OBJECTIVE

To solve the rancidity and shelflife reducing problem in current snack products From general knowledge about oxidation, applying antioxidants into frying oil and doing shelf-life actual test

ANTIOXIDANTS APPLICATION

METHOD

CONTENT:
1. 2. 3. 4.

Oil deterioration Oxidation and anti-oxidation Antioxidants Applying and testing method

1. OIL DETERIORATION
i. ii. iii. iv. v.

Oil deterioration Chemical reactions specification Factors influence oil deterioration Oil deterioration measure Monitoring oil deterioration methods

1. OIL DETERIORATION
i.

Oil deterioration

1. OIL DETERIORATION
i.

Oil deterioration

1. OIL DETERIORATION

ii. Chemical reactions specification: 3 main reactions

Hydrolysis:

breaking down triacylglycerols releasing mono-, di-acylglycerols and FFA

reaction of atmosphere oxygen and lypid causing rancidity, bleaching, nutrients loss & reducing shelf-life both saturated and unsaturated FA undergo produce acids, hydrocarbons, acrolein, ketones, acyclic acids and dimers

Oxidation:

Thermal decomposition:

2. OXIDATION & ANTIOXIDATION

i.

Oxidation
Mechanism of oxidation Factors influence oxidation Oxidation catalysis mechanism Oxidation impacts on products Oxidation measurement

ii.

Anti-oxidation
Anti-oxidation method Anti-oxidation mechanism Factors influence anti-oxidation Choosing anti-oxidation method

2. OXIDATION & ANTIOXIDATION

i.

Oxidation: (also autoxidation)

Definition: Spontaneous reaction of atmospheric oxygen with lipid Objects: Both saturated and unsaturated fatty acid. Unsaturated possess higher oxidative potential Catalysis: Light sensitizer and metal trace. Products: Mainly volatile ketones and aldehydes. Influential factor: Fatty acid composition, temperature, moisture, surface area, pro-oxidants

2. OXIDATION & ANTIOXIDATION

i.

Oxidation (also autoxidation)

Oxidation mechanism: 2 stages
- Hydroperoxides forming ( without off-flavour) - Hydroperoxides decomposition and volatile compounds forming (causing rancidity)
RH Initiation X. O2 ROOROOH ROOR,ROR RH
Dimer, polymer, cyclic, peroxide compounds cleavage Aldehydes, ketones, furans, acids

R.

keto, hydroxyde RO. cleavage Aldehydes Alkyl Radicals Oxoacid

2. OXIDATION & ANTIOXIDATION

i.

o o

Oxidation (also autoxidation)

Oxidation products
Initial stage: hydroperoxides Second stage: hydroperoxides decomposition

2. OXIDATION & ANTIOXIDATION

i.

Oxidation (also autoxidation)

Hydroperoxides Name 2-undecenal decanal

Oxidation products: Final products

Fatty acid Aldehyde formed Flavour Oleic (18:1) 8-OOH 9-OOH

2-decenal, nonanal

10-OOH
11-OOH Linoleic (18:2) 9-OOH 13-OOH Linolenic (18:3) 9-OOH

Nonanal
Octanal 2,4-decadienal 3-nonenal Hexanal 2,4,7-decatrienal Fatty, waxy Green Painty, fishy

3,6-heptadienal
2,4-heptadienal 3-hexenal 3-hexenal propanal

soapy

12-OOH 13-OOH 16-OOH

green bean Green bean

2. OXIDATION & ANTIOXIDATION

i.

Oxidation (also autoxidation)

o

Factors influence rate of lipid oxidation in foods

Fatty acid composition: number, position and geometry of double bonds

Cis-acids: oxdise more rapidly than its trans isomers Conjungated double bonds more reactive than nonconjungated

o o

o
o

Temperature: Autoxidation of saturated fatty acid is extremely slow at room temperature but rapid at high temperature Moisture: oxidation inversely depends on moisture Surface area: oxidation rate increases when surface area of lipid exposed to air raise Pro-oxidants: metals posses 2 or more valency states acting as catalysts Antioxidants

2. OXIDATION & ANTIOXIDATION

i.

Oxidation (also autoxidation)

Catalysis:
o

Acceleration of hydroperoxide decomposition Mn+ + ROOH M(n+1)+ + OH- + RO.

Light sensitizer (sens): oxygen raised to excited state(1O2) by light energy light sens sens* sens* + 3O2 sens + 1O2 Metal trace

Mn+ + ROOH M(n-1)+ + H+ + ROO.

Direct Mn+ + RH

Mn+ + O2 O2. + e Mn+ + O2 + H+ H.O2

Activate of molecular oxygen to give singlet oxygen peroxide radical

M(n-1)+ + H+ + R.

reaction with the unoxidized subtrate:

2. OXIDATION & ANTIOXIDATION

i.

Oxidation (also autoxidation)

Effects of lipid oxidation

o o

Flavor quality loss: Rancid flavor Changes of color and texture Consumer acceptance Economic loss Nutritional quality loss: Essential fatty acids Vitamins Health risks: Toxic compound Growth retardation Heart diseases

2. OXIDATION & ANTIOXIDATION

ii. Antioxidation Preventing singlet oxygen (1O2):

Temperature

Vacuum packing or N2 flush Oxygen scavengers Low permeable film Antioxidants

Temperature

According to the formula: C=Co+kt () Where C: value of index after time t of frying Co: initial value in fresh oil before frying k: rate constant of reaction
Conjungated dienes Conjungated trienes 0.012 0.013 0.009 0.009 0.012

Oxidation index k (h-1) P-Anisidine value 10.784 11.576 12.033 12.689 13.650 % Polar compounds 1.476 1.540 1.670 1.765 1.971

155 165 175 185 195

0.058 0.066 0.085 0.094 0.111

2. OXIDATION & ANTIOXIDATION

ii. Antioxidation Water activity

Rate of oxidation decreases as the water activity is lowered towards the monolayer Moisture released from food acts as protective shield preventing oxygens contact to surface

Metal

ions

Restricting free metals will slow down lipid oxidation Using chelators Packaging

Light

Antioxidants

3. ANTIOXIDANTS
i. ii. iii. iv. v.

Definition Antioxidant categories Ideal antioxidants Consideration of choosing antioxidants Specific antioxidants

3. ANTIOXIDANTS
i.

Deffinition:
Inhibiting

Subtance delay autoxidation by:

formation of free radicals in initial step Interrupting the propagation of free radical chain AH (antioxidant): free radical acceptor or hydrogen donor react primarily with RO2 not with R.
RO2. + AH ROOH + A. RO2. + AH2 ROOOH + HA. HA. + HA. A + AH2

The most common types od lipid soluble antioxidants are mono or polyhydric phenols with ring substituents

3. ANTIOXIDANTS
ii. Antioxidants categories

By mechanism

Chain-breaking antioxidants Preventive inhibitors Synergism Synthetic Antioxidants Natural Antioxidants

By origins

3. ANTIOXIDANTS
ii. Antioxidants categories

By mechanism

Chain-breaking antioxidants Able to compete with the substrate for chain-carrying species Produce a lag period ( induction period IP) due to antioxidants concentration until about 90% of which is destroyed Effectiveness represents the possibility of blocking the radical chain process by reaction with peroxyl radicals Preventive inhibitors Inhibit oxidation by induced decomposition of hydroperoxides by forming stable alcohols or inactive products by non-radical processes Include elemental sulphur, thiols, sulphides, disulphides, metal chelating agents

3. ANTIOXIDANTS
ii. Antioxidants categories

By

Synergism:

mechanism

mixture of antioxidants produce a more activity than sum of activities of the individual ones used separately 2 categories of synergism

Involving action of mixed free radical acceptors Involving the combined action of free radical acceptor and a metal chelating agent

3. ANTIOXIDANTS
ii. Antioxidants categories
By

mechanism
Synergism mechanisms: 2 hypothesis

Synergism
2 mixed free radical acceptors: AH & BH

Dissociation energy of AH > that of BH BH reacts more slowly than AH due to steric hindrance Reactions:

RO2. + AH ROOH + A. A. + BH B. + AH

Result in regeneration of the primary antioxidant Deactivate trace metal Often present as salt of fatty acids Ex.: citric acid, phosphoric acid, polyphosphate, acid ascorbic

Metal complexing agents

3. ANTIOXIDANTS
ii. Antioxidants categories
By

origins

Synthetic antioxidants:

3. ANTIOXIDANTS
ii. Antioxidants categories
By

origin

Natural oxidants

Rosmarinic Acid Carnosol

Caffeic acid

Ferulic acid

3. ANTIOXIDANTS
ii. Antioxidants categories
By

origin

Synthetic antioxidants

BHA (Butylated Hydroxyanisole)

BHT (Butylated Hydroxy Toluene)

Propyl gallate (PG)

3. ANTIOXIDANTS

iii. Ideal antioxidants No harmful physiological effects No contribute off-flavor, odor, color to the food Effective in low concentration Fat soluble Carry through effect no destruction during process Readily available Economical Not absorbable by the body

3. ANTIOXIDANTS

iv. Consideration of choosing antioxidants Safety Anti-oxidation effectiveness Off-odor Off-color Convenience of antioxidant incorporation to foods Carry though effect Stability to pH & food processing Availability Cost Non-absorbable

3. ANTIOXIDANTS
v. Specific antioxidants Tocopherol

4. APPLYING AND TESTING METHODS

i. ii. iii.

iv.

Actual condition of manufacturing application Applying methods Testing methods Consideration of choosing applying and testing method