Lighting up Electrochemiluminescent Inactive Dyes by Intramolecular Resonance Energy Transfer

By virtue of near-zero optical background and photobleaching, electrochemiluminescence (ECL), an optical phenomenon excited by electrochemical reactions, has drawn extensive attention in both fundamental studies and wide applications especially of ultrasensitive bioassay. Developing diverse ECL emitters is crucial to unlock their multiformity and performances, but remains a formidable challenge, due to the rigorous requirements for ECL. Herein, we report a general intramolecular ECL resonance energy transfer (iECL-RET) strategy to light up ECL-inactive dyes in aqueous solutions using an existing high-performance ECL initiators. As a proof-of-concept, a series of luminol donor-dye acceptor based ECL emitters with near unity RET efficiency and coarse/fine tunable emission wavelengths were demonstrated. Different to previous exploitation of new molecule single-handedly to address all the prerequisites of ECL, each unit in the proposed ECL ensemble performed maximally its own functions. The iECL-RET strategy would greatly expand the family members of ECL emitters for more demanding future applications.

Plasmonic nanofocusing spectral interferometry

We describe and demonstrate a novel experimental approach to measure broadband, amplitude- and phase-resolved scattering spectra of single nanoparticles with 10-nm spatial resolution. Nanofocusing of surface plasmon polaritons (SPPs) propagating along the shaft of a conical gold taper is used to create a spatially isolated, spectrally broad nanoscale light source at its very apex. The interference between these incident SPPs and SPPs that are backpropagating from the apex leads to the formation of an inherently phase-stable interferogram, which we detect in the far field by partially scattering SPPs off a small protrusion on the taper shaft. We show that these interferograms allow the reconstruction of both the amplitude and phase of the local optical near fields around individual nanoparticles optically coupled to the taper apex. We extract local light scattering spectra of particles and quantify line broadenings and spectral shifts induced by tip-sample coupling. Our experimental findings are supported by corresponding finite-difference time-domain and coupled dipole simulations and show that, in the limit of weak tip-sample coupling, the measurements directly probe the projected local density of optical states of the plasmonic system. The combination of a highly stable inline interferometer with the inherent optical background suppression through nanofocusing makes it a promising tool for the locally resolved study of the spectral and temporal optical response of coupled hybrid nanosystems.