A highly selective dual-channel Cu2+ and Al3+ chemodosimeter in aqueous systems: Sensing in living cells and microfluidic flows

Abstract

The design and development of fluorescent chemosensors have recently been the focus of considerable attention for the sensitive and specific detection of environmentally and biologically relevant metal ions in aqueous solutions and in living cells. Herein, we report photophysical results for a 1H-pyrrole-2-carboxaldehyde-substituted rhodamine 6G derivative (RCS) that possesses specific binding affinity toward Al3+ and Cu2+ at micromolar concentration levels. In an N,N-dimethylformamide (DMF) and water (v/v=2/8) medium, the RCS chemosensor exhibits a substantially enhanced absorbance intensity at 532nm and a color change from colorless to pink for Cu2+; it also exhibits significant “off–on” fluorescence at 557nm, accompanied by a color change from colorless to fluorescent-yellow upon binding to Al3+. The RCS sensor exhibits extremely high fluorescence enhancement upon complexation with Al3+, and it can be used as a “naked eye” sensor. Through fluorescence titration at 557nm, we confirmed that RCS exhibits a fluorescence response with a remarkable enhancement in emission intensity resulting from the complexation between RCS and Al3+, whereas no emission appeared in the case of competitive metal ions (Cu2+, Al3+, Li+, Na+, K+, Cs+, Mg2+, Ca2+, Fe2+, Co2+, Ag+, Zn2+, Cd2+, Hg2+ and Pb2+) in a DMF and water (v/v=2/8) solution. The reversible ring-opening mechanism of the rhodamine spirolactam induced by Al3+/Cu2+ binding and the 1:1 stoichiometric structure between RCS and Al3+ were adequately supported by Job-plot evaluation, optical titration and FT-IR analysis. The lowest detection limit for Al3+ is 3.20×106M−1 in a DMF and water (v/v=2/8) solution. Al3+-induced chelation-enhanced fluorescence (CHEF) is associated with spirolactam ring opening of the rhodamine unit. Finally, RCS was successfully applied for the bio-imaging of Al3+ in living HeLa cells and for fluorescence imaging of a microfluidic system.