LIPIDS

-
Fats provide a major way of storing - Basic components of cell membranes:
chemical energy and carbon atoms in the phospholipids, glycolipids, and
body. cholesterol.
- Fats surround vital organs to protect them - Lipid is insoluble or sparingly soluble in
from mechanical shock and prevent water but is soluble in non-polar
excessive heat energy loss. organic solvents.
STRUCTURE & CLASSIFICATION
* based on biochemical function *based on the saponification ability of the lipid when
1. Energy-storage lipids placed in a basic aqueous solution
 Triacylglycerols
2. Membrane lipids 1. Saponifiable lipids- converted into two or
 Phospholipids smaller molecules after hydrolysis.
 Sphingoglycolipids  Triacylglycerols
 Cholesterol  Phospholipids
3. Emulsification of lipids  Sphingoglycolipids
- Bile acids  Biological waxes
4. Messenger lipids 2. Nonsaponifiable lipids- cannot be broken up
- Steroid hormones into smaller units since they do not react in water.
- Eicosanoids  Cholesterol
5. Protective-coating lipids  Steroid hormones
- Biological waxes  Bile acids
 Eicosanoids

TYPES OF FATTY ACIDS

Fatty acid
- naturally occurring monocarboxylic acid - building block of lipids

a. Saturated Fatty Acids (SFAs) c. Polyunsaturated Fatty Acids (PUFAs)

- Carbon-carbon bonds are single - Two or more carbon-carbon double
bonds

b. Monounsaturated Fatty Acids (MUFAs)

- Carbon-carbon double bond
a. long-chain fatty acids (C12 to C26)
b. medium-chain fatty acids (C8 and C10)
c. short-chain fatty acids (C4 and C6)

MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO

PHYSICAL PROPERTIES OF FATTY ACIDS
1. Water Solubility
- solubility decreases as carbon chain length increases
- polarity of the carboxyl group is present
2. Melting Point
- melting point increases as the carbon chain length increases
- melting point decreases as the degree of unsaturation increases
ENERGY-STORAGE LIPIDS: TRIACYLGLYCEROLS
Triacylglycerol (triglyceride)
- energy-storage material is usually found in adipocytes (adipocytes are cells in adipose
tissues)
- lipid that is formed by esterification of three fatty acids to a glycerol molecule
- functional group: 3 esters
- 3 esters: compound produced from the reaction of an alcohol with a carboxylic acid
Glycerol
-alcohol involved in triacylglycerol formation
1. Simple triacylglycerol
- triester formed by esterification of glycerol with three identical fatty acid molecules
2. Mixed triacylglycerol
- triester formed by esterification of glycerol with more than one kind of fatty acid molecule
Fat
- triacylglycerol mixture that is solid or semi-solid at room temperature (25°C)
- from animals
- composed largely of triacylglycerols in which saturated fatty acids predominate, although some
unsaturated fatty acids are present
- triacylglycerols can pack closely together because of the " linearity" of their fatty acid chains
- higher melting points
Oil
- triacylglycerol mixture that is liquid at room temperature (25°C)
- from plants
- contain triacylglycerols with larger amounts of mono- and polyunsaturated fatty acids
- triacylglycerols cannot pack as tightly together because of "bends" in their fatty acid chains
- lower melting points

MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO

DIETARY CONSIDERATIONS AND TRIACYLGLYCEROLS

 Coconut oil is highly saturated and is a liquid not because it contains many
double bonds within the fatty acids but because it is rich in shorter-chain fatty
acids, particularly lauric acid.
Saturated Fatty Acids (SFAs) Polyunsaturated Fats (PUFAs)
- “bad fat” - Can be both “good fat” and “bad fat”
- Can increase heart - can reduce heart disease risk but promote the risk
disease risk of certain types of cancers

Monounsaturated Fats Omega-3 Fatty Acids

(MUFAs)
-from fish oils
- “good fat” -cold-water fish or fatty fish (albacore tuna, salmon,
- can decrease both and mackerel) is richer in Omega-3 than the leaner,
heart disease and warm-water fish (cod, catfish, halibut, sole, and
breast cancer risk snapper)
- help reduce the Omega-6 Fatty Acids
stickiness of blood
platelets - from plant oils
- may also dissolve
clots once they form
- most tree nuts and
peanuts are good
sources of MUFAs
Essential Fatty Acids
-
must be obtained from dietary sources because it cannot be synthesized within the body, in
adequate amounts, from other substances
- for proper membrane structure
- starting materials for the production of several biochemically important longer-chain
- needed for omega-6 and omega-3 fatty acids formation
- obtained from human breastmilk (cow milk contains a lesser amount)
a. Linoleic Acid
- (18:2)
- primary member of the omega-6 acid family
- Linoleic acid is the starting material for the biosynthesis of arachidonic acid (starting material
for eicosanoids which help regulate BP, and clotting of blood)
Linoleic Acid (18:2) → Arachidonic Acid (20:4)
b. Linolenic Acid
- (18:3)
- primary member of the omega-3 acid family
- Linolenic acid is the starting material for the biosynthesis of two additional omega-3 fatty
acids
Linolenic Acid (18:3) → EPA (20:5) → DHA (22:6)
EPA- eicosapentaenoic acid ◦ necessary for normal brain development and
DHA- docosahexaenoic acid communication membranes of the brain
◦ also active in the retina of the eye

MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO

CHEMICAL REACTIONS OF TRIACYLGLYCEROLS
Hydrolysis
- reverse of the esterification reaction by which triacylglycerol was formed
- under acidic conditions, the hydrolysis products are glycerol and fatty acids
- under basic conditions, the hydrolysis products are glycerols and fatty acid salts
- hydrolysis of TAG in the body requires enzymes produced by the pancreas

Saponification
- hydrolysis reaction carried out in an alkaline (basic) solution
- products of saponification are glycerol and fatty acid salts
- Steps:
o 1st –hydrolysis of ESTER LINKAGES to produce glycerol and 3 FATTY ACID MOLECULES
o 2nd –FATTY ACID molecules reacts with BASE (NaOH) that produces water and salts
- Micelle- polar portions of the molecules are on the surface, and the nonpolar portions are
located in the interior.
- Soap- carboxylic acid salts
- Detergent- sulfonic acid salts
Hydrogenation
- hydrogen addition across carbon-carbon multiple bonds, which increases the degree of
saturation as some multiple bonds are converted to single bonds
- increases the melting point of the substance
- types:
o COMPLETE: produces an oleic acid residue
o PARTIAL: produces peanut butter, margarine
Oxidation
- molecular oxygen (oxidizing agent) oxidizes the carbon-carbon double bond present in the
fatty acid residues of triacylglycerol
- breaks the carbon-carbon double bond and produces aldehyde and carboxylic acid products
- ex. Sweat
- produces rancid odor

MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO

MEMBRANE LIPIDS
Phospholipids

- Most abundant type

- Up to 80% of the cell membrane are lipids
- contains one or more fatty acids, a phosphate group, a platform molecule (3-carbon
alcohol glycerol or sphingosine) to which the fatty acid(s) and the phosphate group are
attached, and an alcohol attached to the phosphate group
a. glycerophospholipids
- exclusively a component of cell membrane
- not stored
- polar
- glycerol-based phospholipids
- have a head (polar, choline, and phosphate) and two tails (nonpolar, 2 fatty acid
carbon chains)
- contain two fatty acids and a phosphate group esterified to a glycerol molecule
and alcohol esterified to the phosphate group
- 4-ester linkages
- Contain 3 amino alcohols: choline, ethanolamine, and serine
o Phosphatidylcholines
 Lecithins:
 Prevalent in cell membranes
 Hydrolyzed by lecithinase-enzyme
 Found in mayonnaise, ice cream, custards
 Emulsifier
 Made by the liver
o Phosphatidylethanolamines
 Cephalins:
 Found in heart and liver tissue, high conc. in brain
 Important in blood clotting
 found in heart and liver tissue
 high concentrations in the brain
 important in blood clotting
o Phosphatidylserines
 Cephalins
 found in heart and liver tissue
 high concentrations in the brain
 important in blood clotting
b. sphingophospholipids
- sphingosine-based phospholipids
- contains one fatty acid and one phosphate group attached to a sphingosine molecule
and an alcohol attached to the phosphate group
- amide linkage and ester linkage
- have a head (polar, a phosphate group and its esterified alcohol) and two tails
(nonpolar, fatty acid and long carbon chain of sphingosine)
MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO
Sphingoglycolipids
- contains both a fatty acid and a carbohydrate component attached to a sphingosine
molecule
- amide linkage and glycosidic linkage

a. cerebrosides
- simplest sphingoglycolipids
- contain a single monosaccharide unit (glucose or galactose)
- found in the brain (7%)
- found in the myelin sheath of nerves
b. gangliosides
- complex sphingoglycolipids
- branched chain of up to seven monosaccharide residues
- found in gray matter of the brain
- found in myelin sheath
Cholesterol
- no fatty acid residues present
- neither glycerol nor sphingosine is present as the platform molecule
- a steroid (lipid whose structure is based on a fused ring system that involves three 6-
membered rings and one 5-membered ring)
- C27 steroid molecule
- component of cell membranes
- precursor for other steroid-based lipids
- most abundant steroid in the human body
- have limited water solubility
- lipoproteins: protein carrier that helps in the transport of cholesterol in the blood
a. Low-density lipoproteins (LDLs)
- carry cholesterol from the liver to various tissues
- bad cholesterol
b. High-density lipoproteins (HDLs)
- carry excess cholesterol from tissues back to the liver
- good cholesterol

Atherosclerosis- buildup of plaque along the inner walls of arteries

Plaque- mound of lipid material mixed with smooth muscle, cells and calcium

MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO

EMULSIFICATION LIPIDS: BILE ACIDS

Emulsifier- substance that can disperse and stabilize water-insoluble substances as colloidal
particles in an aqueous solution

Bile- fluid containing emulsifying agents that is secreted by the liver, stored in the gallbladder, and
released into the small intestine during digestion

Bile Acid- cholesterol derivative that functions as a lipid-emulsifying agent in the aqueous
environment of the digestive tract (e.g. intestine)
Two Types of Bile Acid
1. Simple Bile Acid 2. Complexed Bile Acid
o steroid monocarboxylic acids o amide linkage
o obtained by oxidation of o has increase polarity and water
cholesterol solubility
o not an emulsifier o emulsifier
o most common amino acid
attachment: glycine (an amino
carboxylic acid) and taurine (an
amino sulfonic acid)
o Ex. glycocholic acid (glycine is the
attachment) and taurocholic acid
(taurine is the attachment)
MESSENGER LIPIDS: STEROID HORMONES
Hormone- produced by a ductless gland, that has a messenger function
Steroid Hormone- cholesterol derivative hormone
Types of Steroid Hormone
1. Sex Hormones 2. Adrenocorticoid Hormones
- control reproduction and - regulate numerous biochemical
secondary sex characteristics processes in the body
c. Estrogens - produced by adrenal glands
- female sex hormones a. Mineralocorticoids
- synthesized in the ovaries and - control the balance of Na+ and K+
adrenal cortex ions in cells and body fluids
- regulation of the menstrual cycle - aldosterone: major
- development of female secondary mineralocorticoid
sex characteristics b. Glucocorticoids
b. Androgens - control glucose metabolism and
- male sex hormones counteract inflammation
- synthesized in the testes and - cortisol: major glucocorticoid
adrenal cortex and synthesized in adrenal
- promote muscle growth glands, functions as anti-
- development of male secondary inflammatory
sex characteristics
c. Progestins
- pregnancy hormones
- synthesized in the ovaries and the
placenta
- prepare the lining of uterus
- suppress ovulation
MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO
MESSENGER LIPIDS: EICOSANOIDS
Eicosanoid
- oxygenated C20-fatty-acid derivative that functions as a messenger lipid
- produced by all cells except RBC’s
- hormone-like
- effects and produced on tissues
Physiological Effects
1. Normal inflammatory response to tissue damage
2. Production of pain and fever
3. Regulation of BP
4. Induction of blood clotting
5. Induction of labor in pregnancy
6. Regulation of sleep-wake cycle
Types of Eicosanoids
1. Prostaglandin
- contains a cyclopentane ring and oxygen-containing functional groups
- when the 8th and 12th carbon atoms of the fatty acid become connected to form a five-
membered ring
- raising body temperature
- inhibiting the secretion of gastric juices
- increasing the secretion of a protective mucus layer into the stomach
- relaxing and contracting smooth muscle
- directing water and electrolyte balance
- intensifying pain
- enhancing inflammation responses
2. Thromboxane
- contains a cyclic ether ring and oxygen-containing functional groups
- promote the formation of blood clots
- produced by blood platelets and promote platelet aggregation
3. Leukotrienes
- contains three conjugated double bonds and hydroxy groups
- found in leukocytes
- inflammatory and hypersensitivity (allergy) responses
PROTECTIVE-COATING LIPIDS: BIOLOGICAL WAXES
Biological wax
- monoester of a long-chain fatty acid and a long-chain alcohol
- fatty acid: 14 to 36 carbon atoms
- alcohol: 16 to 30 carbon atoms
- ester linkage
- water-insoluble
- water-repellent

MTCHM3- Medical Biochemistry Lipids MAHAL C. BARROSO