Free Radicals, Antioxidants, & Ascorbate (Module 3 Lecture 2) Flashcards
What is a molecule with an oxygen radical called?
ROS (reactive oxygen species)
Oxygen’s structure favors additions of elections how?
One at a time, forming oxygen free radicals
List 5 ROSs.
- Superoxide (O2*)
- Hydroxyl radical (OH*)
- Nitric oxide (NO*)
- Hydrogen peroxide (H2O2)
- Hypochlorous acid (HOCl)
Describe the pathway from oxygen to water that includes oxygen free radicals.
oxygen + e- –> superoxide + e- + 2H+ –> hydrogen peroxide + e- + H+ –> water + hydroxyl radical + e- –> water
What is the most potent ROS?
hydroxyl radical OH*
What are two nonezymatic pathways to forming a hydroxyl radical?
- hydrogen peroxide + ferrous iron –> Fe3+ + OH- + OH* (Fenton rxn)
- hydrogen peroxide + superoxide + H+ –> O2 + H2O + OH* (Haber-Weiss rxn)
How do enzymes that use oxygen protect the body from ROS?
By keeping the ROS intermediates tightly bound at the active sites and only releasing ROSs in the form of H2O2.
Name two types of enzymes that use O2
- Oxygenase
2. Oxidase
What do oxygenases do?
Incorporate oxygen directly into the substrate.
What do oxidases do?
Transfer electrons to O2 to reduce it to H2O or H2O2
Where is cytochrome c oxidase found?
In the mitochondrial cristae as Respiratory Complex IV (last step of e- transport chain)
Name two types of oxygenases
- Monooxygenases
2. Dioxygenases
What is the difference between a monooxygenase and a dioxygenase?
Monooxygenases use one of the O2 atoms for the substrate and the other to oxidize a cofactor, whereas dioxygenase incorporates both oxygens into the substrate, usually making a highly reactive peroxide as an immediate product.
Give one detailed example of a dioxygenase.
5-lipoxygenase, which makes 5-hydroperoxiarachidonic acid (5-HPETE) from arahidonic acid (20:4, omega 6)
Note: 5-HPETE is a precursor for active lipids like leukotrienes LTB4 and LTC4 used in inflammatory responses.
Give one detailed example of a monooxygenase.
Cytochrome P450 superfamily of monooxygenases work to hydroxylate:
1. Steroids (by modifying cholesterol rings)
2. Fatty acids
3. Xenobiotics (drugs and foreign chemicals)
4. Carcinogens
Note: 450 in name denotes the wavelength nm at which the prosthetic group’s heme absorbs light on all enzymes in this superfamily.