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Lipids in Foods

Peroxide value of lipids


Cholesterol content of egg yolk
Lipids
§ Lipids represent a very large group of molecules, and constitute one of
the macroconstituents of foods.
§ In general, lipids are soluble in ether, chloroform, or other organic
solvents, but not in water. No other major constituents of foods
(proteins and carbohydrates) are defined by solubility.
§ Triacylglycerols are very hydrophobic, while di- and monoacylglycerols
have both hydrophobic and hydrophilic moieties in their structure and
are soluble in relatively polar solvents.
§ Short-chain fatty acids (C1-C4) are completely miscible in water and
insoluble in non-polar solvents.
§ Simple lipids include ‘fats’ (esters of fatty acids with glycerol) and waxes
(esters of fatty acids with long-chain alcohols).
§ More complex lipids include phospholipids, cerebrosides and
sphingolipids.
Lipid analysis
§ The term ‘lipid’ when applied to foods refers to the broad, total
collection of molecules that are soluble in organic solvents.
§ ‘Total fat’ in a food is defined (by the FDA) as the sum of fatty acids
from C4 to C24, calculated as triglycerides.
§ Nutritional labelling requires accurate and precise qualitative and
quantitative analysis of lipids in foods.
§ Lipid analysis is also needed for determination of whether a food meets
the standard of identity, and to ensure the product meets
manufacturing specifications.
Polyunsaturated fatty acids are very sensitive to oxidation
§ Oxidation may be caused by reactive oxygen species, metal ions, high
temperatures, lipoxygenase.
§ Peroxide value (POV) is used widely as a measure of the degree of
oxidation of a fat or oil.
§ POV is defined as the milliequivalents of peroxide per kilogram of lipid.

Oxidation of lipids
Unsaturated lipid

Lipid peroxyl
Unsaturated lipid Lipid radical
radical

Lipid peroxide

Initiation

Propagation
Principle of the titration to determine POV
§ Peroxides oxidise KI to I2
- Y moles of peroxide will generate Y moles of I2
§ I2 is titrated with sodium thiosulphate (Na2S2O3)
- Na2S2O3 reacts stoichiometrically with I2 (2 moles of Na2S2O3 react
with 1 mole of I2 )
§ Appearance of ‘straw’ colour signifies the approach of the end of the
titration.
§ Starch indicator is added and the mixture turns blue due to the
formation of starch complexes with the small amount of remaining I2.
§ On continuing the titration, the Na2S2O3 reacts with the remaining I2,
resulting in the dissociation of any starch-iodine complex and
disappearance of the blue colour.
§ The first clear sign of the disappearance of the blue colour is the end
point, indicating that all of the I2 has been consumed.
To determine the peroxide value use the formula in the
practical notes:

meq V! − V" ∗ c ∗ 1000 ∗ T


POV =
kg 𝑚

POV = peroxide value


V1 = volume of sodium thiosulfate solution used to titrate the sample
V0 = volume of sodium thiosulfate solution used to titrate the blank
c = molar concentration of the sodium thiosulfate solution
T = titre of the thiosulfate solution (i.e., the number of moles of
thiosulfate corresponding to one mole of peroxide)
m = weight of the oil sample in grams
Cholesterol
§ Ubiquitous steroid in animals
§ Essential component of membranes
- 30-50% of membrane lipids (plasma membrane,
nervous tissue)
– Tightens packing of the lipids in the bilayer but
does not make membranes any less fluid
§ Biosynthetic precursor of metabolic steroids
– hormones, bile salts
§ High blood cholesterol is a major risk factor for
cardiovascular disease
- LDL (“bad” cholesterol) - transport to tissues
- HDL (“good” cholesterol) - mops up excess
§ Endogenous biosynthesis normally accounts for 60-
70% requirement
§ RDI from diet for humans is 300 mg
– brain: 2-2.5 g/100 g; beef, seafood: ~100 mg/100g
– egg yolk ??
Cholesterol in egg yolk
§ Analysis of cholesterol is
performed routinely in food
laboratories for labelling.
§ Enzymatic method in microplates
is widely used.
§ Amount of cholesterol calculated
using Beer-Lambert Law
C = Abs x L x e
§ Abs 570nm = 0.80 is equivalent to 3
µg cholesterol in the microplate
well
§ Aliquot (5 µl) from ? ml of extract
of 10 mg of egg yolk was
dispensed into the well
Basic principles

§ Why do some methods require comparison to calibration


standards, and others do not?

§ Use of microplates for assays

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