Rancidity Flashcards

1
Q

define rancid

A

having a rank, unpleasant, stale flavour or taste due to the decomposition of fats and oils

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2
Q

in vivo, fats and oils are stable- what does stable mean in this context

A

protection by antioxidants and enzymes

biochemical processes eliminate free radicals

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3
Q

once a fat/ oil has been harvested what is lost

A

protection is lost and lipids become more susceptible to hydrolytic and oxidative changes

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4
Q

what are the physical effects of rancidity

A

changes in colour, odor, flavour that are usually undesirable
although they can sometimes be desirable e.g. sour cream

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5
Q

what are the causes of rancidity

A

endogenous enzymes

  • lipases and phospholipases (lipoprotein lipase) cause hydrolytic rancidity
  • present in freshly produced milk
  • can reduce rancidity through heat treatment

enzymes produced by invading microbes

  • e.g. actinobacter
  • their lipases release FFAs from TGs
  • heat stable lipases
  • can be an issue in processed milk products

chemical transformations
- antioxidants start the auto-oxidation process (initiation, propagation, termination)

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6
Q

how can rancidity be controlled

A
  • reduce the activity of endogenous enzymes by reducing temperatures/ heat treating food
  • minimise bacterial growth by heat treating food
  • control oxidation by omitting air
  • controlling rancidity has allowed the development pf fridges and freezers
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7
Q

what is hydrolytic rancidity

A
  • caused by TG hydrolysis producing FFAs
  • measured by an acid-base titration
  • hydrolytic rancidity changes the characteristics of milk, unsalted butter, crude palm oil and fish oil.
  • short chains= volatile e.g. butter
  • long chains= less volatile e.g. butter
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8
Q

what is lipoxygenase

A

an enzyme that catalyses the oxygenation of FA

  • widespread in plants (soybean, carrot, pea)
  • produces derivatives with characteristic tastes and flavours
  • difficult to inhibit
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9
Q

what is ketonic rancidity

A
  • attack fats containing short‐chain fatty acids and produce ketones with a characteristic odour and taste.
  • butter, coconut, and palm kernel oils are most susceptible
  • associated with the growth of xerophilic moulds e.g bread
  • caused by the incomplete beta oxidation of TG to FFA, resulting in the production of ketones and secondary alcohols
  • affects both saturated and unsaturated FAs (8-10 carbons)
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10
Q

what are the chemical mechanisms that cause rancidity

A

chemical hydrolysis

  • water must be present
  • converts TG to FFA and glycerol
  • glycerol is flammable (due to a reduce flash point) so can be dangerous the frying oils
  • risk can be reduced by using sealed fat friers and changing oil regularly
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11
Q

what is a xerophilic mould

A

Xerophilic means “dry loving.” Thus, xerophilic molds are those that can or prefer to grow in “dry” environments.

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12
Q

define auto-oxidation

A

spontaneous oxidation of a substance at ambient temperatures in the presence of oxygen

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13
Q

what are the stages of auto-oxidation

A

initiation
propagation
termination

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14
Q

outline what occurs during the initiation phase of auto-oxidation

A
  • formation of the first radical by a reaction with an excited O2 molecule
  • reaction between unsat FAs and O2 is thermodynamically difficult and slow
  • production of the first few radicals occur due to photosensitisation- this involves an interaction between FA double bond and an excited O2 molecule
  • oxygen in the triplet state is activated by light in the presence of a sensitiser
  • 18:3 FAs are most susceptible
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15
Q

outline what occurs during the propagation phase of auto-oxidation

A

free radicals produced in the initiation phase react freely with other unsaturated FAs to propagate the reaction
most vulnerable to oxidation is the CH2 group next to a double bond
18:3 FAs are most susceptible to propagation due to higher number of double bonds

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16
Q

explain the relevance of autooxidation of PUFAs

A
  • faster reaction than FAs with a single double bond (monoenoics)
  • initial segregation products are unsaturated
  • smaller and more volatile fragments are produced
    increased likelihood of diradicals
17
Q

what is the dietary significance of lipid peroxidation? what is the main source of lipid per oxidation products in the diet?

A

fried food- main source
lipid peroxidation products have adverse effects on the diet (decreased vitamin A levels in lipid rich diets) and a link to arterial disease

18
Q

what provides protection against auto-oxidation

A
  • protective packaging (away from light)
  • suitable storage instructions (dry, dark place)

carotenoids are present in many crude oils, they produce a yellow/ orange colour that is unacceptable to the consumer (oils are refined and bleached to remove these)

19
Q

what is an antioxidant

A

a substance that inhibits oxidation, especially one used to counteract the deterioration of stored food products.

20
Q

what are some examples of radical scavengers

A

vitamin E

  • good scavenger of of peroxyl radicals
  • important inhibitor of the radical chain reaction
  • tocopherol radical produced is non-reactive
  • lipid soluble

vitamin C

  • water soluble scavenger
  • donates hydrogen
  • produced ascorbic radical which is non-reactive
  • ascorbic radical is the lipophilic variant of ascorbic acid
21
Q

what are oxygen scavengers and displacers

A

asc

22
Q

what is an example of protective packaging

A

foil-like packaging

23
Q

how is rancidity measured

A
sensory
- odor
- taste
- colour
Odor is very sensitive and is a method that can be used to directly measure consumer acceptability. Typical smells include acetaldehyde (caused by bacterial spoilage and oxidation) and phenolic (caused by bacterial spoilage by coliforms)

chemically
Hydroperoxides
- primary product
- concentration is determined by titration

Aldehydes

  • secondary product
  • determined by TBA reaction (pink= reaction) and nucleophile and electrophile (red = reaction)

Volatiles
- tertiary product
- measured by gas chromatography
It is best to use all 3 methods as each measures something different
Totox value takes into account more than one type of product

24
Q

what methods are used to predict susceptibility to rancidity

A

Iodine value

  • iodine monochloride binds to unsaturated FA, more double bonds= more iodine mono chloride absorption, more uptake= more susceptibility to rancidity
  • does not take antioxidants into account

Reactive index

  • very rapid
  • indicates the proportion of unsatisfyingly FAs present
  • does not take antioxidants into account

Response to abuse

  • heat oil, bubble through O2, measure Peroxide value over time
  • more unsatisfyingly FA and PUFA = more oxidation
  • can assess different antioxidants which is useful
  • hard to related to actual food products
25
Q

what are oxygen scavengers and displacers

A

An oxygen scavenger is a material in which one or more reactive compounds can combine with oxygen to reduce or completely remove oxygen in fluids and enclosed packaging

  • ascorbic acid reacts with oxygen
  • flushing packaging with nitrogen displaces oxygen