Long-Lifetime Metal–Ligand pH Probe

Abstract

We describe the synthesis and fluorescence spectral characterization of a pH-sensitive metal–ligand complex, [Ru(deabpy)(bpy)2]2+, where deabpy is 4,4′-diethylaminomethyl-2,2′-bipyridine. This metal–ligand complex (MLC) was found to display pH-dependent intensities, emission spectra, and decay times, with the changes centered near the physiological useful pH value of 7.5. The apparent pKavalues were not found to be dependent on ionic strength. The compound was found to be useful for lifetime-based sensing by phase-modulation fluorometry. Global analysis of the intensity decays over a range of pH values revealed two decay times of 235 and 380 ns, associated with the protonated and unprotonated forms, respectively. Because of its long decay time, optical pH measurements could be accomplished by phase-modulation fluorometry with a conveniently low modulation frequency of 700 kHz. The lifetime data were obtained with either a amplitude-modulated laser or with an amplitude-modulated blue-light-emitting diode. This pH-sensitive complex also displays a modest spectral shift with change in pH, allowing its use as a wavelengthratiometric MLC probe. One can imagine lifetime sensors for a variety of blood cations and point-ofcare assays based on long-lifetime metal–ligand complexes and simple solid-state light sources and detectors.