Heal Yourself At Home
DIY SOLUTIONS FOR YOUR HEALTH
AOX - ROS Related Links

ANTIOXIDANT / OXIDANT BALANCE Related Links

Health is a Balancing Act Between OXIDANTS and ANTIOXIDANTS

-A Powerful bioxidative tool

- LIFE'S OXYGEN PARADOX

- Meet Dr. ROS Jeckyll

and Mr. ROS Hyde

Dr. ROS Jeckyll

Mr. ROS Hyde

- Where do Body's ROS Come From?

Ÿ ROS Chart

–    Antioxidants - Oxidant Damage Control

ENZYMATICANTIOXIDANTS

NON-ENZYMATIC ANTIOXIDANTS

Chart of Reactive Oxygen Species (ROS)

Chart of ROS and their Metabolites in the Body

O2⁻and H2O2are primary reactive metabolites of oxygen

OH , LOO•, LO•

O2⁻ H2O2which penetrates membranes andcan be transformed to OH HOCl 1O2*

Oxygen 3 O2

A di-RADICAL

How ROS is Formed from Oxygen

Major Source (s) in Body

Products Generated

Superoxide RADICAL O2⁻

Can not easily get into cells

3 O2 is reduced by addition of 1 electron to outer shells

3 O2 - O2⁻

Phagocytic respiratory burst O2 O2⁻+ H2O2

OH 1O2* NO* ONOO⁻

Dismutation of O2⁻

O2⁻ + O2⁻ + 2H+ H2O2 + 1O2

Haber-Weiss Reaction - As reductant of free transition metals:

E.g. iron-catalyzed

(1) O2⁻ + Fe3+ 3 O2 + Fe2+

(2) Fe2+ + H2O2 Fe3+ + OH+OH—

H2O2

Passes easily into cells

3 O2

Dismutation of O2⁻

O2⁻ + O2⁻ + H2O2 + 1O2*

Haber-Weiss Reaction (2) / Fenton Reaction - Main source ofOH in presence of free transition metals:

E.g. Iron-catalyzed

(2) H2O2 Fe2+ OH+ OH—3+

HOCl H2O2 +Cl- HOCl +OH—

1O2* H2O2 + ClGAS 1O2*+ClGAS +H2O

Hydroxyl RADICAL OH

By reduction of H2O2 -)

Haber-Weiss Reaction: O2⁻ and H2O2 in the presence of freetransition metals produce MOST OH: E.g. Iron-catalyzed

(1) O2⁻ + Fe3+ 3 O2 + Fe2+

(2) 2+ + H2O2 3++ OH+OH—

Normally, most iron confined in RBCs

O3and H2O2

2 O3 +H2O2 OH +3 O2

Radiation

Radiobiological damage

Singlet oxygen

1O2*

NON

Passes easily into cells (because it is neutrally charged)

Therapies 3 O2

Sensitizer with light and oxygen.(Basis of PDT for cancer)

3 O2 +Energy 1O2*

→Sens* Sens + 1O2*

uvO2

Transfer the energy to a new molecule - thereby acting as a catalyst for free radical formation.

Reactions with substrate molecules - leading to the formation of a new free radical by oxidation.

(Olefins, dienes, sulphides, aromatics, hetero-aromatics, terpenes, steroids, fatty acids, flavones, tetracyclines, vitamines, amino acids, proteins, nucleic acids, blood and bile pigments, and synthetic polymers)

(1) Ene reaction – H abstraction/O2 addition

Lipid peroxidation:

RH+ 1O2*

ROOH

Unsaturated lipid Hydroperoxide

1,2-dioxetaneEndoperoxide

(3)Oxygenation - unfinished

1O2* reacts with ascorbate, producing H2O2

Enzymatically

catalyzed by

peroxidases

/lipooxigenasesor myeloperoxidase (MPO) - in neutrophils, monocytes, new macrophages.

Or SOD

H2O2 H2O2 + ClGAS 1O2* +ClGAS +H2O

HOCl O2⁻ HOCl O2⁻ Cl⁻ OH 1O2*

HOCl H2O2 HOCl + H2O2 HCl + H2O + 1O2*

Dismutation of O2⁻ or ROO:

O2⁻ O2⁻ 2H+ H2O2 1O2*

(Non-catalyzed, rate pH-dependent)

O2⁻ O2⁻ 2H+ H2O2 3O2

(Enzymatically w/SOD very fast reaction)

ROO + ROO + 2H+ RO + 1O2*

Endogenously

Respiratory burst of phagocytes; By-product of metabolism

Thermo- decomposition of dioxetanes

Phosphite ozonides:

(RO)3PO3 (RO)3PO + 1O2* Endoperoxides:

E.g. 9,10-diphenylanthracene peroxide (DAP)

Hydroperoxides (ROOH) Endoperoxides

React with some metal ions.

Involves breaking C=C bonds E.g. in carotene, chlorophyll, polyunsaturated fatty acids (PUFAs)

Produce Peroxyl ROO

/Alkoxyl Radicals RO Vital for killer action

Ozone

O2⁻ OH;

Peroxide anionO2 2-;

O3 oxidizes/ionizes organic molecules(saturated hydrocarbons, amines, sulfhydryl groups and aromatic compounds) to chiefly aldehydes, ketones, acids or alcohols.

O3 will oxidize metals (except gold, platinum, and iridium) to metal oxides (much easier to remove) –

2Cu2++2H++ O3 2 Cu3++ H2O+O2

O3 changes oxides into peroxides:

SO2 + O3 SO3 + O2

O3 converts cyanides into cyanates

(1000 X less toxic than cyanide):

CN- + O3 CNO- + O2

O3 1O2* O1*

Excited singlet oxygen MOLECULE

1O2*

Excited oxygen ATOM O1*

Chlorine Dioxide

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