Structure and Classification of Lipids

Section 19.
1
Structure and Classification of Lipids
Lipids
• A lipid is an organic compound found in living organisms
that is insoluble (or only sparingly soluble) in water but
soluble in non-polar organic solvents.
• Unlike other biomolecules, lipids do not have a common
structural features that serves as the basis for defining
such compounds.
• Classification: They are classified on the basis of
solubility not on any functional groups
– Insoluble or sparingly soluble in water
– Soluble in non-polar organic solvents
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Section 19.1
Five Categories of Lipids

• For purposes of simplicity of study lipids are divided into
five categories based on their function:
– Energy-storage lipids - triacylglycerols
– Membrane lipids - phospholipids, sphingoglycolipids,
and cholesterol
– Emulsification lipids - bile acids
– Chemical messenger lipids - steroid hormones and
eicosanoids)
– Protective-coating lipids - biological waxes
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Section 19.1
Structural Formulas
• Lipids exhibit structural diversity
• Some are esters, some are amides, and some are alcohols (acyclic
and cyclic) and some are polycyclic.
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Section 19.2
Types of Fatty Acids
Saturated and Unsaturated Fatty Acids

• Carboxylic acids with linear (unbranched) carbon chain - Fatty acids
are naturally occuring monocarboxylic acids
• Even # of Carbon atoms:
– Long chain fatty acids: C12 - C26
– Medium chain fatty acids: C6 - C11
– Short-chain fatty acids: C4 - C5
• Two Types:
– Saturated - all C-C bonds are single bonds
– Unsaturated
– Monounsaturated: one C=C bond
– Polyunsaturated: 2 or more C=C bonds present - up to six
double bonds are present in fatty acids
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Section 19.2
Saturated Fatty Acids

– Numbering starts from the end of -COOH group
– See structural notation: it indicates number of C atoms
– Example - Lauric acid has 12 C atoms and no double bonds so it is
(12:0)
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Section 19.2
Unsaturated Fatty Acids

• A monounsaturated fatty acid is a fatty acid with a carbon chain in
which one carbon–carbon double bond is present.
• Different ways of depicting the structure
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Section 19.2
Polyunsaturated Fatty Acids (PUFAs)

• A polyunsaturated fatty acid is a fatty acid with a carbon
chain in which two or more carbon–carbon double bonds
are present.
• Up to six double bonds are found in biochemically
important PUFAs.
• Two types of unsaturated fatty acids.
– Omega (ω)-3 fatty acids - An unsaturated fatty acid
with its endmost double bond three carbon atoms
away from its methyl end.
– Omega(ω)-6 fatty acid is an unsaturated fatty acid
with its endmost double bond six carbon atoms away
from its methyl end. Return to TOC

Section 19.2
Selected Unsaturated Fatty Acids of Biological Importance
• Numbering starts from the other end of COOH

• See structural notation: it indicates number of C atoms
• E.g., 18:2 – 18 carbons, 2 double bonds
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Section 19.2
Omega Acids
• Essential Fatty Acids: Must be part of diet
• Nutritionally important Omega-3 and Omega-6 fatty
acids
– Linolenic acid – Omega-3
– Linoleic acid – Omega-6
• Linoleic Acid Deficiency:
– Skin redness - becomes irritated
– Infections and dehydration
– Liver abnormalities
– Children need it the most
– Human milk has more than cow’s milk Return to TOC

Section 19.2
American Diet
• Sufficient in omega 6 fatty acids
• Deficient in omega 3 fatty acids
– Fish - good source for omega 3 fatty acids
• High rate of heart disease may be due to imbalance in
omega 3 and 6 fatty acids
– Ideal ratio: Omega 6 : Omega 3 (4 - 10 g: 1g)
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Section 19.3
Physical Properties of Fatty Acids
• Water solubility: Short chain fatty acids have some

solubility whereas long chain fatty acids are insoluble
– Short chain fatty acids are sparingly soluble because
of carboxylic acid polar group
• Physical properties such as melting point depends on
the number of C atoms and degree unsaturation
Return to TOC

Section 19.3
The Melting Point

• Melting Point Depends Upon:
– Length of carbon chain
– Degree of unsaturation (number of double bonds in a
molecule)
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Section 19.3
Space-Filling Molecules
• The number of bends in a fatty acid chain increase as
the number of double bonds increase
• Less packing occurs
• Melting point is lower
• Tend to be liquids at room temperature
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Section 19.4
Energy-Storage Lipids: Triacylglycerols
Energy-Storage Materials
• With the notable exception of nerve cells, human cells
store small amounts of energy providing materials:
– The most widespread energy storage material -
carbohydrate glycogen
– Present in small amounts
• Storage material is the triacylglycerols:
– Triacylglycerols are concentrated primarily in special
cells (adipocytes)
– Nearly filled with the material.
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Section 19.4
Two Types of Triacylglycerols

• Simple Triacylglycerols: Three identical fatty acids are
esterified
– Naturally occurring simple triacylglycerols are rare
• Mixed Triacylglycerols: A triester formed from the
esterification of glycerol with more than one kind of fatty
acid
– In nature mostly mixed triacylglycerols are found and
are different even from the same source depending
on the feed, e.g., corn, peanut and wheat -fed cows
have different triacylglycerols
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Section 19.4
Difference of Fats and Oils

• Physical State:
– Fats
• Predominantly Saturated
• Solids or semisolids at room temperature
– Oils:
• Predominantly unsaturated
• Liquids at room temperature
• Source:
– Fats: Animal source and tasteless
– Oils: Plants and fish oil
– Pure oils and fats are colorless, odorless Return to TOC

Section 19.5
Dietary Considerations and Triacylglycerols
Studies
• Nations whose citizens have high dietary intakes of fats
and oils tend to have higher incidences of heart disease
and certain types of cancers
• Typical American diet contains too much fat and
therefore the Americans are being asked to reduce their
total dietary fat intake
• Other studies show that risk factor is more than simply
the total amount of triacylglycerols consumed
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Section 19.5
“Good Fats” Versus “Bad Fats”

• Studies indicate that type of dietary fat and amount of dietary fat are
important for balanced diet:
– Current recommended amounts are: total fat intake in calories:
• 15% - Monounsaturated fat
• 10% - Polyunsaturated
• <10% - Saturated fats
• Studies also indicate that:
– Saturated fats are considered “bad fats”
– Monounsaturated fats are considered “good fats”
– Trans-monounsaturated fats are considered “bad fats”
– Polyunsaturated fats can be both “good fats” and “bad fats”
• Omega 3 and 6 are important “good fats”
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Section 19.5
Essential Fatty Acids

• Fatty acids that must be obtained from dietary sources – are not
synthesized within the body
• Two most important essential fatty acids are:
– Linoleic acid (18:2) - omega 6
– Linolenic acid (18:3) - omega 3
• Both are needed for:
– Proper membrane structure
– Serve as starting materials for the production of several
nutritionally important longer-chain omega-6 and
omega-3 fatty acids
• Deficiencies of above two acids may result in skin redness,
infections and dehydration likely and liver abnormalities may
develop
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Section 19.5
Fat and Fatty Acid Composition of Nuts

• Numerous studies now indicate that eating nuts can have a
strong protective effect against coronary heart disease:
– Low amounts of saturated fatty acids
– Nuts also contain valuable antioxidant vitamins, minerals,
and plant fiber protein
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Section 19.6
Chemical Reactions of Triacylglycerols
Partial Hydrolysis
• Chemical Properties due to two functional groups: esters
and alkenes
– Hydrolysis: Partial hydrolysis of triacylglycerols
– Breaking of 1-2 ester bonds to give rise to mono- or
diacylglycerol and fatty acid(s)
– Carried out by enzymes produced by the pancreas
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Section 19.6
Saponification
• Hydrolysis in basic solution: Produce salt of fatty acid
and glycerol
RCOOR’ + NaOH  RCOONa (soap) + R’OH
O
H 2 C OH
H 2C O C R
O
R C CH + 3NaOH HC OH + 3RCOONa
O
O
Soap
H 2C O C R H 2 C OH
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Section 19.6
Hydrogenation
– Addition of hydrogen across double (=) bond - increases degree
of saturation
O
O
H2C O C H2C O C
O O
HC O C + 2H2
HC O C
O O
H2C O C
H2C O C
Oil Solid
– Many food products are produced by partial hydrogenation of

oils and fats
– Peanut oil + H2  Peanut Butter
– Vegetable oil + H2  Margerine
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Section 19.6
Oxidation
• Double bonds in triacylglycerols are subject to oxidation with oxygen
in air (an oxidizing agent )-Leads to C=C breakage
• Remember that oxidation of alkenes may result into two short chain
molecules – an aldehydes or a carboxylic acid:
– The aldehydes and/or carboxylic acids so produced often have
objectionable odors - fats and oils are said to be rancid
– To avoid this unwanted oxidation process antioxidants are
added as preservatives, e.g., Vitamin C and vitamin E are good
antioxidant preservatives.
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Section 19.7
Membrane Lipids: Phospholipids
• All cells are surrounded by a membrane that confines

their contents.
• Up to 80% of the mass of a cell membrane can be lipid
materials and these lipid materials are dominated by
phospholipids.
• A phospholipid contains one or more fatty acids, a
phosphate group, a platform molecule (glycerol or
sphingosine) to which the fatty acid(s) and the
phosphate group are attached, and an alcohol that is
attached to the phosphate group.
Return to TOC

Section 19.7
Glycerophospholipids
• A glycerophospholipid is a lipid that contains two fatty
acids and a phosphate group esterified to a glycerol
molecule and an alcohol esterified to the phosphate
group.
• All attachments (bonds) between groups in a
glycerophospholipid are ester linkages
• Glycerophospholipids have four ester linkages as
contrasted to three ester linkages in triacylglycerols.
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Section 19.7
• Glycerophospholipids undergo hydrolysis and
saponification reactions in a manner similar to that for
triacylglycerols
• The alcohol attached to the phosphate group in a
glycophospholipid is usually one of three amino alcohols:
choline, ethanolamine, or serine - respectively known as
phosphatidylcholines, phosphatidylethanolamines, and
phosphatidylserines.
Return to TOC

Section 19.7
• Structurally glycerophospholipids are alghough similar to
triacylglycerols, they have different biochemical
functions.
– Triacylglycerols serve as energy storage molecules
– Glycerophospholipids function as components of cell
membranes
• A major structural difference between the two types of
lipids is that of their “polarity” – Responsible for the their
differing biochemical functions.
– Triacylglycerols are a non-polar
– Glycerophospholipids are polar.
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Section 19.7
Sphingophospholipids
• Structures based on the 18-carbon monounsaturated
aminodialcohol sphingosine
• contains one fatty acid and one phosphate group
attached to a sphingosine molecule and an alcohol
attached to the phosphate group
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Section 19.7
• Saponifiable lipids
• Sphingophospholipids in which the alcohol esterified to
the phosphate group is choline are called
sphingomyelins.
• Sphingomyelins are found in all cell membranes and are
important structural components of the myelin sheath of
neurons
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Section 19.8
Membrane Lipids: Sphingoglycolipids
• Sphingoglycolipids: Contains both a fatty acid and carbohydrate

• Simple sphingoglycolipids are called cerebrosides: contains a
single monosaccharide unit - either glucose or galactose
– They occur primarily in brain (7% of dry mass)
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Section 19.8
Membrane Lipids: Sphingoglycolipids
Gangliosides
• Complex sphingoglycolipids are called Gangliosides:
contain a branched chain of up to seven
monosaccharide residues.
• Occur in the gray matter of the brain as well as in the
myelin sheath.
Return to TOC

Section 19.9
Membrane Lipids: Cholesterol
Cholesterol-Third major type of membrane lipid

• Lipids: Fused Rings
• Cholesterol: C27 steroid molecule
• A steroid is a lipid whose structure is based on a fused
ring system of three 6 carbon rings and one 5 carbon
ring.
• Important in human cell membranes, nerve tissue and
brain tissue
– Important in chemical synthesis: Hormones,
vitamins essential for life
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Section 19.9
Membrane Lipids: Cholesterol
Cholesterol in Food
• Liver synthesizes cholesterol: ~ 1g everyday; so it is not
necessary to consume in the form of diet
• Cholesterol synthesis decrease if it is ingested but
reduction is not sufficient: Leads to cardiovascular
disease
• Animal Food: Lot of cholesterol
• Plant Food: No cholesterol
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Section 19.10
Cell Membranes
Cells
• Cells are surrounded by plasma membranes:
– Separates aqueous interior of a cell from the aqueous
environment surrounding the cell
– Up to 80% of plasma membrane is lipid material
– The membranes are lipid bilayer made up of phospholipids
• Cells are surrounded by plasma membranes:
– Bilayer: Nonpolar tails of phospholipids in the middle and polar
heads are on the surface
• 6 - 9 billionths of a meter thick or 6-9 nanometer thick
– The membrane is a liquid like structure due to unsaturation in
lipid tails
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Section 19.10
Cell Membranes
Cholesterol
• Cholesterol molecules are also components of plasma membranes:
– Cholesterol helps regulate membrane fluidity – The fused ring
system does nor allow rotation of fatty acid tails in the vicinity
– Fits between fatty acid chains of the lipid bilayer: Make it rigid
– Cholesterol thus acts a membrane plasticizer
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Section 19.10
Cell Membranes
Proteins
• The membranes also contain proteins:
– Responsible for moving substances such as nutrients and electrolytes
across the membrane
– Receptors for hormones and neurotransmitters
• The membrane proteins and some lipids are further reacted with
carbohydrates molecules:
– Act as markers: process by which different cells recognize each other
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Section 19.10
Cell Membranes
Passive Transport
• Transport Across Cell Membranes:
– To maintain cellular processes various molecules transported
across the cell membranes.
– Three types of transport.
• Passive transport
• Facilitated transport
• Active transport
• Passive transport - a substance moves across a cell membrane
by diffusion from a region of higher concentration to a region of
lower concentration.
– Only a few types of molecules, including O2, N2, H2O, urea,
and ethanol, can cross membranes by passive transport
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Section 19.10
Cell Membranes
Facilitated Transport
• Facilitated transport - a substance moves across a cell
membrane with the aid of a membrane protein from a
region of higher concentration to a region of lower
concentration.
– The specific protein carriers or transporters are
involved in the process
Return to TOC

Section 19.10
Cell Membranes
Active Transport
• Active transport - a substance moves across a cell
membrane, with the aid of membrane proteins,
against a concentration gradient with the expenditure
of cellular energy.
– Proteins involved in active transport are called
“pumps.” The needed energy is supplied by
molecules such as ATP.
Return to TOC

Section 19.11
Emulsification Lipids: Bile Acids
• An emulsifier is a substance that can disperse and

stabilize water-insoluble substances as colloidal
particles in an aqueous solution.
• Bile Acids: Cholesterol derivatives that functions as
emulsifying agents that make dietary lipids soluble in
aqueous environment of the digestive tract:
– Approximately one third of cholesterol produced by
liver is converted to bile acids.
– Action similar to soap in washing
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Section 19.11
Emulsification Lipids: Bile Acids
Bile Acids
• Bile acids are tri- or dihydroxy cholesterol derivatives
• The carbon 17 side chain of cholesterol has been
oxidized to a carboxylic acid
• The oxidized acid side chain is bonded to an amino acid
(either glycine or taurine) through an amide linkage
• Bile is a fluid containing emulsifying agents (Bile acids)
secreted by the liver, stored in the gallbladder, and
released into the small intestine during digestion
Return to TOC

Section 19.12
Messenger Lipids: Steroid Hormones
Hormones
• A hormone is a biochemical substance produced by a ductless
gland that has a messenger function.
• Hormones serve as a means of communication between various
tissues.
– Some hormones are lipids.
• The lipids that play the role of “chemical messengers” include:
– Steroid hormones – derivatives of cholesterol
– Eicosanoids- derivatives of arachidonic acid
• There are two major classes of steroid hormones:
– Sex hormones - control reproduction and secondary sex
characteristics
– Adrenocorticoid hormones – control numerous biochemical
processes in the body
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Section 19.12
Sex Hormones
• Classified into three major groups:
– Estrogens - the female sex hormones
– Androgens - the male sex hormones
– Progestins - the pregnancy hormones
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Section 19.12
Adrenocorticoid Hormones
• Produced by the adrenal glands - small organs located
on top of each kidney
• 28 Different hormones have been isolated from the
adrenal cortex
• Two types of adrenocorticoid hormones:
– Mineralocorticoids - control the balance of Na and K
ions in cells
– Glucocorticoids - control glucose metabolism and
counteract inflammation
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Section 19.13
Messenger Lipids: Eicosanoids
• Eicosanoids Arachidonic acid (20:4) derivatives:

– Have profound physiological effects at extremely low
concentrations.
– Eicosanoids are hormone-like molecules
– Exert their effects in the tissues where they are synthesized.
– Eicosanoids usually have a very short “life.”
– Physiological effects of eicosanoids:
• Inflammatory response
• Production of pain and fever
• Regulation of blood pressure
• Induction of blood clotting
• Control of reproductive functions, such as induction of labor
• Regulation of the sleep/wake cycle
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Section 19.13
Three Principle Types

1. Prostoglandins: C20-fatty-acid derivative containing
cyclopentane ring and oxygen-containing functional
groups
– Involved in raising body temperature,
– Inhibiting the secretion of gastric juices,
– Increasing the secretion of a protective mucus layer
into the stomach,
– Relaxing and contracting smooth muscle, directing
water and electrolyte balance, intensifying pain, and
enhancing inflammation responses.
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Section 19.13
Three Principle Types

2. Thromboxanes: C20-fatty-acid derivative containing a
cyclic ether ring and oxygen-containing functional groups
Promote platelet aggregation.
3. Leukotrienes: C20-fatty-acid derivative containing three
conjugated double bonds and hydroxy groups
Promote inflammatory and hypersensitivity (allergy)
responses
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Section 19.14
Protective-Coating Lipids: Biological Waxes
• A biological wax: a monoester of a long-chain fatty acid and a long-

chain alcohol.
• The fatty acids found in biological waxes:
– Generally are saturated fatty acids
– Contain 14 to 36 carbon atoms.
• The alcohols found in biological waxes:
– May be saturated or unsaturated
– May contain 16 to 30 carbon atoms.
Return to TOC

Section 19.14
Protective-Coating Lipids: Biological Waxes
• Properties of Biological waxes : Water-insoluble and water-

repellent because of long nonpolar hydrocarbon chains.
– Humans and animals secrete biological waxes from skin
glands
• Function of biological waxes:
– Protect hair and skin; and keep it pliable and lubricated.
– Impart water repellency to animal fur.
– Birds keep their feathers water repellent and help
minimize loss of body heat
– Plants coat their leaves with a thin layer of biological
waxes to prevent excessive evaporation of water and to
protect against parasite attack. Return to TOC

Structure and Classification of Lipids

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Section 19.

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Five Categories of Lipids

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Saturated and Unsaturated Fatty Acids

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Saturated Fatty Acids

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Unsaturated Fatty Acids

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Polyunsaturated Fatty Acids (PUFAs)

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Selected Unsaturated Fatty Acids of Biological Importance

• Numbering starts from the other end of COOH

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• Water solubility: Short chain fatty acids have some

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The Melting Point

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Two Types of Triacylglycerols

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Difference of Fats and Oils

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“Good Fats” Versus “Bad Fats”

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Essential Fatty Acids

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Fat and Fatty Acid Composition of Nuts

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– Many food products are produced by partial hydrogenation of

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• All cells are surrounded by a membrane that confines

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• Sphingoglycolipids: Contains both a fatty acid and carbohydrate

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Cholesterol-Third major type of membrane lipid

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• An emulsifier is a substance that can disperse and

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