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04/10/2022

LIPIDS and
MEMBRANES
JESSEBEL V. GADOT
SCIE 9 BSED

Lipids and Membranes


Classification of Lipids
Fatty Acids
Simple Lipids
Compound Lipids
Fats and Oils
Biological Membranes

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Lipids
Like organic molecules, biological molecules are grouped into families.
There are four major families of biological molecules
proteins,
nucleic acids,
carbohydrates,
and lipids.

Of these four families, the lipids are the structurally the most diverse.
This is because unlike members of the other three families, members of
this families do no share a common structural feature, but rather share a
common physical property; they are hydrophobic.

Introduction
Lipids are hydrophobic, nonpolar molelcules.

◦ They are soluble in nonpolar solvent.

◦ They are insoluble in polar solvents, such as water

They are isolated from the other biological molecules by


extracting them with nonpolar solvents.

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Classification of Lipids
1. Simple Lipids
2. Compound Lipids
3. Derived Lipids

1. Simple Lipids
o Esters of fatty acids with glycerol and monohydric alcohols.
oDepending upon the constituent alcohols they are further subdivided into:
o 1. fats - also termed as triacylglycerols are esters of fatty acids with
glycerol (Plants-vegetable oils; Animals-ghee and butter)
2. oils and
o 3. waxes - are esters of fatty acids and alcohols other than glycerol
• Plant wax-carnauba wax;
• Insect wax-beeswax;
• Animal wax -lanolin

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2. Compound Lipids
oEsters containing chemical groups in addition to alcohol and fatty acids.
oDepending upon the chemical groups they are further subdivided into :
a. phospholipids - contain phosphate group.
1. glycerophospholipids,
2. sphingophospholipids - if the constituting alcohol is glycerol (e.g., Lecithin) or

3. Sphingomyelin- if the alcohol is sphingosine


b. glycolipids - contain hexose units preferably galactose along with fatty acids
and alcohol e.g., cerebrosides.
c. sulpholipids - Plant sulpholipids contain sulfated hexose with fatty acids and
alcohol.
d. lipoproteins - contain protein subunits along with lipids.
Depending upon density and lipid compound they are further classified as
1. VLDL. 2. LDL and 3. HDL.

3. Derived Lipids
Substances derived from simple and compound lipids by hydrolysis of
alcohols, fatty acids, aldehydes, ketones, sterols and hydrocarbons.

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Fatty Acids
The fatty acids are long chain carboxylic acids synthesized by the
condensation and reduction of acetyl co enzyme-A units by fatty acid
synthase.
The more important ones have nonsystematic names in wide use.
1. Stearic and palmitic acids are saturated (no double bonds),
2. Oleic acid is monounsaturated, and
3. linoleic and linolenic are polyunsaturated All these common fatty

Fatty Acids
All these common fatty acids are cis (E) fatty acids.
Because of the links in the chain caused by the double bonds, the
unsaturated fatty acids tend to be liquids at room temperature (they are
less easy to pack together to form a solid).
Bacteria and plants (which cannot thermoregulate) will use more
unsaturated acids in their cell membranes when they are exposed to
cold: this helps to maintain membrane fluidity.

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Fatty Acids
Fatty acids contain a carboxylic acid group
◦ This should make them quite polar

However, they also contain a long hydrocarbon tail


◦ Which overall, makes them nonpolar.

nonpolar polar

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Fatty Acids
Fatty acids typically contain between 12 and 20 carbons
◦ The number is usually always even.
◦ The nonpolar tails interact with London forces.

nonpolar polar

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Fatty Acids
Melting points for saturated fatty acids:

Melting Temperature {°C} 80

70

60

50

40

30
10 11 12 13 14 15 16 17 18 19 20

No. of Carbons

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Fatty Acids
Some fatty acids contain double bonds

• unsaturated

• monounsaturated

• polyunsaturated

• polyunsaturated

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Fatty Acids

Linolenic acid is one of the omega-3 fatty acids.


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Fatty Acids
Normally the double bonds are cis
◦ This lowers the melting points for fatty acids containing double bonds.
Melting Temperature {°C}

70
60
50
40
30
20
10
0
-10
-20
0 1 2 3 4

No. of Double Bonds

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Fatty Acids
The cis double bonds produce kinks, which disrupt the London forces by
preventing the tails from packing close to one another.

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Fatty Acids
As acids, the carboxylic acid group in fatty acids can react with a base to
produce a carboxylate ion
◦ By donating its proton (H+) to the base the fatty acid becomes negatively
charged

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Fatty Acids
The negative charge makes the polar head portion of the the fatty acid
even more more polar and hydrophilic.

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Fatty Acids
The salts of fatty acids are also called soaps, and are considered
amphipathic, meaning they have a part that is very hydrophobic along
with a part that is very hydrophilic.

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Biochemical Compounds &


Their Interactions with Water
When placed in water,
amphipathic molecules,
form structures, such as
micelles, which attempt
to address the conflict.

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Essential Fatty Acids


Human body is unable to synthesize all fatty acids found in the body.
Those fatty acids that are not synthesized in the body but required for
normal body growth and maintenance are called as essential fatty acids.
These essential fatty acids are to be supplied through diet.
1. Linoleic - is grouped under n-6 family because the 6th carbon from methyl
end possesses the double bond
2. linolenic acids
3. Arachidonic acid is essential but it can be synthesized by the body from
linolenic acid. It is also present in the meat.

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1a. Fats and Oils


Triacylglycerols - the simplest lipids constructed from fatty acids and
glycerol.
- also referred as triglycerides, fats or neutral fats.
Triacylglycerols are composed of three fatty acids esterified to the three
hydroxyl groups of glycerol.

Fats and Oils


Triacylglycerol that are solid at room temperature are called as fats, while
the liquid triacylglycerols are called as oils.
Fats are usually rich in saturated fatty acids and the unsaturated fatty acids
predominate in oils.
Most oil-producing plants store their lipids in the form of triacylglycerols.
Three fatty acids esterified to glycerol known as triglycerides

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Properties of Fats
1. They are insoluble in water and soluble in organic solvents.
2. Pure triacylglycerols are tasteless, odourless, colourless and neutral in
reaction.
3. They have lesser specific gravity (density) than water and therefore
float in water.
4. Though fats are insoluble in water, they can be broken down into
minute droplets and dispersed in water. This is called emulsification.
5. They contain hydrophilic colloidal particles such as proteins,
carbohydrates and phospholipids which act as stabilizing agents.
6. Emulsification greatly increases the surface area of the fat and this is
an essential requisite for digestion of fat in the intestine.

Triglycerides
Triglycerides are a storage form of fatty acids in mammals.
◦ Often when blood tests are done, they measure your triglycyeride levels.

◦ High triglyceride levels in the blood are a risk indicator for artherosclerosis.

*American Heart Association

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Triglycerides
Triglycerides are a combination of three 3 fatty acid molecules with a
glycerol molecule.

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Triglycerides
Glycerol, which is also called
glycerin, is an alcohol with
three hydroxyl groups.
◦ As with the waxes, the fatty
acids can react with the
hydroxyl groups to form esters.

◦ Since there are three hydroxyl


groups, three fatty acids can
react to form three esters.

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Triglycerides
For triglycerides, all three hydroxyls of the glycerol have a fatty acid
residue attached to it.

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Triglycerides

Triglycerides
Just as with fatty acids, where the presence of cis double bonds lower the
melting points, triglycerides made from unsaturated fatty acids have lower
melting points than those made from saturated fatty acids.
◦ Triglycerides from animals tend to have a higher proportion of saturated fatty
acids.

• Most are solids at room temperature and are called fats.


• Examples include: butter, lard and bacon grease
◦ Triglycerides from plants tend to have a higher proportion of unsaturated fatty
acids.

• Most are liquids at room temperature and are called oils.


• Examples include: corn oil, canola oil, peanut oil and olive oil.

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Triglycerides
Triglycerides as primarily used as a form of stored energy.

◦ This is why when you eat more than you need to meet your energy
requirements, the excess energy is stored in the form of fat.

• Fat can store almost twice as much energy per gram as carbohydrates
and proteins

◦ In mammals the fats are stored in the adipose tissue.

◦ Adipose tissue also functions to protect organs from shock and cold.

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Triglycerides
Reactions that involve triglycerides include:
◦ Hydrogenation
◦ Oxidation
◦ Base-catalyzed hydrolysis (saponification)

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Transport of Fats

https://openoregon.pressbooks.pub/nutritionscience/chapter/5e-lipid-transport-storage-util/

Fun Topic !: Fake Fats


Side effects?

Olestra: sucrose Fat : glycerol fatty


fatty acid ester(s) acid ester(s)
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Triglycerides
Hydrogenation of triglycerides
◦ This is the same reaction that we saw in Unit 4 with
the hydrogenation of alkenes.
• Unsaturated fats and oils contain alkenes and can be
hydrogenated to produce saturated fats.
• Commercially, vegetable oils are often hydrogenated to
produce a solid product that has better qualities for making
baked goods.
◦ Animal fats, such as butter and lard, which are naturally
saturated, can also be used, but unlike the vegetable oils,
they come with cholesterol, which is undesirable for health
reasons.

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Oxidation and Reduction


Hydrogenation
◦ Another type of oxidation/reduction reaction is the hydrogenation reaction:
• In this example, an alkene is reduced to an alkane.

◦ This is considered reduction, because the hydrogen is bringing in additional electrons to the
molecule.

• The alkane that is produced in this reaction is considered “saturated” because it can no longer absorb
any more hydrogen atoms.
unsaturated saturated

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Triglycerides
Hydrogenation of triglycerides
◦ This is the same reaction that we saw in Unit 4 with the
hydrogenation of alkenes.
◦ Unsaturated fats and oils contain alkenes and can be
hydrogenated to produce saturated fats.
◦ Commercially, vegetable oils are often hydrogenated to
produce a solid product that has better qualities for
making baked goods.
• Animal fats, such as butter and lard, which are naturally saturated, can
also be used in baking, but unlike the vegetable oils, they come with
cholesterol, which is undesirable for health reasons.

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Triglycerides
Hydrogenation of triglycerides
◦ Total hydrogenation

liquid solid
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Triglycerides
Hydrogenation of triglycerides
◦ Partial hydrogenation

liquid solid

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Triglycerides
Hydrogenation of
triglycerides
◦ Partial
hydrogenation cab
produce trans fats.
• Trans fats have been
found to lower your
HDL (“Good
cholesterol”) levels.

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Triglycerides
Saturated vs Unsaturated Fats

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Triglycerides
Saturated vs Unsaturated Fats

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Triglycerides
Saturated vs Unsaturated Fats

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Triglycerides
Saturated vs Unsaturated Fats

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Triglycerides
Oxidation of triglycerides
◦ Unsaturated triglycerides can react with oxygen to
produce small change fatty acids another small
molecules.
• These often do not smell very good

• This is what happens when butter goes rancid.

◦ This makes solid fats and oils more stable than liquid
oils and is why the solid fats are preferred for deep
frying.

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Triglycerides
Oxidation of triglycerides

These stink !

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Triglycerides
Saponification of triglycerides
◦ Saponification is the base-catalyzed hydrolysis of the
ester bonds in a triglyceride.

◦ This cleaves the esters back into carboxylic acids (fatty


acids) and an alcohol (glycerol).

◦ Because the reaction is base-catalyzed, the base also


reacts with the carboxylic acids to from carboxylate ions

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Reactions With Water


Hydrolysis example:
◦ The base catalyzed hydrolysis of fats produces soap and glycerol

Fat

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1b. Waxes
Waxes are esters made by combining fatty acids with long chain
alcohols.
◦ shows carboxylic acids react with alcohols to from esters.
◦ The carbon number of fatty acids vary from 14 to 34 and that
alcohol from 16 to 30.

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Waxes
 For example, beeswax is an ester of palmitic acid with a 30 carbon
alcohol, triacontanol.

More commonly, waxes are esters of an alcohol other than glycerol


(long chain alcohol, sterol, hydroxycarotenoids, vitamin A) and a long
chain acid (wax esters).
Wax esters are saponified by hot alkaline solutions and give a fatty acid
and an alcohol.
They are soluble in aromatic solvents, chloroform, ethers, esters and
ketones.
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Waxes
Waxes are esters.

14-36 carbons 16-30 carbons

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Waxes
When two more molecules combine to form a larger molecule, the word
residue is used to indicate which molecule that part of the the larger
molecule came from.

came from the fatty acid came from the alcohol


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WAXES
Waxes are the chief storage form of metabolic fuel in marine
phytoplanktons.
Biological waxes have find a variety of applications in the
pharmaceutical, cosmetic and other industries.
Waxes are not easily hydrolysed like fats or digested by lipases.

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Waxes
Waxes are very hydrophobic and are used by plants and animals for
protective, water-proof coatings

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2a. Compound Lipids -


Phospholipids and Glycolipids
Phospholipids and Glycolipids are the stuff
that biological membranes are made of.
◦ Like the soaps, these molecules are highly
aphipathic, and when mixed with water
spontaneously form membranes that are
described as lipid bilayers.

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Phospholipids and Glycolipids

Soaps form Phospholipids form


Micelles Lipid Bilayers

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Phospholipids and Glycolipids


Phospholipids
◦ There a are two types of phospholipids
• Glycerophospholipids

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Phospholipids and Glycolipids


Phospholipids
◦ There a are two types of phospholipids
• Sphingolipids

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Phospholipids and Glycolipids


Phospholipids
◦ The Glycerophospholipids have a structure similar to triglycerides, with one
of the fatty acids replaced with a phosphate.

There is usually
an additional
alcohol attached
to the other side
of the phosphate

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Phospholipids and Glycolipids


Phospholipids
◦ The Glycerophospholipids have a structure similar to triglycerides, with one
of the fatty acids replaced with a phosphate.

phosphoester
bonds
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Glycerophospholipids
The important structural lipid in biological membrane is glycerol
phospholipid which contains glycerol, fatty acids, phosphoric acid and a
nitrogenous base.
Two fatty acids and a phosphate esterified to glycerol

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Glycerophospholipids
Without alcoholic residue (R), it is called as phosphatidic acid.
Depending on the alcoholic residue attached to phosphatidic acid, they
are named as :-
1. Phosphatidyl choline (lecithin)
2. Phosphatidyl ethanolamine (cephalin)
3. Phosphatidyl serine
4. Phosphatidyl inositol
5. Phosphatidyl glycerol (which include monophosphatidyl glycerol and
diphosphatidyl glycerol or cardiolipin).

Phospholipids and Glycolipids


Phosphospholipids
◦ The Glycerophospholipids have a structure similar to triglycerides, with one
of the fatty acids replaced with a phosphate.

“Phosphotidyl-”
refers to everything
but the X

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Phospholipids and Glycolipids


Phosphospholipids
◦ Phospholipids are used commercially as emulsifying agents.
• An emulsifying agent stabilizes an emulsion.
• An emulsion is a colloidal suspension of one liquid in another.
◦ An example is mayonnaise, which is a colloidal suspension of oil and water.

◦ Lecithin, which is another name for the phospholipid


phosphotidylcholine, is used as an emulsifying agent in
mayonnaise and other prepared foods.

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Lecithin
Lecithins are widely distributed in the membranes of cells having both
metabolic and structural functions.
Dipalmityllecithin is a very effective surface active agent preventing
adherence due to surface tension of the inner surfaces of the lungs.
Most phospholipids have a saturated fatty acid in the Cl position but an
unsaturated fatty acid in the C2 position.

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Phospholipids and Glycolipids


Phospholipids
◦ The sphingolipids function similarly to the glycerophospholipids, but
structurally they are different.
• There is not glycerol core

• The glycerol and one of the fatty acids found in glycerophospholipids is replaced with a
molecule called sphingosine.

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Phospholipids and Glycolipids


Phospholipids
◦ The sphingolipids are found in the myelin membranes that insulate the nerve
cells.
◦ Some sphingolipids use sugars for the alcohol portion of the molecule
• These are called glycolipids.

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Sphingophospholipids
The phosphate and fatty acids are
attached to the alcohol sphingosine
instead of glycerol in
sphingophospholipids.
The fatty acids are attached
through an amide linkage rather
than the ester linkage.
The base present is normally
choline. C-1, C-2 and C-3 of the
sphingosine or phytosphingosine
bear functional groups, -OH, -NH2
and -OH respectively, which are
structurally homologous with the
three hydroxyl groups of glycerol.

2b. Lipoproteins
The major lipid components of
chylomicrons and VLDL are
triacylglycerol, whereas the
predominant lipids in LDL and
HDL are cholesterol
andphospholipids respectively.
The protein part of lipoprotein
is known asapoprotein.
Lipoproteins occur in milk,
egg-yolk and also as
components of cell
membranes.

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2b. Lipoproteins
Protein molecules associated with
triacylglycerol, cholesterol or
phospholipids are called lipoproteins.
Triacylglycerols derived from intestinal
absorption or from the liver are not
transported in the free form in circulating
blood plasma, but move as chylomicrons,
as very low density lipoproteins (VLDL) or
as freefatty acids (FF A) - albumin
complexes.
Besides, two more physiologically
important groups of lipoproteins are low
density lipoprotein (LDL) and high density
lipoprotein (HDL).

Lipoproteins
Lipoproteins are used to transport the
water insoluble lipids such as
triglycerides, phospholipids and
cholesterol, in the blood.
◦ Lipoproteins contain lipids and
proteins.
◦ They include:
• Chylomicrons transport primarily
triglycerides from the digestive track.
• LDLs (low density lipoproteins) transport
cholesterol, triglycerides and phospholipids
from the liver to other tissues.
• HDLs (high density lipoproteins) transport
cholesterol and phospholipids back to the
liver.

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Lipoproteins
The HDL and LDL levels in the blood can be used
to assess ones risk for atherosclerosis.
◦ High levels of HDL is considered good
• This is why HDL is sometimes referred to as “good cholesterol”
• > 40 mg/dL is good.

◦ High levels of LDL is considered bad


• This is why LDL is sometimes referred to as “bad cholesterol”
• > 100 mg/dL is bad.

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3. Derived Lipids - Sterols


The characteristic structure of sterol is their steroid nucleus consisting
of four fused rings, three with six carbons (Phenanthrene) and one with
five carbons (cyclopentane).
This parent structure is known as perhydro cyclopentanophenanthrene.
Cholesterol is the most abundant sterol in animals.
Cholesterol is a major component of animal plasma membranes and
occurs in lesser amounts in the membranes of their subcellular
organelles.

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Steroids
Steroids are a type of lipid that is not derived form a fatty acid.
◦ They are based instead on a system of five cycloalkane rings that are fused
together.

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Steroids
Steroids are a type of lipid that is not derived form a fatty acid.
◦ They are based instead on a system of five cycloalkane rings that are fused
together.

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Steroids
Cholesterol is the steroid that used as the starting point for the
synthesis of other steroids.

Note the fused ring


system

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Steroids
◦ Cholesterol is only found in animals
◦ Besides being used to synthesize the other steroids,
cholesterol is dissolved in membranes to keep them
fluid.
• Plants use the alternative strategy of using polyunsaturated fatty
acids to make their phospholipids.

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Biological Membranes
Proteins and polar lipids account for mass of biological membranes.
The relative proportions of protein and lipid differ in different
membranes, reflecting the diversity of biological roles.
Amphipathic molecule~ form a lipid bilayer with the non polar region of
lipids facing outward.
In this lipid bilayer, globular proteins are embedded at regular intervals
held by hydrophobic interactions.
Some proteins protrude from one or other face of the membrane
(peripheral proteins); some span its entire width (integral proteins).
The individual lipid and protein subunits in a membrane form a fluid
mosaic.

Membranes
Fluid mosaic model

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Biological Membrane
The membrane is fluid because the interactions among lipids, between
lipids and proteins are non covalent, leaving individual lipid and protein
molecules free to move laterally.
One of the key functions of a membrane is to control the passage of
substances across it.
They are said to be selectively permeable.
The different membranes of the cell have different selective
permeabilities.

Common Features BM
1. Membranes are sheetlike, just a few molecules thick and form closed
boundaries between cell compartments.
2. Membranes contain lipids and proteins, with small amounts of
carbohydrayes linked to the lipids and proteins.
3. Lipids in membranes are small with hydrophObic and hydrophilic portions.
Lipid bilayers provide a barrier to the diffusion of polar molecules.
4. Characteristic functions of membranes are mediated by specific proteins,
serving as pumps, channels, receptors, energy transducers and enzymes.
5. Membrane components associate through noncovalent interactions.
6. Membranes are asymmetrical, with two sides of the membrane differing
from each other.
7. Lipid and protein molecules often diffuse rapidly in the plane of the
membrane.

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Bilayer Formation
Hydrophobic interactions provide the primary driving force for the
formation of bilayers

Saturated fatty acid chains pack easily and have a higher melting
temperature (Tm). Butter is a solid at room temperature so has a high
Tm.
Unsaturated fatty acids have a lower Tm. Canola oil is a liquid at room
temperature so has a low Tm.

Bilayer Formation
Cholesterol impedes motion of the hydrocarbon tails making membranes less
fluid

The degree of saturation of the "tails" affects the stability of the membrane.
Saturated fats pack more easily than unsaturated fats.
A high percentage ofunsaturated fats lowers the temperature at which a
membrane will become rigid

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FLUID MOSAIC MODEL


The Iipids are arranged in
a bilayer, which is both a
permeability barrier and
solvent for integral
proteins
Some lipids interact with
specific proteins to
produce characteristic
functions of the
membrane.
Lipids diffuse laterally
(horizontally) rapidly but
transversely (vertically)
slowly. Proteins diffuse
laterally.

FLUID MOSAIC MODEL

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Membranes
Transport across membranes

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References:
Gajera, H.P. (2008). Fundamentals of Bicohemistry A
Textbook. International Book Distributing

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