Food Lipids

Lipids

z Lipids consist of a board group of

compounds that are generally soluble in
organic solvents but only sparingly soluble in
water. Glycerol esters of fatty acids,
which make up 99% of the lipids of plant and
animal origin have traditionally been called
fats and oils
Nawar, Lipids Food Chemistry, Fennema Ed. 1996
Lipids are non-polar (hydrophobic)
compounds, soluble in organic solvents.

Fatty acids consist of a hydrocarbon chain

with a carboxylic acid at one end.

CH3(CH2)n-COO-
Non-polar polar
 Saturated Fatty Acids
Systematic name Trivial name Shorthand Molecular
designation wt.
butanoic butyric 4:0 88.1
pentanoic valeric 5:0
hexanoic caproic 6:0 116.1
octanoic caprylic 8:0 144.2
nonanoic pelargonic 9:0 158.2
decanoic capric 10:0 172.3
dodecanoic lauric 12:0 200.3
tetradecanoic myristic 14:0 228.4
hexadecanoic palmitic 16:0 256.4
heptadecanoic margaric 17:0 270.4
(daturic)
octadecanoic stearic 18:0 284.4
eicosanoic arachidic 20:0 312.5
docosanoic behenic 22:0 340.5
 Mono-Unsaturated Fatty Acids
Systematic name Trivial name Shorthand Molecular wt.
designation
cis-9-tetradecenoic myristoleic 14:1(n-5) 226.4
cis-9-hexadecenoic palmitoleic 16:1(n-7) 254.4
cis-9-octadecenoic oleic 18:1(n-9) 282.4
tr-9-octadecenoic elaidic tr18:1(n-9) 282.4
cis-11-octadecenoic vaccenic 18:1(n-7) 282.4
(asclepic)
cis-11-eicosenoic gondoic 20:1(n-9) 310.5
cis-13-docosenoic erucic 22:1(n-9) 338.6
 Poly-Unsaturated Fatty Acids
Systematic name Trivial name Shorthand Molecular
designation wt.
9,12-octadecadienoic linoleic 18:2(n-6) 280.4
6,9,12-octadecatrienoic -linolenic 18:3(n-6) 278.4
9,12,15-octadecatrienoic -linolenic 18:3(n-3) 278.4
6,9,12,15-octadecatetraenoic stearidonic 18:4(n-3) 276.4
5,8,11,14-eicosatetraenoic arachidonic 20:4(n-6) 304.5
5,8,11,14,17-eicosapentaenoic EPA 20:5(n-3) 302.5
4,7,10,13,16,19-docosahexaenoic DHA 22:6(n-3) 328.6
 Lipids

Membrane (polar)
Storage (neutral)
PL O GL

TAG O C(CH2) 14CH3

H2 C O CH=CH(CH 2)12CH 3
O
HO CH O
OC (CH 2) 14CH 3 HC O C(CH2) 7CH=CH(CH 2) 7CH3
O HC N C(CH2) 22CH3
H2 C O
H2 C H
O P O X
HC OC (CH 2) 7CH=CH(CH 2)7 CH3 H2 C
O - O X
O
H2 C
OC (CH 2) 16CH 3
Phospholipids

z Pi is in turn esterified to
OH of a polar head
O
group (X): e.g., serine,
O H2C O C R2
choline, ethanolamine,
glycerol, or inositol. R1 C O CH O

z The 2 fatty acids tend to H2C O P O X

be non-identical. They O
may differ in length glycerophospholipid
and/or the
presence/absence of
double bonds.
Sphingolipids

z Sphingolipids are
OH OH
derivatives of the lipid
sphingosine, which has a H
H2C C CH
long hydrocarbon tail, and a
polar domain that includes H3NH
N+ CH
an amino group.
O C HC
z The amino group of
sphingosine can form an R (CH2 )12
amide bond with a fatty acid
sphingosine
ceramide CH3
carboxyl, to yield a
ceramide.
Sphingolipids

z Sphingomyelin, a ceramide
with a phosphocholine or CH2OH
CH3 O
phosphethanolamine head OH H3C N+ O
H2
C
H2
C O P O

group, is a common H
O
OH
OH CH3 H O OH
constituent of plasma H
H H
phosphocholine H2C C
H CH
membranes H2C C CH
H OH NH CH
z A cerebroside is a sphingosine NH CH
sphingolipid (ceramide) with O C HC
O C HC
a monosaccharide such as
fatty acid R (CH) 2 )12
glucose or galactose as cerebroside with R (CH 2 12

polar head group. -galactose

Sphingomyelin
head group CH
CH3 3
Attributes of Food Lipids

z Three major functions in foods

Energy and health
Influence food flavors
z free fatty acids contribute flavors
z lipids act as solvents for carrying hydrophobic flavors and aromas
(and nutrients)
Texture
z Solid vs liquid
z Emulsions
Attributes determined by types and positions of
fatty acids on glycerol backbone
 sn-1
90
sn-2
Plant
mole % of fatty acid groups

80
70
sn-3 Triglycerides
all
60
50
40 z Cocoa butter
30 ~ equal 16:0, 18:0, 18:1
20 sn-2 primarily unsatd (U)
10 sn-1,3 mostly satd (S)

0 S U
C16:0 C18:0 C18:1 C18:2
fatty acid constituent U U
(Belitz and Grosch, 1999; Springer-Verlag.)
S S
81% (S at sn-1 or sn-3)
15%
Coconut, palm oil richer in 8:0-16:0
Plant Triglycerides
z Coconut oil
80% of triacylglycerols are trisaturated
z Lauric at sn-2
z Octanoic at sn-3
z Myristic or palmitic at sn-1
 sn-1
Plant
60
sn-2 Triglyceride
mole % of fatty acid groups

50 sn-3
all s
40

30 z Peanut Oil
20 ~40% oleic;
40%linoleic
10
sn-2 largely unsatd
0
C16:0 C18:0 C18:1 C18:2 S U
fatty acid constituent U
(Belitz and Grosch, 1999; Springer-Verlag.)
U
U U
Soybean oil similar (< 30%) (> 70%)
 sn-1
mole % of fatty acid groups 90
sn-2
Plant
80
70
sn-3 Triglycerides
all
60
50 z Olive Oil
40 ~75% oleic
30 sn-2 99% unsatd
20 homogeneous

10
S U
0
C16:0 C18:0 C18:1 C18:2 U U
fatty acid constituent
(Belitz and Grosch, 1999; Springer-Verlag.)
U U
(< 30%) (> 70%)
mole % of fatty acid groups 45 sn-1
sn-2
Animal
40
sn-3 Triglycerides
35
all
30
25 z Beef Fat (tallow)
~ equal 16:0, 18:0, 18:1
20
sn-1,2,3 satd (S) &
15 unsatd (U)
10
S S S
5 U U S
0 U S U
C16:0 C18:0 C18:1 C18:2 18% 33% 16%
fatty acid constituent
(Belitz and Grosch, 1999; Springer-Verlag.)
S
S 29%
Pig fat (lard) similar S
 Cocoa Butter vs Animal Fat

z Compare cocoa butter vs tallow (beef fat)

fatty acid composition quite similar
z roughly equal C16:0, C18:0, C18:1
cocoa butter tallow
S S S S S
81% U 15%
U U S U S U

S S S U U
S
29% 33% 16% 18%
Cocoa butter homogeneous: melts sharply at body temp;
Tallow heterogeneous: solid/liquid over wide temp range
(Coultate, 1989; Royal Society of Chemistry)
Animal
30
Triglycerides
bovine milk fat
25 cod oil
20
% fatty
15
acid group
10

0
4:0
6:0
8:0
10:0
12:0
14:0
16:0
16:1
18:0
18:1
18:2
18:3
18:4
20:1
20:5
22:1
22:6
z Milk Fat - Large number of Marine Oils
short-chain fatty acids
Long-chain unsaturated
affects cheese flavor fatty acids
causes milk rancidity
Summary of Fatty Acid Profiles

z Plant fats/oils:
sn-2 largely unsaturated fatty acid (C18:1 & C18:2)
some plant oils contain high unsaturated fatty acid contents
(peanut, soybean, olive, Canola)
other plant oils significantly saturated (cocoa butter)
coconut and palm oil primarily saturated rich in C8:0-
C16:0
z Animal fats/oils:
broader range of fatty acids/triglycerides found
z milk fat (short chains) vs fish oils (long, polyunsatd)
sn-2 often saturated, greater variation in positions
Properties
 Crystallization COOH

C
H OO HOOC

z Crystallization/Melting is HO
OC
balance
entropic considerations
Melt (liquid)
z favor increased molecular motion

and HOO C
C
HOOOC
HO C
attractive intermolecular HOOC
H OO C
interactions H OO C
H OO C
z favor packing molecules close H OO
together
crystal (solid)
Melting Point

z Longer chain fatty acids pack better than shorter

chains
M.P.long > M.P.short
z Saturated fatty acids pack better than unsaturated
M.Psatd > M.P.unsatd
- OOC
- OOC
z Trans fatty acids pack better than cis
M.Ptrans > M.P.cis
hydrogenation increases M.P.
- OOC
Melting Point Trends

Fatty A cid Comm on N am e M.P.

8:0 Caprylic acid 16C
16:0 Palmitic acid 63C
18:0 Stearic acid 69C
20:0 Arachidic acid 75C
18:1 9 (cis) Oleic acid 13C
18:2 9,12 (ci s) Linoleic acid -5C
18:3 9,12,15 (ci s) Linolenic acid -11C
18:1 9 (tr ans) Elaidic acid 46C
18:2 9,12 (trans) Linolelaidic acid 28C
Surfactants (Emulsifiers)

z Surfactants are molecules that lower the

surface tension
Part of molecule interacts favorably with water
z Polar or charged (hydrophilic)
Part of molecule interacts unfavorably with
water
z Hydrophobic

Amphiphilic
Lipid Surfactants

z Fatty Acids

z Monoglycerides and Diglycerides

O O
HO O O
O
HO HO O
Lipid Surfactants

z Phospholipids
Synthetic Emulsifiers

z Tweens
OH O O OH
( O )a (O )b
O

C
O
O
O
( O
)
c
OH
Surfactants

z Mediates interactions between hydrophobic

and hydrophilic phases
Hydrophilic Head

Hydrophobic
Interior

Hydrophilic Head
Emulsion Breakdown: Creaming

z Density differences between droplets and

continuous phase cause droplets to rise or fall
In oil-in-water emulsions, droplets typically rise
z Creaming rate depends on
droplet size
z decrease drop size (e.g. homogenized milk)
viscosity of continuous phase
z add macromolecules (termed stabilizers) to increase
viscosity
Reactions
Reactions of Triglycerides

z Hydrolysis
H2O
triglycerides diglycerides, monoglycerides,
glycerol + fatty acids
saponification (base catalyzed)
enzymatic hydrolysis (lipase catalyzed)
interesterification (randomization)
z Hydrogenation H2
unsaturated lipids saturated lipids
trans isomers
z Oxidation
 Acid Hydrolysis

z Addition of water to cleave ester bond O

also called lipolysis sn-1 CH 2 O C R 1
O
sn-2
R2 C O C H
O
Catalyzed by strong acid sn-3 CH 2 O C R 3
Produces free fatty acids
Lipases

z Can also be catalyzed by

enzymes
sn-1
hydrolases or lipases
O
found in plants and animals
in vivo digestion CH 2 O C R 1
O
R2 C O C H
O sn-3
sn-2
CH 2 O C R 3
 PLA1

PLA2
O C(CH2)14CH3
H2C O

DAG HC O C(CH2) 7CH=CH(CH2)7CH3

O H OPO32-
H2C
O P O H
HO H
O- IP3
OH OH
PLC
H OPO32-

H H
PLD
Hydrolysis: Products

z Small quantities of free fatty acids

contribute flavors to cheese, milk
chocolate
cause off-flavors in milk, fruits and
vegetables
lead to foaming
z removed during commercial production of
food oils
 Saponification

CH 2 OH

HO C H
glycerol
sn-1 O
CH 2 O C R1 + _
3 Na OH CH 2 OH
O
+
R2 C O C H H2 O O
O _
sn-2 Na
+ O C R1
CH 2 O C R3 O
O
sn-3 _ _
O C R2 O C R3
+ Na
+
Na
Interesterification

z Rearrange the fatty acids so they become distributed

randomly among triacylglycerol molecules of the fat
z Improves consistency of fats
z Applications:
Manufacture of shortenings
Lard (want ~10% tri-saturated glycerides)
z Forms large and coarse crystals
z Shortenings posses grainy consistency and poor baking
performances
z Randomization improves plastic range
Production of high stability margarine blends and hard butters
with desirable melting qualities and crystallization behavior
Interesterification

Free fatty acids

P O hydrolysis O O P
P + O P O
+ P
P O H2 O
OH OH
16:0 18:1 OH + OH
OH OH
P P H2 O
O + O Modify
O P esterification nutritional and
physical
properties
Hydrogenation
z Addition of hydrogen across double bonds

H2/Ni trans oleic

Hydrogenation

z Rate is determined by
Nature of substrate
Type and concentration of catalyst
Pressure (concentration of H2)
Temperature
Agitation
Hydrogenation: Products

Produces triglycerides with higher melting

points
liquid semi-solid
Convert soft-fats into firmer fats
Useful in margarine, peanut butter, baked
goods
Improves oxidative stability
Fat Replacers
Olestra, Fat replacer
Olestra vs Triglycerides

Calories 75
Fat Calories 0
Total fat 0 g Calories 160
Saturated fat 0 g Fat Calories 90
Total fat 10 g
Ingredients: Potatoes, Saturated fat 2.5 g
Olestra, Salt, -Tocopheryl
Acetate (Vit E), Vitamin A
Ingredients: Potatoes, Corn
Palmitate, Tocopherols (to
and/or Cottonseed Oil, Salt
protect flavor), Vitamin K,
Vitamin D

(cf. www.olean.com)
Lipids and Health
Trans Fatty Acids

z Trans fats refers to triglycerides containing unsaturated

fatty acids in the trans conformation
Found in partially hydrogenated fats or oils
Help to solidify food (melting point higher than cis)
z FDA adopted new food labeling
z labels give weight of trans fat
z restrict low fat definitions by trans fat content
Some margarines are sold as trans free
z No hydrogenation
z Mix satd and unsatd fats
z Tend to be soft spreads
Alternatives for trans-FA in Foods

z Modification of the hydrogenation process

Increase the degree of hydrogenation
z Interesterification
Expensive
Use 85% un-hydrogenated liquid vegetable oil and 15% fully
hydrogenated vegetable oil (hardstock)
z Use of fractions high in solids
Derived from coconut, pal and palm kernel oils
Prepared by reducing the temperature of an oil sample so that
the more saturated fraction solidifies
z Use of trait-enhanced oils
High oleic acid oils
Plant breeding, sunflower and canola
Saturated Fat & Health

z Risk of heart disease correlates with

cholesterol level in bloodstream (serum
cholesterol) LDL
liver
low density lipoproteins (LDL)
z carry cholesterol to cells
high density lipoproteins (HDL)
z carry cholesterol away serum
HDL
z Fat affects cholesterol regulation
Fat consumption with cholesterol raises serum
cholesterol levels
 Health
z Depends on what type of
saturated/unsaturated fat

18:1
Improved lowers serum
cholesterol + cholesterol
18:2
removal
8:0
6:0 10:0 18:0 neutral

Worsened 18:1
cholesterol (trans)
removal 12:0
raises serum
- cholesterol
14:0
Dietschy (1998) 16:0
 Lipoproteins
VLDL (Vance and Vance, 1996; Elsevier)
(30-80 nm)
LDL HDL
LDL (5-12 nm)
(18-25 nm) Protein
rich
Chylomicron
Lipid poor
(75-1200 nm)
Protein poor
Lipid rich

Lipoproteins transport lipids throughout body

Essential Fatty Acids
PUFA requirements
a. should make up to 3% of fatty acid intake
b. PUFA deficiencies cause growth
retardation, skin lesions, neurological
and visual abnormalities
Role of polyunsaturated fatty acids
3 and 6 fatty acids are precursors to
potent bioactive compounds
1. Prostaglandins
a. Platelet antiaggregate
2. Thromboxanes
a. Platelet aggregate