BIOCHEM LECTURE Perez, Marianne

FINAL: Lipids

Review: 2. Non-saponifiable – these substances can’t be hydrolyzed

• Ester - An ester is a chemical compound derived from an
acid (organic or inorganic) in which at least one –OH
hydroxyl group is replaced by an –O– alkyl (alkoxy) group.
To put it in simple terms, esters are a group of chemical
compounds which are formed by bonding of an alcohol
group with a group of organic acids, by losing water
molecules
LIPIDS
• The word lipid is derived from a Greek word “lipos” which
means FAT.
• These are heterogenous group of compounds; unlike
proteins, nucleic acids, polysaccharides, lipids are not
polymers rather they are small molecules and don’t have
common structural feature.
• They organic compounds found in living organisms that are
insoluble (or only sparingly soluble) in water but soluble in
nonpolar organic solvents.
• Make up 18-25% of body mass in lean adults
a. Cholesterol
b. Steroid Hormones
c. Bile Acids
d. Eicosanoids
TYPE OF LIPIDS:
1. Simple lipids. These consist of long chain fatty acids which
may be either free or combined with an alcohol by an
ester linkage. They include the triglycerides
(triacylglycerols) and the waxes.
2. Compound lipids – aside from fatty acids and alcohols,
they contain additional groupings such as phosphoric acid,
sugars, nitrogenous bases or proteins. Included in this
group are the phospholipids, glycolipids and lipoproteins
3. Derived lipids products obtained after the hydrolysis of
simple and compound lipids which possess the
characteristics of lipids. They include cholesterol and the
sex and adrenocortical hormones.

Classification according to Biological Functions:

1. Energy-storage lipids – triacylglycerol
• those containing hydrocarbon side chains serve as
energy stores
2. Membrane lipids – phospholipid, glycolipids, and
cholesterol
• Structural components of cell membranes that serves
as protective barrier
Simple Lipids: A. Triacylglycerols (triglycerides)
• Protective functions in bacteria, plants, insects, &
vertebrates, serving as a part of the outer coating
• Lipid that contains a glycerol molecule and three fatty
acids bonded together by ester bond
between the body of the organism and the
environment. • They function within the body as energy-storage materials.
3. Emulsification lipids – bile acids • Triacylglycerols are concentrated primarily in special cells
4. Messenger lipids – steroid hormones and eicosanoids (adipocytes) that are nearly filled with the material.
• Many intra- and intercellular signaling events involve • Adipose tissue containing these cells is found in various
lipid molecules parts of the body: under the skin, in the abdominal cavity,
in the mammary glands, and around various organs.
5. Protective coating – waxes
Functions as insulator and shock absorber.
Classification according to Saponification Reaction: • The fat content of normal humans allows them to survive
1. Saponifiable – these substances can be hydrolyzed into starvation for 2 or 3 months
smaller molecules
a. Triacylglycerols
b. Phospholipids
c. Sphingoglycolipids
d. Biological Waxes
BIOCHEM LECTURE Perez, Marianne
FINAL: Lipids

Chemical Reactions of Triacylglycerols:

Hydrolysis
• Reverse of the esterification reaction
• Requires the presence of an acid or a base
• Under acidic and basic conditions, the hydrolysis products
are glycerol and fatty acids
• Complete hydrolysis - all three fatty acids are removed
• Partial Hydrolysis - one or more FA residues remain
attached to glycerol

Esterification
• In the esterification reaction a single molecule of glycerol
reacts with three fatty acid molecules each of three
hydroxyl groups present is esterified to produce a
triacylglycerol
Saponification
• A reaction carried out in an alkaline (basic) solution. Its
products are glycerol and fatty acid salts.

Types of Triacylglycerols:
• Simple triacylglycerol is a triester formed from the
esterification of glycerol with three identical fatty acid
molecules.
• Mixed triacylglycerol is a triester formed from the
esterification of glycerol with more than one kind of fatty Hydrogenation
acid molecule. • It involves hydrogen addition across carbon - carbon
multiple bonds, which increases the degree of saturation
Fats and Oils: as some double bonds are converted to single bonds
Fats Oils
FAT is a triacylglycerol OIL is a triacylglycerol
mixture that is a solid or mixture that is a liquid at
semi-liquid at room room temperature (25
temperature (25-degree degrees Celsius). Generally,
Celsius). Generally, fats are oils are obtained from plant
obtained from animal sources
sources. Oxidation
Fats are composed of Oils contain triacylglycerols
• The carbon - carbon double bonds present in the fatty acid
triacylglycerols in which with larger amounts of
residues of a triacylglycerol are subject to oxidation with
saturated fatty acids mono- and polyunsaturated
molecular oxygen (from air) as the oxidizing agent
predominate, although some fatty acids than those in fats
unsaturated fatty acids are • Such oxidation breaks the carbon - carbon bonds,
present producing both aldehyde and carboxylic acid products
BIOCHEM LECTURE Perez, Marianne
FINAL: Lipids

Simple Lipids: B. Biological Waxes

• A monoester lipid that contains one fatty acid (C14 to C36)
esterified to an alcohol (C16 to C30)
• Due to this very long chain of hydrophobic hydrocarbon,
waxes are highly insoluble in water that serves its function
as water-repellent

Fatty Acids:
• A fatty acid has a carboxyl group at the polar end and a
hydrocarbon chain at the nonpolar tail. It is an important
building block on almost all lipids (not all).
• Fatty acids are amphipathic compounds because the
carboxyl group is hydrophilic, and the hydrocarbon tail is
hydrophobic.
• The carboxyl group can ionize under the proper conditions.
• A fatty acid that occurs in a living system normally contains
an even number of carbon atoms, and the hydrocarbon
chain is usually unbranched.
Essential and Non-Essential Fatty Acids:
• Non-essential Fatty acids - Fatty acids that can be
synthesized in the body
• Essential Fatty acids - Fatty acids that must be obtained
from the diet; these are precursors of eicosanoids
o Omega-6 fatty acid
o Omega-3 fatty acid
Cis and Trans Fatty Acids:

Types of Fatty Acid:

• Saturated Fatty Acid - is a fatty acid with a carbon chain in
which all carbon–carbon bonds are single bonds.
• Unsaturated Fatty Acid - is a fatty acid with a carbon chain
has at least one carbon–carbon double bond
o Monounsaturated Fatty Acid - contains one carbon–
carbon double bond
Compound Lipids: A. Phospholipids
o Polyunsaturated Fatty Acid - contains two or more
• Phospholipids consist of four components: fatty acids,
carbon–carbon double bonds
glycerol or sphingosine, phosphate, and alcohol attached
to phosphate.
• Phospholipids are the major lipid constituents of cell
membranes
Types:
1. Glycerophospholipid/ Phosphoglyceride
• Contains two fatty acids and a phosphate group esterified
to glycerol and an alcohol bonded to the phosphate
BIOCHEM LECTURE Perez, Marianne
FINAL: Lipids

2. Sphingophospholipid • Another group is called ganglioside, glycolipid with a

• Contains one fatty acid and a phosphate group esterified
to sphingosine and an alcohol bonded to the phosphate
Glycerophospholipid:
• consist of glycerol, two fatty acid molecules, a phosphate,
and alcohol.
• The common amino alcohol groups of phosphoglycerides
are the amino acid serine, ethanolamine, choline, glycerol,
and the inositol.
• When these alcohols are bonded to the phosphatidyl (or
phosphatidate; without the amino alcohols) there names
become phosphatidylcholine (lecithin),
phosphatidylethanolamine, and phosphatidylserine (both
are also known as cephalins)
• The polar head group of a glycerophospholipid is soluble in
water. The nonpolar tail chains are insoluble in water but
soluble in nonpolar substance.
• This structural feature is very important in the formation
of the cell membrane
complex carbohydrate moiety that contains more than
three sugars
• found as markers on cell membranes and play a large role
in tissue and organ specificity. Gangliosides are also
present in large quantities in nerve tissues
• act as specific receptors for certain pituitary glycoprotein
hormones and certain bacterial protein toxins such as
cholera toxin.
Derived Lipids: A. Steroids
• Steroids consist of four fused rings called steroid nucleus.
• It is not derived from fatty acids.
• a lipid whose structure is a fused-ring system that involves
three 6-membered rings and one 5-membered ring

Sphingophospholipid:
• Sphingosine is an 18-carbon monounsaturated
aminodialcohol
• The amino group of the sphingosine backbone in Steroids: Cholesterol
sphingophospholipid is linked to a fatty acid by an amide • Cholesterol’s structure differs markedly from that of other
bond. In addition, the hydroxyl group of sphingosine is membrane lipids in that (1) there are no fatty acid
esterified to phosphoryl choline residues present and (2) no glycerol nor sphingosine is
• When the alcohol that is attached to the phosphate group present as the platform molecule.
is choline, then the sphingolipid is termed as • Part of steroid family - a lipid whose structure is a fused-
sphingomyelins ring system that involves three 6-membered rings and one
• Same with phosphoglycerides, the two long hydrocarbon 5-membered ring
chains are the two nonpolar tails and the phosphate group
with alcohol is the polar head.
• Sphingomyelin – found in cell membranes and myelin
sheath that surrounds some nerve cell axons

Compound Lipids: B. Glycolipids

• Glycolipids contain a carbohydrate group (attached
through a glycosidic bond) in combination with glycerol or
Membrane Lipids: Cholesterol
sphingosine and fatty acids.
• Aside from an important part of membrane molecule,
• They play a role in the regulation of cellular interactions,
cholesterol is also a pre-cursor for other steroid-based
growth and development.
lipids including bile acids, steroid hormones, and vitamin
• Glycolipids serve as cell surface receptors for certain
D.
hormones and a number of drugs
• It is most abundant steroid in the body; 25% by mass of
• One group is called cerebroside where the sugar moiety is
cell membranes
either glucose (glucocerebroside) or galactose
• Although cholesterol comes from dietary intake, most of it
(galactocerebroside)
is synthesized by our body in liver and a little in intestine
• They are found in nerve (myelin sheath) and brain cell’s
(0.80 - 1 kg per day)
cell membrane (7% of dry mass in brain)
BIOCHEM LECTURE
FINAL: Lipids
• Since cholesterol is insoluble in water, it is carried by
lipoproteins
Lipoproteins
• Lipoproteins are large water-soluble complexes formed by
a combination of lipid and protein that transport insoluble
lipids through the blood between different organs and
tissues
• Lipoproteins consist of a lipid core containing nonpolar
triacylglycerol and cholesterol ester surrounded by a single
layer of amphipathic phospholipids and free cholesterol
molecules with some proteins
4 Main Lipoproteins:
• Chylomicrons - transport exogenous (externally supplied;
in this case, dietary) triacylglycerols and cholesterol from
the intestines to the tissues.
• VLDL (Very Low Density Lipoproteins – Transport of
triacylglycerol from liver to peripheral tissues
• LDL (Low Density Lipoproteins) - carries cholesterol from
liver to various tissues, if this exceeds, cholesterol in the
blood increases and atherosclerosis occur
• HDL (High Density Lipoproteins) – carries excess
cholesterol from tissues to liver
Steroid Hormones
• Hormone – a biochemical structure produced by ductless
gland that serves as means of communication
• Sex hormones - controls reproduction and secondary sex
characteristics.
• Adrenocorticoid hormones - it regulates numerous
biochemical processes in the body.
o Mineralocorticoids (e.g. aldosterone)- controls the
balance of Na+ and K+ ions in cells and body fluids.
o Glucocorticoids (e.g. cortisol) - controls glucose
metabolism and counteract inflammation.
Bile
• Bile is a fluid that contains emulsifying agents that is
secreted by the liver, stored in the gallbladder, and
released in the small intestine during digestion.
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• It contains the bile acids, bile pigments, cholesterol and
bile salts.
• The bile acids increases the solubility of cholesterol in the
bile fluid
• The imbalance between cholesterol level and bile acid
levels can increase precipitation of cholesterol that forms
the gallstones which may also lead to Jaundice – a
condition that occurs due to high level of bilirubin, a bile
pigment
Bile Acids structure:
Types:
• Simple bile acid – free bile acid (not the actual emulsifiers)
o They are tri- or dihydroxy cholesterol derivatives.
o The carbon 17 side chain of cholesterol has been
oxidized to a carboxylic acid
• Complex
o The oxidized acid side chain is bonded to an amino acid
(either glycine or taurine) through an amide linkage
Emulsification Lipids: Bile Acids
• Emulsification - is the process of dispersing two or more
immiscible liquids together to form a semi-stable mixture
by an emulsifier or emulsifying agent
• Bile acids (supplied by bile) in the body serves as
emulsifiers between fat globules and the water
environment of the digestive tract to facilitate absorption
Derived Lipids: B. Eicosanoid
• Eicosanoid – an oxygenated C20 fatty acid derived from
arachidonic acid produced by all cells except red blood
cells
group of lipids made at sites of tissue
damage or infection that are involved in
dealing with injury and illness.
Prostaglandin They control processes such as
inflammation, blood flow, the formation of
blood clots and the induction of labor
substance made by platelets that causes
Thromboxane blood clotting and constriction of blood
vessels. It also encourages platelet
aggregation
produced by leukocytes and its derivatives
regulate immune responses by triggering
Leukotriene contractions in the smooth muscles lining
the bronchioles, causing inflammation
during asthma and allergic rhinitis
Lipid bilayer asymmetry
• The arrangement of different membrane molecules
BIOCHEM LECTURE
FINAL: Lipids
3 Lipid Membranes:
• Phospholipids
• Glycolipids
• Cholesterol
Cell Membrane
• is a lipid-based structure that separates a cell’s aqueous-
based interior from the aqueous environment surrounding
the cell
• lipid bilayer is a two-layer-thick structure of phospholipids
and glycolipids in which the nonpolar tails of the lipids are
in the middle of the structure and the polar heads are on
the outside surfaces of the structure.
Functions of Cell Membrane:
• Protection - serve as boundaries and containers of all cells
and of the organelles within eukaryotic cells
• Transportation - membranes are semipermeable barriers
to the flow of substances into and out of cells and
organelles; it involves the lipid bilayer as well as the
membrane proteins
• Catalysis - enzymes can be bound — in some cases very
tightly— to membranes, and the enzymatic reaction takes
place on the membrane
• Signal receptors - proteins bind specific biologically
important substances that trigger biochemical responses
in the cell
Transport across Cell Membranes:
2 Types of Cell Transport:
1. Passive Transport - the transport process in which a
substance moves across a cell membrane without the
expenditure of any cellular energy.
2. Active Transport - is the transport process in which a
substance moves across a cell membrane with the
expenditure of cellular energy (ATP)
Passive Transport
1. Diffusion - movement of molecules across a
semipermeable membrane from areas of higher
concentration to areas of lower concentration until
equilibrium is reached.
• Does not need energy
• example: diffusion of O2 and CO2
2. Facilitated Diffusion - is a type of diffusion in which the
molecules move from the region of higher concentration
to the region of lower concentration assisted by a
transmembrane proteins.
• Example: glucose and some ions
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3. Osmosis- process by which water molecules diffuse across
a cell membrane from an area of higher concentration to
an area of lower concentration
Types of Solutions:
• Hypertonic Solutions: contain a high concentration of
solute relative to another solution (e.g. the cell's
cytoplasm). When a cell is placed in a hypertonic solution,
the water diffuses out of the cell, causing the cell to
shrivel.
• Hypotonic Solutions: contain a low concentration of solute
relative to another solution (e.g. the cell's cytoplasm).
When a cell is placed in a hypotonic solution, the water
diffuses into the cell, causing the cell to swell and possibly
explode.
• Isotonic Solutions: contain the same concentration of
solute as another solution (e.g. the cell's cytoplasm). When
a cell is placed in an isotonic solution, the water diffuses
into and out of the cell at the same rate. The fluid that
surrounds the body cells is isotonic
Active Transport
1. Endocytosis - process by which cells ingest external fluid,
macromolecules, and large particles, including other cells
a. Pinocytosis - the uptake of extracellular fluids and
dissolved solutes
b. Phagocytosis - process where a cell uses its plasma
membrane to engulf particles, microbes or fragments
of dead cells
2. Exocytosis - the fusion of secretory vesicles with the
plasma membrane and results in the discharge of vesicle
content into the extracellular space and the incorporation
of new proteins and lipids into the plasma membrane