Polydopamine-embedded Cu(2-x)Se nanoparticles as a sensitive biosensing platform through the coupling of nanometal surface energy transfer and photo-induced electron transfer.

Full understanding and easy construction of specific biosensing principles is necessary for disease diagnostics and therapeutics in the hope of creating new types of biosensors. Herein, we developed a new conceptual nanobiosensing platform by coupling nanometal surface energy transfer (NSET) and photo-induced electron transfer (PET) with polydopamine-embedded Cu(2-x)Se nanoparticles (Cu(2-x)SeNPs@pDA) and DNA-conjugated fluorescent organic dyes. The new prepared Cu(2-x)SeNPs@pDA has intense and broad localized surface plasmon resonance (LSPR) absorption over UV to near infrared (NIR) wavelengths, with different affinities toward ssDNA versus dsDNA. It also exhibits a high multiplexed fluorescence quenching ability, and thus can act as an acceptor in the energy transfer and electron transfer interactions between Cu(2-x)SeNPs@pDA and fluorescent organic dyes. As a proof of concept, a new biosensing platform has been successfully developed to target biomacromolecules such as DNA and proteins, in which the NSET and PET interactions between Cu(2-x)SeNPs@pDA and three different DNA-conjugated fluorescent dyes have been identified using steady-state and time-resolved fluorescence. A simple mathematical model was further applied to simulate the respective contributions of the coexisting NSET and PET to the total quenching observed for each DNA-conjugated dye in this sensing system. This study highlights the importance of understanding the mechanistic details of NSET and PET coupling processes, and the disclosed coupling mechanism of NSET and PET (NSET©PET) in the systems of Cu(2-x)SeNPs@pDA with wide wavelength range dyes provides new opportunities for sensitive biosensing applications.