Self‐assembly Induced Enhanced Electrochemiluminescence of Copper Nanoclusters Using DNA Nanoribbon Templates

Copper nanoclusters (CuNCs) are attractive electrochemiluminescence (ECL) emitters as Cu is comparatively inexpensive, nontoxic, and highly abundant. However, their ECL yield is relatively low. Herein, we report that orderly self‐assembly of CuNCs using DNA nanoribbon as the template (DNR/CuNCs) conferred the CuNCs with improved ECL properties compared with individual CuNCs in both annihilation and co‐reactant processes. The DNR/CuNCs resulted in a high ECL yield of 46.8 % in K2S2O8, which was ≈68 times higher than that of individual CuNCs. This strategy was successfully extended to other ECL emitters, such as gold nanoclusters and the Ru(bpy)32+/TPrA system. Furthermore, as an application of DNR/CuNCs, a DNR/CuNC‐based ECL biosensor with higher sensitivity was constructed for dopamine determination (two orders of magnitude lower than that previously reported), showing that DNR/CuNCs have a potential for application in ECL bioanalysis as a new type of superior luminophore candidate. The concept of self‐assembly induced enhanced electrochemiluminescence (SIEECL) using programmable DNA nanoribbon was proposed for the first time. This novel concept is confirmed in various ECL emitters, such as copper nanoclusters, gold nanoclusters and Ru(bpy)32+/TPrA system. Accelerated electron transfer reaction and reduced energy gap contribute to the enhancement of ECL.