 18.70.

Cyclic Structures of Monosaccharides

Using Fischer projections to show the structure of cyclic sugar is unsatisfactory because
way the C-O-C bond is represented.
• AFischer
somewhat
Note: All colour figures,
projections
more
schemes and tables satisfactory
are copied
areOrganic
unsatisfactory
from Bruice P. Y.,representation is given
Chemistry, Prentice
for
Hall, 8th. by adepicting
Haworth projection.
Ed, 2017

cyclic structures, so the alternative Haworth projection

An Introduction to Medicinal Chemistry G. Patrick oxford University press 5th Ed 2013

Monosaccharidesiscontain
used aldehyde or ketone group can form hemiacetal internally.
So D-glucose in solution exists in three different forms.

anomeric carbon
anomeric carbon
HC O
H OH H OH HO H
H OH HO H H OH
HO H O HO H O
H OH
H OH H OH
H H OH H
CH2OH CH2OH CH2OH

-D-Glucose 36% D-Glucose 0.02% -D-Glucose 64%

Fischer projections to show the structure of cyclic sugar

• α-form:
There is the open-chain form ofmp 146 which
D-glucose
oC,
has been mentioned before and there are two
+112.2 o specific-D-glucose.
-D-gluc
rotation-D-glucose
We know the two cyclic forms are
melts at 146 0C, whereas
• β-form:
–D-glucose melts at 150 0C; mp 150 oC,
–D-glucose has a specific rotation of + 112.20 –D-glucose has a specific rotation of +
0
18.7 . +18.7 o specific rotation
In a Haworth projection of D-pyranose, the six-member ring is represented as being flat
 H OH H OH
a-d-Glucose b-d-Glucose

Formation of Anomers
Mutarotation of A- and B -D-Glucose
• Cyclization process is reversible
In an aqueous solution, the Haworth structure of a - -glucose opens to give the open
D

– mutarotation
chain of D-glucose withofanα- and group.
aldehyde β-formsAt any occurs
given time, there is only a trace
amount of the open chain because it closes quickly to form a stable ring structure. How-
– results in open
ever, when the all three forms
chain closes again itbeing
can form present
b -D-glucose. In this process called
mutarotation, each isomer converts to the open chain and back again. As the ring opens
(ie. open-chain,
and closes, the ¬ OH groupα-onand
carbonβ-forms)
1 can form either the a or b isomer. An aqueous
glucose solution contains a mixture of 36% a-D-glucose and 64% b -D-glucose.

Open chain with

aldehyde
CH2OH CH2OH H group CH2OH
O H O O OH
H H O H
H H H
C C C
OH H OH H OH H
HO HO H HO
OH H
a Isomer ! Isomer
H OH H OH H OH
a-d-Glucose d-Glucose b-d-Glucose
(36%) open chain (trace) (64%)

Haworth Structures of Galactose

Chemistry: an introduction to general, organic, and biological chemistry, 11th ed. KC. Timberlake. ISBN 978-0-321-69345-7
 Formation of Anomers
Formation of Anomers
• • Polymers of α- and β-forms give rise to compounds
anching in
gen. amylopectin glycogen
glycogen. Polymers of α- and β-forms give rise to compounds with different
he branching in
amylopectin glycogen

Is Right
with different properties
properties
ntist Is Right
• –Example:
starch vsstarch andare
cellulose cellulose are bothofpolymers
both polymers glucose of glucose
he mouth have an enzyme that converts sucrose to a polysaccharide called dextran. Dextran is
d units
in thejoined
ucose and
tran, (α-(α-vsvsβ-form
mouthmainly
have an
unitsbacteria
joined mainly
hiddenβ-formrespectively)
enzymea@1,3′-
through
through
that converts
respectively)
plaqueand
in thea@1,3′-
sucrose to a polysaccharide
and a@1,6′-glycosidic
a@1,6′-glycosidic
attack tooth enamel.
linkages. About
linkages.
called10%
This isAbout
dextran. Dextran
of dental
10% of dental
the chemical
is
plaque
basisplaque
for your
of dextran, and bacteria hidden in the plaque attack tooth enamel. This is the chemical
ot to eat candy. This is also why sorbitol and mannitol are the saccharides added to “sugarless” basis for your
ing not to eat candy. This is also why sorbitol and mannitol are the saccharides added to “sugarless”
be converted to dextran.
nnot be converted to dextran.
CH2OH
O
O
HO CH2OH
HO O
Cellulose
Cellulose O
an a-1,4′-glycosidic linkage HO CH2OH
Cellulose is is
Cellulose thethemajor
majorstructural
structural component
component of ofplants.
plants. Cotton,
HOCotton, forfor example,
example, is composed
O is composed of about
of about
O
90% cellulose,
90% cellulose,andandwood
woodisisabout
about50% cellulose.Like
50% cellulose. Likeamylose,
amylose, cellulose
cellulose is composed
is composed of unbranched
of unbranched
chains HO
chains of of d-glucoseunits.
d-glucose units.Unlike
Unlike amylose,
amylose, however,
however,
three subunits
the
theglucose
glucose
of amylose
unitsHOin cellulose
units are joined
in cellulose by by
are joined
linkages rather than by linkages
b-1,4′-glycosidic linkages rather than by a@1,4′-glycosidic linkages (see page 970).
b-1,4′-glycosidic a@1,4′-glycosidic (see pageO 970).

intramolecular
intramolecular
hydrogen bond
hydrogen bond

CH OH
O H O OH CH2OH O
O 2
CH2OH OH O CH2OH O
O O H O O
HO O O O
HO OH O CH2OH O H O OH O
OH CH2OH O H OH
a b-1,4′-glycosidic linkage
a b-1,4′-glycosidic linkage
three subunits of cellulose
three subunits of cellulose
Organic Chemistry, 4th ed. Paula Yurkanis Bruice ISBN 978-0131407480
Physical Properties of Starch and Cellulose
Organic Chemistry, 4th ed. Paula Yurkanis Bruice ISBN 978-0131407480
 Formation of Tautomers
• Since there are multiple hydroxy groups, ring closure
can happen either on C5-hydroxy (more common) or on
C4-hydroxy (less common)
– forms either a 6-membered ring or a 5-membered ring
– referred to as the pyranose or furanose form
– both tautomers are present in solution
H O
CH2OH C
CH2OH
O H C OH
C5-OH C4-OH HO O
OH HO C H
OH OH OH
ring closure H C OH ring closure
OH
H C OH OH
OH
CH2OH
pyranose form D-Glucose furanose form

both α- and β- open-chain both α- and β-

forms present form forms present
99% 0.25% <1%
 Disaccharides
Sugars on cell surface: A and B
Has antibodies against: None
Can receive blood from: O, A, B, and AB
Can donate blood to: AB

• Most carbohydrates donors

eople with type O blood are universal donors, and in nature
only. Thosecontain
with type B more
blood can than one
accept blood
monosaccharide unitfrom
e with type AB blood are universal acceptors. People
type A blood can accept blood from type A or type O
type B or type O donors only. Type O people can
accept blood only from type O donors.

• CommonTestdisaccharides include
your knowledge with Problems sucrose, maltose, lactose
20.57–20.59.

• The bond linking monosaccharide units together to form di-,

beets. In sucrose, carbon 1 of a- -glucopyranose bonds to carbon 2 of
oligo-, or-fructofuranose
polysaccharides are called glycosidic bonds
production of sucrose, sugar D
sugar beet is boiled with D by an a-1,2-glycosidic bond. Because the anomeric carbons
and the resulting solution is of both the glucopyranose and fructofuranose units are involved in forma-
– formed
Sucrose crystals separate and
ected. Subsequent boiling to
when
tion the anomeric
of the glycosidic –OHmonosaccharide
bond, neither combines unit withis the –OH of another
in equilibrium
saccharide
trate the solution followed with its open-chain form. Thus, sucrose is a nonreducing sugar.
ing yields a dark, thick syrup
as molasses.
CH2OH
O CH2OH A unit of
O a-D-glucopyranose
1 HO
OH HO 1
HO
OH
OH a-1,2-Glycosidic
O bond O A unit of
HOCH2 HOCH2
b-D-fructofuranose
O O
2 2
HO HO
CH2OH
1 1CH2OH

OH OH
Sucrose

(Glucose + Fructose)
 of D - galactopyranose bonded by a b-1,4-glycosidic bond to carbon 4 of
D-glucopyranose. Lactose is a reducing sugar, because the cyclic hemiacetal
OH
Disaccharides
of the D-glucopyranose unit is in equilibrium
can be oxidized to a carboxyl group.
with its open-chain form and
Lactose

C. Maltose A unit of b-D-Glucopyranose

A unit of CH2OH
Maltose
b-Dderives its name from itsOH
-Galactopyranose presence
HO in malt, the juice from sprouted Maltose is an in
O
barley and other cereal 4 grains. It consists CH
of two
2OH units of D-glucopyranose
b-1,4-Glycosidic bond syrups.
joined by a glycosidic
CH2OH bond
OH between carbon 1 (the O anomeric carbon) of
HO 4 CH2OH
one unit and carbon
O 4 O of the other unit. HO Because the O oxygen atomOon the
anomeric carbon of the first OH
glucopyranose unit OHis 1alpha, the bond join-
OH 1 HO OH
ing the two units is an a-1,4-glycosidic bond.
b-1,4-Glycosidic bond Following are a Haworth
OH
projection and a chair conformation for b-maltose, so named because
OH
the iOH groups on the anomeric carbon of the glucose unit on the right
Lactose
are beta. (Glucose + Galactose)

C. Maltose
a-1,4-Glycosidic bond
Maltose derives its name from its presence in malt, the juice from sprouted Maltose is an ingredient in
barley and other cereal grains. It consists of twoCH 2OH
units of D-glucopyranose syrups.
4 bondCH
joined by a1 glycosidic between O
2OH carbon 1 (the anomeric carbon) of
one unit HO
O and carbon
O
4 of the other unit. Because the oxygen atom on the
HOCH
anomeric
2 carbon of theOH HO unit is alpha, the
first glucopyranose 1 bond join-
O
ing the two units is an a-1,4-glycosidic bond. Following CH2OH
OHare a4Haworth
OH
projection andOH a chair conformation for b-maltose, so named O because O
HO
the iOH groups on the anomeric carbon of the glucose unit on the right
HO OH
are OH
beta. HO OH
Maltose
(Glucose + Glucose)
a-1,4-Glycosidic bond
 Polysaccharides
• Long chains of monosaccharides covalently linked
together by glycosidic bonds to form polysaccharides
• Examples are glycogen and starch
• Polysaccharides may be composed of one or more
types of monosaccharide
• Polysaccharides may be linear or branched
 Polysaccharides – Glycogen
• Excess glucose is stored as glycogen granules in animals
• It is found in greatest abundance in liver and muscle cells.
• Consists entirely of glucose units.
• Linear chains are linked by α-(1,4) glycosidic linkages.
• It has numerous α-(1,6) glycosidic linkages at branching
points.
 Polysaccharides – Starch
• Exists in plants as insoluble starch granules
• Consists of 2 polysaccharide forms:
– Amylose
– Amylopectin
• Amylose is composed of long unbranched chains of
D-glucose residues joined by α-(1,4) glycosidic
linkages.
• Amylopectin is the branched form. It contains linear
glucose chains of glucose molecules bound with
α-(1,4) glycosidic linkages and α-(1,6) glycosidic
linkages occur at every 25-30 residues, causing
branching.

31
 Starch Structure
• Amylose: Straight chain that forms coils with α-(1,4) glycosidic
linkages. Most common type of starch.

α-(1,4) glycosidic linkage

• (2) Amylopectin: Branched chains of glucose residues that are bound
together by the combination of α-(1,4) and α-(1,6) glycosidic linkages/
bonds.

α-(1,6) glycosidic bond

32
α-(1,4) glycosidic bond
Structure Comparison
Self-check:
• Explain why it is not possible to isolate pure
β-D-glucose from solution.
• Give an example of:
– a ketohexose
– an aldopentose
LIPIDS
 Lipids
Bioorganic compounds that are generally insoluble in water
(hydrophobic) are called lipids.

These are classified based on their physical property and not

on their structure.

Hence they have a variety of structures.

• Oils, Fats & Waxes H 2C O
O triacylglycerol beeswax

H3C(H2C)14
O

O (CH2)29CH3
• Cholesterols and Steroids HC O
O

• Terpenoids O
prostaglandin PGE2
H 2C O
• Prostaglandins COOH

OH
cholesterol

HO H

H H
menthol β-carotene
HO
 Waxes
Spermaceti wax from sperm whale oil

Beeswax
 Oils and Fats
• Glycerols are compounds in which there are three OH groups
• Fats are esters of long-chain carboxylic acids* with glycerol
• Fats = Triglycerides that are solids at room temperature
• Oils = Liquid triglycerides
*Long-chain carboxylic acids = fatty acids

O O
H2C OH HO H 2C O
O Esterification O
+
HC OH HO HC O
O O
H2C OH HO H 2C O

glycerol long-chain carboxylic acid triacylglycerol

(fatty acid) (acyl triglyceride)
 Triglycerides
• Triacylglycerols are lipids used for energy
storage and each molecule consists of three
fatty acid molecules covalently bonded to a
glycerol molecule.
 Triglycerides
• If one glycerol reacts (via esterification) with one fatty
acid, a monoglyceride is formed
• When one glycerol reacts with three fatty acids, a
triglyceride is formed.

• Fatty acids connected to the glycerol backbone may be

saturated or unsaturated.
• The unsaturated fatty acid may have one or more
double bonds. If there is a double bond, the fatty acid
will kink.
 Fatty Acids
• Fatty acids are long-chain carboxylic acids
• Most naturally occurring fatty acids contain
– an even number of carbon atoms and are unbranched because they are
synthesized from acetate (a 2-carbon compound)
– can be saturated (no C–C double-bonds), or unsaturated (contain C–C
double-bonds)
– polyunsaturated fatty acids (PUFAs) contain more than one double-bond
– double-bonds are cis- configuration, and are always separated by one CH2
group (ie. not conjugated)
– the cis double-bond results in the fatty acid having a lower melting point
cf. saturated ones with same carbon numbers
O
O
OH
OH

stearic acid oleic acid

octadecanoic acid (9Z)-octadecenoic acid
cis-9-octadecenoic acid
 18 stearic acid interactions between
octadecanoic acid the molecules (Section 2.9). COOH 69
The double bonds in unsaturated fatty acids generally have the cis configuration. This
Examples of Fatty Acids
3-D Molecules:
Stearic acid; Oleic acid; configuration produces a bend in the molecules, which prevents them from packing
Linoleic20 arachidic
acid; Linolenic acidacid eicosanoic acid COOH 77
together as tightly as fully saturated fatty acids. As a result, unsaturated fatty acids have

Unsaturated
Table 26.1 Common Naturally Occurring Fatty Acids

16 palmitoleic acid (9Z )-hexadecenoic acid COOH Melting

0
Number point
of carbons Common name Systematic name Structure °C
18 oleic acid (9Z )-octadecenoic acid COOH 13
Saturated
12 lauric acid dodecanoic acid COOH 44

18 linoleic acid (9Z,12Z )-octadecadienoic acid COOH −5

14 myristic acid tetradecanoic acid COOH 58

18 linolenic acid (9Z,12Z,15Z )-octadecatrienoic acid COOH − 11

16 palmitic acid hexadecanoic acid COOH 63
20 arachidonic acid (5Z,8Z,11Z,14Z )-eicosatetraenoic acid COOH − 50
18 stearic acid octadecanoic acid COOH 69

20 EPA (5Z,8Z,11Z,14Z,17Z )-eicosapentaenoic acid COOH − 50

20 arachidic acid eicosanoic acid COOH 77

Unsaturated

16 palmitoleic acid (9Z )-hexadecenoic acid COOH 0

18 oleic acid (9Z)-octadecenoic acid COOH 13

Organic Chemistry, 4th ed. Paula Yurkanis Bruice ISBN 978-0131407480

18 linoleic acid (9Z,12Z)-octadecadienoic acid COOH −5
 14 myristic acid interactions between
tetradecanoic acid the molecules (Section 2.9). COOH 58
The double bonds in unsaturated fatty acids generally have the cis configuration. This
Examples of Fatty Acids
3-D Molecules:
Stearic acid; Oleic acid; configuration produces a bend in the molecules, which prevents them from packing
Linoleic16 palmiticacid
acid; Linolenic acid hexadecanoic
together as fully saturated fatty acids. As a result, unsaturatedCOOH
acid
as tightly 63have
fatty acids

1826.1 stearic
Table Commonacid Naturally
octadecanoic
Occurring acid
Fatty Acids COOH 69
Melting
Number
20 arachidic acid eicosanoic acid COOH point
77
of carbons Common name Systematic name Structure °C

Unsaturated
Saturated
12 lauric acid dodecanoic acid COOH 44
16 palmitoleic acid (9Z )-hexadecenoic acid COOH 0

14 myristic acid tetradecanoic acid COOH 58

18 oleic acid (9Z)-octadecenoic acid COOH 13

16 palmitic acid hexadecanoic acid COOH 63

18 linoleic acid (9Z,12Z)-octadecadienoic acid COOH −5
18 stearic acid octadecanoic acid COOH 69

18 linolenic acid (9Z,12Z,15Z)-octadecatrienoic acid COOH − 11

20 arachidic acid eicosanoic acid COOH 77
20 arachidonic acid (5Z,8Z,11Z,14Z)-eicosatetraenoic acid COOH − 50
Unsaturated

16
20 palmitoleic
EPA acid (9Z )-hexadecenoic acid
(5Z,8Z,11Z,14Z,17Z)-eicosapentaenoic acid COOH − 050

18 oleic acid (9Z)-octadecenoic acid COOH 13

Organic Chemistry, 4th ed. Paula Yurkanis Bruice ISBN 978-0131407480

18 linoleic acid (9Z,12Z)-octadecadienoic acid COOH −5
 Sources
Reference of Fatty Acids
list of saturated fatty acids
Common Systematic Formula Common source
Name Name

Butyric Butanoic CH3(CH2)2COOH butterfat

Caproic Hexanoic CH3(CH2)4COOH butterfat, coconut, palm nut oils

Caprylic Octanoic CH3(CH2)6COOH Coconut, palm, nut oils, butterfat

Capric Decanoic CH3(CH2)8COOH Coconut, palm, nut oils, butterfat

Lauric Dodecanoic CH3(CH2)10COOH Coconut, palm, nut oils, butterfat

Myristic Tetradecanoic CH3(CH2)12COOH Coconut, palm, nut oil, animal fats

Palmitic Hexadecanoic CH3(CH2)14COOH practically all animal, plant fats

Stearic Octadecanoic CH3(CH2)16COOH animal fat, plant fats

Arachidic Eicosanoic CH3(CH2)18COOH peanut oil

 Properties of Fatty Acids
• Long chain carboxylic acids with non-polar hydrocarbon tail and a
polar head group
• Molecules having both hydrophobic and hydrophilic properties
are also known as amphipathic molecules
• However, because of the very long hydrocarbon chain, fatty acids
generally exhibit a hydrophobic nature
• The carboxylic acid group can react with alkalis to form salts
– these salts are amphipathic (amphiphilic) and can act as surfactants/
detergents
O O
+ NaOH
OH O-Na+

hydrocarbon chain carboxylic

non-polar acid
polar
 Chemical Reactions of Lipids
Esterification and Hydrolysis Reactions
O O
H2C OH HO H 2C O
O Esterification O
+
HC OH HO HC O
O Acid Hydrolysis O
H2C OH HO H 2C O

glycerol long-chain carboxylic acids triacylglycerol

fatty acids triglyceride
acyl groups

Saponification Reaction
O

H 2C O H2C OH
O O
+NaOH
+ +Na-O
HC O HC OH
O Saponification

H 2C O H2C OH
3 molecules of
glycerol trilaurate glycerol sodium dodecanoate
(sodium laurate)
 Unsaturated Fatty Acids
• Contain at least one double bond between
carbons
– monounsaturated
– polyunsaturated
• Delta nomenclature (Δ)
1. Number of carbons in the fatty acid
2. Number of double bonds
3. Number of carbons from the carboxylic acid (alpha)
end to the first carbon in the double bond(s)
• Oleic acid (C18:1Δ9), linoleic acid (C18:2Δ9,12),
linolenic acid (C18:3Δ9,12,15)
 Unsaturated Fatty Acids
• Omega nomenclature (ω)
– Location of unsaturated bonds are counted from the end
1. Number of carbons in the fatty acid
2. Number of double bonds
3. Number of carbons from the methyl end (aka Omega
end) to the first carbon in the double bond closest to
the methyl end

• Oleic acid (C18:1ω-9), linoleic acid (C18:2ω-6,9),

linolenic acid (C18:3ω-3,6,9)

https://www.liquisearch.com/fatty_acid/nomenclature
 Nomenclature of Fatty Acids
α-end

O Stearic acid
ω-end (saturated)
OH C18:0

O
Oleic acid
OH C18:1Δ9
ω-9

O
Linoleic acid
OH C18:2Δ9,12
ω-6,9

O
Linolenic acid
OH C18:3Δ9,12,15
ω-3,6,9
 Effect of Structure on Melting Points
Some important fatty acids:
No. of Carbon Name Formula Melting point
Saturated
C16:0 Palmitic acid CH3(CH2)14–COOH 63 oC
C18:0 Stearic acid CH3(CH2)16–COOH 70 oC

Monounsaturated
C16:1 Palmitoleic acid CH3(CH2)5CH=CH(CH2)7–COOH -1 oC
C18:1 Oleic acid CH3(CH2)7CH=CH(CH2)7–COOH 13 oC

Increase in chain length (more C) à increase in melting point of the lipid

(more likely to be solid at room temperature)
Increase unsaturation (more double bonds) à decrease melting point
(more likely to be liquid at room temperature) 50
 Effect of Structure on Melting Points

• Cis configuration will create a

bend or kink in the fatty acid
chain that is not found in
saturated fatty acids
• These kinks prevent
unsaturated fatty acids from
One cis- Cis packing closely together
double double
bond bond • As a result, they form less
London dispersion forces
C18:0 C18:1 C18:2 between the fatty acids
• This leads to fatty acids with
Extracted from: Seager SL, Slabaugh MR,
2005, Organic and Biochemistry for lower melting points 51
TODAY, 5th ed., pg.229 AY 18/19
 Effect of Structure on Melting Points
Trans isomer Cis isomer

trans
cis

“Kink” “Kink”

Trans form of cis form creates

fatty acids. more space in
the layer and
prevent tight
Packs better packing.
than cis form.

• The cis form of the fatty acid usually bends with greater angle (e.g. 90°)
• The trans form of the fatty acid bends with smaller angle (as compared to the cis form)
Kink on fatty acid carbon chain affects
packing density Packed tightly

Saturated fatty acids

If you put many fatty acids side-by-
side together …

… saturated fatty acids are packed Unsaturated fatty

more tightly than unsaturated fatty

acids – trans form

acids.

… the cis form of unsaturated fatty Unsaturated fatty

acids cannot be packed as tightly as acids – cis form

trans form of unsaturated fatty 29

acids.
Not packed tightly
 Non-essential vs Essential Fatty Acids
• Most fatty acids are considered as non-essential
fatty acids
– This means that the body can synthesize them when
needed
• Essential fatty acids cannot be synthesized in the
body, but are required for normal functioning of the
body
– Therefore, they have to be supplied in the diet as fats
• Essential fatty acids can be found in fish, shellfish,
canola oil, sunflower seed, leafy vegetables etc.
 Essential Fatty Acids
• Examples of essential fatty acids include linoleic
(omega-6 fatty acid) and linolenic acids
(omega-3 fatty acid)
– Both are found in plant and fish oils
• These essential fatty acids are used by our
bodies to make:
– certain hormones, vitamins, and
– prostaglandins (hormone-like substance used to
regulate e.g. blood pressure, blood clotting).
 Phospholipids
• Replacement of a fatty acid (acyl) in triacylglycerol by a
phosphate group produces phospholipids
• Phospholipids (or phosphoglycerides) are lipids
containing glycerol, two long chain fatty acids, and a
phosphate group
Phosphate
group
G Fatty acid
L
Y Glycerol
C backbone
E
Fatty acid
R Ester bond
O
L
Phosphate group
2 Fatty acids
 Phospholipids
A phospholipid molecule contains a hydrophilic,
polar head and a hydrophobic, non-polar tail.

Hydrophilic Hydrophobic
The phosphate group is The carbon chain is non-polar. 50
charged 2-, so it can interact It is hydrophobic and cannot
with H2O molecules. interact with H2O molecules.
 Formation of micelles and bilayers
• In water, phospholipids organise themselves into
micelles and lipid bilayers.
• The hydrophilic portion of phospholipids face
outwards and interacts with the surrounding
water molecules. Hydrophobic tails point inwards
and aggregate to form a hydrophobic core.

Water molecule
Hydrophilic, polar head of
phospholipid (grey) interacts with the
surrounding water molecule.
The hydrophobic tail portion
aggregates to form a hydrophobic
core.
Formation of micelles and bilayers
Phospholipids can assemble into various
structures.
1. Liposomes or vesicles: made of a
phospholipid bilayer forming a hollow centre,
and containing a hydrophilic core surrounded
by a hydrophobic layer. Useful for
transporting hydrophilic substances
internally.
2. Micelles: made of a phospholipid monolayer,
and containing a hydrophobic core. Useful for
transporting hydrophobic substances
internally.
3. Phospholipid bilayers which resemble sheets,
containing a hydrophilic surface and a
hydrophobic centre. Useful for forming
membrane walls.

Picture source: retrieved from http://en.wikipedia.org/wiki/File:Phospholipids_aqueous_solution_structures.svg

The phospholipid bilayer is a main component
of cell membranes

53

Source: Brooker et al. Biology. 2nd edition.

 Biological Functions
• Structural components of cell membrane

Source: Brooker et al. Biology. 2nd edition.

Self-check:
• How are lipids classified?
• Explain why linoleic acid (C18:2) has a lower
melting point than stearic acid (C18:0)