A cellular NO sensor based on aggregation-induced electrochemiluminescence and photoelectron transfer of a novel ruthenium(II) complex

Abstract

Here, we present a dual amplification strategy of electrochemiluminescence (ECL) based on aggregation-induced and photoelectron transfer (PET) inhibition using a designed ruthenium-based complex for the highly sensitive detection of nitric oxide (NO). A novel ruthenium(II) complex ([Ru(phen)2(DA-phen)]2+, DA-phen: 5,6-diamino-1,10-phenanthroline) was synthesized that uses the O-diaminophenyl group for specific recognition of NO and the ruthenium metal center with 1,10-phenanthroline as the luminophore. In the first step, the 1,10-phenanthroline groups function as the aggregation part. Increasing the volume fraction of a poor solution (H2O: fw, v%) in the DMSO mixture system from 0% to 80% yielded an increase in the fluorescence (FL) and electrochemiluminescence (ECL) intensities by 3- and 42-fold when compared with the FL and ECL intensities in pure DMSO, respectively. The second step involves a PET process. Reacting the complex with NO in physiological pH aqueous media under aerobic conditions to afford its triazole derivative, [Ru(phen)2(TA-phen)]2+ (TA-phen: 5,6-triazole-1,10-phenanthroline), inhibited the electron transfer process, yielding a remarkable further increase in the FL and ECL efficiencies of the Ru(II) complex. The ECL intensities was 86-fold higher in the presence of NO. This dual amplification strategy enabled the sensitive detection of NO from 1.8 × 10–10 to 1.8 × 10–5 M with a detection limit of 60 pM (S/N = 3) and offered excellent specificity with no detectable interference by RNS and metal ions. Furthermore, selective NO detection in cells was achieved using this complex. Thus, this assay should be suitable for applications in environmental toxicology research and early clinical diagnosis.