Detection of multiple metal ions exclusively at bilayer interface: Does the nature of the membranous aggregates affect the sensitivity?

Abstract

A pyrenylated fluorogenic probe has been designed that can detect heavy metal pollutants exclusively at the bilayer interface. The compound, due to extensive self-aggregation, showed no interaction with metal ions in the bulk solution phase. However, effective, nanomolar level detection of multiple metal ions, such as Cu2+, Hg2+, and Ni2+, etc. was achieved exclusively in vesicular aggregates. The optical response towards metal ions, including selectivity and sensitivity, largely depends on the microenvironment around the probe molecules, governed by the nature of the bilayer membrane (polarity, order, interfacial hydration, etc). In zwitterionic membranes, like DPPC, Hg2+-induced fluorescence quenching was witnessed along with red-shifted emission maxima. On the contrary, turn-off responses along with blue-shifted in maxima were noted upon addition of both Cu2+ and Ni2+ ions in the anionic phospholipid vesicle, DPPA. Moreover, an improvement in sensitivity was witnessed when the probe was embedded into phospholipid vesicles with a fluid-like liquid crystalline phase. The larger mobility of the probe molecules on the bilayer membrane, resulting in ease of reorganization, might be the probable reason for this.