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Titanium dioxide (TiO 2 ) is a unique material for biosensing applications due to its capability of hosting enzymes. For the first time, we show that TiO 2 can accumulate reactive oxygen species (ROS) under daylight irradiation and can support the catalytic cycle of horseradish peroxidase (HRP) without the need of H 2 O 2 o be present in the solution. Phenolic compounds, such as hydroquinone (HQ) and 4-aminophenol (4-AP), were detected amperometrically in flow-injection analysis (FIA) mode via the use of an electrode modified with TiO 2 impregnated with HRP. In contrast to the conventional detection scheme, no H 2 O 2 was added to the analyte solution. Basically, the inherited ability of TiO 2 o generate reactive oxygen species is used as a strategy to avoid adding H 2 O 2 in the solution during the detection of phenolic compounds. Electron paramagnetic resonance (EPR) spectroscopy indicates the presence of ROS on titania which, in interaction with HRP, initiate the electrocatalysis toward phenolic compounds. The amperometric response to 4-AP was linear in the concentration range between 0.05 and 2 μM. The sensitivity was 0.51 A M -1 cm -2 , and the limit of detection (LOD) 26 nM. The proposed sensor design opens new opportunities for the detection of phenolic traces by HRP-based electrochemical biosensors, yet in a more straightforward and sensitive way following green chemistry principles of avoiding the use of reactive and harmful chemical, such as H 2 O 2 .

analytical chemistry

Amperometric Flow-Injection Analysis of Phenols Induced by Reactive Oxygen Species Generated under Daylight Irradiation of Titania Impregnated with Horseradish Peroxidase