Wavelength-dependent photoelectrochemical response demonstrated by the determination of acetaminophen and rutin in differential molecularly imprinted polymers strategy

Herein, the excitation wavelength-dependent responses of the molecularly imprinted polymer (MIP) photoelectrochemical (PEC) sensors were investigated, using acetaminophen (AP), rutin (RT) and perfluorooctanoate (PFOA) as the model templates, pyrrole as functional monomer, CuInS2@ZnS/TiO2 NTs as the basic photoelectrode. With wavelength λ > 240 nm, the photocurrent of MIPPFOA enhanced at higher concentrations of PFOA. With increasing AP concentration, the photocurrents of MIPAP could decline with λ < 271 nm, not change at λ = 270 nm, or increase with λ > 270 nm. As RT concentration increased, the photocurrents of MIPRT could decrease (λ < 431 nm), not change (λ = 431 nm) or increase (λ > 431 nm). The PEC responses depend on the comprehensive interaction of two contrary mechanisms from the template molecules within the MIP membrane. The photocurrent is enhanced by the role of the electron donor for photo-generated holes but attenuated due to the steric hindrance effect and the excitation light intensity loss via absorption or scattering. The apparent molar absorption coefficient of AP and RT within MIP membranes are 9.1–19.4 folds of those measured from dilute solutions. By using a routine UV lamp as the light source, the photocurrents of MIPRT at 254 nm and MIPAP at 365 nm were used to determine RT and AP, with the detection limits of 5.3 and 16 nM, respectively. The interference from the non-specific adsorption of interferents on the surfaces of MIPAP and MIPRT was reduced by one order of magnitude via a differential strategy.