Catalytic metals, ascorbate and free radicals: combinations to avoid.
Trace levels of transition metals can participate in the metal-catalyzed Haber-Weiss reaction (superoxide-driven Fenton reaction) as well as catalyze the oxidation of ascorbate. Generally ascorbate is thought of as an excellent reducing agent; it is able to serve as a donor antioxidant in free radical-mediated oxidation processes. However, as a reducing agent it is also able to reduce redox-active metals such as copper and iron, thereby increasing the pro-oxidant chemistry of these metals. Thus ascorbate can serve as both a pro-oxidant and an antioxidant. In general, at low ascorbate concentrations, ascorbate is prone to be a pro-oxidant, and at high concentrations, it will tend to be an antioxidant. Hence there is a crossover effect. We propose that the "position" of this crossover effect is a function of the catalytic metal concentration. In this presentation, we discuss: (1) the role of catalytic metals in free radical-mediated oxidations; (2) ascorbate as both a pro-oxidant and an antioxidant; (3) catalytic metal catalysis of ascorbate oxidation; (4) use of ascorbate to determine adventitious catalytic metal concentrations; (5) use of ascorbate radical as a marker of oxidative stress; and (6) use of ascorbate and iron as free radical pro-oxidants in photodynamic therapy of cancer.
Buettner
G R
GR
ESR Facility and Radiation Research Laboratory, University of Iowa, Iowa City, 52242-1101, USA.
Jurkiewicz
B A
BA
D000818:Animals; D000975:Antioxidants; D001205:Ascorbic Acid; D002384:Catalysis; D002614:Chelating Agents; D005609:Free Radicals; D006801:Humans; D008670:Metals; D051379:Mice; D016877:Oxidants; D010084:Oxidation-Reduction; D018384:Oxidative Stress; D012867:Skin / Q000378:metabolism / Q000528:radiation effects; D014466:Ultraviolet Rays
D000975:Antioxidants; D002614:Chelating Agents; D005609:Free Radicals; D008670:Metals; D016877:Oxidants; D001205:Ascorbic Acid