Lipida/Lemak

Lipids
5 Maret 2013

Lipids
Lipids are
Biomolecules that contain fatty acids or a steroid
nucleus.
Soluble in organic solvents but not in water.
Named for the Greek word lipos, which means fat.
Extracted from cells using organic solvents.

Types of Lipids
The types of lipids containing fatty acids are
Waxes.
Fats and oils (triacylglycerols).
Glycerophospholipids.
Prostaglandins.
Not steroids, as they do not contain fatty acids.

Structures of Lipids

Fatty Acids

Fatty Acids
Fatty acids
Are long-chain
carboxylic acids.
Typically contain 12-18
carbon atoms.
Are insoluble in water.
Can be saturated or
unsaturated.

CLASSIFICATION AND
NOMENCLATURE
8

10

11

12

13

14

15

Unsaturated Essential Fatty Acids

17

18

19

20

BIOCHEMISTRY
21

Saturated Fatty Acids

Saturated fatty acids have
Single CC bonds.
Molecules that fit closely together
in a regular pattern.
Strong attractions between fatty
acid chains.
High melting points that make
them solids at room temperature.

22

Some Saturated Fatty Acids

23

Unsaturated Fatty Acids

Unsaturated fatty acids
Have one or more double C=C bond
Typically contain cis double bonds.

24

Cis and Trans Fatty Acids

Unsaturated fatty acids can be
Cis with bulky groups on same side of C=C.
CH3 (CH2)5
(CH2)7 COOH cis
C=C
H

Trans have bulky groups on opposite sides of C=C.

CH3 (CH2)5
H
C=C
H

trans
(CH2)7 COOH
25

26

Properties of Unsaturated Fatty

Acids
Unsaturated fatty acids
Have kinks in the fatty
acid chains.
Do not pack closely.
Have few attractions
between chains.
Have low melting points.
Are liquids at room
temperature.

kinks in
chain

27

Unsaturated Fatty Acids

28

Comparing Melting Points of

Some Fatty Acids

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

29

Learning Check
Assign the melting points of 17C, 13C, and 69C
to the correct fatty acid. Explain.
stearic acid (18 C) saturated
oleic acid (18 C) one double bond
linoleic acid (18 C) two double bonds

30

Solution
Stearic acid is saturated and would have a higher
melting point than the unsaturated fatty acids.
Because linoleic has two double bonds, it would have
a lower mp than oleic acid, which has one double
bond.
stearic acid mp 69C saturated
oleic acid mp 13C
linoleic acid mp -17C most unsaturated

31

Omega-6 and Omega 3- Fatty

Acids
Fatty acids
In vegetable oils are mostly omega-6 with
the first C=C at C6.
linoleic acid
CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH
6

In fish oils are mostly omega-3 with the

first C=C at C3.
linolenic acid
CH3CH2(CH=CHCH2)3(CH2)6COOH
3

Copyright 2007 by Pearson Education, Inc. 32

Publishing as Benjamin Cummings

Some Omega-6 and Omega-3

Fatty Acids

33

34

Learning Check
Write a fatty acid with 10 carbon atoms that is:
A. saturated
B. monounsaturated omega-3
C. monounsaturated omega-6

35

Solution
Write a fatty acid with 10 carbon atoms that is:
A. saturated
CH3CH2CH2CH2CH2CH2CH2CH2CH2COOH

B. monounsaturated omega-3
CH3CH2CH=CHCH2CH2CH2CH2CH2COOH

C. monounsaturated omega-6
CH3CH2CH2CH2CH2CH=CHCH2CH2COOH
36

Waxes, Fats, and Oils

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

37

Waxes
Waxes are
Esters of saturated fatty acids and long-chain alcohols.
Coatings that prevent loss of water by leaves of plants.
TABLE 17.2

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

38

Fats and Oils: Triacylglycerols

Fats and oils are
Also called triacylglycerols.
Esters of glycerol.
Produced by esterification.
Formed when the hydroxyl
groups of glycerol react with the
carboxyl groups of fatty acids.

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
39

Triacylglycerols
In a triacylglycerol,
Glycerol forms ester bonds with three fatty acids.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

40

Formation of a Triacylglycerol
glycerol

three fatty acids

O

triacylglycerol

CH2

OH

HO C
O

(CH2)14CH3

CH

OH

HO C
O

(CH2)14CH3

HO C

(CH2)14CH3 CH2 O C

CH2

OH

O
(CH2)14CH3

O
CH O C

(CH2)14CH3

+ 3H2O

O
CH2 O C

(CH2)14CH3
41

Olive Oil
Olive oil
Contains a high
percentage of oleic
acid, which is a
monounsaturated fatty
acid with one cis
double bond.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

42

Learning Check
What are the fatty acids in the following triacylglycerol?
O
CH2

(CH2)16CH3

O
CH

CH2

C (CH2)7CH CH(CH2)7CH3
O
C

(CH2)12CH3

43

Solution
O
CH2

(CH2)16CH3

O
CH

CH2

Stearic acid

C (CH2)7CH CH(CH2)7CH3
O
C

(CH2)12CH3

Oleic acid

Myristic acid

44

Melting Points of Fats and Oils

A triacylglycerol that is a fat
Is solid at room temperature.
Is prevalent in meats, whole milk, butter, and cheese.
A triacylglycerol that is an oil
Is liquid at room temperature.
Is prevalent in plants such as olive and safflower.

45

Oils with Unsaturated Fatty Acids

Oils
Have more unsaturated fats.
Have cis double bonds that cause kinks in the
fatty acid chains.
Cannot pack triacylglycerol molecules as close
together as in fats.
Have lower melting points than saturated fats.
Are liquids at room temperature.

46

Diagram of Triacylglycerol with

Unsaturated Fatty Acids

Unsaturated fatty acid

chains have kinks that
do not allow close
packing.
Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

47

Saturated and Unsaturated Fatty

Acids In Fats and Oils

48
Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Chemical Properties of
Triacylglycerols

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

49

Chemical Properties of
Triacylglycerols
The chemical reactions of triacylglycerols are similar
to those of alkenes and esters.
In hydrogenation, double bonds in unsaturated
fatty acids react with H2 in the presence of a Ni or
Pt catalyst.
In hydrolysis, ester bonds are split by water in the
presence of an acid, a base, or an enzyme.

50

Hydrogenation of Oils
The hydrogenation of oils
Adds hydrogen (H2) to the carbon atoms of double bonds.
Converts double bonds to single bonds.
Increases the melting point.
Produces solids such as margarine and shortening.

51
Copyright 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

Hydrogenation
O
CH2

(CH2)5CH CH(CH2)7CH3

O
CH

CH2

Ni

C (CH2)5CH CH(CH2)7CH3
O
C

+ 3HO
2

(CH2)5CH CH(CH2)7CH3 CH2

(CH2)14CH3

O
glyceryl tripalmitoleate
(tripalmitolean)

CH

CH2

C (CH2)14CH3
O
C

(CH2)14CH3

glyceryl tripalmitate
(tripalmitin)

52

Trans Fatty Acids and

Hydrogenation
Trans fatty acids
Are formed during hydrogenation when cis double
bonds are converted to trans double bonds.
In the body behave like saturated fatty acids.
Are estimated to make up 2-4% of our total
Calories.
Are reported in several studies reported to raise
LDL-cholesterol and lower HDL-cholesterol.

53

54

Learning Check
(1) True or (2) False
A. There are more unsaturated fats in vegetable oils.
B. Vegetable oils have higher melting points than fats.
C. Hydrogenation of oils converts some cis-double
bonds to trans- double bonds.
D. Animal fats have more saturated fats.

55

Solution
(1) True or (2) False
A. T There are more unsaturated fats in vegetable oils.
B. F Vegetable oils have higher melting points than fats.
C. T Hydrogenation of oils converts some cis-double
bonds to trans- double bonds.
D. T Animal fats have more saturated fats.

56

Hydrolysis
In hydrolysis,
Triacylglycerols split into glycerol and three fatty acids.
An acid or enzyme catalyst is required.
O

CH2

CH

CH2

C
O

(CH2)14CH3

C (CH2)14CH3
H2O
+3
O
C

(CH2)14CH3

H+
CH2 OH
CH

OH

CH2

OH

+3

HO C

(CH2)14CH3

57

Saponification and Soap

Saponification
Is the reaction of a fat with a strong base.
Splits triacylglycerols into glycerol and the salts of
fatty acids.
Is the process of forming soaps (salts of fatty
acids).
With KOH gives softer soaps.

58

Saponification
O
CH2 O C

(CH2)14CH3

O
CH O C

(CH2)14CH3

O
CH2 O C

(CH2)14CH3

+ 3NaOH

CH2 OH
CH OH

+ 3
CH2 OH

O
Na+ -O C

(CH2)14CH3

soap
59

Learning Check
Write the product of the following reaction.
O
CH2

O C
O

(CH2)5CH CH(CH2)7CH3

CH

C (CH2)5CH
O

CH2

(CH2)5CH

CH(CH2)7CH3

H2
+3

Ni

CH(CH2)7CH3

60

Solution
O
CH2

C
O

CH

C (CH2)14CH3
O

CH2

(CH2)14CH3

(CH2)14CH3

61

Cholesterol
Cholesterol
Is the most abundant steroid in the body.
Has methyl CH3- groups, alkyl chain, and -OH
attached to the steroid nucleus.
CH3
CH3

CH3

CH3

CH3

HO
62

Cholesterol in the Body

Cholesterol in the body
Is obtained from meats,
milk, and eggs.
Is synthesized in the liver.
Is needed for cell
membranes, brain and
nerve tissue, steroid
hormones, and Vitamin D.
Clogs arteries when high
levels form plaque.

A normal, open artery.

An artery clogged by
cholesterol plaque
Copyright 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings

63

Cholesterol in Foods
Cholesterol is
Synthesized in
the liver.
Obtained from
foods.
Considered
elevated if
plasma
cholesterol
exceeds 200
mg/dL.

TABLE 17.4

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

64

Steroid Hormones
low solubility in water
transported by proteins,
can pass through
membranes

Vitamin A and D
Isoprene is a common
precursor for sterols, Vitamin
D and Vitamin A

CH2=C(CH3)-CH=CH2

D vitamins derived from

Sterols

LIPID OXIDATION

Introduction
Oxidative deterioration of lipids containing any
number of carbon-carbon double bonds

Fatty acids
Cholesterol

Produces various primary and secondary byproducts that influence food quality
Oxidized foods can cause oxidative stress in
biological systems and cause diseases

Implications to meat (food) products

A major cause of quality deterioration

Develop rancidity in raw or fatty tissues

Produces WOF in cooked meats
Oxidized flavors in oils

Loss of functional properties

Loss of nutritional values
Formation of toxic compounds
Forms colored products

Production of toxic compounds

Many secondary by-products of lipid oxidation are
potential carcinogens
Hydroperoxides are known to damage DNA
Carbonyl compounds may affect cellular signal
transduction
Aldehydes: 4-HNE and MDA
Epoxides and hydrogen peroxide by-products are
known carcinogens

Types of Rancidity
Hydrolytic rancidity
Lipase
Free fatty acids provide aroma
Oxidative rancidity
Radical oxidation
Aldehydes and other compounds provide aroma

Oxidative Rancidity
Part 1: Form lipid hydroperoxides
Part 2: Break down lipid hydroperoxides

Oxidative Rancidity
Initiation
A radical is formed
Propagation
Radicals react and transfer their unpaired electron
to other compounds
Termination
Two radicals combine to stop the reaction

Reactive Oxygen Species and Free

Radicals
Reactive Oxygen Species
Triplet oxygen
Superoxide
Singlet Oxygen
Hydroperoxyl radical
Hydroxyl radical
Hydrogen peroxide
Ozone
Peroxyl radical (ROO.)
Alkoxyl radical (RO.)
Iron-oxygen complexes (ferryl and perferryl
radicals)
Thiyl radicals (RS.)
Nitric oxide (.NO)

76

Reactive Oxygen Species - Ground-state oxygen (3O2)

Oxygen is the most important factor on the development of lipid
oxidation
Ground state oxygen is itself a radical, with two unpaired electrons
each located in a * antibonding orbital
Ground state oxygen has its outermost pair of electrons parallel
spins: does not allow them to react with most molecules
Ground-state or triplet oxygen is not very reactive
Can be activated by the addition of energy, and transformed into
reactive oxygen species

Singlet oxygen (1O2)

Formed from triplet oxygen
Conversion of oxygen to singlet state can be
accomplished by photosensitization in the
presence of suitable sensitizers, such as
chlorophyl, or heme pigments myoglobin or
hemoglobin or by their derivatives
Has a pair of electrons with opposite spins

The Pentadiene Structure

H H H
C C C C C
H H H
RH

R
H

.
Radical Migration

Addition of Oxygen
- Propagation R

+O2
.

ROO +RH

ROO

ROOH

+R

Each methylene interrupter can lead to three possible lipid hydroperoxides!

Termination

Part 2: Hydroperoxide Breakdown

(1)

(2)

Factors affecting rate

Fatty acid composition

Temperature
Water activity
Metal ions
Oxygen
Light

Types of Fatty Acids and Oxidation Rates

As # of double bonds increases # and reactivity of
radicals increases
Type of Fatty Acid

18:0
18:19
18:29,12
18:39,12,15

Rate of Reaction Relative to Stearic Acid

1
100
1200
2500

Measurement of lipid oxidation

Direct measurement of free radicals

Electron spin resonance

Spin trapping methods

Indirect approach: Measures markers of free radicals

Thiobarbituric acid reacting substances (TBARS)

Lipid chromatography: Fluorometric compounds

Gas chromatography: Gaseous compounds

Conjugated dienes (CD)

Peroxide value

Iodine Value

TBA analysis

Implications of Lipid Oxidation to

Human Health

Oxidative Stress

Prevention of Lipid Oxidation in Meat

1. Interrupt the free-radical chain mechanism:

phenolic antioxidants
2. Function as being preferentially oxidized:
ascorbate
3. Chelating agents for free iron
4. Changing environments: packaging
5. Dietary modification of fatty acids, vitamin E
enrichment

Synthetic antioxidants

TBHQ

PG

Natural antioxidants

Flavone

Isoflavone

Epicatechin

Quercetin
Tocopherol

Sesamol

Iron Chelating Agents

Phosphate
EDTA
Citric acid
DTPA
Desferrioxamine

Ideal Antioxidants
No harmful physiological effects
Not contribute an objectionable flavor, odor,
or color to the product
Effective in low concentration
Fat soluble
Carry-through effect no destruction during
processing
Readily available
Economical
Non-absorbable by the body

You are what you eat!