Download - Anti Oxidants Cosmetics
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M Zaky
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CONTOH BAHAN ALAM SEBAGAIANTIOKSIDAN
MANGGIS (MANGOSTEEN) SPIRULINA KUNYIT
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KEDELAI (ISOFLAVONES) MENGKUDU BIJI ANGGUR
BLUEBERRY RASPBERRY WOLFBERRY
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What Do We Concern Frequently in Our Life?
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Can We Slow Down the Clock of Aging?
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What is Aging ?Aging is mainly due to the cumulative result of free
radical oxidative damage of the cells and tissues of
the body that arises primarily as a result of aerobicmetabolism.
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• Lipid oxidation of membranes
• Formation of age pigment
• Cross linkage of proteins
• DNA damage
• Mitochondrial function decline
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Aging Mechanism
Aging is a complex multifactorial process in
which free radical oxidative damage plays an
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very mportant ro e, ut ree ra ca ox at vedamage may not be the exclusive mechanism
of physiological decline.
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Free Radicals
• Free radicals are produced during variousmetabolic processes
•
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radicals react with lipids (membranes),
proteins and DNA
• Can cause extensive cell damage• Damage repair of DNA can lead to mutation
• Mutation can lead to cancer
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Reactive Oxygen Species
• Oxygen centered radicals : superoxide anion (·O2-),
hydroxyl radical (HO·), hydroperoxyl radical
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(HOO·), peroxyl radical (ROO·)
• Oxygen centered non-radicals : hydrogen peroxide
(H2O2), singlet oxygen (1O2)
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Antioxidants are classified into five types :
Primary antioxidant s: those compounds, mainly phenolicsubstances, that terminate the free radical chains in lipid
oxidation.For example :
1. Natural antioxidant : tocopherols,
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Synthetic antioxidant butylated hydroxyanisole (BHA), butylatedhydroxytoluene (BHT), etc, belong to this group, and functionas a electron donors.
2. Oxygen scavengers, which react with oxygen, and can thusremove it in a closed system. The regeneration of phenolicantioxidants, an entirely different mechanism. For example,ascorbic acid (vitamin C), ascorbyl palmitate etc.
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3. Secondary antioxidants which function by decomposingthe lipid hydroperoxides into stable end products. Forexample, dilauryl thiopropionate and thiodipropionicacid.
4. Enzyme antioxidants which function either by removingdissolved oxygen. For example, superoxide dismutase,
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, , .
5. Chelating agents which chelate metallic ions such ascopper and iron that promote lipid peroxidation through
a catalytic action. The chelates are sometimes referredto as synergist since they greatly enhance the action ofphenolic antioxidants. For example, citric acid, aminoacids, EDTA, etc.
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R-OO-H
Initiation
Pro tion
O2Carbon-centered Free Radical
Initiating
Event
R••••
ChainLipid Hydroperoxide
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HH
=
R-H ROO••••
Peroxyl Radical Terminationvia Antioxidant
α−TO••••α−TOH
Reaction
R-OO-HLipid Hydroperoxide
Polyunsaturated fat
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R
R
.OH
H
H2O +
R
R
.
R
O2
R
R
R
OO.
R
+
R
+
1. Initiation
2. Propagation
Hydrogen Abstraction
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R .ROO
.R R
OOH
R
R
. R
R.+
R
R
R
R
3. Termination
Lipid crosslinkage
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Free RadicalsFree Radicals: Any species capable of independent
existence that contains one or more
unpaired electrons A molecule with an unpaired electron
in an outer valence shell
R3C. Carbon-centered
R3N. Nitrogen-centered
R-O. Oxygen-centeredR-S. Sulfur-centered
ProoxidantsProoxidants
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Non-Radicals: Species that have strong oxidizing
potential
Species that favor the formation ofstrong oxidants (e.g., transitionmetals)
H2O2 Hydrogen peroxideHOCl- Hypochlorous acid
O3 Ozone1O2 Singlet oxygen
ONOO- Peroxynitrite
Men+ Transition metals
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Exogenous sources of free radicalsExogenous sources of free radicals
• RadiationUV light, x-rays, gamma rays
• Chemicals that react to form peroxidesOzone and singlet oxygen
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• em ca s a promo e superox e orma onQuinones, nitroaromatics, bipyrimidiulium herbicides
• Chemicals that are metabolized to radicals
e.g., polyhalogenated alkanes, phenols, aminophenols• Chemicals that release iron
ferritin
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Reactive Oxygen Species.
The 1- 5 % consumed oxygen is converted to reactive
oxygen during normal aerobic metabolism.
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Effect of Reactive Oxygen Species on
Degenerative Diseases
• Dermatitis
• Age pigment
• Heart attack • Cataractogenesis
• Retinal damage
• Hepatitis
• Liver injury
HeartGastro intestinal SkinEye
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Reactive Oxygen SpeciesJoints
• Arthritis
Lung
• Asthma
• Hyperoxia
Multiorgan failure
• Cancer
Vessels
• Atherosclerosis
• Vasospasms
Teeth
• Periodontis
Brain
• Trauma
• Stroke
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How to Slow Down Aging?
Only 9% of Americans eat the recommended fiveservings of fruits and vegetables per day, therefore
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slow down aging process by increasing
consumption of fruits and vegetables.
The antioxidants in apple keep doctors away.
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Pro-oxidants
• Irradiation -- γ -ray, x-ray, and ultra violet rays
• Inflammation and macrophages
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,
• Autoxidation of electron transport carriers
• Air pollutants
• Metal catalyzed oxidation systems
• Lipid peroxidation
• Glycation and glycoxidation products
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Antioxidants
Proteins and Enzymes:
Superoxide dismutase, catalase, glutathione peroxidase,
glutathione transferase, glutathion reductase, thiol specific
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,
Metabolites and Vitamins:
Vitamin C and E, Bilirubin, Uric Acid, GSH/GSSG.
NADH/NAD, Mg, Mn, Zn, Lipoic Acid and Carotenoids
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Antioxidant Mechanisms
• Hydrogen donating compounds
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• Enzymes
• Metal chelators
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3O2 + SensitizerEndoperoxide
Enzyme
Singlet Oxygen Formation
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H2O2 + O2-Ozone
OH + O2-
1O2
O2- + O2
-H2O2+ HO2- . .
.
..
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Oxidative Stress
The increase of the reactive oxygen species which leads
to oxidative damage in foods or body.
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AntioxidantReactive
Oxygens
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Antioxidants
RO•, •O2-
HO•, HOO•, H2O2
ROO• , 1O
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RO•, ·O2-
HO· HOO·
H2O2,
ROO•, 1O2,
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VariousVariousVariousVarious CosmeticsCosmeticsCosmeticsCosmetics Rich inRich inRich inRich inAntioxidantAntioxidantAntioxidantAntioxidant
Strating Material Process
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Antioxidant Enrichment In vitro Antioxidant Evaluation
Antioxidant Stability
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Biological Activities of Phytochemicals
• Antioxidants Carotenoids tocopherol
catechins quercetin
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• Anticancer Agent s Isoflavones lignans
• DNA repair Agents Vanillin cinnamaldehyde
coumarin anisaldehyde
daidzein
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Naturally Occurring Tocopherols
αααα-tocopherol
-
CH3
CH3
CH3
H CH3CH3CH3CH3 H
HO
H3CO
phytyl tail
CH3
HO
h t l tail
2R 4’R 8’R
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γ γγ γ -tocopherol
δδδδ-tocopherol
CH3
CH3CH3
O
CH3
HO
H3CO
phytyl tail
CH3 CH3
HO
O
phytyl tail
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Tocopherol as an antioxidant
O
R3
R2
HO
R1
Chromane Head
Phythyl Tail .
OCH 3
CH 3
O
CH 3
(CH2)3CH(CH2)3CH(CH2)3CH(CH3)2
CH 3 CH 3
R•••• + TOH → → → → RH + TO••••
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R1 R2 R3
α CH3 CH3 CH3
β CH3 H CH3
γ H CH3 CH3
δ H H CH3
3
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Tocopherol Functions• Specific role in a required metabolic
function has not been found
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• a or unc on appears o e as a a -soluble, “ chain-breaking” antioxidant
– Peroxyl radical scavenger
– Protects polyunsaturated fatty acids(PUFAs) within membranes and
lipoproteins
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Resonance of Antioxidant Radicals
O H
O. ORO , ROO ROH , ROOH••
C (CH )33
OCH3
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OCH3 O C H3
O C H3 O CH3
.
O
.O
.
C (CH )33 C (CH )33
C (CH )3
3C (CH )3
3
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• Transfer of phenolic hydrogen to reactive
Antioxidant Mechanism of Tocopherol
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• Scavenging of singlet oxygen
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TerpenesCommon examples and plant parts:
• Cinnamon –in bark
• Peppermint – in “hairs” on leaves
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• Lemon - in the rind
• Rose – in the petals
• Ginger – in the rhizome
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CAROTENOIDS
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Quenching Mechanism of β- Caroteneon Singlet Oxygen
1O2 +1β-Carotene 3O2 +
3β-CaroteneEnergy transfer
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3 β-Carotene Radiationless Energy transfer 1β-Carotene
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CH3CH2
CH3O
Eugenol Anethole
Shikimic Acid Natural Products
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OMeOH
OH
CO2CH
3
Methyl SalicylateCinnamaldehyde
CHO
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O
OH
OH
O
O
OH
OH
OH
O
Shikimic Acid Flavones
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O
OH
OH
OH
OH
+
An Anthocyanidin
An IsoflavoneA Flavone
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Anthocyanidin
R1
R1 R2 R3
Pelargonidin H OH H
ANTHOCYANINS
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OOH
OH
OH
R3
+Cyanidin OH OH H
Delphinidin OH OH OH
Peonidin O-Me OH H
Petunidin O-Me OH OH
Malvidin O-Me OH O-Me
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Soybean
O
R OOH1
2R
CO
H
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Genistein OH OH
Genistin OH O-glucose
Daidzein H OH
Daidzin H O-glucose
Isoflavone R1 R2
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Tea
O HO H
O H
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Epicatechin
HO
O H
O
O H
O H
HO
O H
O
O H
O H
Epigallocatechin
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1. Ferric Thiocyanate method or
Ferric Reducing Antioxidant Power (FRAP)or Cupric Reducing Antioxidant
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ROOH + 2 Fe++ + 2 H+ C C
OH OH
+ 2 Fe+++
2 Fe+++
+ 6 CNS-
Fe Fe (CNS)6 [ ]
ChromophoreChromophoreChromophoreChromophore (500 nm)
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N N
NO2
NO2
.N N
NO2
NO2H
2. By DPPH (1,1-Diphenyl-2-Picrylhydrazyl)
(Free Radical Scavenging )
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NO2 NO2
DPPHDPPHDPPHDPPH
Chromophore (532 nm)
Assesment of radical scavenging activity : the activeconstituents will bleach the purple of DPPH giving awhite-yellowish color
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Oxidation Mechanism
Two types of oxidation mechanism incosmetics:
-
ce of oxygen via a radical-chain mechanism
Non-radical oxidation proceeds in thepresence of ozone, single oxygen, etc.
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AUTO OXIDATION
Auto-oxidation is a radical chain reaction occurring due to the presence of 20%
rtant reaction to be noted to prevent theoxidation of cosmetics. Auto-oxidationresponse is accelerated or inhibited bymany factors including heat, light (uv),metal ions, water, proteins, etc.
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Prevention of oxidation
Suppress the initiation and chain transfer reaction phases.
n a on orage n a coo oca on, using UV absorbents, Using Chelating Agent
Addition of compounds to prevent generation of radicals: Tocopherol, BHT,BHA, Gallic Acid esters, NDGA (nordih
ydroguaiaretic acid)2014-11-10 43
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Sesquestering Agents
Metalic ions can cause changes in perfume and color and can also promot
block the action of pharmaceutical agent and can cause transparency to be lost through precipitaion, for lotions
etc. Compounds used to deativate these metallic ions are called sequester
ing agents.2014-11-10 44
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Sesquestering Agents
Sodium Edetat (EDTA)
Phosphoric Acid
Ascorbic acid
Succinic acid
Gluconic acid Sodium polyphosphat
Sodium metaphosphate2014-11-10 45