Lipids
Stephanie Mae K. N. Sor, RMT, MD
Objectives
• To have an introduction to the different types of lipids, their common
characteristics, and their different functions
• To have an overview on fatty acids, their nomenclature, and properties
as well as about energy storage molecules
• To discuss the different membrane lipids and the difference in structure
for each type
• To discuss the bile acids and their role in emulsifying fats during
digestion
• To discuss the various steroid hormones and eicosanoids along with
their physiologic roles as messenger lipids
• To discuss biological waxes and their purpose
Lipids
• Fats
• Storage of chemical energy
• Source of Carbon atoms
• Protection & Shock absorption – surround & insulate vital body organs
• Thermoregulation – prevent excessive heat loss
• Cell membrane component – phospholipids, glycolipids, cholesterol
• Chemical messengers
Lipids
• Fats
• Insoluble in water
• Soluble in nonpolar
organic solvents
• Wide structural diversity
• Can be classified based on
biochemical function
• Can also be classified
based on saponification
Classification of Lipids
BASED ON FUNCTION BASED ON SAPONIFICATION
1. Energy storage Reaction that occurs when a lipid is
• triacylglycerols placed in a basic aqueous solution
2. Membrane component 1. Saponifiable – hydrolysis occurs
• phospholipids & lipids are converted into 2 or more
• sphingoglycolipids, smaller molecules
• cholesterol • Triacylglycerols
3. Emulsification • Phospholipids
• Sphingoglycolipids
• bile acids • Biological waxes
4. Messenger 2. Nonsaponifiable – does not react
• steroid hormones, with water
• eicosanoids • Cholesterol
5. Protective coating • Steroid hormones
• biological waxes • Bile acids
• Eicosanoids
Fatty Acids
Fatty Acid
• Naturally occurring monocarboxylic acid
• Usually contain
1. Even number of carbons
2. unbranched carbon chain
3. Double bonds in a cis configuration (if present)
• Characterized according to length
• Short-chain (C4 to C6)
• Medium-chain (C8 to C10)
• Long-chain (C12 to C26)
• Usually found as part of the structure of more complex lipid molecules
• Usually referred to by their common names
Saturation
• Fatty acids may be classified
based on the presence or
absence of carbon-carbon
double bonds
• Saturated fatty acids
• all C-C bonds are single bonds
• Monounsaturated Fatty Acids
• one double bond
• Polyunsaturated Fatty Acids
• >1 double bond
Delta Nomenclature
• 2 numbers separated by a colon is used to denote length &
number of C-C double bonds
• Carboxyl atom is C1
• Enclosed in parenthesis: Capital delta (Δ) with superscript indicating
location of C-C double bonds
Omega Nomenclature
• C1 is the carbon atom on the methyl (noncarboxyl) end (ω)
• Family is determined by the location of the C-C double bond closest
to the omega end
Physical Properties of Fatty Acids
• Determined by length and
degree of unsaturation
• Water solubility
• length ↑ solubility ↓
• Melting point
• length ↑ MP ↑
• saturation ↑ MP ↑
Energy Storage Lipids
Triacylglycerols (TAG)
• Triglycerides
• Most abundant type of lipid in the
human body
• Lipid formed by esterification of
3 fatty acids to 1 glycerol
molecule → triester + 3 H2O
• Location: within fat cells
(adipocytes) found beneath the
skin, in the abdominal cavity, in
the mammary glands, and
around various organs
• Simple – identical FAs
• Mixed – >1 type of FA
Fats and Oils
FATS OILS
• TAG mixture that is solid or • TAG mixture that is liquid at
semisolid at room temp room temp
• Saturated fatty acids predominate • MUFAs and PUFAs predominate
• Odorless, colorless, tasteless • Odorless, colorless, tasteless
when pure when pure
• Animal source • Plant source
• Fish source
Dietary Considerations and TAGs
• Both the type of dietary fat and amount of dietary fat are important
• Recommendations:
• Limit to 30% of total calories
§ Less than 10% saturated fat
§ Up to 15% monounsaturated fat
§ Up to 10% polyunsaturated fat
• Intake of omega-3 fatty acids – from deep/coldwater fish oils
(albacore tuna, salmon, mackerel)
Essential Fatty Acids
• Fatty acid needed by the body that must be obtained from the diet as
the body cannot synthesize them
• Linoleic & Linolenic acid
• Needed for proper membrane structure
• Starting material for production of longer-chain fatty acids
• Arachidonic Acid – eicosanoids
• EPA & DHA – for normal brain & retinal development
Reactions of TAGs
HYDROLYSIS
• Reverse of the esterification
reaction by which the TAG was
formed
• Requires the help of enzymes
produced by the pancreas
1. An outer FA is removed first,
producing a DAG
2. The other outer FA is removed,
producing a MAG
3. If enzymes remove all 3 FAs, a
molecule of free glycerol is
produced
Reaction of TAGs
SAPONIFICATION
• Hydrolysis reaction carried out in alkaline (basic) solution
• Requires the help of enzymes produced by the pancreas
1. Hydrolysis of ester linkages to produce glycerol & 3 fatty acids
Fat or oil + 3 H2O → 3 FAs + Glycerol
2. Acid-base reaction between the fatty acid molecules and the base in
the alkaline solution, producing water and salts
3FAs + 3 NaOH → 3 FA salts + 3H2O
Reactions of TAGs
HYDROGENATION
• Addition of hydrogen across C-C
double bonds
• Multiple bonds are converted into
single bonds → ↑ saturation →
↑ Melting Point
• Complete hydrogenation
• Partial hydrogenation
• May convert cis to trans in some
instances
Trans Fatty Acids
• Unanticipated result of partial
hydrogenation of oils
• Affect blood cholesterol levels in
a similar manner to that of
saturated fats
• ↑ LDL cholesterol
• Does not raise HDL cholesterol
• tFAs in diet
• 15-20% present in meat & dairy
• 80-85% commercially produced
food prepared by partially
hydrogenated cooking oils
Reaction of TAGs
OXIDATION
• Molecular oxygen (O2) serves as the oxidizing agent
• Breaking of C-C double bonds produce both aldehyde and
carboxylic acid
• Short-chain aldehydes and carboxylic acids often have foul odors
• Body Odor – due to rapid oxidation of triacylglycerols (oils) in sweat
promoted by skin microorganisms
Essential Fatty Acids
• Fatty acid needed by the body that must be obtained from the diet as
the body cannot synthesize them
• Linoleic & Linolenic acid
• Needed for proper membrane structure
• Starting material for production of longer-chain fatty acids
• Arachidonic Acid – eicosanoids
• EPA & DHA – for normal brain & retinal development
Membrane Lipids
Phospholipids
• Lipid that contains
§ 1 or more fatty acids
§ Phosphate group
§ Platform molecule – can be glycerol or sphingosine
§ Alcohol attached to phosphate
• Most abundant type of membrane lipid
Glycerophospholipids
• Phospholipid that has glycerol
as its platform molecule
• Lipid that contains
§ 2 fatty acids
§ Phosphate esterified to Glycerol
§ Alcohol esterified to PO4 group
• All attachments between its Choline
(a quaternary ammonium ion)
groups are ester linkages
• Head + 2 tails structure
• Can undergo hydrolysis and Ethanolamine
(positive ion form)
saponification in a manner
similar to TAGs
Glycerophospholipids
PhosphatidylCHOLINE
• Lecithins
• Cell membrane
• Lung surfactant
• Egg yolk, soybeans
• Emulsifiers - mayonnaise, ice
cream, custards
PhosphatidylETHANOLAMINE &
PhosphatidylSERINE
• Cephalins
• Found in heart, liver, brain
• Blood clotting
Sphingophospholipids
• Phospholipid that has
sphingosine as its platform
• Sphingosine –18–C amino
dialcohol hydrocarbon chain
• Attachments to sphingosine are
§ S+FA – amide linkage
§ S+PO – ester linkage
§ P+A – ester linkage
• Head + 2 tails structure
• Can also undergo hydrolysis
and saponification in a manner
similar to TAGs
• S + Choline = Sphingomyelin
Sphingoglycolipids
• Lipid that contains
§ Fatty acid
§ Carbohydrate group – mono or disaccharide
§ Platform molecule –sphingosine
• Head + 2 tails structure
• Also undergo hydrolysis and saponification
• Cerebrosides
• monosaccharide (Glucose or Galactose)
• Myelin sheath
• Gangliosides
• more complex branched chain of
up to 7 monosaccharide residues
• grey matter & myelin sheath
STEROID
Cholesterol a lipid whose structure is
based on a fused-ring
• C27 steroid molecule system that involves
• Most abundant steroid in the three 6-membered rings
& one 5-membered ring
body – precursor of other steroids called the steroid nucleus
• Structure
§ C3: –OH Cholesterol is a compact
§ C10, C13: –CH3 molecule with limited
water solubility
§ C5-C6: =
§ C17 – 8C side chain
• Cell membranes
• Brain & nerve tissue
• Virtually all fluids
• Mostly synthesized by the liver &
intestines
Cholesterol
• Distributed by protein carriers called lipoproteins
• Bad (LDL): Liver → Tissues
• Good (HDL) : Tissues → Liver
↑ dietary cholesterol
↓
↑ blood cholesterol
↓
↑ LDL transport or
↓ HDL transport
↓
plaque formation &
ATHEROSCLEROSIS
Emulsification Lipids
Bile Acids
• Cholesterol derivative that
functions as a lipid-emulsifying
agent in the digestive tract
• 1/3 to ½ of liver cholesterol
produced is used to replenish
bile acid stores
• Bile – fluid containing emulsifying
agents that are secreted by the
liver, stored in the gallbladder,
and released into the small
intestine during digestion
Bile Acids
Simple – oxidation of cholesterol → steroid monocarboxylic acids
• Di- or tri- hydroxy cholesterol derivatives
• C17 side chain has been oxidized to a COOH
Bile Acids
Complexed
• Simple bile acids + attached
amino acid on C17 via an
amide linkage
• Taurine
• Glycine
• Enhanced emulsifying ability
due to additional polarity and
water solubility
Messenger Lipids
Steroid Hormones
Hormones – biochemical substance
• hormone that is a produced by endocrine (ductless) glands
cholesterol derivative that serve as a means of communication
between various tissues
SEX HORMONES - control
reproduction & secondary sex
characteristics
§ Androgens – male sex
§ Estrogens – female sex
§ Progestins – pregnancy
Synthetic hormones
• Oral contraception
• Abortifacient
• Anabolic steroids
Steroid Hormones
ADRENOCORTICOID
HORMONES
§ Mineralocorticoids
• Regulate balance of
Na+ & K+ ions in cells and
body fluids
• Aldosterone
§ Glucocorticoids
§ Control glucose metabolism
§ Counteract inflammation
§ Cortisol
Eicosanoids
• Oxygenated C20 fatty acid Functions
derivative that functions as a • Mediation of inflammation
messenger lipid • Production of pain and fever
• Precursor: Arachidonic Acid • Regulation of blood pressure
• Produced by almost all cells • Blood clotting
except RBCs • Control of reproductive
• Exert their effects in the tissues functions, e.g. induction of labor
where they are synthesized • Regulation of sleep-wake cycle
• Prostaglandins
• Thromboxanes
• Leukotrienes
Eicosanoids
PROSTAGLANDIN
• C20 structure containing a
cyclopentane ring + oxygen-
containing functional groups
• C8 and C12 become connected
to form a ring
• Inhibit secretion of gastric acid
• Increase protective mucus layer of
the stomach
• Contract or relax smooth muscle
• Raise body temperature
• Intensify pain
• Enhance inflammatory response
• Antithrombotic effect
Eicosanoids
THROMBOXANES
• C20 structure containing a cyclic
ether ring + oxygen-containing
functional groups
• C8 and C12 become connected
to form a ring
• Promote formation of blood
clots – released by platelets to
promote platelet aggregation
Eicosanoids
LEUKOTRIENES
• C20 structure containing
3 conjugated double bonds
and hydroxy groups
• Mediate inflammation and
hypersensitivity
Biological Waxes
Biological Waxes
• Monoester of long-chain fatty acid + long-chain alcohol
• Fatty acids
• saturated
• 14-36 carbon atoms
• Alcohols
• saturated or unsaturated
• 16-30 carbon atoms
• Water-insoluble, water-repellent
Functions
• Humans & animals –protect hair & skin to keep it pliable & lubricated
• Birds – keep feathers water-repellent & minimize loss of body heat
• Plants – prevent excessive evaporation and protect against parasitism
• Pharmaceuticals, Cosmetics, Polishing
References
• Kennelly, P. J., Botham, K. M., McGuinness, O., Rodwell, V. W., & Weil,
P. A. (2022). Harper’s Illustrated Biochemistry, Thirty-Second Edition.
McGraw-Hill Education / Medical.
• Lieberman, M., & Peet, A. (2017). Marks’ Basic Medical Biochemistry: A
Clinical Approach. LWW.
• Nelson, D. L. (2016). Principles of Biochemistry 7e.
• Stoker, H. S. (2015). General, organic, and biological chemistry.
Cengage Learning.
