VITAMINS

- assist in the regulation of biological

processes

5 CATEGORIES BASED ON FUNCTION

1. Energy-stored lipids
LIPIDS – triacylgycerols

- Belong in heterogeneous class of 2. Membrane lipids

naturally occurring organic compounds
classified together on the basis of
common solubility properties
 insoluble in water but soluble in organic
solvents including diethyl ether,
dichloromethane, and acetone
- Lipids are amphiphilic/ amphiphatic
molecules (have bother hydrophilic and
hydrophibic portion)
- Bulk or their structure is nonpolar or
hydrophobic
- Another part of their structure is polar/
hydrophilic
– phospholipids, sphingoglycolipods, and
cholesterol
3. Emulsification lipids
– bile acids, synthesize in liver, stored in
gall bladder
4. Chemical messenger lipids
– steroid hormones and eicosanoids
5. Protective-coating lipids
– biological waxes (ex. Canobal wax, parafin
wax)

CELL STRUCTURE TRIGLYCERIDES

- Creates a barrier for the cell - Energy stored lipids
- Controls flow of materials - Adipose-tissue containing cells:
 under the skin
ENERGY STORAGE  abdominal cavity
- Fats stored in adipose (several fat cells)  mammary glands
tissue  other various organs
- a triester of glycerol with three fatty acids
 ADIPOSE- found below skin/ abdomen  In most triglycerides, two or three
different fatty acid components are
present

HORMONES AND VITAMINS

HORMONES
- important as chemical messengers
- communication between cells
  The hydrophobic character of
triglycerides is caused by the long
nonpolar hydrocarbon chains of fatty
acid components
 The ester groups, although polar, are
buried within a non polar environment,
which makes triglycerides insoluble in
water
2 TYPES OF TRIGLYCERIDES
1. SIMPLE TRIACYGLYCEROLS
- three identical fatty acids are esterified
- naturally occurring simple triacylglycerols
are rare
2. Mixed tricylglycerols
- 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 (ex:
corn, peanut, and wheat-fed cows have
different triacylglycerols
FATTY ACID
- components of triglycerides have certain
things in common:
1. Practically all are unbranched carboxylic acids
2. They range in size from about 10-20 carbons
3. They contain an even number of carbon atoms
4. Apart from the -COOR ester groups,
triglycerides have no functional groups, except
that some have one or more carbon-carbon
double bonds in the fatty acid hydrocarbon
chains
5. In most fatty acids that have carbon-carbon
double bonds, the cis isomers predominate
Cis isomers = found on same side
Trans isomers = opposite in side
SATURATED AND UNSATURATED FATTY ACIDS
1. SATURATED
- all C-C bonds are single bonds
- number 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)
 STRCUTURAL COMMON STRUCTURE
NOTATION NAME
12:0 Lauric Acid
14: 0 Myristic Acid
16:0 Palmitic Acid
(found in
vegetables)
18:0 Stearic Acid
20:0 Arachidic Acid

2. UNSATURATED POLYUNSATURATED FATTY ACID (PUFAs)

- monounsaturated; one C=C bond - a carbon chain in which two or more
- polysaturated; 2 or more C=C bonds carbon-carbon double bonds are
present up to six double bonds are present
present in fatty acid - up to six double bonds are found in
- a monounsaturated fatty acid is a fatty biochemically important PUFAs
acid with a carbon chain in which carbon- - two types of unsaturated fatty acids:
carbon double bond is present  Omega (ω)-3 fatty acids- an unsaturated
- different ways of depicting the structure fatty acid with its endmost double bond
three carbon atoms away from its
methyl end
 Omega (ω)- 6 fatty acid is an unsaturated
MONOUNSATURATED FATTY ACIDS fatty acid with its endmost double bond
16:1 9 ω-7 Palmitoleic six carbon atoms away from its methyl
Acid end
18:1 9 ω-9 Oleic Acid
OMEGA ACIDS
- essential fatty acids: must be part of diet
- nutritionally important Omega-3 and
NOTE: Omega-6 fatty acids
Delta- start  Linolenic acid- Omega 3
Omega- last  Linoleic acid- Omega 6
-ate = ester
-ric = fatty acid

LINOLEIC ACID DEFICIENCY:

- Skin redness- becomes irritated
- Infections and dehydration
- Liver abnormalities
- Children need it the most
- Human milk has more that cow’s milk

TRIGLYCERIDES
- the physical properties of triglycerides
depend on the fatty acid
- Melting point of fatty acids increases as
the number of carbons in the
hydrocarbon chain increases and as the
number of double bonds decreases
- Triglycerides rich in unsaturated fatty
acids are generally liquid at room
temperature and are called oils
- Triglycerides rich in saturated fatty acids
are generally semisolids or solids at room
temperature and are called fats
ENERGY- STORAGE LIPIDS: TRIACYLGLYCEROLS
DIFFERENCE OF FATS AND OILS
FATS:
 Predominantly saturated
 Solids or semisolids at room temperature
 Predominantly obtained from animals
 Tasteless, odorless, colorless
 <10% - Saturated fats
- Studies also indicate that:
 saturated fats = “bad fats”
 monounsaturated fats = “good fats”
 trans - monounsaturated = “bad fats”
 polyunsaturated fats = “bad or good fats”
- Omega 3 and 6 = important good fats
TRIGLYCERIDES
- Hardening- the reduction of some or all
of the carbon-carbon double bonds of an
unsaturated triglyceride using
H2/transition metal catalyst, which
converts a liquid triglyceride to a
semisolid.
- Margarine and other other butter
substitutes are produced by partial
hydrogenation of polyunsaturated oils
derived from corn, cottonseed, peanut,
and soybean oils

OILS:
 Predominantly unsaturated
 Liquids at room temperature
 Obtained from plants and fish oil
 Odorless, colorless

DIETARY CONSIDERATIONS AND

TRIACYLGLYCEROLS
- High dietary intakes of fats and oils: higher
incidence of heart disease and certain types
of cancers
- typical American diet: contains too much fat
GOOD FATS VS BAD FATS
- type of dietary fat and amount of dietary
fat are important for balanced diet:
- total fat intake in calories
 15% - Monounsaturated fat
 10% - Polyunsaturated
  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

TRIGLYCERIDES
- Saponification: hydrolysis in basic
solution
- hydrolysis of fats and oils in aqueous
NaOH
- produces glycerol and a mixture of fatty
acid sodium salts called soaps

ESSENTIAL FATTY ACIDS

- Not synthesized within the body
- two most important:
 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 CHEMICAL REACTIONS OF TRIACYLGLYCEROLS
production of several nutritionally
important longer- chain omega-6 and GREASE AND FATTY ACID MICELLE
omega-3 fatty acids - ”tail” of a fatty acid is a long hydrocarbon
chain -> hydrophobic
BIOCHEMICALLY IMPORTANT OMEGA-3 AND - ”head” of a the molecule is a carboxyl
OMEGA-6 FATTY ACIDS group -> hydrophilic
- Main component of soap:
OMEGA- 3 ACID OMEGA-6 ACID  their tails are soluble in oil dirt
Linolenic acid (18:3) Linoleic acid (18:2)  heads are soluble in water to emulsify
and wash away the oily dirt
Eicosapentaenoic acid Arachidonic acid (20:4)
(20:5)
Docosahexaenoic acid
(20:6)

CHEMICAL REACTIONS OF TRIACYLGLYCEROLS

PARTIAL HYDROLYSIS
- Chemical properties due to two
functional groups: Ester and Alkenes
 CHEMICAL REACTIONS OF TRIACYLGLYCEROLS

HYDROGENATION (REDUCTION)
- addition of hydrogen across double (=)
bond - increases degree of saturation
- many food products are produced by
partial hydrogenation of oils and fats
- peanut oil + H2 -> Peanut Butter
- Vegetable oil + H2 -> Margarine

LIPI
DS OXIDATION
- double bonds in triacylglycerols are
SAPONIFIABLE: subject to oxidation with oxygen in air (an
oxidizing agent): Leads to C=C breakage
1. Glycerol Esters - oxidation of alkenes result into two short
a.Triglycerides chain molecules: an aldehydes or a
- fats and oils carboxylic acid:
b.Phosphoglycerides  Often have objectionable odors- fats and
- phosphatidyl cholines (lecithin) oils are said to be rancid
- phosphatidyl ethanolamines and  To avoid this unwanted oxidation process
phoshatidyl serines (cephalins) antioxidants are added as preservatives.
(ex: vitamin C and vitamin E are good
2. Non- Glyerol Esters antioxidant preservatives
a. Waxes
b. Sphingolipids COMPLEX LIPIDS

NON- SAPONIFIABLE

1. Steroids
a. Cholesterol
b. Steroid hormones
c. Bile salts

2. Eicosanoids
a. Prostaglandins
b. Thromboxanes
c. Leukotrienes
SAPONIFIABLE LIPIDS
3. Fat-soluble vitamins
a. Vit A, D, E, K PHOSPHOLIPIDS
-contain an alcohol, two fatty acids, and a
phosphate ester
-in glycerophospholipids, the alcohol is glycerol
In spingolipids, the alcohol is sphingosine
GLYCOLIPIDS
-complex lipids that contain a carbohydrate
BIOLOGICAL MEMBRANES
- Complex lipids form the membranes
around cells and around small structures
within cells
- in 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 and shielded from the
aqueous environment
 The major driving force for the formation
of lipid bilayers is hydrophobic
interaction
 The arrangement of hydrocarbon tails in
the interior can be rigid (if rich in
saturated saturated fatty acids) or fluid
(if rich in unsaturated fatty acid)
GLYCEROPHOSPHOLIPIDS (GLYCEROL ESTERS)
- Glycerophospholipids (phosphoglycerides)
are the second most abundant group of
naturally occurring lipids
- Found almost exclusively in plants and
animal membranes: 40%- 50%
phosphoacylglycerols; 50%- 60% proteins
- The most abundant glycerophospholipids
are derived from phosphatidic acid, a
molecule in which glycerol is esterified
with two molecules of fatty acid and one
of phosphoric acid
- The three most abundant fatty acids in
phosphatidic acids are palmitic (16:0),
stearic (18:0), and oleic (18:1)
- A phosphatidic acid
- the fatty acid on carbon 2 of glycerol is
always unsaturated
- if the other alcohol is choline, the
glycerophospholipid is called a
phosphatidylcholine (common name
lecithin)
- found in egg yolks and soybeans
- synthesized in the liver
- food industry: emulsifiers (in mayonnaise,
ice cream, etc)
CEPHALINS
- another group of glycerophospholipids in
which the additional phosphate ester is
provided by either ethanolamine or
serine
- found in heart, liver and brain; involved in
blood clotting
SPHINGOLIPIDS (NON- GLYCEROL ESTERS)
- contain the long- chain aminoalcohol,
sphingosine, from which this class of
compunds in named
- The sphingolipid myelin is found in the
coatings of nerve axons
GLYCOLIPIDS (NON- GLYCEROL ESTER)
GLYCOLIPID
- a complex lipid that contains
carbohydrates and ceramides
 The carbohydrate is either glucose or
galactose
  The cerebrosides are ceramide mono- or 3. VERY- LOW DENSITY LIPOPROTEIN (VLDL)
oligosaccharides -occure primarily in the - carries triglycerides (fats) synthesized by
brain and in the myelin sheath of nerves the liver

4. CHYLOMICRONS
STEROIDS (NON- SAPONIFIABLE LIPIDS) - carry dietary lipids synthesized in the
- a group of plant and animal lipids that intestines
contains this tetracyclic ring structure

CHOLESTEROL
- the most abundant steroid in the
human body, and also the most
important
- It is the precursor of all steroid
hormones and bile acids

STEROID HORMONES
- Cholesterol is first converted to
progesterone and then to both sex
hormones and adrenocorticold hormones LOW DENSITY LIPOPROTEIN

LIPOPROTEINS COMPARISON AND PROPERTIES OF HUMAN

- carriers of cholesterol LIPOPROTEINS
- most lipoproteins contain a core of
hydrophobic lipid molecules surrounded
by a shell of hydrophilic molecules such
as proteins and phospholipids. LOW DENSITY LIPOPROTEIN STRUCTURE
- 4 kinds of Lipoproteins:

1. HIGH- DENSITY LIPOPROTEIN (HDL)

- good cholesterol
- consists of about 33% protein and 30%
cholesterol

2. LOW- DENSITY LIPOPROTEIN (LDL)

- bad cholesterol
- contains about 25% protein and 50%
cholesterol

CHOLESTEROL TRANSPORT
- Transport of cholesterol from the liver
starts out as a large VLDL particle
- VLDL is carried in the serum
- As fat is removed, its density increases
and it becomes LDL, LDL stays in the
plasma for about 2.5 days
- LDL carries cholesterol for cells where
specific LDL receptors bind it
- After binding, LDL is taken into cells
where enzymes liberate free cholesterol
and cholesteryl esters
STEROID HORMONES
MALE SEX HORMONES
- synthesized in the testes from
cholesterol
- responsible for the development
of male secondary sex
characteristics
FEMALE SEX HORMONES
- synthesized in the ovaries from
progesterone
- responsible for the development of
female secondary sex characteristics and
control of the menstrual cycle
- Progesterone-like analogs are used in oral
contraceptives
BILE SALTS
- oxidation products of cholesterol
- synthesized in the liver, stored in the gall
bladder, and secreted into the intestine
where they emulsify dietary fats and aid
in their absorption and digestion
 - Aspirin- inactivates the enzyme needed
for prostaglandin synthesis
EICOSANOIDS
- Oxygenated derivatives of
polyunsaturated 20-carbon containing
fatty acid
- hormone-like molecules exerting effects
only in tissues where they are synthesized
- mediates:
 Inflammation response
 Production of fever and pain
 Regulation of blood pressure
 Induction of blood clotting

PROSTAGLANDINS
- not stored in tissues as such, but are
synthesized from membrane-bound 20-
carbon polyunsaturated fatty acids in
response to specific physiological triggers
- one such polyunsaturated fatty acid is
arachidonic acid
EICOSANOIDS: PROSTAGLANDINS
- Prostaglandins - a family compounds that
have the 20-carbon skeleton of
prostanoic acid
- involved in:
 Raising body temperature
 Inhibiting secretion of gastric juices
 Relaxing and contracting smooth muscle
 Directing water and electrolyte balance
 Intensifying pain
 Enhancing inflammation response
COX ENZYMES
- The COX (cyclooxygenase) enzyme occurs
in two forms:
 COX-1- Catalyzes the normal physiological
production of prostaglandins
 COX 2- responsible for the production of
prostaglandins in inflammation
- When a tissue is injured or
damaged, special inflammatory
cells invade the injured tissue and
interact with resident cells, for
example, smooth muscle cells
- The interaction activates COX-2
and prostaglandins are
synthesized
THROMBOXANES
- derived from arachidonic acid
- Thromboxane A2 induces platelet
aggregation and vasoconstriction
- Aspirin and other NSAIDs inhibit the
synthesis of thromboxanes by inhibiting
the COX enzyme
 These information were gathered from our past
notes in Biochemistry

LEUKOTRIENES
- synthesized from arachidonic acid
- they occur mainly in leukocytes
- they produce muscle contractions,
especially in the lungs and thereby can
cause asthma- like attacks. They are 100x
more potent than histamine
- associated with various inflammatory and
hypersensitivity responses
- several recently-developed anti-asthma
drugs inhibit the synthesis of leukotrienes

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