Lipids

10/8/19 1:09 PM

Lipids do not have building blocks

Definition
• A heterogenous class of naturally occurring organic compounds that are insoluble
(or only sparingly soluble) in water but soluble in organic solvents, such as diethyl
ether, dichloromethane, and acetone.
• Structurally diverse
Categories based on function
• Energy - storage lipids: triacylglycerol - fats and oils
• Membrane lipids: phospholipids, sphingoglycolipids, cholesterol
• Emulsification lipids: bile acids
• Messenger lipids: steroid hormones, eicosanoids
○ Communication between cells and environment
• Protective - coating lipids: biological waxes - simplest structures
Fatty Acids - seen in most components
• Naturally occurring monocarboxylic acids
• Nearly always contain an even number of carbon atoms and have a carbon chain
that is unbranched
• Characterized as long-chain fatty acids (C12 to C26), medium-chain fatty acids (C8
to C10), or short-chain fatty acids (C4 to C6)
• May be saturated or unsaturated
○ Saturated (SFAs) - C-C single bonds
○ Unsaturated - C=C double bonds
§ Monounsaturated (MUFAs) - one double bond
§ Polyunsaturated (PUFAs) - more than one
• For most unsaturated fatty acids, the cis isomer predominates; trans isomers are
Docosanhexan…. Acids
rare
DHA - omega 3 acid
Fatty Acids
• Saturated fatty acids are solids at room temperature; the regular nature of their
hydrocarbon chains allows them to pack together in such a way as to maximize
interactions (by LDF) between their chains
• Unsaturated fatty acids have lower melting points than their saturated
counterparts
○ Becomes less tightly packed because of double bonds
○ More double bonds = higher melting points
• Selected Saturated and unsaturated
○ Saturated:
§ Lauric acid - coconut oil (12:0)(12 carbons, 0 double bond)
§ Myristic
§ Palmitic acid - palm oil
§ Stearic
§ Arachidic
○ Unsaturated
§ Palmitoleic
§ Oleic Acid - Olive Oil
§ Linoleic
§ Linolenic
§ Arachidonic
Omega-fatty acids
• Start numbering at the end (omega),
Essential Fatty Acids --> polyunsaturated fatty acids
• Fatty acids needed in the human body that must be obtained from dietary sources
because they cannot be synthesized within the body, in adequate amounts, from
other substances. Examples: Linoleic and linoleic acids

Triacylglycerides
• Neutral lipids - no charged groups
• Function within the body as energy-storage materials
• Concentrated primarily in special cells called adipocytes
• Produced from the triesterification reaction between glycerol and 3 fatty acids
○ Dehydration reaction
• Simple triacylglycerol
○ All three are the same
○ Ex. 3 lauric acids: trilaurin
○ Ex. 3 stearic: tristearin
• Mixed triacylglycerol
○ If there is different
○ Named based by position
§ Stearic, oleic, linoleic
§ 1-stearoyl-2-oleoyl-3-linoleoylglycerol

Amphipathic - may nonpolar and polar part

Fats and Oils
• Oils
○ rich in unsaturated fatty acids
○ Liquid at room temp
○ Generally obtained from plant sources
• Fats
○ Rich in saturated fatty acids
○ Generally semisolids or solids at room temp
○ Generally obtained from animal sources

Reactions of triacylglycerol
• Hydrolysis (acid-catalyzed and enzyme-catalyzed):
○ produces glycerol and free fatty acids
○ Acid: complete hydrolysis
§ All ester bonds are hydrolyzed
○ Enzyme : eventually complete hydrolysis
§ Called lipases
□ Hydrolyzes ester bonds and lipids
§ Step-by-step
§ TAG --> DAG + FA --> MAG +FA --> Glycerol +FA
○ Base-catalyzed hydrolysis (saponification):
§ produces glycerol and salts of fatty acid
§ In water, soap molecules spontaneously cluster into micelles, a
spherical arrangement of molecules such that their hydrophobic parts
are shielded from aqueous environment, and their hydrophilic parts are
in contact with the aqueous environment
• Hydrogenation:
○ addition of hydrogen across double bonds of unsaturated fatty acids
○ Oil can be converted to fat
§ Triolein ---> Tristearin
○ Margarine is a product of partial hydrogenation
§ Some double bonds are not hydrogenated
§ The double bonds that are left are transformed into trans
• Oxidation (with molecular oxygen from air):
○ breaks carbon-carbon bonds producing unpleasant and obnoxious odors and
flavors (rancidity)
○ Can be avoided by adding antioxidants, such as vitamins C and E (naturally
occurring), BHA and BHT (synthetic).

Membrane Lipids: Phospholipids

• Phospholipids
○ Amphipathic
○ A lipid containing one or more fatty acids, a phosphate group, a platform
molecule to which the fatty acid/s and the phosphate group are attached,
and an alcohol that is attached to the phosphate group
○ Include glycerophospholipids and sphingophospholipids
• Glycerophospholipids
○ With charged groups
○ Lipids that contain 2 fatty acids and a phosphate group esterified to a
glycerol molecule and an alcohol esterified to the phosphate group
○ 2 ester and phosphoester bonds
○ Phosphatidylcholine (lecithin)
§ Net charge: 0
○ Phosphatidylethanolamine (cephalin)
§ Net charge: 0
○ Phosphatidylserine
§ Net charge: -1
○ Amphipathic - with polar and nonpolar parts
§ Polar head, 2 Nonpolar tails
• Sphingophospholipids
○ Lipids that contain 1 fatty acid and a phosphate group attached to a
sphingosine molecule
○ Fatty acid bonds to amine --> becomes amide
○ Amide and phosphoester bonds
○ Sphingomyelin
§ Abundant in myelin sheath
§ Net charge: 0
○ Polar head and 2 nonpolar tails
• Sphingoglycolipids
○ Lipids that contain fatty acids and carbohydrate component attached to a
sphingosine molecule
○ Gylcosidic and amide bonds
○ Cerebrosides and gangliosides
○ If carbohydrate is monosaccharide: cerebroside
○ If carbohydrate is oligosaccharide: gangliosides

Steroids
• Cholesterol
○ A steroid, whose structure is based on a fused ring system that involves three
6-membered rings and one 5-membered rings
○ Cholesterol is the most abundant steroid in the human body, and also the
most important
§ It is the component of plasma membranes in all animal cells
§ It is the precursor of all steroid hormones and bile acids
○ Amphipathic because there's a hydroxy group
○ Used to synthesize vitamin D
○ Transported by lipoproteins

Functions of Lipoproteins
• Chylomicrons
○ Carry triglycerides from intestine to other tissues
• VLDL
○ Bind triglycerides synthesized in liver , carry to adipose tissue for storage
• LDL
○ Carry cholesterol to peripheral tissues and help regulate cholesterol levels in
those tissues
• HDL
○ Binds to plasma cholesterol and transport it from peripheral tissues to liver

Cell Membranes
• A lipid-based structure that separated a cell's aqueous-based interior,,,
• On aqueous solution, complex lipids spontaneously form into a lipid bilayer, with a
back-to-back arrangement of lipid monolayers
• Polar (hydrophilic) head groups are in contact with the aqueous environment
• Nonpolar (hydrophobic) tails are buried within the bilayer

Fluid mosaic model

• Lipids and Proteins
○ Role of protein: function of membranes such as transport

Membrane Proteins
• Important structural components of cell membranes
• Two types
○ Integral
§ If you want to remove, you have to destroy the lipid bilayer such as
detergents
○ Peripheral
§ Interact only with polar head
§ Easily removed without destroying the lipid bilayer
• Transport across cell membrane
○ Process by which substances can cross cell membranes
○ Common transport mechanisms: facilitated transport, and active transport
○ High to low conc - no need for energy
○ Low to high - need for energy
§ Passive Transport
□ Simple diffusion
□ Diffusion thru ion channel
□ Facilitated diffusion
® Transporter/carrier
§ Active transport

Emulsification Lipids: Bile Acids

• Emulsifier
○ A substance that can disperse and stabilize water-insoluble substances as
colloidal particles in an aqueous solution
• Bile Acid
○ A cholesterol derivative that functions as a lipid-emulsifying agent in the
aqueous environment of the digestive tract ~33% of daily production of
cholesterol by the liver is converted to bile acids
○ 3 types produces from cholesterol by biochemical oxidation
§ Cholic Acid
§ 12-deoxycholic acid
§ 7-deoxycholic acid
○ Bile acids always carry an amino acid attached to the side-chain carboxyl
group via an aide linkage

Messenger Lipids: Steroid Hormones

• Hormone
○ A biochemical substance, produced by a ductless gland, that has a messenger
function
○ Serve as a means of communication between various tissues
○ Steroid hormone
§ A hormone that is a cholesterol derivative.
§ Major classes
□ Sex hormones
® Estrogen
◊ Estradiol
® Androgen
◊ testosterone
® Progestin
◊ Progesterone
□ Adrenocorticoid hormones
® Produced by adrenal glands, organs on top of kidneys
® Natural: aldosterone and cortisol
® Synthetic: cortisone and prednisone
® Types
◊ Mineralocorticoids
} Control the balance of Na+ and K+ ions in cells
and body fluids
◊ Glucocorticoids
} Control glucose metabolism and counteract
inflammation

Messenger Lipids: Eico(20)sanoids

• Eicosanoid
○ An oxygenated C20 fatty acid derivative that functions as a messenger lipid
• Produced by almost all cells, except red blood cells, from arachidonic acid
• 3 principal types
○ Prostaglandins
§ Raise body temp, inhibit secretion of gastric juices, increase secretion of
a protective mucus layer into the stomach, intensify pain, enhance
inflammation responses
○ Thromboxane
§ Promote formation of blood clots, promote platelet aggregation
○ Leukotrienes
§ Involved in various inflammatory and hypersensitivity

Protective-Coating Lipids: Biological Waxes

• Biological wax: a lipid that is a monoester of a long-chain fatty acid and a long
chain alcohol
• Biological vs mineral wax
○ Mineral wax (or paraffin wax): a mixture of long-chain alkanes obtained from
the processing of petroleum