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(Biochem A) Lipid Chemistry-Alcantara (Gradelifting Fairies)
(Biochem A) Lipid Chemistry-Alcantara (Gradelifting Fairies)
LIPID CHEMISTRY
Lipid Function
Transcribed By: JDVQ -Metabolic fuel
Lectured By: Dr. Alcantara 1. Fatty Acid -building blocks for other
lipids
LIPIDS -Main storage form of fatty
- a heterogeneous class of naturally 2. Triglycerides acids and chemical energy in
occurring organic compounds classified adipose
together on the basis of common solubility -Component of membranes
properties 3. -source of arachidonic acid,
Phospholipids Inositol triphosphate and
- insoluble in water diglyceride for signal
- soluble in aprotic/non polar organic transduction (cell to cell
solvents (diethyl ether, chloroform, communication)
methylene chloride, and acetone) -component of membrane
4.
- Amphipathic in nature (both polar & non
Sphingolipids
polar)
In terms of structure, it includes: -component of membranes
Open Chain forms 5. Cholesterol -precursor of bile salts &
fatty acids, triacylglycerols, sphingolipids, steroid hormones
phosphoacylglycerols, glycolipids, -derived from it are: bile acid,
ipid-soluble vitamins (ADEK) steroid hormones & vit D
eicosanoids: prostaglandins, leukotrienes, -lipid digestion & absorption
6. Bile salts of long chain fatty acids
and thromboxanes
-main product of cholesterol
Cyclic forms (benzene ring, benadryn rings
metabolism/degredaton
etc.) -intracellular signal that
7. Steroid regulate gene expression in
hormones(estrogen,testosterones), and bile hormones target cells
acids (readily pass
FUNCTIONS OF LIPIDS: through
1. Energy source – most impt function membrane
- 9 calories per gram fat in the form of TAGS enabling direct
Adipose (TAG) → Fatty acids(oxidation) → action to DNA)
CO2 + H2O + ATP
-regulators of physiological
*1g protein = 9 cal ; 1g
8. Eicosanoids functions
2. Major component of cell membrane (20 C
• Phosphoglycerides – most abundant containing
• Sphingolipids cmpds)
• Free cholesterol
-vision (vit A); calcium metab
9. Vitamins (vit D); antioxidant (vit E);
blood coagulation (vit K)
-Metabolic fuel
10. Ketone -ex.acetoacetic acid,
bodies hydroxybutamic acid
LIPID CLASSIFICATIONS Fatty acids are divided into:
Short chain -- 2 to 4 carbon atoms
1. Simple lipids include fats and waxes which
are esters of -initially digested by lingual lipase in saliva then
fatty acids with various alcohols: in stomach by gastric lipase
a. Fats: Esters of fatty acids with glycerol. Medium chain -- 6 to 12 carbon atoms
Oils are fats in the liquid state. Long chain -- 14 to 26 or more carbon atoms
b. Waxes: Esters of fatty acids with -digested by pancreatic lipase
higher molecular weight monohydric alcohols. • Human cells = long-chain variety
2. Complex lipids are esters of fatty acids • Naturally occurring fatty acids: even number of
containing groups in addition to an alcohol and carbon atoms
one or more fatty acids. They can be divided into R-COOH RCOO- + H+
three groups: *presence of carboxylic grp makes it a weak acid
a. Phospholipids: Lipids containing, in that can ionize to carboxylate
addition to fatty acids and an alcohol, a *in blood (pH 7.4), fatty acid pKa=4: charge is
phosphoric acid residue. They frequently have negative, anion
nitrogen-containing bases (eg, choline) Length of fatty acid plays a role in its chemical
and other substituents. In many phospholipids character:
the alcohol is glycerol (glycerophospholipids), • Usually contain even numbers of carbons (can
but in sphingophospholipids it is sphingosine, contain odd, depending on how they are
which contains an amino group. biosynthesized)
b. Glycolipids (glycosphingolipids): • FA that contains C=C: unsaturated
Lipids containing a fatty acid, sphingosine, and
carbohydrate. *Unsaturated fatty acids have lower melting
c. Other complex lipids: Lipids such as points than their saturated counterparts; the
sulfolipids and amino lipids. Lipoproteins may greater the degree of unsaturation, the lower the
also be placed in this category. melting point
3. Precursor and derived lipids: These include
fatty acids, glycerol, steroids, other alcohols,
fatty aldehydes, ketone bodies), hydrocarbons,
lipid-soluble vitamins and micronutrients, and
hormones.
LIPID CLASSES:
1. FATTY ACIDS AND THEIR DERIVATIVES (Because the regular nature of their aliphatic
chains allows the molecules to be packed in
Chemical formula: R-COOH close, parallel alignment)
*R = represents the alkyl chain composed of - Greater energy needed to melt them
carbon and hydrogen atoms also known as
HYDROCA.. (Because the interaction between neighboring
Carboxyl part (COOH) – polar part chains is weak, but the regular packing allows
Alkyl chain (R) – non polar part due to absence of these forces to operate over a large portion of
O2 the chain)
C1 = carboxylate
C2 = α-carbon
C3 = β-carbon
Methyl group = ω-carbon
Omega -3 family:
Alpha-linoleic acid (ALA)
- Minor component of tissues
- source: Vegetable oils (soy,canola,linseed,
Rapeseed) and leafy vegetables
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EICOSANOIDS Omega 3 FA : alpha linolenic acid
- Anti-inflammatory
A. Prostaglandins
- Prostaglandins of the one and three series
- a family of compounds that have the 20-carbon (PGE1 and PGE3 ) and less inflammatory
skeleton of prostanoic acid leukotrienes
- First detected in seminal fluid, from prostate *Since they compete for the same enzymes
giving rise to its name (elongase& desaturase), the more omega-6 FA
we ingest, the less we are able to utilize the
B. Leukotrienes beneficial influences of the omega-3 FA. Humans
still require both omega-6 and omega-3 fats, but
- Found in white blood cells (leukocytes) the optimal ratio is considered to be 2:1
- Consists of 3 conjugated double bonds
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3. WAXES
- complex mixtures of nonpolar lipids
- also contain hydrocarbons, alcohols, fatty acids,
aldehydes and sterols (steroid alcohols).
- Found as protective coatings for plants and
animals
Examples:
Triglycerides or Triacyglycerides
- All three OH groups of glycerol are Esterified
- Most common lipid material
Uses:
In humans:
- Hydrolyzed by lingual &/or gastric lipase to *before we continue note:
glycerol + FFA, mainly by pancreatic lipase SIMPLE LIPIDS – contain FA & glycerol
- Main storage form (triglyceride)
COMPLEX LIPIDS – have additional molecules
In industry (Phosphates, sugar etc.)
- Production of soap by saponification or alkaline *phospholipid- contains phosphate
hydrolysis due to use of NaOH *glycolipids – contain sugar, alcohol backbone is
- Hydrolyzed by NaOH creating glycerol + H2O glycerol
sol soap
In animals
- Major storage and transport form of FA
- Insulation in low temperatures
- Makes fur and feathers water-repellent
In plants
- Energy reserve in fruits and seeds
SOAPS
• Salts formed by saponification
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4. PHOSPHOLIPIDS
2 types:
Phospoglycerides
- Molecules that contain glycerol, fatty acids,
phosphate and alcohol
Spingolipids Biological Importance:
- contain sphingosine instead of glycerol
- classified as sphingolipids due to sphingosine as a. Lecithin / phosphatidylcholine
alcohol backbone - surfactants or surface-acting agents
- Classified as phospholipid due to phosphate - play an essential role in reducing surface
content tension in lung alveoli
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- Consist of ceramide bound to an oligosaccharide
that contains an acidic sugar such as N-
acetylneuraminicacid
5. SPHINGOLIPIDS
**CERAMIDE
- contain sphingosine (long chain amino alcohol) - Plays an important role in the formation of 4 classes
or one of its derivatives - consist of a fatty acid bound to sphingosine
- Found in plants and animals - parent compound/backbone of sphingolipids
**SULFATIDES- sulfated cerebrosides, or cerebroside-
- Abundant in nervous system for normal cell sulfate esters.
function in brain
6. ISOPRENOIDS
- Bares structural similarity to phospholipids
- With repeating 5 carbon units (isoprene)
A. TERPENES – in perfumes
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cyclopentanoperhydrophenanthrene ring - HORMONES
steroid nucleus that consists of three fused Types: Sex Hormones, Glucocorticosteroids,
cyclohexane rings (A,B,C) joined to a Mineralocorticoteroids
cyclopentene ring (D)) SIDE CHAIN CLEAVAGE- process of converting
do not contain aromatic rings except ESTROGEN cholesterol to different hormones (cutting OH)
C3 &C7 always has side groups
1. SEX HORMONES:
each type is distinguished by placement of C-C
Androgens (male sex hormone)
double bonds and other substituents (hydroxyl, - Synthesized in testes (leydig cells) & adrenal
carboxyl, alkyl) cortex
- Responsible for the dev’t of male secondary sex
characteristics
*TESTOSTERONE
– 19 carbon atoms (Carbons 18 and 19 are in
methyl groups)
– one of the more potent androgen
*ESTROGEN
– Contain 18 carbon atoms (Carbon 18 is found
in a methyl group)
– Unlike other steroids, the A ring of the steroid
nucleus of estrogen is aromatic
– Estradiol has OH groups attached to carbons 3
and17
*Some sources of cholesterol:
Egg – more than 200mg of cholesterol
Shrimp- almost 200mg cholesterol
Bile acid
- End product of cholesterol degradation
- 24-C steroids secreted into the bile to emulsify
dietary fats
- Cholic acid is a major human bile acid
PROGESTERONE
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– synthesized in the corpus luteum - a neutral lipid core: composed of Cholesteryl
– cointain 21 carbons (as do the adrenocortical esters and TAG (2 major non polar lipids)
steroids) -The core is surrounded by a layer of
– has an acetyl group joined at carbon 17 Phospholipid, free cholesterol and protein
- Charged and polar residues on the surface of
2. GLUCOCORTICOSTEROIDS a lipoprotein enable it to dissolve in blood
- Produced by adrenal cortex - Transport nonpolar lipids to the blood by
- Raise serum glucose level packaging it in the form of Alipoprotein
- hydroxyl or keto group at carbon 11 is found to
Two laboratory techniques are used to
correlate with glucocorticoid activity
separate lipoproteins from one another:
*CORTISOL
Ultracentrifugation - separates them
– potent glucocorticoid with weak according to their differing densities
mineralocorticoid activity
Electrophoresis - separates them on a basis
– Detected by urinary 17-hydroxycorticosteroid of their varying net charges
assay that detects all 21-carbon steroids with a
17-OH group CHYLOMICRONS
- the least dense because it consist mainly of
3. MINERALOCORTICOSTEROIDS triglycerides with small amounts of cholesterol,
- Produced by adrenal cortex phospholipids &proteins
- Promote renal sodium retention - do not migrate when subjected to
electrophoresis, because their high triglyceride
ALDOSTERONE (no charge)content
– potent mineralocorticoid (presumably due to its - blood appears milky due to the high
aldehyde group at carbon 18) but a weak concentration of chylomicrons after a fatty meal
glucocorticoid - Lipoprotein lipase hydrolyzes triglycerides
bound in lipoproteins yielding monoglycerides
and free fatty acids
7. LIPOPROTEIN - Heparin, an anticoagulant, also helps to clear
chylomicrons from the blood
- Lipids must bind to proteins to make them
- Produced in small intestines
water soluble for transport in the blood
*Free fatty acids, for example, avidly bind to
HYPERCHYLOMICRONEMIA /
serum albumin and will displace albumin-bound FREDERICKSON‘S TYPE 1
drugs from their binding sites HYPERLIPOPROTEINEMIA
- inherited absence of lipoprotein lipase
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- LDL fraction is markedly elevated in TYPE II Mono-UFA = ↑ HDL, ↓ LDL
HYPERLIPOPROTEINEMIA and is associated with PUFA maintains HDL, ↓ LDL
ATHEROSCLEROSIS(hardening of arteries) Trans FA = ↓ HDL, ↑ LDL