Bettelheim / Brown / Campbell / Farrell / Torres

Introduction to General, Organic, and Biochemistry 11e

Lipids

William H. Brown Beloit College www.cengage.com/chemistry/bettelheim

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Classification Based on Biochemical
Function
• Energy-storage lipids (Triacyglycerols)
• Membrane lipids (phospholipids,
sphingoglycolipids, cholesterol)
• Emulsification lipids (bile acids)
• Messenger lipids (steroid hormones and
eicosanoids)
• Protective-coating lipids (biological waxes)

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Classification Based on Saponification
• Saponifiable lipids (triacyglycerols,
phospholipids, sphingoglycolipids,
biological waxes)
• Nonsaponifiable lipids (cholesterol,
steroid hormones, bile acids,
eicosanoids)

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Fatty acids
• Most frequently encountered building blocks
• Naturally occurring monocarboxylic acid
• Carbon length
• Long-chain fatty acids
• Medium-chain fatty acids
• Short-chain fatty acids

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Saturated and Unsaturated Fatty
Acids
• Saturated fatty acid
• Carbon-Carbon binds are single bonds

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Saturated and Unsaturated Fatty
Acids
• Monounsaturated fatty acid
• One Carbon-Carbon double bond is present

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Saturated and Unsaturated Fatty
Acids
• Polyunsaturated fatty acid
• 2 or more Carbon-Carbon double bonds

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Unsaturated Fatty Acids and Double Bond
Position
•

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Unsaturated Fatty Acids and Double Bond
Position
•

20:5

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Physical Properties of Fatty Acids
• Water solubility
• Solubility decreases as carbon chain length
increases
• Melting points
• As carbon chain length increases, melting point
increases
• The greater the degree of unsaturation, the greater
the reduction in melting points

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Energy-Storage Lipids: Triacylglycerols
• Concentrated in adipocytes
• Skin, abdominal cavity, mammary glands
• Much efficient at storing energy than glycogen
• Most abundant type of lipid in human body
• Functional group: Triesters
• A single molecule of glycerol reacting with three fatty acids

Glyerol 13
Energy-Storage Lipids: Triacylglycerols
• Simple triacylglycerol
• Triester formed from esterification of glycerol with three
identical fatty acid molecules
• Mixed triacylglycerol
• Triester formed from esterification of glycerol with more
than one kind of fatty acid molecule.

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Energy-Storage Lipids:
Triacylglycerols
• Oils
• Triglycerides rich in unsaturated fatty acids that are
generally liquid at room temperature
• plant sources
• Fats
• Triglycerides rich in saturated fatty acids that are
semisolids or solids at room temperature
• Animal sources

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Chemical Reactions of Triacylglycerols
• Hydrolysis
• Saponification
• Hydrogenation
• Oxidation

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Chemical Reactions of Triacylglycerols
• Hydrolysis
• The reverse
esterification
• Undergoes during
digestion
• Acidic condition
• Products:
glycerols and
fatty acids
• Basic condition
• Products:
glycerols and
fatty acid salts
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Chemical Reactions of Triacylglycerols
• Saponification
• Carried out in alkaline solution
• First step: Hydrolysis of ester linkages producing glycerol and
fatty acids
• Fat or oil + 3H2O → 3 fatty acids + glycerol
• Second step: reaction between fatty acid and base (NaOH)
• 3 fatty acids + 3NaOH → 3 fatty acid salts + 3 H2O

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Chemical Reactions of Triacylglycerols
• Hydrogenation
• Hydrogen addition across carbon-carbon multiple
bonds
• Increases degree of saturation as double bonds
are converted to single bonds (increases melting
point)

---CH₂-CH₂ -CH=CH-CH₂ -CH₂ --- + H₂ → ---CH₂-CH₂-CH₂-CH₂-CH₂-CH₂---

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Chemical Reactions of Triacylglycerols
• Oxidation
• Oxidizing agents break carbon-carbon double
bonds present in fatty acid residues of TAG
producing both aldehyde and carboxylic acid
products
• Rancid odor

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Membrane Lipids: Phospholipids
• 80% of the mass of cell membranes are lipid
• Give cells their individuality by separating them from
their environment.
• Phospholipids
• Sphingoglycolipids
• Cholesterol

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Membrane Lipids: Phospholipids
• Most abundant type of membrane lipid
• Contains:
• one or more fatty acids
• phosphate group
• a platform molecule to which the FA and phosphate
group are attached
• Alcohol attached to the phosphate group
G
L FATTY ACID
Y
C FATTY ACID
E
R
O PHOSPHATE ALCOHOL
L
Glycerophospholipids 22
Cell Membranes
• Lipid-based structure that separates a cell’s
aqueous-based interior from the aqueous
environment surrounding the cell.
• Controls movement of substances into and
out of the cell.
• Phospholipids, glycolipids, cholesterol
• Structure:
• Insoluble to water
• Head and two tails structure
(phospholipids and sphingoglycolipids)
• Polar head, nonpolar tail (lipid bilayer)
• Cholesterol- membrane rigidly

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Membrane Lipids: Sphingoglycolipids
• Contains fatty acid and carbohydrate component
attached to sphingosine molecule

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Membrane Lipids: Cholesterol
• No fatty acid residues present
• Neither glycerol nor sphingosine are present
• Steroid
• Structure is based on a fused-ring that involves 6-
membered ring and one 5-membered ring
• Steroid nucleus

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Membrane Lipids: Cholesterol
• C₂₇ steroid molecule
• Component of cell membranes
• Precursor for other steroid-based lipids

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13

10
5
3 6

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Lipoproteins
Lipoproteins: Carriers of cholesterol.
• High-density lipoprotein (HDL) (“good cholesterol”)
• 33% protein and 30% cholesterol
• Low-density lipoprotein (LDL) (“bad cholesterol”)
• 25% protein and 50% cholesterol
• Very-low density lipoprotein (VLDL)
• carries triglycerides (fats) synthesized by the liver
• Chylomicrons
• carry dietary lipids synthesized in the intestines

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Levels of LDL and HDL
• Most of the cholesterol is carried by LDL.
• Normal plasma levels : 175 mg/dL.
• Familial hypercholesterolemia
• not enough LDL receptors and plasma levels
of cholesterol may rise as high as 680 mg/dL

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Levels of LDL and HDL
• High levels of cholesterol = premature
atherosclerosis and heart attacks.
• high LDL with low HDL is a symptom of
faulty cholesterol transport and a warning of
possible atherosclerosis

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Emulsification Lipids: Bile Acids
• Emulsifier
• Substance that can disperse and stabilize water-insoluble
substances as colloidal particles in an aqueous solution.
• Bile acids
• Facilitate absorption of dietary lipids in the intestine
• Derivatives of cholesterol
• Secreted by the liver, stored in gallbladder, released in
small intestine during digestion

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Messenger Lipids: Steroid Hormones
• Hormone
• Biochemical substance, produced by ductless
gland, that has a messenger function.
• Steroid hormone
• Cholesterol derivative hormones
• Classes: Sex hormones and Adrenocorticoid
hormones

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Sex Hormones
1. Estrogens – female sex hormones
2. Androgens – male sex hormones
3. Progestins – pregnancy hormones

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Sex Hormones
• Oral contraceptives
• Suppress ovulation
• Mixture of synthetic estrogen and synthetic
progestin
• Anabolic steroid
• Steroid drugs used by athletes illegally for muscle
build up

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Adrenocorticoid Hormones
• Produced by adrenal glands
1. Mineralocorticoids – control the balance of Na⁺ and
K⁺ ions in cells and body fluids
2. Glucocorticoids – control glucose metabolism and
counteract inflammation

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Messenger Lipids: Eicosanoids
• Eicosanoid
• Oxygenated C₂₀ fatty acid derivative that functions as a
messenger lipid
• “eikos” - twenty
• Arachidonic acid- precursor; 20:4 fatty acid
• Physiologic effects:
• Inflammatory response
• Production of pain and fever
• Regulation of blood pressure
• Induction of blood clotting
• Control of reproductive functions (labor)
• Regulation of sleep/wake cycle
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Types of Eicosanoids
• Prostaglandins
• Thromboxanes
• Leukotrienes

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Prostaglandins
• C₂₀ fatty acid that contains a cyclopentane ring and oxygen-
containing functional groups
• Functions:
• regulating raising body temperature
• Inhibiting secretion of gastric juices
• Increasing secretion of protective mucus layer in stomach
• Enhancing inflammation response

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Thromboxanes
• C₂₀ fatty acid that contains a cyclic ether ring and
oxygen-containing functional groups
• Promote formation of blood clots
• Produced by platelets and promote platelet
aggregation

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Leukotrienes
• C₂₀ fatty acid that contains three conjugated double
bonds and hydroxyl group
• Found in WBC
• Elevated levels are related to:
• Inflammation and allergic reaction

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Protective-coating Lipids
• Biological Wax
• Monoester of long-chain fatty acid and long chain
alcohol
• Function
• Protection of hair and skin
• Example:
• Lanolin – skin creams
• Mineral wax
• Paraffin waxes

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Saponifiable and Nonsaponifiable
Lipids
• Saponification
• Reaction of hydrolysis reaction carried out in basic solution
Saponifiable Nonsaponifiable
TAG (3 ester linkages) Cholesterol
Glycerophospholipids Bile acids
(4 ester linkages)
Sphingophospholipids Steroid hormones
(1 amide and 2 ester
linkages)
Sphingoglycolipids Eicosanoids
(1 amide, 1 ester, 1
glycosidic linkage)
Biological waxes
(1 ester linkage)

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Lipids

End

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