anti oxidants cosmetics

8/17/2019 Anti Oxidants Cosmetics

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2014-11-10 1

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

anti oxidants cosmetics

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