Reconfiguration of
chemical sensors, intended as the capacity of
the sensor to adapt to novel operational scenarios, e.g., new target
analytes, is potentially game changing and would enable rapid and
cost-effective reaction to dynamic changes occurring at healthcare,
environmental, and industrial levels. Yet, it is still a challenge,
and rare examples of sensor reconfiguration have been reported to
date. Here, we report on a reconfigurable label-free optical sensor
leveraging the versatile immobilization of metal ions through a chelating
agent on a nanostructured porous silica (PSiO2) optical
transducer for the detection of different biomolecules. First, we
show the reversible grafting of different metal ions on the PSiO2 surface, namely, Ni2+, Cu2+, Zn2+, and Fe3+, which can mediate the interaction
with different biomolecules and be switched under mild conditions.
Then, we demonstrate reconfiguration of the sensor at two levels:
1) switching of the metal ions on the PSiO2 surface from
Cu2+ to Zn2+ and testing the ability of Cu2+-functionalized and Zn2+-reconfigured devices
for the sensing of the dipeptide carnosine (CAR), leveraging the well-known
chelating ability of CAR toward divalent metal ions; and 2) reconfiguration
of the Cu2+-functionalized PSiO2 sensor for
a different target analyte, namely, the nucleotide adenosine triphosphate
(ATP), switching Cu2+ with Fe3+ ions to exploit
the interaction with ATP through phosphate groups. The Cu2+-functionalized and Zn2+-reconfigured sensors show effective
sensing performance in CAR detection, also evaluated in tissue samples
from murine brain, and so does the Fe3+-reconfigured sensor
toward ATP, thus demonstrating effective reconfiguration of the sensor
with the proposed surface chemistry.