Antioxidant

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DEFINITION OF ANTIOXIDANT
Antioxidant means "against
oxidation”. Any substance at low
concentrations compared to that of
an oxidizable substrate that
significantly delays or prevents
oxidation of that substrate is
called as antioxidant.
Antioxidants play vital role in
preserving the quality of food and
maintaining health of human being.
NEED OF ANTIOXIDANTS
Oxidation reaction causes food
deterioration . The oxidative
deterioration of fats and oils, when
present as a component in foods, is
responsible for rancid odour and flavor
with a consequent decrease in nutritional
quality, . This is caused by the formation
of primary hydroperoxides and secondary
potentially toxic compounds through
auto-oxidation of unsaturated fatty acids
consisting of a free radical chain
mechanism . The direct oxidation of
unsaturated lipids with the double bond
in a singlet state (no unpaired
electrons, paired electrons are in the
same orbital and have opposite spin) by
oxygen in its ground triplet state (two
free electrons in separate orbitals with
same spin direction) is spin forbidden. To
overcome this spin barrier, initiators or
catalysts are required to start the lipid
oxidation process by removing an
electron from either the lipid or oxygen or
by changing the electron spin of the
oxygen. As only trace amounts of
catalysts are needed, many situations
that appear to be spontaneous or
uncatalyzed are actually driven by
contaminants or cThus, exposure of lipids
to initiators like light, metals, singlet
oxygen and sensitizers (chlorophyll,
hemoproteins, and riboflavin), or
preformed hydroperoxide decomposition
products causes generation of primary
hydroperoxides. Lipoxygenase-catalyzed
oxidation also produces hydroperoxides
[1]. The addition of antioxidants is
required to control the oxidative
deterioration.
MECHANISM OF ACTION
Primary Antioxidant
Primary antioxidants work in three main
ways
to curb the oxidation reaction.
RH R• + H• .
ROO• + RH ROOH + R• ...
(iii)
ROOH RO• + OH• ...
(iv)
RO• + RH ROH + R• .
Chain Breakers or Free Radical
Interceptors
Most of the primary antioxidants that
act as
chain breakers or free radical interceptors
are
mono or polyhydroxy phenols with
various
ring substitutions. As primary
antioxidants
(AH), they work on hydrogen atom
transfer
mechanism. In this, the antioxidant,
reacts
with highly reactive radical lipid and
peroxy
radicals (ROO•) and transfer one
hydrogen
atom to radical to form stable organic
lipid
derivatives and antioxidant radicals (A•)
that
are more stable and less readily
available to
participate in propagation reactions.
Primary
antioxidants have higher affinities for
peroxy
radicals than lipids and react
predominantly
with peroxy radicals (Figure 3) [3].
 Fig. 3: Mechanism of Primary

Antioxidant Activity (AH is an Antioxidant

Molecule).
Single Electron Transfer Mechanism
In single electron transfer mechanism
(Figure
4), an electron is donated to free
radical to
form energetically stable anion, while
the
antioxidant forms a cation radical which
is
also a less reactive species.
R• -
+ AH electron abstraction form------- R +
+
AH
Technique for evaluation of
antioxidants::

Table 1.
Different techniques used to measure antioxidant activity.
Techniques Antioxidant Capacity Principle of the Method End-Product Determination
Assay
Spectrometry ORAC Antioxidant reaction with Loss of fluorescence of
peroxyl radicals, induced by 2,2′- fluorescein
azobis-2-amidino-propane
(AAPH)
HORAC Antioxidant capacity to quench Loss of fluorescence of
OH radicals generated by a fluorescein
Co(II) based Fenton-like system
TRAP Antioxidant capacity to scavenge Chemiluminescence quenching
luminol-derived radicals,
generated from AAPH
decomposition
CUPRAC Cu (II) reduction to Cu (I) by Colorimetry
antioxidants
FRAP Antioxidant reaction with a Colorimetry
Fe(III) complex
PFRAP Potassium ferricyanide reduction Colorimetry
by antioxidants and subsequent
reaction of potassium
ferrocyanide with Fe3+
ABTS Antioxidant reaction with an Colorimetry
organic cation radical
DPPH Antioxidant reaction with an Colorimetry
organic radical
Fluorimetric Analysis Emission of light by a Recording of fluorescence
compound, which has absorbed excitation/emission spectra
light or other electromagnetic
radiation of a different
wavelength
Electrochemical Voltammetry The reduction or oxidation of a Measurement of the current of
Techniques compound at the surface of a the
working electrode, at the cathodic/anodic peak
 Techniques Antioxidant Capacity Principle of the Method End-Product Determination
Assay
appropriate applied potential,
resulting in the mass transport of
new material to the electrode
surface and in the generation of a
current
Amperometry The potential of the working Measurement of the
electrode current generated by the
is set at a fixed value with oxidation/
respect reduction of an electroactive
to a reference electrode analyte
Biamperometry The reaction of the analyte Measurement of the current
(antioxidant) flowing
with the oxidised form of a between two identical working
reversible electrodes, at a small potential
indicating redox couple difference and immersed in a
solution containing the analysed
sample and a reversible redox
couple
Chromatography Gas chromatography Separation of the compounds in a Flame ionisation or thermal
mixture is based on the conductivity
repartition between a liquid detection
stationary phase and a gas
mobile phase
High performance Separation of the compounds in a UV-Vis (e.g., diode array)
liquid chromatography mixture is based on the detection,
repartition between a solid fluorimetric detection, mass
stationary phase and a liquid spectrometry or electrochemical
mobile phase with different detection
polarities, at high flow rate and
pressure of the mobile phase

Antioxidants have many applications, including:

 Treating oxidative stress
Antioxidants can be used to treat oxidative stress, which is when there are too many free
radicals in the body. Oxidative stress can lead to chronic illnesses like cancer, heart disease,
and diabetes.

 Preventing cardiovascular disease

Antioxidant supplements and therapy can help prevent damage caused by free radicals, which
can reduce complications from cardiovascular disease and arthrosclerosis.

 Antibacterial properties
Antioxidants can act as antibacterial agents by inhibiting the production of nucleic acid, the
permeability of the outer membrane, and cytoplasm leakage.
 Skincare
Superoxide dismutase (SOD) is an antioxidant enzyme that is naturally produced by the body
and is important for skin health.
 Dairy products
Dairy products are a good source of antioxidants and may help protect against chronic
diseases.
Antioxidants work by scavenging free radicals from cells and preventing or reducing
the damage caused by oxidation. They can also control oxidative reactions by
inhibiting, delaying, or hindering the oxidation of biomolecules.

Aromatic compounds

Plants that have smell and taste properties and are also used as medicines due to their therapeutic
properties are called aromatic plants. Plants and essential oils have been used to obtain aromatic
foods and beverages since the beginning of human history. Their use in hiding smells, attracting
the attention of others, controlling health problems, and providing welfare to people and animals
shows a cultural and economic status. Essential oils are usually liquid, transparent, multicolored,
and complex. The existing compounds they contain are volatile. These compounds are
characterized by a strong odor and are secondarily synthesized to protect plants from microbes
and insects