LIPIDS PT 1

Lipids?  organic compound found in living organisms that is insoluble (or only
sparingly soluble) in water
 soluble in nonpolar organic solvents.
 Contain nonpolar carbon–carbon and carbon–hydrogen bonds.

TYPES & FUNCTIONS of  Energy-storage lipids (triacylglycerols)

LIPIDS  Membrane lipids (phospholipids, sphingoglycolipids, and cholesterol)
 Emulsification lipids (bile acids)
 Messenger lipids (steroid hormones and eicosanoids)
 Protective-coating lipids (biological waxes)

FUNCTIONS of LIPIDS:  STORAGE

 our bodies store some carbohydrates in the form of glycogen for
quick energy when we need it, energy stored in the form of fats has
much greater importance for us.
 The reason is simple: The burning of fats produces more than twice
as much energy (about 9 kcal/g) as the burning of an equal weight
of carbohydrates (about 4 kcal/g).
 Membrane Components
 lack of water solubility of lipids is an important property because our
body chemistry is so heavily based on water.
 body constituents, including carbohydrates and proteins, are soluble
in water.
 The body needs insoluble compounds for the membranes that
separate compartments containing aqueous solutions, whether they
are cells or organelles within the cells.
 Lipids provide these membranes.
 Messengers
 Lipids also serve as chemical messengers. Primary messengers,
such as steroid hormones, deliver signals from one part of the body
to another part.
 Secondary messengers, such as prostaglandins and thromboxanes,
mediate the hormonal response.

Classification by  Hydrolyzable lipids can be converted into smaller molecules by

Hydrolysis hydrolysis with water. E.g. waxes, triacylglycerols, and phospholipids.
 Nonhydrolyzable lipids cannot be cleaved into smaller units by aqueous
hydrolysis. Nonhydrolyzable lipids tend to be more varied in structure.
 E.g. steroids and fat-soluble vitamins.

Fatty Acids:  Naturally occurring monocarboxylic acid.

Lipid Building Blocks  Hydrolyzable lipids are derived from fatty acids
 Fatty acids are practically all unbranched carboxylic acids.
 They range in size from about 10 to 20 carbons.
 They contain an even number of carbon atoms.
 Apart from the -COOH group, they have no functional groups, except
that some do have double bonds.
 In most fatty acids that have double bonds, the cis isomers
predominate.
 The nonpolar part of the molecule (comprised of C-C and C-H bonds) is
not attracted to water, so it is said to be hydrophobic (water fearing).
 The polar part of the molecule is attracted to water, so it is said to be
hydrophilic (water loving).

 A saturated fatty acid (SFA) is a fatty acid with a carbon chain in which
Saturated Fatty Acids
all carbon–carbon bonds are single bonds.

Monounsaturated Fatty  Monounsaturated Fatty Acid (MUFA) with a carbon chain in which one
Acids carbon–carbon double bond is present.
 double bonds in naturally occurring fatty acids are cis.

Polyunsaturated Fatty  fatty acid with a carbon chain in which two or more carbon–carbon
Acid double bonds are present.

Position of the Double  two numbers separated by a colon are used to specify the number of
Bond carbon atoms and the number of carbon–carbon double bonds present,
 no. of carbon atoms : number of C-C double bond
 eg: 18: 0, means 18 Carbons and zero double bond
 position of the double bond= ∆
 Eg: 18:3(∆9,12,15)
 Delta= right to left
 Omega= left to right
 An (ω) omega-3 fatty acid is an unsaturated fatty acid with its endmost
double bond three carbon atoms away from its methyl end
 omega-6 fatty acid is an unsaturated fatty acid with its endmost double
bond six carbon atoms away from its methyl end.
Physical Properties of  Water solubility for fatty acids is a direct function of carbon chain
Fatty Acids length; solubility decreases as carbon chain length increases.
 Melting points for fatty acids are strongly influenced by both
carbon chain length and degree of unsaturation (number of
double bonds present). As the number of double bonds in the
fatty acid increases, the melting point decreases.

Energy-Storage Lipids:  (triglycerides), are the most abundant lipid category

Triacylglycerols  chemically inert, highly hydrophobic and have a high energy
density
 composed of three fatty acid units joined to glycerol, a trihydroxy
alcohol
Fats and Oils  A triglyceride is called a fat if it is a solid at 25°C
 Oil if it is a liquid at that temperature.
 These differences in melting points reflect differences in the
degree of unsaturation and number of carbon atoms in the
constituent fatty acids.
 Triglycerides obtained from animal sources are usually solids,
while those of plant origin are generally oils.
 Fats are composed largely of triacylglycerols in which saturated
fatty acids predominate, although some unsaturated fatty acids
are present.
 Fats are generally obtained from animals; hence the term animal
fat.
 Pure fats and pure oils are colorless, odorless, and tasteless.

 These two acids

Essential Fatty Acids  are needed for proper membrane structure
 serve as starting materials for the production of several
nutritionally important longer-chain omega-6 and omega-3 acids

Lipid Storage Diseases  Complex lipids are constantly being synthesized and decomposed
in the body.
 In several genetic diseases classified as lipid storage diseases,
some of the enzymes needed to decompose the complex lipids
are defective or missing.
 Complex Carbohydrates

COMPLEX CARBOHYDRATES
 A lipid that contains
Membrane Lipids:  one or more fatty acids,
Phospholipids  a phosphate group,
 a platform molecule to which the fatty acid(s) and the phosphate
group are attached,
 alcohol that is attached to the phosphate group.
 The platform molecule on which a phospholipid is built may be the
3-carbon alcohol glycerol or a more complex C18 aminodialcohol
called sphingosine.


 a lipid that contains two fatty acids and a phosphate group
 Phospholipids:
 Glycerophospholipids esterified to a glycerol molecule and an alcohol esterified to the
phosphate group.
 The alcohol attached to the phosphate group in a
glycophospholipid is usually one of three amino alcohols: choline,
ethanolamine, or serine
 Glycerophospholipids function almost exclusively as components
of cell membranes and are not stored.

 Phospholipids:  lipid that contains one fatty acid and one phosphate group
Sphingophospholipids attached to a sphingosine molecule and an alcohol attached to
the phosphate group.
 All phospholipids derived from sphingosine have the
 fatty acid attached to the sphingosine -NH2 group
 the phosphate group attached to the sphingosine terminal -
OH group
 an additional alcohol esterified to the phosphate group.
lipid that contains both a fatty acid and a carbohydrate component
attached to a sphingosine molecule
 cell membrane constituents especially enriched in the central
nervous system


The Myelin Sheath and  Forty percent of the human brain is white matter.
Multiple Sclerosis  White matter consists of nerve axons wrapped in a white lipid
coating, called the myelin sheath (70% lipids and 30% proteins),
which provides insulation and allows the rapid conduction of
electrical signals.
 Multiple sclerosis: myelin sheath gradually deteriorates.
Symptoms, which include muscle weariness, lack of coordination,
and loss of vision, may vanish for a time but later return with
greater severity
Membrane Lipids:  Cholesterol is a steroid.
Cholesterol  A steroid is a lipid whose structure is based on a fused-ring
system that involves three 6-membered rings and one 5-
membered ring
 Cholesterol is a C27 steroid molecule that is a component of cell
membranes and a precursor for other steroid-based lipids.
 the most abundant steroid in the human body.
 Within the human body, cholesterol is found in cell membranes
(up to 25% by mass), in nerve tissue, in brain tissue (about 10%
by dry mass), and in virtually all fluids.
 Every 100 mL of human blood plasma contains about 50 mg of
free cholesterol and about 170 mg of cholesterol esterified with
various fatty acids.
 Most of it is biosynthesized by the liver and (to a lesser extent) the
intestine. Typically, 800–1000 mg are biosynthesized each day.

Cell Membranes  A lipid-based structure that separates a cell’s aqueous-based

interior from the aqueous environment surrounding the cell.
 Phospholipids contain a hydrophilic polar head and two nonpolar
tails composed of C-C and C-H bonds.
 When phospholipids are mixed with water, they assemble in an
arrangement called a lipid bilayer, with the ionic heads oriented
 on the outside and the nonpolar tails on the inside.
 Lipid bilayer is a two-layer thick structure of phospholipids and
glycolipids

Emulsification Lipids: Bile  A bile acid: cholesterol derivative that functions as a lipid-
Acids emulsifying agent in the aqueous environment of the digestive
tract.
 They 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.
 One end of the molecule is strongly hydrophilic because of the
negative charge, and the rest of the molecule is largely
hydrophobic.
 Bile salts can disperse dietary lipids in the small intestine into fine
emulsions, thereby facilitating digestion.
 Bile salts breakdown products of cholesterol (cholesterol is
eliminated via bile salts), and they solubilize deposited cholesterol
in the form of bile salt–cholesterol particles.

Messenger Lipids: Steroid  A hormone is a molecule that is synthesized in one part of an

Hormones organism, which then elicits a response at a different site.
produced by a ductless gland, that has a messenger function.
 Sex hormones: control reproduction and secondary sex
characteristics
 Adrenal cortical steroids: regulate numerous biochemical
 processes in the body

Steroid Hormones: Sex  The sex hormones can be classified into three major groups:
Hormones  Estrogens—the female sex hormones
 Androgens—the male sex hormones
 Progestins—the pregnancy hormones

Steroid Hormones:  Produced by the adrenal glands, small organs located on top of
Adrenal cortical steroids each kidney, at least 28 different hormones have been isolated
from the adrenal cortex

Messenger Lipids:  Eicosanoid is an oxygenated C20 fatty acid derivative that

Eicosanoids functions as a messenger lipid.
 Not stored within cells but rather synthesized as required
 The metabolic precursor for most eicosanoids is arachidonic acid,
the 20:4 fatty acid.

Eicosanoids :  a messenger lipid that is a C20-fatty-acid derivative that contains

Prostaglandins a cyclopentane ring and oxygen-containing functional groups.
 One of a number of hormone-like substances that participate in a
wide range of body functions such as the contraction and
relaxation of smooth muscle, the dilation and constriction of blood
vessels, control of blood pressure, and modulation of
inflammation.

The Mode of Action for  Injury or damage to bodily tissue is associated with the process
Anti-Inflammatory Drugs of inflammation.
  Inflammation response is mediated by prostaglandin molecules,
high concentrations of prostaglandins present in areas of
inflammation.
 Prostaglandins can promote pain reduction, yet they can also
cause it.
 Inflammation is one of the earlier steps to healing.
 The mode of action for most anti-inflammatory drugs now in use
involves decreasing prostaglandin synthesis within the body by
inhibiting the action of one or more of the enzymes needed for
prostaglandin synthesis.

Eicosanoids :  a messenger lipid that is a C20-fatty-acid derivative that contains

Thromboxanes a cyclic ether ring and oxygen-containing functional groups.
 An important function of thromboxanes is to promote the
formation of blood clots.
 Thromboxanes are produced by blood platelets and promote
platelet aggregation

Eicosanoids :  Messenger lipid that is a C20-fatty-acid derivative that contains

Leukotrienes three conjugated double bonds and hydroxy groups
 Leukotrienes cause tightening of airway muscles and the
production of excess mucus and fluid.
 These chemicals play a key role in allergies, allergic rhinitis, and
asthma, also causing a tightening of your airways, making it
difficult to breathe.

Protective-Coating Lipids:  biological wax is a lipid that is a monoester of a long-chain fatty

Biological Waxes acid and a long chain alcohol.
 The fatty acids found in biological waxes generally are saturated
and contain from 14 to 36 carbon atoms.
 The alcohols found in biological waxes may be saturated or
unsaturated and may contain from 16 to 30 carbon atoms
 LIPIDS PT 2
Lipids  Lipids are a heterogeneous group of organic compounds that are insoluble in
water and soluble in non-polar organic solvents.
 They naturally occur in most plants, animals, microorganisms and are used
as cell membrane components, energy storage molecules, insulation, and
hormones.

Chemical  The chemical properties of triacylglycerols (fats and oils) are typical of esters
Reactions of and alkenes because these are the two functional groups present in
Triacylglycerol triacylglycerols.
s Four important triacylglycerol reactions are
 Hydrolysis
 Saponification
 Hydrogenation
 oxidation

Hydrolysis  Hydrolysis of a triacylglycerol is the reverse of the esterification reaction by

which it was formed .
 Complete hydrolysis of a triacylglycerol molecule always gives one glycerol
molecule and three fatty acid molecules as products
 Hydrolysis is the breakdown of a substance by the addition of water.
 Fats and oils are hydrolyzed by moisture to yield glycerol and 3 fatty acids.
  Hydrolysis of fats and oils leads to rancidity of food product characterized by
unpleasant flavor and aroma thereby making it undesirable.

Metabolism of  Complete metabolism of a triacylglycerol yields CO2 and H2O, and a great
Triglycerides deal of energy.
 Our long-term energy needs are provided by triacyl glycerols, because they
store 9 kcal/g, whereas carbohydrates and proteins store only 4 kcal/g

Saponification
 A hydrolysis reaction carried out in an alkaline (basic) solution.
 For fats and oils, the products of saponification are glycerol and fatty acid
salts
 The first step is the hydrolysis of the ester linkages to produce glycerol and
three fatty acid molecules:
 Soap making involved heating lard (fat) with lye (ashes of wood, an impure
form of KOH).
 The cleansing action of soap is related to the structure of the carboxylate
ions present in the fatty acid salts of soap and the fact that these ions readily
participate in micelle formation.
 A micelle is a spherical cluster of molecules in which the polar portions of the
molecules are on the surface, and the nonpolar portions are located in the
interior.
Hydrogenation
 It involves hydrogen addition across carbon–carbon multiple bonds, which
increases the degree of saturation as some double bonds are converted to
single bonds.
 With this change, there is a corresponding increase in the melting point of the
substance.
 After hydrogenation, liquid oils that once contained more unsaturated fatty
acids become semisolid or solid (upon complete hydrogenation) and behave
like saturated fats
 Hydrogenation is a way to prevent oxidation of oils and ensure longer shelf
life.
 Trans fats are a result of the partial hydrogenation of unsaturated fatty acids,
which cause them to have a trans configuration, rather than the naturally
occurring cis configuration.

Oxidation
 The carbon–carbon double bonds present in the fatty acid residues of a
triacylglycerol are subject to oxidation with molecular oxygen (from air) as the
oxidizing agent.
 Such oxidation breaks the carbon–carbon bonds, producing both aldehyde
and carboxylic acid products.