Measurement of dioxygen by electrocatalytic reduction on microelectrodes modified with Nafion and methyl viologen.
Nafion/methyl viologen (MV) has been chemically modified on a gold disk microelectrode (GDME). The electrochemistry of the Nafion/MV modified GDME is investigated by cyclic voltammetry (CV). Linear sweep voltammetry (LSV) and differential pulse amperometry (DPA) show that the Nafion/MV modified GDME exhibits very high electrocatalytic activity toward dioxygen reduction with good reproducibility and high sensitivity. The electrocatalytic peak current is found to be linear with the dioxygen concentration in the range of 3.44x10(-7) to 2.59x10(-4) mol l(-1) (at 25 degrees C), with a correlation coefficient of 0.9978. The detection limit (signal/noise=3) is calculated to be 0.19 mumol l(-1). The response time of the microsensor for dioxygen measurement is less than 15 s. For ten parallel measurements for 8.50 mumol l(-1) dioxygen, the relative standard deviation (RSD) is found to be 2.7%. The sensitivity of the microsensor is 0.17 nA mumol(-1) l(-1). This microsensor has been successfully employed to measure the concentration of dioxygen in real samples. The quantity of dioxygen, released from the three kinds of chloroplasts of plant leaves under different illumination, is monitored by the Nafion/MV modified gold microsensor. In order to survey the dioxygen concentration in vivo, a Nafion/MV modified carbon fiber microelectrode (CFME) is fabricated by a modification procedure similar to that of the Nafion/MV GDME. As a preliminary test, the dioxygen levels in the different areas of rat brain are determined by the Nafion/MV modified carbon fiber microsensors. The mechanism of the catalytic reaction is also addressed.