Dr. drh. Trini Susmiati, MP.
DEPARTMENT OF BIOCHEMISTRY
FACULTY OF VETERINARY
UNIVERSITAS GADJAH MADA
Characteristics of Fat Storage
Most of the bodys energy stores are
triglycerides storage is in adipose,
source is dietary or anabolism (synthesis) from
COH or AA carbon skeletons
remember obesity?
adipose can remove FAs from the blood and
enzymes can put them back
Lipid Characteristics
Lipid = a compound that is insoluble in water,
but soluble in an organic solvent (e.g., ether,
benzene, acetone, chloroform)
lipid is synonymous with fat, but also
includes phospholipids, sterols, etc.
chemical structure: glycerol + fatty acids
Types of Lipids
Lipids with fatty acids
Waxes
Fats and oils (trigycerides)
Phospholipids
Sphingolipids
Lipids without fatty acids
Steroids
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Lipids consist of two parts
1. Glycerol
2. Fatty Acids
a. Saturated fatty acids
b. Unsaturated fatty acids
. Monounsaturated
. Polyunsaturated (PUFA)
Essential Fatty Acids
Only recently determined as essential (1930)
body can synthesize cholesterol, phospholipids
research: same as AAs but via addition (EFAs
added improved growth, NEFAs didnt)
requirement determined by depleting fat
reserves of subject animal: difficult
Nutritional Uses of Lipids
We already know that lipids are concentrated
sources of energy (9.45 kcal/g)
other functions include:
1) provide means whereby fat-soluble nutrients
(e.g., sterols, vitamins) can be absorbed by
the body
2) structural element of cell, subcellular
components
3) components of hormones and precursors for
prostaglandin synthesis
Saturated vs. Unsaturated Fatty Acids
saturated: the SFAs of a lipid have no double bonds
between carbons in chain
polyunsaturated: more than one double bond in the chain,
most common polyunsaturated fats contain the Polyunsatu-
rated fatty acids (PUFAs) oleic, linoleic and linolenic acid
unsaturated fats have lower melting points:
stearic (SFA) melts at 70oC, oleic (PUFA) at 26oC
Saturated = CC bonds
Unsaturated = one or more C=C bonds
COOH
palmitic acid, a saturated acid
COOH
palmitoleic acid, an unsaturated fatty acid
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Fatty Acids Commonly Found in Lipids
Sat. Fatty Acids Formula Melting Point (oC)
Butyric C4H8O2 Liquid
Palmitic C16H22O2 63
Stearic C18H36O2 70
Unsat. Fatty Acids Formula Melting Point (oC)
Oleic C18H34O2 Liquid
Linoleic C18H32O2 Liquid
Linolenic C18H30O2 Liquid
Essential Fatty Acids (most animals)
Salmonids need n-3 FAs for membrane
flexibility in cold water
Trout can elongate and desaturate n-3 FAs
Linoleic acid (18:2 n-6) is the most essential
Addition of arachidonic is also helpful in
deficient diets, but can be synthesized from
linoleic (maybe sparing effect)
EFAs, like EAAs, must be dietary
Essential Fatty Acids (fish)
Most NEAA found in marine food webs
Essential fatty acids (to date):
linoleic (18:2 n-6; terrestrials; fish - not really)
linolenic (18:3 n-3; terrestrials; fish)
arachidonic (20:4 n-6; marine maybe)
eicosopentaenoic acid (20:5 n-3, marine)
docosohexaenoic (22:6 n-3, marine)
Why? Because elongation beyond 18 carbons is very
difficult in marine fish (lack pathways)
actual EFA requirement is a matter of whether the fish is
FW/SW or WW/CW
Lipids as Crustacean Energy Sources
Largely, n-6 FAs (linoleic) used for energy
as temperature drops, requirement for
monounsaturated and PUFAs increases
change in temperature = change in diet
cold water species = increased dietary HUFAs
maturation animals: increased requirement for
20:4 n-6, 20:5 n-3 and 22:6 n-3 for proper
spawning
Fatty Acid Nomenclature
1. Nomenclature reflects location of double
bonds.
2. Also used are common names (e.g., oleic,
stearic, palmitic).
3. Linoleic is also known as 18:2 n-6.
4. This means the FA is 18 carbons in length,
has 2 double bonds, the first of which is on
the 6th carbon.
5. Arachidonic = 20:4 n-6
Structures
Saturated fatty acids
Fit closely in regular pattern
COOH
COOH
COOH
Unsaturated fatty acids
Cis double bonds
H H
C C
cis double bond COOH
Saturated fatty acids
Unsaturated fatty acids
Lipids are classified :
1. Simple lipid
a. Fatty acids
b. neutral fats (monoglyceride,
diglycerde, and triglyceride)
c. waxes
2. Complex lipids
a. Phospholipids
b. Glycolipids
c. Lipoproteins
3. Derived lipids
Lipids are classified :
Lipid Classes
simple: FAs esterified with glycerol
compound: same as simple, but with other compounds
also attached
phospholipids: fats containing phosphoric acid and
nitrogen (lecithin)
glycolipids: FAs compounded with CHO, but no N
derived lipids: substances from the above derived by
hydrolysis
sterols: large molecular wt. alcohols found in nature
and combined w/FAs (e.g., cholesterol)
Fats and Oils :
Formed from glycerol and fatty acids
O ester bonds
CH2 OH HO C (CH2)14CH3 O
O
CH2 O C (CH2)14CH3 + H2O
CH OH + HO C (CH2)14CH3
O O
CH2 OH HO C (CH2)14CH3 CH O C (CH2)14CH3 + H 2O
O
glycerol palmitic acid (a fatty acid)
CH2 O C (CH2)14CH3 + H 2O
Esters of glycerol and
fatty acids/tryglycerides
Properties of Triglycerides
Hydrogenation
Unsaturated compounds react with H2
Ni or Pt catalyst
C=C bonds CC bonds
Hydrolysis
Split by water and acid or enzyme catalyst
Produce glycerol and 3 fatty acids
O
CH2 O C (CH2)16CH3 Stearic acid
O
CH O C (CH2)7CH CH(CH2)7CH3
Oleic acid
O
CH2 O C (CH2)12CH3 Myristic acid
Hydrogenation
O O
CH2 O C (CH2)5CH CH(CH2)7CH3 CH 2 O C (CH 2)14 CH 3
O O
Ni
CH O C (CH2)5CH CH(CH2)7CH3 + 3 H2 CH O C (CH 2)14CH 3
O O
CH2 O C (CH2)5CH CH(CH2)7CH3 CH 2 O C (CH 2 )14CH 3
Hydrogenation converts double bonds in oils
to single bonds. The solid products are used
to make margarine and other hydrogenated
items.
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Hydrolysis
Triglycerides split into glycerol and three
fatty acids (H+ or enzyme catalyst)
O
CH2 O C (CH2)14CH3
O
H+
CH O C (CH2)14CH3 +3 H2O
O
CH2 O C (CH2)14CH3
CH2 OH O
CH OH + 3 HO C (CH2)14CH3
CH2 OH
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Saponification and Soap
Hydrolysis with a strong base
Triglycerides split into glycerol and the
salts of fatty acids
The salts of fatty acids are soaps
KOH gives softer soaps
O
CH2 O C (CH2)16CH3
O
CH O C (CH2)16CH3 + 3 NaOH
O
CH2 O C (CH2)16CH3
CH2 OH O
+-
CH OH + 3 Na O C (CH2)14CH3
salts of fatty acids (soaps)
CH2 OH
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Omega Fatty acid
Cis- Trans Fatty acid
Function of Fat
Fat in Food Energy
1. Essential nutrient
2. Flavor and Satisfaction
Fat in Body
1. Adipose Tissue
2. Cell membrane Structure
Animal
Food Fats
Sources of Fat
1. Meat Fat (bacon, sausage.)
2. Dairy Fats and products (cream, butter, cheese)
3. Egg yolk
Plant Fat
1. Monounsaturated, polyunsaturated Fatty acid
2. Vegetable oil (sunflower, corn, soybean, cotton
seed, olive oil)
Characteristics of Food Fat Sources
Visible Fat
Butter, margarin, salad oils and dressing,
shirteninig fat meat
Invisible Fat
Chees, cream portion of homogenised milk,
egg yolk, nuts, seeds, olives..
Digestion of lipids
1. In mouth
mechanical digestion
Lingual Lipase
2. In stomach
mechanical digestion
Gastric lipase
3. In small intestine
Bile acid, Pancreatic Lipase,
Cholesterol esterase, Phospholipase
Essential Fatty Acids
Only recently determined as essential (1930)
body can synthesize cholesterol, phospholipids
research: same as AAs but via addition (EFAs
added improved growth, NEFAs didnt)
requirement determined by depleting fat
reserves of subject animal: difficult
Essential Fatty Acids (most animals)
Salmonids need n-3 FAs for membrane flexibility in cold water
trout can elongate and desaturate n-3 FAs
Linoleic acid (18:2 n-6) is the most essential addition of arachidonic
is also helpful in deficient diets, but can be synthesized from linoleic
(maybe sparing effect)
EFAs, like EAAs, must be dietary
Saturated vs. Unsaturated Fats
saturated fats tightly packed, clog arteries as
Atherosclerosis because of double bonds,
polyunsaturated fats do not pack well -- like building a wall
with bricks vs. irregular-shaped objects
plant fats are much higher in PUFAs than animal fats
Lipid Digestion/Absorption
Fats serve a structural function in cells, as sources of energy,
and insulation
the poor water solubility of lipids presents a problem for
digestion: substrates are not easily accessible to digestive
enzymes
even if hydrolyzed, the products tend to aggregate to larger
complexes that make poor contact with the cell surface and
arent easily absorbed
to overcome these problems, changes in the physical state of
lipids are connected to chemical changes during digestion and
absorption
Saturated vs. Unsaturated FAs Plant
vs. Animal Fat
corn soy tallow lard
Sat. FAs
Myristic 3
Palmitic 7.0 8.5 27 32.2
Stearic 2.4 3.5 21 7.8
Unsat. FAs
Oleic 45.6 17 40 48
Linoleic 45.0 54.4 2 11
Linolenic 7.1 0.5 0.6
Arachid.
Lipid Digestion/Absorption
Fats serve a structural function in cells, as sources of
energy, and insulation
The poor water solubility of lipids presents a problem for
digestion: substrates are not easily accessible to
digestive enzymes
Even if hydrolyzed, the products tend to aggregate to
larger complexes that make poor contact with the cell
surface and arent easily absorbed
To overcome these problems, changes in the physical
state of lipids are connected to chemical changes during
digestion and absorption
Five different phases:
1. Hydrolysis of triglycerides (TG) to free fatty
acids (FFA) and monoacylglycerols
2. Solubilization of FFA and
monoacylglycerols by detergents (bile
acids) and transportation from the intestinal
lumen toward the cell surface
3. Uptake of FFA and monoacylglycerols into
the cell and resynthesis to triglyceride
4. Packaging of TGs into chylomicrons
5. Exocytosis of chylomicrons into lymph
Absorption of lipids
Enzymes Involved in Digestion of Lipids
lingual lipase: provides a stable interface with aqueous
environment of stomach
pancreatic lipase: major enzyme affecting triglyceride
hydrolysis
colipase: protein anchoring lipase to the lipid
lipid esterase: secreted by pancreas, acts on cholestrol
esters, activated by bile
phospholipases: cleave phospholipids, activated by
trypsin
What about Bile???
1. These are biological detergents synthesized by the
liver and secreted into the intestine.
2. They form the spherical structures (micelles)
assisting in absorption.
3. Hydrophobic portion (tails of FA) are located to the
inside of the micelle, with heads (hydrophillic
portion) to the outside.
4. They move lipids from the intestinal lumen to the cell
surface.
5. Absorption is by diffusion (complete for FA and
monoglycerides, less for others)
Factors Affecting Absorption of Lipids
amount of fat consumed ( fat = digestion =
absorption)
age of subject ( age = digestion)
emulsifying agents
chain length of FAs (> 18C = digestibility)
degree of saturation of FA ( sat = digestibility)
Overheating and autooxidation (rancidification at
double bond)
optimal dietary calcium = optimal FA absorption (high
Ca = absorption)
QUIZ:
Tulis nama, NIM, tanda-tangan, dan tanggal di
pojok kanan-atas
SOAL:
1. Jelaskan perbedaan antara asam lemak dan lipida !
2. Jelaskan perbedaan asam lemak jenuh dan tidak-
jenuh !
3. Sebutkan fungsi asam lemak dan lipida secara umum
!
4. Gambarkan struktur trigliserida dengan:
R1 : asam palmitat
R2 : asam butirat
R3 : asam fosfat
Intramolecular Rearrangement in
Propionate Oxidation Requires Coenzyme
B12
Regulation of Fatty Acid Synthesis and Breakdown
