The use of a photocatalyst (photosensitizer)
which produces singlet
oxygen instead of enzymes for oxidizing analytes creates opportunities
for designing cost-efficient and sensitive photoelectrochemical sensors.
We report that perfluoroisopropyl-substituted zinc phthalocyanine
(F64PcZn) interacts specifically with a complex phenolic
compound, the antibiotic rifampicin (RIF), but not with hydroquinone
or another complex phenolic compound, the antibiotic doxycycline.
The specificity is imparted by the selective preconcentration of RIF
in the photocatalytic layer, as revealed by electrochemical and optical
measurements, complemented by molecular modeling that confirms the
important role of a hydrophobic cavity formed by the iso-perfluoropropyl groups of the photocatalyst. The preconcentration
effect favorably enhances the RIF photoelectrochemical detection limit
as well as sensitivity to nanomolar (ppb) concentrations, LOD = 7
nM (6 ppb) and 2.8 A·M–1·cm–2, respectively. The selectivity to RIF, retained in the photosensitizer
layer, is further enhanced by the selective removal of all unretained
phenols via simple washing of the electrodes with pure buffer. The
utility of the sensor for analyzing municipal wastewater was demonstrated.
This first demonstration of enhanced selectivity and sensitivity due
to intrinsic interactions of a molecular photocatalyst (photosensitizer)
with an analyte, without use of a biorecognition element, may allow
the design of related, robust, simple, and viable sensors.