A Rationally Designed, Spiropyran-Based Chemosensor for Magnesium

Magnesium ions (Mg2+) play an important role in mammalian cell function; however, relatively little is known about the mechanisms of Mg2+ regulation in disease states. An advance in this field would come from the development of selective, reversible fluorescent chemosensors, capable of repeated measurements. To this end, the rational design and fluorescence-based photophysical characterisation of two spiropyran-based chemosensors for Mg2+ are presented. The most promising analogue, chemosensor 1, exhibits 2-fold fluorescence enhancement factor and 3-fold higher binding affinity for Mg2+ (Kd 6.0 µM) over Ca2+ (Kd 18.7 µM). Incorporation of spiropyran-based sensors into optical fibre sensing platforms has been shown to yield significant signal-to-background changes with minimal sample volumes, a real advance in biological sensing that enables measurement on subcellular-scale samples. In order to demonstrate chemosensor compatibility within the light intense microenvironment of an optical fibre, photoswitching and photostability of 1 within a suspended core optical fibre (SCF) was subsequently explored, revealing reversible Mg2+ binding with improved photostability compared to the non-photoswitchable Rhodamine B fluorophore. The spiropyran-based chemosensors reported here highlight untapped opportunities for a new class of photoswitchable Mg2+ probe and present a first step in the development of a light-controlled, reversible dip-sensor for Mg2+.