FRAGMENT OF BIOCHEMISTRY HANDOUT BY SCHOLIA TUTORIAL CLUB, CHEM

REVIEW GROUP
SLRM2013

REVIEW PROPER 5: LIPIDS

PART 1: INTRODUCTION
Lipids are known to many as fats (the solid form) or oils (the liquid form), but they
are not readily easy to define based on their structure. While the reality is that the
structure of different lipids can be very diverse, their common denominator lies in
that they are extremely non-polar, and thus insoluble in polar solvents like water.
Given that lipids have diverse structure that we will tackle later, rightfully they have
different diverse physiological uses such as the following:
- Creation of cell membranes (phospholipids)
- Storage of energy in bulk (triacylglycerols, steroids)
- Formation of myelin sheaths in brain (sphingolipids)
- Vitamins (A, D, E, K only)
- Control of body processes by hormones (steroidal hormones)
- Trigger of pain and asthma responses (prostaglandins and leukotrienes)
PART 2: STRUCTURE AND PROPERTIES
Lipids are too diverse to classify under one scheme. The one used below may be
more useful in this general course, dividing lipids first by structure (if the lipid
contains fatty acids or not) followed by their classification by function (storage,
structural, physiological)
Fatty acid long chain carboxylic acids
- their non-polar hydrocarbon portion outweighs the polar carboxyl portion
- can be further divided into two: saturated and unsaturated
Physical Properties:
1. Polarity/Solubility as the carbon length increases, London dispersion
forces intensify and fatty acids become even less polar and consequently less
soluble in polar solvents such as water (medium lengths are sufficient enough
to induce immiscibility)
2. Melting and boiling points increasing carbon length increases forces of
attraction that hold the molecules more, and increases their melting and
boiling points.

A great fact of unsaturation in natural fatty acids is that the double bond
elicits a cis-isomer. This produces a bend in the linear structure, and reduces
area for London dispersion forces. This is why unsaturated fatty acids have
significantly lower boiling and melting points.

FRAGMENT OF BIOCHEMISTRY HANDOUT BY SCHOLIA TUTORIAL CLUB, CHEM

REVIEW GROUP
SLRM2013
3. Compaction straight chain (saturated) fatty acids induce a very large area
for attractive forces and the longer chain saturated fatty acids are solids in
room temperature.
The bends produced by cis unsaturated fatty acids greatly reduce area for
these forces and thus are almost always found as liquids in room
temperature.
No fatty acid is small enough to have forces weak enough to make them
appear as gas in room temperature.
Reactivity:
1. Addition reactions the most significant is hydrogenation, for it is in the
addition of hydrogen that we saturate an unsaturated fatty acid.
2. Substitution reaction the most significant is esterification, because it
allows the fatty acids to become the lipids that are most essential in
biological systems (ex. Triacylglycerols, sphingolipids etc.)
3. Oxidation the most significant is auto oxidation (rancidification)
wherein fatty acids are oxidized by atmospheric oxygen to produce acids and
aldehydes that give the unpleasant taste/color and unusual color in oils
exposed to air in a long time.
4. Peroxidation fatty acids that can be autoxidized to form hydroperoxides,
which allow them to crosslink to each other forming a solid film overtime. This
forms the basis for drying oils in the paint industry.
PART 3: CLASSIFICATION
Storage fatty acid derivatives
1. Triacylglycerols three (tri) fatty acid groups (acyl) are esterified to a
glycerol molecule. Triacylglycerols, as esters, have no polar portion and along
with cholesteryl esters are very non-polar lipids found stored in the body
tissues. These are used when the primary sources of energy (sugars) are
depleted.

Structural fatty acid derivatives

1. Glycerophospholipids fatty acids (lipids) are esterified to glycerol
(glycerol) wherein carbon of the glycerol is bonded to a phosphate instead of
a fatty acid, further bonded to a head group X. These are the most
abundant lipids in molecules. The phosphate group grants additional polarity
to the glycerophospholipids.

FRAGMENT OF BIOCHEMISTRY HANDOUT BY SCHOLIA TUTORIAL CLUB, CHEM

REVIEW GROUP
SLRM2013

The head groups give the difference between different glycerophospholipids.

For example, lecithin contains the head group choline (thus, they are called
phosphatidylcholines) which is the most abundant phospholipid in membrane.
Other glycerophospholipids are cardiolipins, cephalins and phosphoinositides.
2. Sphingholipids instead of glycerol being the backbone where fatty acids
are esterified to, the 18-C alcohol sphingosine takes place. One sphingolipid
is called sphingomyelin (head group being choline) because it is an abundant
lipid in nerve myelin sheaths. Some sphingolipids have carbohydrates
attached to them (cerebroside = one carbohydrate, ganglioside = several
carbohydrates).

3. Waxes - the backbone is actually a long chain monohydroxy alcohol (in

contrast to glycerol and sphingolipid, which has multiple hydroxyl groups).
Their linear structure powerfully increases their non-polar forces of attraction
(why waxes are used as water repellants, in example for fruits. Naturally
present in plants such as cutin and suberin)

The other lipids are not fatty acid derivatives, and usually are those which induce a
physiological effect on the body (hormone-like, etc)
1. Eicosanoids wide array of physiological lipids that originate from arachidonic
acid
a. Leukotrienes eicosanoids that contract smooth muscle. Targets of some
antiasthma drugs (ex. Montelukast)
b. Thromboxanes promote platelet aggregation and vasoconstriction.
c. Prostaglandins most known to induce inflammation, and thus are targets of
some anti-inflammatory drugs (ex. Aspirin)
2. Vitamins vital amines known to assist in maintenance of many biochemical
processes. Most of these are used as cofactors in enzymes that catalyze reactions
in the body essential for it to remain living. (ex. ADEK: Vitamin A helps in eyesight,
Vitamin D regulates calcium in the body, Vitamin E is a powerful antioxidant, and
Vitamin K contributes in clotting of wounds)
3. Steroids lipids having a polycyclic backbone
(cyclopentanoperhydrophenanthrene).

FRAGMENT OF BIOCHEMISTRY HANDOUT BY SCHOLIA TUTORIAL CLUB, CHEM

REVIEW GROUP
SLRM2013

Some steroids have very important physiological functions such as cholesterol

(stabilizes fluidity in cell membrane) and cholesterol derived steroid hormones
(ex. Cortisone, progesterone, testosterone)
Other lipids that we would give even less importance in general biochemistry are
pigments which reflect (and thus, show us) colors of many living creatures (ex.
Beta-carotene is a terpenoid, lipid pigment), and terpenes (a wide array of lipids
with wide array of functions originating from the building unit isoprene; cholesterol
is one terpenoid compound, as well as many volatile oils in perfumes and even
rubber).