LIPIDA

Lipids a broad group of

compounds that are generally
soluble inorganic solvents, but
only sparingly soluble in water
C , H, O -- but less O
2
than carbs

Triglycerides = fats/oils
Cholesterol: technically a
complex lipid
ROLES OF FAT
Provides concentrated source of energy at
9 calories / gram; reserve of energy in
the body
Carries essential fatty acids, fat-soluble
vitamins
Enhances palatibility/texture, flavor,
satiety
Cushions organs, insulation
Components of cell membranes

LIPIDA
Asam lemak Jenuh C
4
-C
8
= berupa cairan;
>C
8
= berupa padatan
Adanya ikatan rangkap menurunkan titik
cair
Konfigurasi struktur asam lemak jenuh
sangat berbeda sekali dengan asam lemak
tidak jenuh
Adanya ikatan rangkap menyebabkan
adanya isomer geometrik (cis dan trans)
Ikatan rangkap bentuk cis kurang stabil
dibanding trans
ROLE OF LIPIDS IN FOOD
Enhance Flavor
Satiety
Texture
Solid to Liquid
Enhance Tenderness of Pie Crusts
Flakiness : croissant
Carry fat-soluble vitamins
Can be visible or hidden
Lipids classification
Major Class Subclass Description

Simple lipids Acyl glycerols Glycerol + fatty Acids
Waxes Long chain alcohol + long chain FA

Compound PAG Glycerol + FA +phosphates + other
lipids group N-containing
Sphingolipids Sphingosine + FA + phosphat + Choline
Cerebrocides Sphingosine + FA + simple sugar
Gangliosides Sphingosine + FA + complex carbohydate
moiety

Derived Materials that carotenoids, steroids,
lipids meet lipid def. Fat soluble vitamins
(other than two
class)
Neutral lipids
Glycerides:
Ester of glycerol -
mono glycerides,
diglycerides and
triglycerides

Waxes :
simple esters
of long chain alcohols

H
3
C (CH
2
)
14
C
O
O CH
2
(CH
2
)
28
-CH
3
long chain alcohol
fatty acid
CH
2
OH
CH
2
OH
OH H OH
OH
OH
glycerol is a prochiral molecule
O
OH
OH
R
O
O
OH
O
R
O
R
O
O
O
R
O
R
O
O R
O
MONOGLYCERIDE
DIGLYCERIDE
TRIGLYCERIDE
Function: storage of energy in compact form and
cushioning

GLYCERIDE
H

H--COH


H--COH +


H--COH

H
O

HO-C-R

O

HO-C-R

O

HO-C-R

H O
H--C--O--CH + H
2
O
O
H--C--O--CH + H
2
O
O
H--C--O--CH + H
2
O
H
(Ester bond)
TRIGLISERIDA
Glyserol + 3 FAs Triglyseride + 3 H
2
O
esterification


hydrolysis
H
H--C--OH

H--COH +

H--C--OH
H
Fatty Acid
Fatty Acid
Fatty Acid
H O

H--C--O--Cfatty acid

O

H--C--O--Cfatty acid

O

H--C--O--Cfatty acid

H
TRIGLISERIDA
Triasilgliserol/Trigliserida (Lipida netral)
Triglyceride = glycerol with 3 fatty acid
chains
(CH
2
)
14
H
3
C CH
2
-OH
cetyl alcohol
(CH
2
)
24
H
3
C CH
2
-OH
hexacosanol
(CH
2
)
28
H
3
C CH
2
-OH
triacontanol (myricyl alcohol)
Waxes
Long chain alcohol + long chain FA
Examples of long chain monohydric
alcohols found in waxes

Fatty acids
Carboxylic acid derivatives of long chain
hydrocarbons
General structure:
CH3 (CH2)n COOH
n is always even
Chain of C with -COOH end
H- along -C- chain

Nomenclature
Stearate stearic acid C18:0 n-
octadecanoic acid
-Long chain FA > 12 Carbons
-Medium chain FA 6 - 10 Carbons
-Short chain FA < 6 Carbon
Classification of Fatty Acids C
chain
The chain length has an effect on
how liquid a fat/oil is at room
temperature

Common fatty acids
n = 4 butyric acid (butanoic acid)
n = 6 caproic acid (hexanoic acid)
n = 8 caprylic acid (octanoic acid)
n = 10 capric acid (decanoic acid)
n = 12 lauric acid (n-dodecanoic acid; C
12:0
)
n = 14 myristic acid (n-tetradecanoic acid; C
14:0
)
n = 16 palmitic acid (n-hexadecanoic acid; C
16:0
)
n = 18 stearic acid (n-octadecanoic acid; C
18:0
)
n = 20 arachidic (eicosanoic acid; C
20:0
)
n = 22 behenic acid
n = 24 lignoceric acid
n = 26 cerotic acid
Fatty acids
Fatty acids can be classified either as:
according to chain length:
saturated or unsaturated
essential fatty acids vs those that can be
biosynthesized in the body:
linoleic and linolenic are two
examples of essential fatty acid

Classification of Fatty Acids double
bond
Saturated fatty acids
No double bonds
solid at room temp

Monounsaturated FA
One double bond
liquid at room temp

Polyunsaturated FA (PUFA)
>= 2 double bonds
liquid at room temp
Omega 3 FA from fish
The building block of lipids are fatty
acids
Omega end alpha end

Note that all carbons have two hydrogens this is a fully saturated fatty
acid.

H H H H H H H H H H H H H H H H H O
H-C--C--C--C--C--C--C--C--C--C--C--C--C--C--C--C--C-C-OH
H H H H H H H H H H H H H H H H H
Unsaturated fatty acids
Monoenoic acid (monounsaturated)







H
3
C
HOOC
Double bond is always
cis in natural fatty acids.
This lowers the melting
point due to kink in
the chain
Monounsaturated Fatty Acid (MUFA)
Structure
H H H H H H H H H H H H H H H O
H-C--C--C--C--C--C--C--C--C=C--C--C--C--C--C--C--C--C-OH
H H H H H H H H H H H H H H H H H

Omega end

Alpha end


When two Hs are lost from two adjacent Carbons, a double bond is
formed. This is an unsaturated FA

Polyunsaturated Fatty Acid (PUFA) Structure
H H H H H H H H H H H H O
H-C--CC=C--C--C=C--C--C=C--C--C--C--C--C--C--C--C-OH
H H H H H H H H H H H H H H H H

omega end alpha end
Two or more double bonds results in
a polyunsaturated fatty acid.

Unsaturated fatty acids
Monoenoic acids (one double bond):
16:1, 9 w7: palmitoleic acid (cis-9-hexadecenoic acid
18:1, 9 w9: oleic acid (cis-9-octadecenoic acid)
18:1, 9 w9: elaidic acid (trans-9-octadecenoic acid)
22:1, 13 w9: erucic acid (cis-13-docosenoic acid)
24:1, 15 w9: nervonic acid (cis-15-tetracosenoic
acid)

Unsaturated fatty acids
Dienoic acid: linoleic acid
(CH
2
)
4
CH
3
CH=CH CH
2
CH=CH (CH
2
)
7
COOH
cis
linoleic acid
Unsaturated fatty acids
Polyenoic acid (polyunsaturated)
COOH
CH
3
Unsaturated fatty acids
Trienoic acids (3 double bonds)
18:3;6,9,12 w6 : g-linolenic acid (all cis-6,9,12-
octadecatrienoic acid)
18:3; 9,12,15 w3 : a-linolenic acid (all-cis-9,12,15-
octadecatrienoic acid)
Tetraenoic acids (4 double bonds)
20:4; 5,8,11,14 w6: arachidonic acid (all-cis-
5,8,11,14-eicosatetraenoic acid)
Unsaturated fatty acids
Pentaenoic acid (5 double bonds)
20:5; 5,8,11,14,17 w3: timnodonic acid or
EPA (all-cis-5,8,11,14,17-eicosapentaenoic
acid)*
Hexaenoic acid (6 double bonds)
22:6; 4,7,10,13,16,19 w3: cervonic acid or
DHA (all-cis-4,7,10,13,16,19-
docosahexaenoic acid)*

Both FAs are found in cold water fish oils
RCO
2
H + NaHCO
3
RCO
2
()
Na
(+)
+ CO
2
+ H
2
O
RCO
2
H + (CH
3
)
3
N: RCO
2
()
(CH
3
)
3
NH
(+)

RCO
2
H + AgOH RCO
2
()
Ag
(+)
+ H
2
O
Special reactions of fatty acids
Carboxylic acids react with bases to form ionic salts,
In the case of alkali metal hydroxides and simple
amines (or ammonia) the resulting salts have
pronounced ionic character and are usually soluble
in water.
Heavy metals such as silver, mercury and lead form
salts having more covalent character and the water
solubility is reduced, especially for acids composed
of four or more carbon atoms.
PHOSPHOLIPID
Phospholipid
MONOLAYER
BILAYER
Gambar. Liposom
OH
NH
2
OH
NH
2
OH
HO
R
long chain hydrocarbon
attach fatty acid here
attach polar head group here
sphingosine
Based on sphingosine instead of glycerol

Sphingolipids
SPHINGOLIPID
NH
O
HO
R
P
O
O-
O
N(CH
3
)+
R'
O
usually palmitic acid
phosphatidyl choline
(also can be
ethanolamine)
Sphingomyelin
NH
O
HO
R
R'
O
SUGAR
polar head is a sugar
beta linkage
Glycolipids
GLYCOLIPIDS
Lipoproteins
particles found in plasma that transport lipids
including cholesterol
lipoprotein classes
chylomicrons: take lipids from small intestine
through lymph cells
very low density lipoproteins (VLDL)
intermediate density lipoproteins (IDL)
low density lipoproteins (LDL)
high density lipoproteins (HDL)
A multi-ringed structure
Do not have a glycerol backbone
Waxy substance
Do not readily dissolve in water
Cholesterol is a sterol

Sterols
Cholesterol
Sterol family member
Found in large amounts in the plasma membrane
Fill spaces between neighboring phospholipid
molecules
Tend to make bilayers more rigid and less
permeable


HO
H H
H
O
H H
H
R
O
usually palmitate
Cholesterol and cholesterol esters
The hydroxyl at C-3 is hydrophilic; the rest
of themolecule is hydrophobic; also 8
centers of asymmetry

Functions of cholesterol
serves as a component of membranes
of cells (increases or moderates
membrane fluidity)
precursor to steroid hormones and bile
acids
storage and transport cholesterol
esters

Less common fatty acids
iso isobutyric acid,
Branched
odd carbon fatty acid
propionic acid
hidroxy fatty acids
ricinoleic acid,
dihydroxystearic acid,
cerebronic acid
cyclic fatty acids
hydnocarpic,
chaulmoogric acid

H
3
C
R
CH
3
(CH
2
)
12
-CO
2
H (CH
2
)
10
-CO
2
H
chaulmoogric acid
hydnocarpic acid
H
3
C
R
CH
3
Stereospecific numbering
C-1 and C-3 of the glycerol molecule become
sn1 and sn3 respectively

carbon 2 of triglycerides is frequently
asymmetric since C-1 and C-3 may be
substituted with different acyl groups

by convention: the hydroxyl group at C-2 to
the left and use the designation of sn2 for
that particular substituent

Emulsifier
Hydrophilic end
(attracts water)


Hydrophobic end
(attracts lipid)
Emulsification
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
GLYCOLIPIDS
Cerebrosides
One sugar molecule
Galactocerebroside in neuronal membranes
Glucocerebrosides elsewhere in the body
Sulfatides or sulfogalactocerebrosides
A sulfuric acid ester of galactocerebroside
Globosides: ceramide oligosaccharides
Lactosylceramide
2 sugars ( eg. lactose)
Gangliosides
Have a more complex oligosaccharide attached
Biological functions: cell-cell recognition; receptors for
hormones
Lipoprotein classes
Chylomicrons B48 85%
VLDL B100/E 20% 55%
IDL B100/E 35% 25%
LDL B100 60% 5%
HDL AI/II/E 20% 5%
protein choles. triglycerides

LDL is not measured but calculated:
LDL-C = total cholesterol - (HDL-C + TG/5)
(Triglycerides must be <4.5 mmol/L or < 400 mg/dL)
LDL molecule
STEROID NUMBERING SYSTEM
A B
C
D
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Testosterone
(a steroid hormone)
Vitamin D3
(cholecalciferol)