8.

Lipids – Fats & Oils

Chapter 15
 Lipids
A lipid is an organic substance found in
living systems that is insoluble in water but
is soluble in organic solvents.

Lipids vary widely in their structures. They have

mostly C,H and some have a few polar atoms/
functional groups.
Lipids include:
fats and oils
steroids
waxes
Fats & oils make up 95% of the nutritional lipids,
the other 5% are steroids. Waxes are functional
only.
Fats are solid triglycerides
Oils are liquid triglycerides
 Fats and Oils
The Triglycerides We Eat
CH2-O2C-R
HOCH2-CHOH-CH2OH CH-O C-R’ Fatty acid side
2
(glycerol) chains
CH2-O2C-R”

Triglycerides/fatty acids are characterized/named

by:
1) The length/number of carbons in the side
chains
2) The number of carbon-carbon double bonds in
the side chains(the degree of unsaturation).
 Representative Fatty Acids
C12-C18(also C20) Dietary Fats and Oils
CH3-(CH2)12-COOH (1)
CH3-(CH2)14-COOH (2)
(3)
CH3-(CH2)16-CO2H
(4)
CH3-(CH2)7-CH=CH-(CH2)7-CO2H (5)
CH3-(CH2)4-CH=CH-CH2-CH=CH-(CH2)7-CO2H (6)
CH3-CH2-CH=CH-CH2-CH=CH-CH2-CH=CH-(CH2)7-CO2H
Name Mp(oC) Class
(1) Myristic acid 58 Saturated C-14
(2) Palmitic acid 63 Saturated C-16
(3) Stearic acid 71 Saturated C-18
(4) Oleic acid 4 Monounsaturated C-18
(5) Linoleic acid -5 Polyunsaturated C-18
(6) Linolenic acid - 11 Polyunsaturated C-18
Fatty Acid Content of some Fats/Oils
Canola (Canadian-oil-low acid)
• Oil from Canadian rapeseed
• Has “ideal ratio” of omega-6 to omega-3
fatty acids of 2:1
• Also very low in saturated fat
 Olive oil
• Deemed to be the most “heart healthy”
• Highest % of monounsaturated fatty acids
• Extra virgin (1st press)
 Oxidation of Organic Compounds,
eg. fatty acids
O2
-C-C-C-COOH -
C-COH-C-COOH saturated
difficult O2
-
C=C-C-COOH -COH-COH-C-COOH
unsaturated easy
oxidation = decomposition = rancidity
more saturated = more stable, ie. longer ‘shelf life’,
eg. commercial baked goods
more unsaturated = faster deterioration, ie.
need antioxidants to protect compounds(in the
body?)
Hydrolyse: to convert (lyse = to cleave) a compound
into other substances through the action of water.

-H 2O
R-C=O R-C=O
O-H HO-R’ +H2O O-R’

acid + alcohol ester

(fatty acid + glycerol triglyceride)

 FATTY ACIDS (TRIGLYCERIDES)
 
Solid: longer chains
saturated(only C-C)
eg. animal fat, butter
 
Liquid: unsaturations (C=C)
eg. many vegetable oils
(olive, sunflower)
Unsaturates can’t fit well into a solid lattice
 R e a c tio n s (M e ta b o lic )

O 2
C 2 p ie c e s + C O 2 +
F a tty A c id
H 2O + e n e r g y
*
H um ans cannot m ake:

* “ E s s e n tia l” F a tty A c id s : L in o le ic : 1 8 ( 9 ,1 2 )
L in o le n ic : 1 8 ( 9 ,1 2 ,1 5 )
 Body fat is stored energy

The body converts the unused carbohydrates,

proteins and triglycerides that make up our
macronutrients into small globules of fat that
end up in the specialized cells of adipose
tissue, the fatty tissue of the body.

One pound of adipose tissue stores, and

provides when needed, ~3500 Cal of energy.
The high energy density of fat - its ability
to store energy (9 Cal/gram) compactly in
relatively little space and with relatively
little weight, compared with carbohydrates
and proteins (4 Cal/gram), allows us to
carry stores of energy with us.

It give humans and other animals the

mobility and freedom necessary for
survival
 Water in the Camel’s Hump
C54H108O6 + 78O2 54CO2 + 54H2O + zillion Cal
(triglyceride from C18H36O2 x 3 ie glycerol tristearate)
Metabolism requires oxygen, produces energy, carbon
dioxide and water
 Fat = Essential Energy

Most of our long term energy supplies operates

via the formation, storage and metabolism of
body fat (triglycerides).

Short term energy storage, from one meal to

another, occurs through a starch-like substance
called glycogen(a carbohydrate).
 Adipose Tissue / Fat
Adipose tissue forms cushioning shields around our
major organs, protecting them against damage from
physical shock and provides insulation to our
bodies, guarding against a rapid loss of body heat
to the external environment .
Fats carry the flavours and vitamins of many of
our foods although fats have no flavours of their
own, eg. carrying vitamins A, D, E and K from
our foods to our tissues.
Fatty acids form not only the triglycerides but other
compounds as well, including such vital classes as
prostaglandins and phospholipids.
 R e a c tio n s (“ S y n th e tic ” )

Io d in e # ( s a t. u n s a t.)
I I
C C C C
I I
C C C C Io d in a tio n
H H
C C C C
H H
H y d ro g e n a tio n

u n s a tu ra te d s a tu ra te d
Saponification/Hydrolysis of a Triglyceride
O O
+
CH2 O R CH2 OH + R O Na
O O
3NaOH / H2O +
CH O R' CH OH + R' O Na
Heat
O O
+
CH2 O R'' CH2 OH + R'' O Na

triglyceride glycerol soaps

Omega - 3 Fatty Acids - Especially in Fish Oils !
Mainly 20 & 22 C’s, polyunsaturated and
1st ‘ene’ is 3 from -end.
Eicosapentaenoic acid (EPA): 20(5,8,11,14,17)
mp –50OC !
Docosahexaenoic acid (DHA): 22(5,8,11,14,17, 20)

 - alpha end
COOH

 - omega end

also -linolenic: 18(9,12,15)

 Why ‘Omega – 3’ FA ?

Low incidence of heart disease amongst

populations that eat lots of fat BUT mostly as fish !
eg. Inuit & Greenlanders

Sat Mono Poly(16 &18) -3(20 &22)

Cod 15 29 20 35
Herring 20 5 21
53

Don’t like fish? Try omega 3 eggs!

 Omega-3 eggs

• Chickens are fed flaxseed, which contains

high levels of omega-3 fatty acids. After 10
days, this modifies the fat content in the
egg yolk to contain more omega-3 fatty
acids and less saturated and omega-6’s
• In 1997, this was the Canadian New
Product of the year
Omega-3 Chickens
 Omega-3 meats
• Present work (Guelph) on chickens,
turkeys, pigs to obtain meat with high
omega-3 fat content via diet alterations
• Coming soon to a supermarket near you!
 Other omega -3 enriched
products
• Orange juice
• Other fruit juices
 Cis vs. Trans Fatty acids
• Almost all natural unsaturated fatty acids
have cis stereochemistry in C=C’s.
• Small amounts of trans are produced in
stomachs of ruminating animals by partial
enzymatic hydrogenation of
polyunsaturated fats, and thus are present in
small amounts in milk and butter
Commercial Hydrogenation of Fatty Acids

H H H H H R
partial H2 catalyst
C C R C C R + C C
R R H H R H

‘cis’ ‘trans’
unsaturated saturated unsaturated
natural natural unnatural
good bad bad
 An unwanted byproduct
• Trans fats increase the level of Low density
lipoprotein (LDL).
• Thus they are deemed to be “heart
unhealthy” since LDL tends to deposit
cholesterol in the arteries rather than
transport it (as does HDL) to cells for use
in cell membrane construction.
How are trans fats metabolized?
• Catabolism (breakdown) of all fats
• Catalyzed by lipases to free FA’s and
glycerol
• FA’s split by beta oxidation into 2C units
(Acetyl Co), or propionyl CoA if odd #C’s
• Need bile salts to emulsify fats and allow
absorption by the intestine (occurs 1 st)
 Also have anabolism

• Macromolecules (ie Proteins) synthesized

using 2C units derived from fat metabolism,
amino acids etc
• Essential link between energy producing
(catabolic) and energy utilizing (anabolic)
pathways is ATP (adenosine triphosphate)
• Details much beyond the scope of this
course!!
‘Trans’ = Saturated; in shape and ‘badness’ !
Incomplete Labels !
‘Trans Fats’ - Misleading Labels
‘Trans Fats’ – an Informative Label
 H3C
Cholesterol - a
steroidal alcohol CH3
(atherosclerosis!) CH3

CH3
H3C

HO
Cholesterol (animal "fat")

High – red meat, egg yolks, dairy products

Low – egg whites, yoghurt

None ! – fruits, veggies, vegetable oils

 Properties of Cholesterol

very insoluble in water, C27H46O

solid, mp. 149o
compact, stiff/rigid
 Cholesterol is Absolutely Essential !
The average male (80kg/170lb) contains ~220gm

About: in 80kg male (~gms)

50% in cell membranes blood 16
muscle 45
40% converted to bile
brain 50
acids to ‘emulsify/
adipose
transport’ lipids (liver>
tissue 45
gall bladder> intestines)
skin 18
liver 8
some converted to heart/kidney, etc. 8
hormones (testosterone, adrenal glands 2
estrogens, cortisone) alimentary tract 7
Cell Membrane Structure (lipid bilayer)
 Cholesterol Transport in vivo
• Cholesterol is insoluble in water, hence to transport it
through the bloodstream, our bodies wrap it in a
sheath of proteins and varying amounts of
triglycerides to form lipoproteins.
• High Density Lipoproteins (HDL’s) transport excess
cholesterol to the liver for disposal “good cholesterol”
• LDL’s (Low Density Lipoproteins) and VLDL’s tend
to deposit cholesterol on arterial walls “bad
cholesterol”
Structural features: HDL vs LDL
• HDL contains unsaturated cis Fatty acids
• LDL contains more saturated and trans
fatty acids
• Both contain apolipoproteins and
phospholipids which are oriented with
hydrophobic part on inside and outer
hydrophilic edges exposed
 Cholesterol in gallstones
• Bile : used in fat digestion
• Contains water, cholesterol, bile salts , proteins
and bilirubin (waste product)
• If bile contains too much cholesterol, it can
harden into gallstones
• Extraction of cholesterol from gallstones
(removed by surgery) is a common lab
experiment!
• Size can range from grains of sand up to golf
ball!
 Source of bile acid
• Produced in liver
• Stored and concentrated in the gallbladder
• Secreted into small intestine
• If gallstone blocks exit duct, then
gallbladder may need to be removed
• Fat digestion becomes more difficult, but
not impossible
Gallstones
 Some real ones!!
• Courtesy of the Ottawa Hospital!
Some Risk factors for gallstones
• Gender: Women 2x as likely; excess estrogen
from pregnancy, BC pills, HRT all may increase
cholesterol levels
• Weight: even moderate obesity
• Diet: high fat, low fibre diet increases level of
cholesterol in bile
• Rapid weight loss: crash diets as body tries to
metabolize fat
• Age.>60: body secretes more cholesterol into bile
 Lipid Content (mg) per serving
of common foods
• Includes cholesterol
• Saturated fatty acids
• Unsaturated fatty acids
 Fat and Oil Content
Food Cholesterol Saturated Monounsaturated Polyunsaturated
Beef 91 2.7 2.7 0.5
Butter 219 50.5 23.4 3
Cheese ,cheddar 105 21.1 9.4 0.9
Cheese , cottage dry 7 0.3 0.1 0.02
Chicken (no skin) 85 1.3 1.5 1
Corn oil 0 12.7 24.2 58.7
Eggs , whole 548 3.4 4.5 1.4
Frankfurter (all beef) 51 12.7 14.8 1.2
Margarine,stick(coin oil ) 0 13.2 45.8 18
Milk , skim 2 0.1 0.05 0.007
Milk whole 14 2.3 1.1 0.1
Olive oil 0 13.5 73.7 8.4
Peanut butter 0 9.7 23.3 15.2
Peanut oil 0 16.9 46.2 32
Safflower oil 0 9.1 12.1 74.5
Salmon (pink , canned) 35 1 1.8 2.7
Tuna (canned in water ) 63 0.2 0.1 0.2
Turkey (no skin ) 69 1 0.6 0.9
Yogurt (plain , lowfat) 6 1 0.4 0.04
 Note
• No cholesterol in products derived from
plant sources!!
 Canada (Cholesterol, mmol/L)
Risk Level Total LDL HDL

Low <4.5 <3.5 1.2

Border-line 5.0-6.0 4.0 1.0

High >6.0 >4.5 0.9

Total / HDL should be 4.0 or less

 USA (Cholesterol, mg/dL)
Risk Level Total LDL HDL

Low <200 <130 50

Border-line 200-239 130-159

High >240 >160 35

Cholesterol Related compounds
• 7-dehydrocholesterol (functions as a
cholesterol precursor in blood serum) gets
converted in vivo (epidermal cells) to
Vitamin D by the action of sunlight
Are you getting enough Vitamin D?

• Deficiency leads to poor teeth and bone

development (rickets) in children
• Vitamin D is added to milk to offset lack of
sunlight in winter ; aids in Ca absorption
• Darker skin prevents UV action
• Some MS connection (2009)-all people
should be taking supplements of it.
 Can one get too much Vitamin D?
• Yes-overuse of Vitamin D supplements can
lead to excessive absorption of Calcium
and formation of Ca deposits in kidneys
• Exposure to sunlight is not a problem;
Melanin formation (tanning) stops the UV
induced reaction
• Recent claims re: Cancer retardation are
controversial
 Conclusions?
• Drink your milk (and less carbonated
sodas)
• Take cod liver supplements if no exposure
to sunlight
• Some exposure to sunlight is good (~1 hour
per day)
• Avoid mega doses of any fat soluble
vitamin
Phospholipids
 Phospholipids
nonpolar tails
(HC)

‘-’ or R polar head

(charged)
a phosphatidic acid
Phospholipid Bilayer = Cell Membrane/Wall
-water outside cell- hydrophilic surface

hydrophobic
interior of cell
wall

-water inside cell-

Phosphoglyceride Aggregate = Cell Wall

-cell exterior-

-cell interior-
 Lecithin - Another Phospholipid

(emulsifying agent in egg yolks for mayonnaise,

candy, cake dough)
 Egg yolks
• Yolk; weighs~20 grams; 33% of weight of total
egg liquid
• 50% water, 16% protein, 34% lipid
• ~6.8 x9 =61.2 Cal from fat; 3.2 x4=12.8 Cal from
protein
• Total ~74 Cal. vs. 15 Cal in egg white
• Functions as stored food for the embryo
• Supermarket eggs do not contain an ovum, since
they have not been fertilized (no rooster!)
Egg structure
 Lipids in Egg yolk
• ~ 66% fat, 30% phospholipid (lecithin),
4% cholesterol
• Lecithin (~2 grams per yolk) acts as an
emulsifier to “solubilize’’ the fat in the
water of the yolk
• Egg yolks used commercially to produce
mayonnaise, an emulsion
 Origin of Phospholipids
• Biosynthesized in humans from
glycerophosphate and Fatty acid CoA
• ATP (adenosinetriphosphate) is needed as
a phosphorylating agent
 Emulsifying power of an egg yolk
• 2 grams per yolk of lecithin (MW~800)
• # of moles =2/800= 1/400
• # of molecules=1/400 x Avogadro’s
number
• 1/400 x 6.02 x 1023~ 1.5 x1021 molecules!
 Surface Area
• Consider a layer of lecithin one molecule
thick on the surface of water
• The polar head of one lecithin molecule
takes up about 1.6 x 10-15 square inches
• Thus the total surface area of oil protected
by lecithin=1.6 x10-15 x 1.5x1021 sq inches
• Or 2.4 million square inches
 How big is a football field (US)
• 100 yards x 50 yards= 5000 square yards
• In a square yard there are 36 x 36 =1296
square inches
• Thus in 2.4 million square inches, there are
2,400,000 /1296= 1851 square yards (or
about 1/3 of a football field)
 So………….
• The surface area of oil protected by the
lecithin in an egg yolk covers over 1/3 of a
football field
• Hence huge emulsifying power

• Ref. “The Curious Cook” by Harold

McGee, McMillan 1990
Salmonella Enteritidis (SE bacteria)

• From fecal matter ; egg comes out by same path as

fecies; eggs are washed and sanitized before sale
• Can get into yolk or white, before the shell is formed if
the hen’s ovaduct or ovaries have been contaminated
• Raw eggs should not be consumed
• SE causes severe abdominal pain, nausea in humans,
particularly if taking antacids
• SE can be destroyed by acid, antibiotics
• Not fatal but can cause ~2 weeks of discomfort!
 Commercial mayonnaise
• Made with Pasteurized eggs to avoid SE
• Heat at 55-70oC kills bacteria
Soy Lecithin: comes from soybean oil
 Lecithin in Chocolate
• Acts as surfactant (0.5 to 1%) to aid in the flow
of liquid chocolate
• Polar end surrounds sugars ( OH groups)
• Non polar end interacts with fat
• Hershey Plant (Smiths Falls) closing 2006 due to
Salmonella in soy lecithin (Dec 2/06 reopening)-
then permanent closure in 2007.
• Salmonella bacteria (normally from undercooked
poultry) enter small intestine causing infection
 How can Salmonella get into soy
Lecithin products?
• Soybeans are often left to dry on open
ground, hence are subject to soil fecal
contaminant unless sterilized (roasted)
 Waxes = (large mol.wt.) Esters (R-COOR’)

Birds/insects - water repellant feathers/exoskeletons

Leaves/fruit - minimize water evaporation
Humans - to plug up ears!
 
beeswax; R= C15, R’= C30;
carnauba wax(Brazilian palm): R= C31, R’= C34
*spermaceti(whales): R= C15, R’= C16(mp.31oC)

Whales have 4 tons*(in head). While swimming on

surface(37oC) it is a liquid. When they dive (1000m) to
feed, the oil solidifies, increases in density, and whale
can stay submerged without effort until ready to return
to surface where oil remelts for buoyancy.
 Density of solids vs. liquids
• Behavior of whale oil is normal-ie liquid is
less dense than the solid
• Water is the only substance on the planet in
which the solid (ice) is less dense than the
liquid
• Water at 4oC is the most dense!
 Soaps/Detergents
Chp.13

Contain a nonpolar fat component (tail) and a

polar head
Bipolar Behaviour of Soaps, etc.
 CH3(CH2)8 SO3- Na+

alkylbenzene sufonate(anionic)

Detergents = CH3(CH2)13OSO3– Na+

alkyl
Synthetic Soaps sulfate(anionic)

ie. CH3(CH2)8O(CH2CH2O)nH
  hydrocarbon tail +
polar/charged head (nonionic)

CH3(CH2)11N+(CH3)Cl –
trimethylalkylammonium(cationic)
 A Typical Soap Molecule

hydrophyllic hydrophobic
‘hates’ H2O
‘loves’ H2O
Soap makes Grease ‘water-soluble’
 Soaps in Hard water
• Curd formation due to insoluble Fe, Ca and
Mg carboxylates
• Water softeners: exchange Na for Fe, Ca
and Mg ions, increasing solubility of the
carboxylates
• Detergents function better in hard water
because sulfonates are soluble
 Problem Set #3
• Chapt 15 # 1,8,9,10,11,25,29
• Chapt 13#1
• Chapt 16 #1,9,11,12,18