A fluorescent approach for detecting and measuring reduction reaction byproducts near cathodically-biased metallic...

During tribocorrosion of biomedical alloys, potentials may shift cathodically across the metal-oxide-electrolyte interface resulting in the increased reduction of local oxygen and water molecules. The products of reduction are thought to include reactive oxygen species (ROS) as well as hydroxide ions. Using fluorescent probes, developed for labeling intracellular ROS-based hydroxyl radicals (OH·) and hydrogen peroxide (H₂O₂), ROS generation due to reduction reactions at cathodically biased CoCrMo alloy surfaces was measured directly. Using terephthalic acid (TA) and pentafluorosulfonylbenzene-fluorescein (PFF) as fluorescent dosimeters, it was found that OH· and H₂O₂ concentrations increased up to 16 h and 2 h, respectively. Decreases in fluorescence past these time points were attributed to the continuous onset of reduction reactions consuming both the ROS and/or dosimeter. It was also found that voltages below and including -600 mV (vs. Ag/AgCl) produced measurable quantities of H₂O₂ after two hours of polarization, with concentrations increasing with decreasing potentials up to -1000 mV. The detection and quantification of ROS in a clinical setting could help us better understand the role of ROS in the inflammatory response as well as their impact on corrosion behavior of biomedical alloys.