Dissolved oxygen amperometric sensor based on layer-by-layer assembly using host-guest supramolecular interactions

摘要

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using the host-guest binding of a supramolecular complex at a host surface by combining a self-assembled monolayer (SAM) of mono-(6-deoxy-6-mercapto)-β-cyclodextrin (PCDSH), iron (III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeTMPyP) and cyclodextrin-functionalized gold nanoparticles (CDAuNP). The supramolecular modified electrode showed excellent catalytic activity for oxygen reduction. The reduction potential of oxygen was shifted about 200 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare gold electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves probably 4-electrons with a rate constant (k_(obs)) of 7 x 10~4 mol~(-1) Ls~(-1). A linear response range from 0.2 up to 6.5 mg L~(-1), with a sensitivity of 5.5μL A Lmg~(-1) (or 77.5μA cm~(-2) L mg~(-1)) and a detection limit of 0.02 mg L~(-1) was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 3.0% for 10 measurements of a solution of 6.5 mgL~(-1) oxygen.