Photoelectrochemical Approach to Apoptosis Evaluation via Multi-Functional Peptide- and Electrostatic Attraction-Guided Excitonic Response.

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.