Lipids

26-1
Definisi (=Fessenden)

Bhs Yunani Lipos = lemak

Senyawa yang tak larut dalam air
yang dapat dipisahkan dari sel &
jaringan dengan cara ekstraksi
menggunakan pelarut organik yang
relatif non polar, mis. dietil eter
atau kloroform
Golongan ester organik

26-2
Lipids (LEMAK)
 Lemak: Kelompok senyawa heterogen yang
secara alami keberadaannya dikelompok
bersama dengan senyawa organnik berdasarkan
sifat kelarutannya.
• Lemak tidak larut air tapi larut dalam pelarut organik
aprotik., including diethyl ether, methylene chloride,
and acetone.
 Lemak termasuk:
• Trigliserida, fosfolipid, prostaglandins, prostacyclins,
dan vitamin larut lemak.
• Kolesterol, hormon steroid, feromon.

26-3
 Klasifikasi, menurut Bloor
LIPId

sederhana majemuk

•Tersusun atas C, H, O •Tersusun atas C, H, O, P, N,

•Klasifikasi: S
1. Lemak (fat) = ester residu •Klasifikasi:
penyusunnya gliserol Dan asam
lemak, co: tripalmitin, tristearin 1. phospolipid
2. Lilin (wax) = ester residu
penyusunnya alkohol suku tinggi
2. sphingolipid
Dan asam lemak, co: 3. inositollipid
cholesterilpalmitat, dll
26-4
 KLASIFIKASI LEMAK
1. Berdasarkan sumbernya : lemak nabati dan lemak
hewani
2. Berdasarkan jenis asam lemak penyusunya : lemak
jenuh dan lemak tak jenuh
3. Berdasarkan jumlah jenis asam lemak penyusunnya:
lemak berasam 1, lemak berasam 2 dan lemak
berasam 3 = 1 palmito, 2 stearo, 3 olein
4. Berdasarkan bentuknya pada suhu kamar: lemak
padat (fat) dan lemak cair (minyak)

26-5
GLISERIDA
 Sebagian besar lemak dan minyak dalam alam terdiri
dari 98- 99% trigliserida.
 Trigliserida  ester gliserol dan asam lemak yang
tepatnya disebut triasilgliserol.
 Bila asam lemak dalam trigliserida adalah sama maka
disebut trigliserol sederhana ; bila berbeda dinamakan
trogliserol campuran.
 Bila satu asam lemak bergabung dengan gliserol,
maka lemak tersebut dinamakan monogliserida dn bila
dua, digliserida

26-6
Komponen Penyusun

1. Gliserol = gliseril
= propanatriol 1,2,3 alkohol

H2C – CH – CH2
| | |
OH OH OH
 Sifat :
1. Pada suhu kamar → zat cair, kental, rasanya manis
2. Higroskopis
3. Larut dalam air

26-7
 Komponen Penyusun

2. Asam-asam lemak
 Asam monokarboksilat dengan rantai
lurus Dan radikal karboksilnya terletak di
ujung rantai karbon
 Mempunyai jumlah aton C yang genap
 Berupa asam lemak jenuh Dan asam
lemak tak jenuh

26-8
Beberapa asam lemak yang biasa ditemukan

26-9
Fatty Acids
 Asam lemak: Asam karboksilat yang berasal dari hidrolisis
lemak hewani, minyak nabati, atau membran fosfolipid.
 Hampir semua memiliki jumlah atom karbon genap, sebagian
besar antara 12 dan 20, dalam rantai yang tidak bercabang.
 Tiga asam lemak yang paling melimpah adalah palmitat (16:
0), stearat (18: 0), dan asam oleat (18: 1), di mana angka
pertama adalah jumlah karbon dan yang kedua adalah jumlah
ikatan rangkap dalam rantai hidrokarbon .
 Pada sebagian besar asam lemak tak jenuh, isomer cis
mendominasi; isomer trans jarang terjadi.
 Asam lemak tak jenuh memiliki titik leleh yang lebih rendah
daripada asam jenuhnya; semakin besar derajat
ketidakjenuhan, semakin rendah titik lelehnya.
26-10
Fatty Acids (Asam lemak)
 The most common fatty acids.
Carbon Atoms: Common Melting Point
Double Bonds Name (°C)
Saturated Fatty Acids
12:0 Lauric acid 44
14:0 Myristic acid 58
Higher 16:0 Palmitic acid 63
melting 18:0 Stearic acid 70
point 20:0 Arachidic acid 77
Unsaturated Fatty Acids
16:1 Palmitoleic acid 1
Lower 18:1 Oleic acid 16
melting 18:2 Linoleic acid -5
18:3 Linolenic acid -11
point
20:4 Arachidonic acid -49
26-11
Triglycerides
• example: a triglyceride derived from one molecule
each of palmitic acid, oleic acid, and stearic acid, the
three most abundant fatty acids in the biological world.

O p almitate (16:0)
oleate (18:1)
O CH2 OC(CH2 ) 1 4 CH3
stearate (18:0)
CH3 ( CH2 ) 7 CH=CH(CH2 ) 7 COCH O
CH2 OC(CH2 ) 1 6 CH3

26-12
Triglycerides
 Triglyceride: Ester dari gliserol dengan 3 asam
lemak.

Reaksi Saponification
O
O CH2 OCR CH2 OH RCOOH
1 . NaOH, H2 O
R'COCH O HOCH + R'COOH
2 . HCl, H2 O CH2 OH
CH2 OCR'' R''COOH
A triglyceride 1,2,3-Prop anetriol Fatty acids
(Glycerol, glycerin)

26-13
Triglycerides
 Sifat fisik tergantung pada komponen asam
lemak.
 Titik lebur meningkat ketika jumlah karbon dalam
rantai hidrokarbonnya meningkat dan ketika
jumlah ikatan rangkap menurun.
 Minyak: Trigliserida yang kaya asam lemak tak
jenuh umumnya cair di kamar.
 Lemak: Trigliserida yang kaya asam lemak jenuh
pada umumnya semi padat atau padat pada suhu
kamar.

26-14
Sabun dan detergen
 Sabunalami dibuat dengan mereaksikan lemak
hewani lainnya dengan NaOH, dalam suatu reaksi
yang disebut saponifikasi (Latin, sapo, soap).
O
O CH2 OCR saponification
RCOCH + 3 N aOH
O
CH2 OCR CH2 OH O
A triglyceride - +
CHOH + 3 RCO N a
(a triester of glycerol)
CH2 OH Sodium soaps
1,2,3-Propanetriol
(Glycerol; Glycerin)

COO-Na+

26-15
Soaps and Detergents
 Sabun bersih dengan bertindak sebagai agen
pengemulsi:
 Rantai hidrokarbon hidrofobiknya yang panjang
tidak larut dalam air dan cenderung
mengelompok sedemikian rupa sehingga
meminimalkan kontak dengan air.
 Disisi lain, Kelompok karboksilat hidrofilik polar,
cenderung tetap berhubungan dengan molekul
air di sekitarnya.
 Didorong oleh dua kekuatan ini, molekul sabun
secara spontan berkelompok menjadi misel.
26-16
Soaps and Detergents
• micelle: Susunan molekul organik berbentuk bola
dalam air terkelompok sehingga bagian hidrofobiknya
terkubur di dalam bola dan bagian hidrofiliknya berada
di permukaan bola dan bersentuhan dengan air.

• ketika sabun dicampur dengan minyak, minyak, dan

lemak yang tidak larut dalam air, bagian nonpolar dari
misel sabun “melarutkan” molekul-molekul kotoran
nonpolar ini dan mereka terbawa dalam air pencuci
yang bersifat polar.

26-17
Soaps and Detergents
• A soap micelle: nonpolar (hydrophobic) hydrocarbon
chains cluster in the inside and polar (hydrophilic)
carboxylate groups lie on the surface.

26-18
Soaps and Detergents
 Soaps form water-insoluble salts when used in
water containing Ca(II), Mg(II), and Fe(III) ions
(hard water).
- + + 2+
2 CH3 ( CH2 ) 1 4 COO Na Ca
A s odium soap
(soluble in water as micelles )
- 2+
[ CH3 ( CH2 ) 1 4 COO ] 2 Ca + 2 N a+

Calcium salt of a fatty acid

(insoluble in water)

26-19
Synthetic Detergents
 The design criteria for a good detergent are:
• a long hydrocarbon tail of 12 to 20 carbons.
• a polar head group that does not form insoluble salts
with Ca(II), Mg(II), or Fe(III) ions.
 The most widely used synthetic detergents are
the linear alkylbenzenesulfonates (LAS).

26-20
Synthetic Detergents
1 . H2 SO 4
CH 3 ( CH2 ) 1 0 CH 2
2 . Na OH
Dodecylbenzene

- +
CH 3 ( CH2 ) 1 0 CH 2 SO 3 Na

Sodium 4-dodecylbenzenesulfonate
(an anionic detergent)

 Also added to detergent preparations are:

• foam stabilizers.
• bleaches.
• optical brighteners.

26-21
Prostaglandins
 Prostaglandins:A family of compounds that have
the 20-carbon skeleton of prostanoic acid.
5 3 1
7
9
8 6 4 2 COOH
10

11 12 14 16 18 20
13 15 17 19
Pros tanoic acid

26-22
Prostaglandins, origin
 Prostaglandins are not stored in tissues as such,
but are synthesized from membrane-bound 20-
carbon polyunsaturated fatty acids in response
to specific physiological triggers.
• One such polyunsaturated fatty acid is arachidonic
acid (notice the all cis configurations).
9 8 6 5
COOH

11 12 14 15
Arachidonic acid

26-23
 Prostaglandins, examples
• Among the prostaglandins synthesized biochemically
from arachidonic acid are:
O
9

PGE2 COOH
15
11
HO
HO H
HO
9
PGF2 COOH
15
11
HO
HO H
PGE2 generated in macrophages of the liver and lungs
triggers the earliest phase of fever following any infection
26-24
Prostaglandins
 Research on the involvement of PGs in
reproductive physiology has produced several
clinically useful derivatives.
• (15S)-15-methyl-PGF2 is used as a therapeutic
abortifacient.
extra methyl group
HO at carb on -15
9

COOH
15
11
HO
HO CH3
(15S)-15-Methyl-PGF2

26-25
Prostaglandins
• The PGE1 analog, misoprostol, is used to prevent the
ulceration associated with the use of aspirin.
O
COOH
PGE 1
16
15
HO
HO H

O
COOCH 3
Misoprostol
HO CH 3

15 16
HO

26-26
Eicosanoids
 The prostaglandins are members of an even
larger family of compounds called eicosanoids,
all of which contain 20 carbons and are derived
from polyunsaturated fatty acids.
1
HOOC 5

9 6
8 1 O 7
O COOH H
9 8
H 14 20
15 20 15
11 O 12 14 11
13 13
OH OH OH
Th romboxane A2 Prostacyclin
(a potent vasoconstrictor) (a p latelet aggregation inhib itor)

26-27
Eicosanoids
 Leukotrienes are found primarily in white blood
cells.
• One function is constriction of smooth muscles,
especially those of the lungs.
HO
11 9 7 1
6 COOH
5
20
S O COOH glycine
14
N COOH
L-cysteine H
HN L-glutamic acid
Leukotriene C 4 (LTC4) N H2
(a smooth muscle constrictor) O

26-28
Steroids
 Steroids: A group of plant and animal lipids that
have this tetracyclic ring structure.

C D

A B

 The features common to the ring system of most

naturally occurring steroids are illustrated next.

26-29
Steroids
• The fusion of rings is trans and each atom or group at
a ring junction is axial.
• The pattern of atoms or groups along the ring
junctions is nearly always trans-anti-trans-anti-trans.
• The steroid system is nearly flat and quite rigid.
• Most have have axial methyl groups at C-10 and C-13.

CH3
CH3 H

H
H
H

26-30
Cholesterol

H3 C

H3 C
H
H H
HO

26-31
Androgens
 Androgens - male sex hormones.

OH O
H3 C H3 C
H
H3 C H H3 C H

H H H H
O HO
Testosterone Androsterone

26-32
Synthetic Anabolic Steroids
• A way to increase the testosterone concentration is to
use a prohormone, which the body converts to
testosterone; for example “andro”.
OH
H3 C HO CH3 H3 C
H3 C
H3 C H
CH3 H

H H H H
O
O H
Meth androstenolon e Meth enolone
O
H3 C OC(CH2 ) 8 CH3 H3 C O

H CH3 H3 C H

H H H H
O O
N and rolon e decan oate 4-An dros tene-3,17-dione
(an dro) 26-33
Available on the internet, dangerous
 Generic Name: methandrostenolone
Danabol / Dianabol has always been one of the most popular anabolic
steroids available. Danabol / Dianabol's popularity stems from it's almost
immediate and very strong anabolic effects. 4-5 tablets a day is enough to
give almost anybody dramatic results. It is usually stacked with deca
durabolin and testosterone enanthate. Along with strong anabolic effects
comes the usual androgen side effects, users often report an overall sense
of well being. Danabol / Dianabol is a strong anabolic and androgenic
product. It most often produced dramatic gains in size and strength. Danabol
/ Dianabol was also shown to increase endurance and glycogen retention.
 The down side is that this drug is responsible for a number of side effects. It
is an alpha alkylated 17 compound, which is quite toxic to the liver. Average
dosages for Danabol / Dianabol have been in the range of 15mg to 30mg a
day oral or 50mg to 100mg a week by injection. Regarded by many athletes
as being one of the most effective oral steroids ever produced. It was not
known as the "Breakfast of Champions" for nothing. Danabol / Dianabol is
still one of the most effective strength and size building oral steroids
probably second only to Anadrol 50 but it is not as harsh on the system as
Anadrol 50 is.
26-34
Estrogens
 Estrogens - female sex hormones.
CH3
C= O O
H3 C H3 C
H
H3 C H H

H H H H
O HO
Proges terone Estrone
OH O
H3 C H3 C
H
H3 C H H3 C H

H H H H
O HO
Testosterone Androsterone
26-35
Synthetic Estrogens
 Progesterone-like analogs are used in oral
contraceptives.
HO
H3 C C CH
"Nor" refers to the absence
of a methyl group here.
The methyl group is present H H
in ethindrone
H H
O
Norethindrone

26-36
Glucorticoid Hormones
• Synthesized in the adrenal cortex.
• Regulate metabolism of carbohydrates.
• Decrease inflammation.
• Involved in the reaction to stress.
CH2 OH CH2 OH
C= O C= O
H3 C H3 C
O OH HO OH
H3 C H H3 C H

H H H H
O O
Cortisone Cortisol

26-37
Mineralocorticoid Hormones
• Synthesized in the adrenal cortex.
• Regulate blood pressure and volume by stimulating
the kidneys to absorb Na+, Cl-, and HCO3-.
CH2 OH
OH
O C=O
CH

H3 C H

H H
O
Aldos terone

26-38
Bile Acids
 Synthesized in the liver, stored in the gallbladder,
and secreted into the intestine where their
function is emulsify dietary fats and aid in their
absorption and digestion.
OH COOH

H H
HO OH
H

26-39
Biosynthesis of Steroids
 The building block from which all carbon atoms
of steroids are derived is the two carbon acetyl
group of acetyl-CoA
Stage 1: synthesis of isopentenyl pyrophosphate from
three molecules of acetyl-CoA.
Stage 2: synthesis of cholesterol.
Stage 3: conversion of cholesterol to other steroids.
bile acids (e.g., cholic acid)
sex hormones (e.g., testosterone and es trone)
choles terol
mineralocorticoid hormones (e.g., aldosterone)
glucocorticoid hormones (e.g., cortisone)

26-40
Vitamin E

OH Four isoprene units, joined

head-to-tail, beginning here
and ending at the aromatic ring

Vitamin E ( -Tocopherol)

26-41
Phospholipids
 Phospholipids are the second most abundant
group of naturally occurring lipids.
• They are found almost exclusively in plant and animal
membranes, which typically consist of 40% -50%
phospholipids and 50% - 60% proteins.
• The most abundant phospholipids are esters of
phosphatidic acid (glycerol esterified with two
molecules of fatty acid and one of phosphoric acid).
• The three most abundant fatty acids in phosphatidic
acids are palmitic acid (16:0), stearic acid (18:0), and
oleic acid (18:1).

26-42
Phosphatidic acids, an example
A phosphatidic acid

• Further esterification with a low-molecular weight

alcohol gives a phospholipid.
26-43
Phospholipids
• Among the most common of these low-molecular-
weight alcohols are:

26-44
Phospholipids, an example
A lecithin

In aqueous solution, phospholipids spontaneously

form into a lipid bilayer, with a back-to-back
arrangement of lipid monolayers.
26-45
Biological Membranes
 Fluidmosaic model: A biological membrane
consists of a phospholipid bilayer with proteins,
carbohydrates, and other lipids embedded on the
surface and in the bilayer.
• fluid: Signifies that the protein components of
membranes “float” in the bilayer and can move freely
along the plane of the membrane.
• mosaic: Signifies that the various components of the
membrane exist side by side, as discrete units rather
than combining to form new molecules and ions.

26-46
Biological Membranes
• Fluid-mosaic model of a biological membrane showing
the lipid bilayer and membrane proteins on the inner
and outer surfaces of the membrane and penetrating
the thickness of the membrane.

26-47
Fat-Soluble Vitamins
 Vitaminsare divided into two broad classes on
the basis of their solubility:
• Those that are fat soluble, and hence classified as
lipids.
• Those that are water soluble.
 The fat-soluble vitamins include A, D, E, and K.

26-48
Vitamin A
• Occurs only in the animal world.
• Found in the plant world in the form of a provitamin in
a group of pigments called carotenes.

26-49
Vitamin A
 The best understood role of Vitamin A is its
participation in the visual cycle in rod cells.
• the active molecule is retinal (vitamin A aldehyde),
which forms an imine with an -NH2 group of the protein
opsin to form the visual pigment called rhodopsin.
• the primary chemical event of vision in rod cells is
absorption of light by rhodopsin followed by
isomerization of the 11-cis double bond to the 11-trans
configuration.

26-50
Vitamin A and the Chemistry of Vision

26-51
Vitamin D
A group of structurally related compounds that
play a role in the regulation of calcium and
phosphorus metabolism.
• The most abundant form in the circulatory system is
vitamin D3.

26-53
Vitamin E
 VitaminE is a group of compounds of similar
structure, the most active of which is -
tocopherol.

• In the body, vitamin E functions as an antioxidant; it

traps peroxy radicals of the type HOO• and ROO•
formed as a result of oxidation by O2 of unsaturated
hydrocarbon chains in membrane phospholipids.
26-54
Vitamin K
 Thename of this vitamin comes from the German
word Koagulation, signifying its important role in
the blood-clotting process.

26-55