LIPIDS

Types of Lipid
Lipids with fatty acids
- Waxes - Fats and oils

- Phospholipids
- Sphingolipids

Lipids without fatty acids

- Steroids

Properties of Fatty Acid

Long-chain carboxylic acids
Insoluble in water Typically 12 -18 carbon atoms (even number)

Some contain double bonds

Described by systematic, common and abbreviated names

O C OH

Carboxyl end Polar head

Long hydrocarbon chain Nonpolar tail

General Fatty Acid Structure

Fatty Acid Chain Length

Three groups of chain length Short chain: 2 to 6 CN (volatile fatty acids) Acetic acid ( 2 CN), Butyric acid (4 CN) Medium chain: 8 10 CN Caprylic acid (8 CN), Capric acid (10 CN) Long chain: 12 24 CN Palmitic acid (16 CN), Stearic acid (18 CN)

 As chain length increases, melting point increases

Fatty acids derived from plants and animals

have an even number of carbons Mostly long chain 16 CN (palmitic) to 18 CN (stearic) fatty acids are most prevalent.

Nomenclature of Saturated Fatty Acids

1. Based on IUPAC system Example:
Systematic name Numerical Abbreviation Hexanoic 6:0 Decanoic 10:0 Hexadecanoic 16:0

Common Name Caproic acid Capric acid Palmitic acid

Nomenclature of Unsaturated Fatty Acids

Anoic is changed to enoic presence of a double bond Terms di-, tri-, tetra- and so on are added # of

double bond First position of the double bond numbered by delta () Examples:
Common Name Systematic name Numerical Abbreviation Oleic acid 9-octadecenoic acid 18:1 9 Linoleic acid 9,12- octadecadienoic acid 18:2 9

Fatty acid Nomenclature

Stearic acid

Systematic name: Octadecanoic Numerical: 18:0

Fatty acid Nomenclature

Oleic acid

Systematic name: 9octadecenoic Numerical: 18:1 9

Fatty acid Nomenclature

Linoleic acid

Systematic name: 9,12octadecadienoic Numerical: 18:2 9

Fatty acid Nomenclature

Linolenic acid

Systematic name: 9,12,15octadecatrienoic Numerical: 18:3 9

2. Named according to the location of the first double bond from the noncarboxyl end (count from the methyl end) Omega system (e.g., omega 3, 3) nsystem (e.g., n3)

3. Name according to location of Hs Cis or trans fatty acids

Saturated & Unsaturated Fatty Acids

Saturated = CC bonds Unsaturated = one or more C=C bonds
COOH palmitic acid, a saturated acid COOH palmitoleic acid, an unsaturated fatty acid

Structures
Saturated fatty acids
Fit closely in regular pattern

COOH COOH COOH

Unsaturated fatty acids

Cis double bonds

H C C

cis double bond

COOH

Properties of Saturated Fatty Acids

Contain only single CC bonds
Closely packed Strong attractions between chains High melting points Solids at room temperature

Properties of Unsaturated Fatty Acids

Contain one or more double C=C bonds Nonlinear chains do not allow molecules to pack closely

Few interactions between chains

Low melting points Liquids at room temperature

Learning Check Q1
How would the melting point of stearic acid compare to the melting points of oleic acid and linoleic acid? Assign the melting points of 17C, 13C, and 69C to the correct fatty acid. Explain. stearic acid (18:0) saturated oleic acid (18:1) one double bond linoleic acid (18:2) two double bonds

Solution Q1
Stearic acid is saturated and would have a higher melting point than the unsaturated fatty acids. Because linoleic has two double bonds, it would have a lower mp than oleic acid, which has one double bond. stearic acid mp 69C oleic acid mp 13C linoleic acid mp -17C

Fats and Oils

Formed from glycerol and fatty acids
O CH2 OH CH CH2 OH OH + HO C O (CH2)14CH3

HO C (CH2)14CH3 O HO C (CH2)14CH3

glycerol

palmitic acid (a fatty acid)

Esters of glycerol and fatty acids

ester bonds O CH2 CH CH2 O O O C O C (CH2)14CH3 O C + H 2O H2O (CH2)14CH3 + H2O

(CH2)14CH3 +

Acylglycerols
Exist as mono-, di- and triesters known as monoacylglycerols (MAG), diacylglycerols (DAG) and triacylglycerols (TAG).
TAG the most common in food
MAG and DAG additives in food such as

emulsifier Free fatty acid (FFA) cytotoxic owing to their ability to disrupt cell membrane organization

TAG Nomenclature TAG contains only one FA (e.g. stearic acid, St) Tristearin , tristearate, glycerol tristearate, tristearoyl glycerol, StStSt or 18:0-18:0-18:0
TAG contains more than one FA If stereospecific location of each FA is known 1-palmitoyl-2-oleoyl-3-stearoyl-sn-glycerol or sn-POSt or sn-16:0-18:1-18:0 If stereospecific location is not known palmitoyl-oleoyl-stearoyl-glycerol or POSt or 16:0-18:1-18:0

Triglycerols Structure
Fatty Acid glycerol Fatty Acid Fatty Acid

Learning Check Q2
What are the fatty acids in the following triglyceride?

O CH2 CH CH2 O O O C O C (CH2)7CH CH(CH2)7CH3 O C (CH2)12CH3 (CH2)16CH3

Solution Q2
What are the fatty acids in the following triglyceride?
O CH2 CH CH2 O O O C O C (CH2)7CH CH(CH2)7CH3 O C (CH2)12CH3 (CH2)16CH3

Stearic acid
Oleic acid

Myristic acid

Composition of Fats
Coconut oil Saturated - 97% Monounsaturated 6% Polyunsaturated 2%

Palm Oil Saturated 50% Monounsaturated 39% Polyunsaturated 11%

Olive Oil Saturated 14% Monounsaturated 73% Polyunsaturated 11%

Soybean oil Saturated 15% Monounsaturated 23% Polyunsaturated 62%

Complex Lipids-Phospholipids
TAG with phosphate group typically at sn-3 position
E.g. phosphatidylcholine or also known as lecithin.

Phospholipids
Significant use in feed industry as emulsifiers
Lipids form emulsion in water

Phospholipid sources:
Liver, egg yolk,
Soybeans, wheat germ Peanuts

Sphingolipids
Contain sphingosine base Include: sphingomyelin (sphingophospolipid), ceramides, cerebrosides and gangliosides Found in cell membrane

Sterols
Compounds with multi-ring structure

Insoluble in water Present both in plant and animal foods Major sterol is cholesterol
However, cholesterol is found only in animal

products (manufactured in liver) High content in organ meats and egg yolk

Common Sterol Compounds

Cholesterol (a sterol)

Vitamin D3 (cholecalciferol)

Testosterone (a steroid hormone)

Stigmasterol (a phytosterol)

Waxes
An ester of a long-chain acid and a long chain alcohol.
Added to the surface of fruits to slow

dehydration during storage fruit coating

Physicochemical Properties of Lipids

TAG molecules have a tuning-fork structure
Non-polar molecules Fat solid at room temp. Oil liquid at room temp.
sn 2-FA sn 1-FA

sn 3-FA

Thermal Properties
The most important thermal properties; Specific heat capacity (Cp) Thermal conductivity () Melting point (Tmp) Entalphy of fusion ( Hf) These thermal properties determine the total amount of heat must be supplied (or removed) from a lipid system to change its temp from one value to another.

Mp and Hf depend on a. Packing of the TAG molecules within the crystal The more effective the packing, the higher the Mp b. Chain length Higher value for TAG with Saturated FA Straight chain Symmetrical TAG Stable polymorphic forms

 Thermal stability can be characterized by

Smoke point temp at which the sample

begins to smoke Flash point temp at which the volatile products generated by the lipid can be temporarily ignited by application of a flame Fire point temp at which the evolution of volatiles continuous combustion

Crystallization and Melting of Food Lipids

The physical state (solid or liquid) of the lipids plays important role in their production and in determining their final quality attributes Example
Margarine strongly influenced by the

crystallization behaviour of the lipids that they contain.

Solid Fat Content (SFC) Pure TAG has narrow MP similar TAG melts at similar temp Mixed TAG has broad MP diff TAG melts at diff temp Desirable plastic rheological properties MP with the broad range of temperatures.

Solid fat content (cont.) Can be measured by Dilatometry Nuclear Magnetic Resonance (NMR) Differential Scanning Calorimetry (DSC) SFC-temp profile are used to determine the functional and sensory properties of many fatty foods Eg. Margarine; SFC at 10C storage SFC at 28C spreadability SFC at 37C waxiness