Lipids

• Lipids are compounds that are soluble in non-

polar organic solvents, but insoluble in water.
• Can be hydrophobic or amphipathic
 Fatty acids
• Amphipathic molecule

• Polar carboxyl group& Non-polar

hydrocarbon tail

• Diverse structures
(>100 different types)

• Differ in chain length

• Differ in degree of unsaturation

• Differ in the position of double bonds

• Can contain oxygenated groups

The structures of some typical fatty acids. Note that most naturally occurring
fatty acids contain even numbers of carbon atoms and that the double bonds are
nearly always cis and rarely conjugated

Fig. 8-1, p.185

[1] Lipids:
Biological Importance, Structures and Physical properties

 More soluble in organic solvents than water.

 Nonpolar lipids (fats or oils) store energy.
 Amphiphilic lipids (phospholipids and sterols) help make up
biological membranes.
 Steroids (found in membrane) are precursors to many
hormones
 Some are involved in light-absorbing pigments, are enzyme
cofactors (vitamin K), hormones (estrogens, testosterone),
signal molecules (prostaglandins), electron carriers
(ubiquinone) or help solubilize other lipids during digestion
(bile acids).
[2] Storage Lipids: Fatty acids (FA) and derivatives

(1) Fatty acids: Carboxylic acids with hydrocarbon chains

(4-36 carbons) O
C
R OH

Saturated 18:0 Unsaturated 18:1(9)

Trans

Cis
 Trans

• Trans & Cis

Cis
 General Structure

pKa = 4.7
R-COOH R-COO‒

(At pH 7.0, in what form does it mostly exist?)

- Most FAs have an even number of C atoms in an

unbranched chain (usually 14-24, 16-18 is common)

- Saturated FAs: all carbon atoms “saturated” with H

C#  8: oily liquid (low m.p.)

C# ≥ 10: waxy solid (high m.p.)
.

Fig. 8-1a, p.185

Fig. 8-1b, p.185
Fig. 8-1c, p.185
Fig. 8-1d, p.185
Fig. 8-1e, p.185
Fig. 8-1f, p.185
Table 8-1, p.186
Table 8-2, p.186
 Unsaturated FA: are all oily liquids
- Monounsaturated FA: one double bond
- Polyunsaturated FA: two or more double bonds
(double bonds never conjugated)
- Fluidity of lipid bilayer alters as a function of the lipid composition.
(the more unsaturated, lower m.p., the less rigid)

 16:0  16-carbon saturated palmitic acid

18:1  18-carbon oleic acid with one double bond
20:2(9,12)  a 20-carbon FA with one double bond between C-9 and C-10
and another bet/ C-12 and C-13

O
12 9
C
cis cis 1 OH
Melting Points of Fatty Acids and their Solubility in Water
(2) Triacylglycerols (TAG, triglycerides, fats, or neutral fats):
Fatty acids joined by ester linkages that can be simple (all same FA) or mixed
(different FA)

The general formula is:

Nonpolar, essentially insoluble in water.

O
CH2O C R1
HC O C R2
CH O OC R
2 3

O
Triacylglycerols are formed from glycerol and fatty acids.

Fig. 8-2, p.187

Fig. 8-2a, p.187
Fig. 8-2b, p.187
 Triglycerides
• Triacylglycerol
– 3 fatty acids linked to glycerol
– ester linkage = between OH & COOH
Dehydration synthesis

dehydration synthesis

enzyme

enzyme

enzyme
 Saturated fats
• All C bonded to H
• No C=C double bonds
– long, straight chain
– most animal fats
– solid at room temp.
• contributes to
cardiovascular disease
(atherosclerosis)
= plaque deposits
 Unsaturated fats
• C=C double bonds in
the fatty acids
– plant & fish fats
– vegetable oils
– liquid at room temperature
• the kinks made by double
bonded C prevent the
molecules from packing
tightly together

mono-unsaturated?
poly-unsaturated?
Saturated vs. unsaturated
saturated unsaturated
Triacylglycerols serve as energy reservoirs in animals making
them the most abundant class of lipids and make up most fats
and oils in animals and plants.
 Stored in the adipocytes (fat cells) that can be almost entirely
filled with fat globules –thermal insulation.
(penguins, hibernating bears).

 Energy storage, fat or glycogen?

- Energy yield from (more reduced) lipids is two times that for
an equal weight of glycogen.
(Fat content of a normal human enables them to survive
starvation for 2-3 months, the glycogen supply would only offer a
day!)
- Unhydrated fats are lighter than hydrated carbohydrates.
 no extra weight to carry.
- But, readily soluble glycogen for instant access.
Butter is made from milk, vegetable oil is made from vegetables,
and margarine is “partially hydrogenated vegetable oil.”
Why do these three forms of edible fat differ in physical
characteristics?

Partially hydrogenated vegetable oils contain “trans fats,”

Naturally unsaturated fats contain (almost) all cis double bonds.
Trans fats have trans double bonds, which are very rarely found
in nature

Trans Fats 101: Why they are bad for you.

http://www.umm.edu/features/transfats.html
 http://en.wikipedia.org/wiki/Trans_fat

Oleic acid Elaidic acid

a cis unsaturated fatty acid a trans unsaturated fatty acid
that comprises 55–80% often found in partially
of olive oil. hydrogenated vegetable oils.

These fatty acids are geometric isomers

(chemically identical except for the arrangement of the double bond).
Hydrolysis of
triacylglycerols. The
term
“saponification”
refers to the
reactions of glyceryl
ester with sodium
or potassium
hydroxide to
produce a soap,
which is the
corresponding salt
of the long-chain
fatty acid

Fig. 8-3, p.187

 Waxes: Esters of long-chain fatty acids (C14 ~ C36) with long chain (C16 ~ C30)
alcohols
- mp = 60 ~ 100C
- Energy storage form in plankton.
- Water repellent in birds, plants.
- Wide applications: ointments, polishes, etc.
WAXES

Carnauba wax

Spermaceti
Fig. 8-6a, p.189
[3] Structural Lipids in Membranes
All membrane lipids are amphipathic:
hydrophilic head + hydrophobic (bulky) tail

(1) Glycerophospholipids: belong to phospholipids

 glycerol + 2 FA (C1 & C2) + phosphate (C3)
 The major component of biological membranes
A phosphatidyl ester (phosphoacylglycerol)

Fig. 8-4, p.188

Fig. 8-4a, p.188
Fig. 8-4b, p.188
Phosphatidylcholine(
LECITHIN)

Fig. 8-5a, p.188

(Cephaline)

Fig. 8-5b, p.188

Fig. 8-5c, p.188
Definition: Antiphospholipid syndrome, or APS, is an autoimmune
disorder in which the body's immune system reacts against certain
normal substances present in blood. A person with APS will have a
greater than average tendency to form blood clots

APS is associated with greater odds of pregnancy loss. An estimated 10% to 25%
of women with recurrent miscarriages have APS, and a person with APS will
often have no other symptoms of the disorder until she experiences recurrent
miscarriages. Some controversy exists over whether APS causes late or early
pregnancy losses. Most doctors agree that APS can cause late losses but the
evidence is unclear on whether APS causes early losses.
As part of the normal recurrent miscarriage workup, doctors test for specific
antibodies called anticardiolipin antibodies or lupus anticoagulant antibodies.
Testing positive for these antibodies may indicate APS.
Doctors usually treat the condition by having the woman take low-dose aspirin
and injections of a blood thinner called heparin during pregnancy. This course of
action reduces the odds of forming blood clots and increases the odds of a
successful pregnancy.
Fig. 8-5d, p.188
Fig. 8-5e, p.188
Fig. 8-5f, p.188
Sphingolipids

Fig. 8-6b, p.189

(2) Sphingolipids
 Major membrane components made from sphingosine
- the FA may differ.
 Sphingomyelin is prominent in myelin, a membranous sheath
that surrounds/insulates axons of some neurons.
 Prominent in membranes of neurons.
 Some serve as recognition sites on the cell surface
 Human Blood Type
www.diseaseworld.com/ms.htm

Multiple Sclerosis affects over 2.5 million people worldwide.

It results when the protective myelin sheath which surrounds nerves
disintegrates.
This causes the nerve impulses to the brain to become distorted.
A person who has this condition may suffer from fatigue, vision problems,
slurred speech, poor coordination, numbness and tingling, muscle cramps,
spasms and other unpleasant symptoms.
The condition can vary in severity from month to month and year to year.
Glycosphingolipids (GSLs) and gangliosides are a
group of bioactive glycolipids that include
cerebrosides, globosides, and gangliosides. These
lipids play major roles in signal transduction, cell
adhesion, modulating growth factor/hormone receptor,
antigen recognition, and protein trafficking. Specific
genetic defects in lysosomal hydrolases disrupt normal
GSL and ganglioside metabolism leading to their
excess accumulation in cellular compartments,
particularly in the lysosome, i.e., lysosomal storage
diseases (LSDs). The storage diseases of GSLs and
gangliosides affect all organ systems, but the central
nervous system (CNS) is primarily involved in many.
 (3) Cholesterol
 The metabolic precursor of steroid hormones that regulate physiological
functions such as sexual development and carbohydrate metabolism, and of
bile acids.
 (3) Cholesterol
 The development of atherosclerosis is strongly correlated with the level of
plasma cholesterol. Atheromas (arterial thickenings) contain pasty yellow
deposits of almost pure cholesteryl esters.
 Steroids
• ex: cholesterol, sex hormones
• 4 fused C rings
– different steroids created by attaching different
functional groups to rings

cholesterol
 Cholesterol
• Important cell component
– animal cell membranes
– precursor of all other steroids
• including vertebrate sex hormones
– high levels in blood may contribute to
cardiovascular disease
 Cholesterol
Important component of cell membrane

helps keep
cell membranes
fluid & flexible
From Cholesterol  Sex Hormones
• What a big difference a few atoms can make!
Hypercholesterolemia
Introduction:
Hypercholesterolemia, or high cholesterol, occurs when there is
too much cholesterol in the body. Cholesterol is a soft, waxy, fat-
like substance that is a natural component of all the cells of the
body. Your body makes all the cholesterol it needs. Any added
cholesterol, which comes through the foods you eat, can cause
harm.

Source: http://www.umm.edu/altmed/articles/hypercholesterole
mia-000084.htm#ixzz2RDH3xf73
Follow us: @UMMC on Twitter | MedCenter on Facebook
High cholesterol raises your risk for heart disease, heart attack,
and stroke. When there is too much cholesterol circulating in
the blood, it can create sticky deposits (called plaque) along the
artery walls. Plaque can eventually narrow or block the flow of
blood to the brain, heart, and other organs. And blood cells
that get caught on the plaque form clots, which can break loose
and completely block blood flow through an artery, causing
heart attack or stroke.

Source: http://www.umm.edu/altmed/articles/hypercholestero
lemia-000084.htm#ixzz2RDHFQFO6
Follow us: @UMMC on Twitter | MedCenter on Facebook
Risk Factors:
Some factors increase a person's risk of having high
cholesterol. While some of these cannot be changed, many
can be. The most important risk factors for high cholesterol
are:
Being overweight or obese
Eating a diet high in saturated fat and trans fatty acids (found
in processed and fried foods)
Not getting enough exercise
Family history of heart disease
High blood pressure
Smoking
Diabetes

Source: http://www.umm.edu/altmed/articles/hypercholeste
rolemia-000084.htm#ixzz2RDHVYP25
Follow us: @UMMC on Twitter | MedCenter on Facebook
Diagnosis:
Most people don't have any symptoms of high cholesterol. A
blood test is the only way to check levels of cholesterol in
your blood. If your levels are above 200 mg/dL or your HDL is
below 40, your doctor may do a fasting lipid profile (a test
performed after you abstain from food for 12 hours).
Although cholesterol levels above 200 are generally
considered high, what's considered safe for each person
depends on whether you are at risk for, or have, heart
disease.

Source: http://www.umm.edu/altmed/articles/hypercholeste
rolemia-000084.htm#ixzz2RDHiq4tP
Follow us: @UMMC on Twitter | MedCenter on Facebook
Total cholesterol levels:
Desirable: Below 200 mg/dL
Borderline high: 200 - 239
High: Above 240

Source: http://www.umm.edu/altmed/articles
/hypercholesterolemia-
000084.htm#ixzz2RDHrspIW
Follow us: @UMMC on Twitter | MedCenter
on Facebook
LDL cholesterol levels:
Optimal for people with heart disease or who are at high
risk: Below 70 mg/dL
Optimal for people at risk of heart disease: Below 100
Optimal: 100 - 129
Borderline high: 130 - 159
High: 160 - 189

Source: http://www.umm.edu/altmed/articles/hypercholest
erolemia-000084.htm#ixzz2RDHxtKhc
Follow us: @UMMC on Twitter | MedCenter on Facebook
HDL cholesterol levels:
Poor: Below 40 mg/dL
Acceptable: 40 - 59
Optimal: 60 or above
Triglyceride levels:
Optimal: Below 150 mg/dL
Borderline high: 150 - 199
High: Above 200

Source: http://www.umm.edu/altmed/articles
/hypercholesterolemia-
000084.htm#ixzz2RDIE3vKH
Follow us: @UMMC on Twitter | MedCenter
on Facebook
Diet
A healthy diet can help you lose any extra pounds. Even losing just 5 or 10
pounds may help lower your cholesterol. To eat a healthy diet:
Cut down on saturated fats and trans fats. No more than 10% of your daily
calories should come from saturated fat, and you should avoid trans fats
completely. Based on data from 4 studies, it is estimated that a 2% increase in
energy intake from trans fats increases the incidence of heart disease by 23%.
Choose unsaturated fats, such as olive oil and canola oil, instead.
Eat whole grains -- whole wheat bread and pasta, oatmeal, oat bran, and brown
rice.
Eat more fruits and vegetables, which are high in fiber and can help lower
cholesterol levels. Studies show that plant based diets are associated with
decreases in total cholesterol and LDL cholesterol of up to 15%.
Limit cholesterol in your diet. The highest amounts are found in egg yolks,
whole milk products, and organ meats.
Eat fatty fish. The American Heart Association recommends that people eat at
least 2 servings of fatty fish (such as salmon or herring) each week.
Eat phytosterols and stanols found in nuts, seeds, vegetable oils, and fortified
food products, such as orange juice.
In biology, the membrane fluidity refers to
the viscosity of the lipid bilayer of a cell membrane.
The membrane phospholipids incorporate fatty
acids of varying length and saturation. Shorter-chain
fatty acids, and ones with greater unsaturation, are
less stiff, less viscous and have lower melting points.
Changes in membrane-dependent functions, such
as phagocytosis and cell signalling, are hypothesized
to depend upon the cell-membrane fluidity