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Chlorophyll a π-Cation Radical as Redox Mediator in Superoxide Dismutase (SOD) Mimetics
Authors:Dr Łukasz Orzeł  Dr Dorota Rutkowska-Zbik  Prof Rudi van Eldik  Prof Leszek Fiedor  Prof Grażyna Stochel
Institution:1. Faculty of Chemistry, Jagiellonian University, Kraków, Poland;2. Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Kraków, Poland;3. Faculty of Biochemistry, Biophysics and Biotechnology, Jagiellonian University, Kraków, Poland
Abstract:The extensive speciation of copper(II) chloride in organic solvents varies with concentration, temperature, pressure and oxygen content, providing the ability to switch between different chlorophyll transmetalation pathways. We found that one of them is exceptionally suitable for the formation and stabilisation of the chlorophyll π-cation radical. This is due to unique redox cycling, which is coupled to the generation and transformation of various reactive oxygen species. In the presence of a proton donor, our system shows behavior which resembles that of superoxide dismutase (SOD). Regardless of light, chlorophyll acts as an electron transfer mediator.
Keywords:chlorophyll a  π-cation radical  reactive oxygen species  redox cycling  SOD mimicking
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