In
this work, hydrazine-functionalized perylene diimide derivative
supramolecular (HPDS), a novel self-enhanced donor–acceptor-donor
(D-A-D) type aggregates with excellent photoelectric activity, was
synthesized by a facile one-pot green route and further applied in
construction of coreactant-free photoelectrochemical (PEC) biosensor
for ultrasensitive DNA assay. Impressively, the HPDS formed by D-A-D
units not only possessed effectively shorted electron-transfer path
between donor and acceptor, but also presented a desiring aggregate
state via the π–π stacking of perylene core and
hydrogen bonding of the terminal moiety, thereby acquiring a high
density electron flow for generating the extremely high PEC signal.
Experimental data showed that the well film-formed HPDS aggregate
could produce an exciting photocurrent intensity about 6-fold stronger
than that of precursor perylene dianhydride with donor N2H4 in detection buffer and even 12-fold than that of perylene
dianhydride only. In this respect, the resultant HPDS aggregate as
a novel self-enhanced PEC signal tag was adopted to fabricate the
coreactant-free PEC biosensor with the help of target dual-recycling-induced
bipedal DNA walker cascade amplification strategy for ultrasensitive
DNA (a fragment of TP53 gene) assay. The proposed biosensor showed
a high sensitivity with a low detection limit down to femtomole level,
providing a new avenue for sensitive bioanalysis and clinical diagnosis.