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III Lipids and Membranes
III Lipids and Membranes
LIPIDS and
MEMBRANES
JESSEBEL V. GADOT
SCIE 9 BSED
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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.
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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. 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
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:
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
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
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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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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.
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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.
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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.
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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
◦ 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/
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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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◦ 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 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.
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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.
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Waxes
Waxes are esters.
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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.
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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There is usually
an additional
alcohol attached
to the other side
of the phosphate
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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).
“Phosphotidyl-”
refers to everything
but the X
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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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• The glycerol and one of the fatty acids found in glycerophospholipids is replaced with a
molecule called sphingosine.
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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.
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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.
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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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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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