The excitonic response
between nanomaterials is distance-dependent,
and thus, interparticle distance is a key factor in fabricating diverse
photoelectrochemical (PEC) systems. Current studies focus on DNA-mediated
regulation of interparticle distance. However, limited by high demands
of base-pairing and flexibility of DNA, it is hard for DNA to achieve
precise regulation, especially in a short distance. To pursue better
PEC performances in bioanalyses, alternative biological materials
should be explored to replace DNA as new “distance controllers”.
In this work, a peptide with three functional sequences is designed
to control interparticle distance between positive-charged Au nanoparticles
((+) AuNPs) and negative-charged CdTe quantum dots ((−) CdTe
QDs). Relying on the function of binding sequence, (+) AuNPs and (−)
CdTe QDs may be separated to a certain distance by the multifunctional
peptide. In this case, the excitonic response is relatively weak,
and an evident PEC response can be observed. Because it contains the
substrate sequence of caspase-3, the peptide is cleaved in the presence
of caspase-3. As a result, without the support of intact peptide,
electrostatic attraction plays a dominant role, leading to the aggregation
of oppositely charged AuNPs and CdTe QDs, which strengthens the excitonic
response and attenuates the PEC response. On the basis of these principles,
a novel PEC approach was fabricated to sensitively quantify caspase-3.
Meanwhile, caspase-3 in staurosporine-treated A549 cells are also
determined by the approach, and the obtained results agree well with
the fluorescent intensity of confocal images, manifesting that the
proposed PEC method can monitor apoptosis in a label-free strategy.
Overall, the study reveals the capability of peptides in controlling
interparticle distance of nanomaterials, which may accelerate the
development of peptide-based PEC analytical methods.