Biological Chemistry 1B

Week 6 & Week

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LIPIDS
 Lipids
Lipids
Organic molecules that are
insoluble in water but soluble in
organic solvents.
Made mostly from carbon and
hydrogen but do contain a small
amount of oxygen
Classified as Fats (solid at TR) and
oils (liquid at TR)
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 METABOLIC ROLES
1. Major energy storage molecules for body
(triglycerides).
2. Energy source for tissues & cells (lipolysis).
3. Steroid hormones.
4. Cell membranes.
5. Insulates against temperature extremes.
6. Protects organs from shock.
7. Immunity (eicosanoids).
8. Blood clotting (eicosanoids).
9. Joint lubrication.
10. Skin sebum.
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 Classes of Lipids
 Lipids can be divided into 2 classes depending on
their chemical structure:
1. Lipids containing fatty acids
A. Waxes
B. Phospholipids
C. Triglycerides
2. Lipids that do not contain fatty acids
A. Steroidal hormones
B. Cholesterol

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 DIETARY SOURCES
 Major dietary sources of lipids:
 Saturated
 meat , chicken, fish
 dairy – milk, yoghurt, cheese, eggs
 coconut and palm meats and oils
 lard, shortening from animal fats
 Unsaturated
 nuts and nut oils
 seeds and seed oils
 margarine
 Fish and fish oils

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 Daily Intakes

Total

30-35% of macronutrient intake

 7-10% Saturated Fat

 ~10 % Polyunsaturated Fat
 >10% Monounsaturated Fat

20-25% of macronutrient intake weight loss

<20% body goes into “starvation mode” – fat stored

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 Fatty Acids
A fatty acid is a
chain of carbons
linked together and
surrounded by
hydrogen
molecules.

 These hydrocarbons are

found in lipids and contain
a carboxyl acid group
and a methyl group at the
other.
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 Fatty Acids
Saturated
 Solid at room temperature, from animal sources
 Saturated hydrocarbon.
 No double bonds
 Eg. butter

Monounsaturated
 Liquid at room temperature, from plant sources.
 Alkenes with only one C=C double bond
 Eg. Olive oil

Polyunsaturated
 Liquid at room temperature, from plant sources.
 Alkene with more than one C=C double bond
 E.g.: canola oil

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 Fatty Acids
Have varying lengths between 4 and 24 carbons usually
in even number.

They are classified as

Short chains (< than 6 carbons)
Medium chains (6-10 carbons)
Long chains (> 10 carbons)

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 Fatty Acids
Unsaturated fatty acids can have a “Cis” form or a
“Trans” form
In nature the “cis” form is more common
The type affects solubility in water
The “cis” form is more soluble than the “trans” form
The “cis” form changes the shape of the molecule (i.e. is
not linear any more)
Human body can digest “cis” forms & some animal
“trans” but not manufactured hydrogenated “trans fatty
acids”

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 Saturated FA’s
 Saturated FA do not have any DB, all Carbons are attached to a
Hydrogen
 SFA’s only have single bonds between C and H
 There is a strong attraction between the FA’s giving a solid shape at TR
 Examples include:

 Lauric acid – found in coconuts

 Has a chain of 12 carbons

 Palmitic – found in palm kernels

 Has a chain of 16 carbons

 Stearic acid – found in animal fat

 Has a chain of 18 carbons

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 Monounsaturated FA’s – Omega 9
 Omega-9 = oleic acid
 1st DB @ C9 written as Ω -9 or ω or n
 Has a chain of 18 carbons
 Has only 1 DB along the chain
 Written as Ω -9; C18:1
 Cis form

 Omega-9 = Elaidic acid

 1st DB @ C9 written as Ω -9 or ω or n
 Has a chain of 18 carbons
 Has only 1 DB along the chain
 Written as Ω -9; C18:1
 Trans form

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 Polyunsaturated FA ‘s - Omegas 3 &
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 Are named according to the place of the 1st double bond starting from the
methyl group (CH3) end
 Omega-3 = alpha-linolenic acid (-linolenic)
 1st DB @ C3 written as Ω -3 or ω or n
 Has a chain of 18 carbons
 Has 3 DB along the chain
 Written as Ω -3; C18:3

 Omega-6 = linoleic acid

 1st DB @ C6 written as Ω -6 or ω or n
 Has a chain of 18 carbons
 Has 2 DB along the chain
 Written as Ω -6; C18:2

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  Omega-6 = Arachidonic acid
 1st DB @ C6 written as Ω -6 or ω or n
 Has a chain of 20 carbons
 Has 4 DB along the chain
 Written as Ω -6; C20:4

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 Essential Fatty Acids
Polyunsaturated fatty acids that cannot be made by
the human body and must be obtained from external
sources i.e.: diet – are termed Essential Fatty Acids.
These are:
Linoleic acid (omega-6 EFA)
 eg: nuts, seeds, eggs, .

Linolenic acid (omega-3 EFA)

 oily fish and nuts.

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 Omega 3 and 6
 Omega 3 - alpha-linolenic acid
 EPA (eicosapentaenoic acid)
 DHA (docosahexaenoic acid)
 Essential for normal growth and development
especially in the eyes and brain
 Omega 6 - linoleic acid
 Can synthesise “arachidonic acid”
 Needed for synthesis of prostaglandins,
leukotrienes, and thromboxane

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 Prostaglandins
 a.k.a. eicosanoids
 Produced from arachidonic acid
 Different types: i.e. E or F whether it has a ketone or a
hydroxyl group respectively
 Can increase or decrease BP
 Can stimulate contraction or relaxation of smooth
muscles
 In injured tissues - produce pain and inflammation
NSAIDs (e.g. aspirin, naproxen) block the formation of
arachidonic acid into prostaglandins.

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 Lipids that contain fatty acids
 There are 3 types of lipids that contain fatty acids:

 Waxes

 Phospholipids

 Triglycerides

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 Waxes
Type of lipid containing fatty acids.
Waxes are made up of 1 saturated fatty acid + alcohol.
Have characteristic texture and semi-solid consistency.
Not biologically significant for human beings.

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 Triglycerides
Type of lipid containing fatty acids.
Our dietary fats & oils are all triglycerides.
Fat: triglyceride that is solid at room temperature.
Usually contains higher % of saturated fatty acids.
Oil: triglyceride that is liquid at room temperature.
Usually contains higher % of unsaturated fatty acids.

NOTE: Melting point of triglycerides increases as

degree of fatty acid saturation increases.

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 Triglyceride molecular structure
A triglyceride is made of 3 fatty acids and 1 glycerol

Each triglyceride can carry 3 different types of

fatty acids.

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 Glycerol
Glycerol is a three carbon alcohol used to form
triglycerides.
The only part of a lipid that can be metabolised to
glucose.

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 Chemical Properties of TGC’s
 Triglycerides can undergo a number of
reactions. Those of significance are:
1. Hydrogenation
2. Hydrolysis
3. Saponification
4. Oxidation

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 1. Hydrogenation
 A chemical process by which MUFA’s and PUFA’s
are made semi-solid.
 The addition of hydrogen to the double bond to
increase the saturation (& therefore the melting point)
of the fatty acids.
 H2(g) bubbled through with a Ni catalyst to facilitate
addition of H to C=C bonds (e.g: margarine.)

i.e.: -C=C- + H2  H-C-C-H.

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  Advantages
 Protection against oxidation
 Liquids changed into solids

 Disadvantages
 Makes PUFAs more saturated
 Synthesis of trans-fatty acids
 Due to their reactive nature and unnatural shape trans fatty
acids have been implicated in many diseases – e.g.:
cardiovascular disease, some cancers

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 2. Hydrolysis
 Addition of water to ester bonds to form
glycerol (alcohol) + 3 fatty acids.
 Requires very strong acid eg. HCl or
enzymes ie: lipases, to occur.
 This is how we digest triglycerides

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 3. Saponification
 Heating a fat up in the presence of a
strong base /alkali (eg: NaOH) causes
hydrolysis of the ester bonds to form
glycerol (alcohol) + 3 fatty acid salts.
 These salts are soap.
 NaOH – solid soap; KOH – liquid soap
 The use of KOH or unsaturated fatty acids
give softer soaps

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 4. Oxidation
The addition of O2 &/or loss of H+ &/or loss of e-.
The C=C in polyunsaturated fatty acids are very reactive & can be
oxidized by free radicals (i.e.: free radical “steals” e - to make a
pair).
 Free Radical: atom/molecule with an unpaired electron.
 Oxidized fatty acids can be very dangerous due to their high
reactivity ie. unstable, volatile, destructive
Antioxidants: molecules designed to prevent oxidation of
fatty acids by becoming e- donors themselves (ie:
Kamikaze molecules – sacrifice themselves to keep us
healthy - eg: vitamins A, C, E, Se,Zn, Coenzyme Q10).
Ketone Bodies

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 Phospholipids
a.k.a. “glycerophospholipids”

Made up of glycerol (an alcohol) + 2 fatty acids +

phosphate (PO4) group.

Phospholipids are bipolar with the fatty acids forming

the non-polar tail.

Phospholipids form the major part of the cell

membranes, bile, detergent and the protective myelin
sheath layer around neurons.

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 Phospholipids are
components of the cell.
Their structure includes
a phosphate molecule

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 Lipids containing no fatty acids
 Lipids that contain no fatty acids, but have a steroidal skeleton – i.e.
they are all made of rings.

 Fat Soluble, stored in adipose tissue ie. Fat cells

 Produced in adrenal glands –adrenal cortex
 Cross the cellular & nuclear membranes & directly interact with
DNA.
 In the human body there are 2 types:
1. Steroidal hormones
2. Cholesterol

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 Steroidal Hormones
 Hormones: chemical messengers
 Steroid Hormones
 chemical messengers that are fat soluble & have the steroid skeleton at the
core of their structure. Steroid hormones exert their effect by
 Important steroid hormones include:
 Mineralcorticoids eg. Aldosterone, regulate water & electrolyte
homeostasis
 Glucocorticoids eg. Cortisone, regulate metabolism & resistance to stress
 Androgens eg. Masculising hormones, testosterone, androsterone , can be
converted to female hormones, regulate “male” factors in both sexes -libido
 Anabolic Hormones
 Derivatives of testosterone to enhance muscle mass and decrease body
fat
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 1. Cholesterol
The most abundant steroidal lipid in human body
Is part of the family of sterols
 Sterols have an oxygen atom on carbon 3
 Other types of steroids have a carbonyl group (C=O) on C3.

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 Is a vital component of cellular membranes,
myelin sheaths, brain tissue, nerve tissue, vitamin
D, bile, and steroidal hormones.

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  Is obtained
 From dietary sources (animal products

only) (about 15%)

 Or made by the liver (about 85%)

 A diet high in cholesterol will decrease

synthesis by the liver

 A diet high in saturated fats will increase

synthesis of cholesterol by the liver

 Is transported with triglycerides by
lipoproteins

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 Lipoproteins
Their role is to solubilise the hydrophobic lipids
(phospholipids, cholesterol, and triglycerides)
The protein part of the lipoproteins contains signals that
cells use to take-up or release lipids.
Are spherical particles composed of
Mostly proteins and phospholipids on the outer layer
Triglycerides and cholesterol on the inner layer

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 There are different types of lipoproteins
Chylomicrons
 Transport dietary lipids to the tissues
Very Low Density Lipoproteins
 Transport endogenous lipids from the liver to other tissues
Low Density Lipoproteins (LDL)
 A VLDL that has unloaded its TGs (thus mostly left with cholesterol)
 Transport cholesterol to tissues
 a.k.a. “Bad” cholesterol.
High Density Lipoproteins (HDL)
 Transport lipids to the liver from other tissues.
 a.k.a. “Good” cholesterol

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