Novel pyrazoline and pyrazole "turn on" fluorescent sensors selective for Zn2+/Cd2+ at λem 480 nm and Fe3+/Fe2+ at λem 465 nm in MeCN.

A small series of simple pyrazoline and pyrazole based sensors, all derived from the same chalcone precursors, were synthesised, characterised and screened for their fluorescence "turn on" properties in the presence of multiple metals. Pyrazole 8 displayed an excellent fluorescence profile with approx. 20× fold increase in λem 480 nm with Zn2+ compared to a 2.5× fold increase with Cd2+. Pyrazole 9 displayed a 30× fold increase at λem 465 nm for Fe3+ compared to Fe2+ with a Fe3+ limit of detection of 0.025 µM. The corresponding pyrazolines displayed contrasting properties with important implications for future pyrazoline and pyrazole sensor design.

Furo[3,2-c]coumarin-derived Fe3+ Selective Fluorescence Sensor: Synthesis, Fluorescence Study and Application to Water Analysis.

Furocoumarin (furo[3,2-c]coumarin) derivatives have been synthesized from single step, high yielding (82-92%) chemistry involving a 4-hydroxycoumarin 4 + 1 cycloaddition reaction. They are characterized by FTIR, 1H-NMR, and, for the first time, a comprehensive UV-Vis and fluorescence spectroscopy study has been carried out to determine if these compounds can serve as useful sensors. Based on the fluorescence data, the most promising furocoumarin derivative (2-(cyclohexylamino)-3-phenyl-4H-furo[3,2-c]chromen-4-one, FH), exhibits strong fluorescence (ФF = 0.48) with long fluorescence lifetime (5.6 ns) and large Stokes' shift, suggesting FH could be used as a novel fluorescent chemosensor. FH exhibits a highly selective, sensitive and instant turn-off fluorescence response to Fe3+ over other metal ions which was attributed to a charge transfer mechanism. Selectivity was demonstrated against 13 other competing metal ions (Na+, K+, Mg2+, Ca2+, Mn2+, Fe2+, Al3+, Ni2+, Cu2+, Zn2+, Co2+, Pb2+ and Ru3+) and aqueous compatibility was demonstrated in 10% MeOH-H2O solution. The FH sensor coordinates Fe3+ in a 1:2 stoichiometry with a binding constant, Ka = 5.25 × 103 M-1. This novel sensor has a limit of detection of 1.93 µM, below that of the US environmental protection agency guidelines (5.37 µM), with a linear dynamic range of ~28 (~2-30 µM) and an R2 value of 0.9975. As an exemplar application we demonstrate the potential of this sensor for the rapid measurement of Fe3+ in mineral and tap water samples demonstrating the real-world application of FH as a "turn off" fluorescence sensor.

Multicellular aggregation of maltol-modified cells triggered by Fe(3+) ions.

The synthesis of a maltol-derived hydrazide is described which, once attached to a cell surface, induces rapid multicellular aggregation selectively in the presence of Fe(3+) ions. Heterocellular aggregates are also reported.

Simple pyrazoline and pyrazole "turn on" fluorescent sensors selective for Cd2+ and Zn2+ in MeCN.

An efficient two-step synthesis of pyrazoline ligand is described which is an effective "turn on" fluorescent sensor for Cd(2+) in MeCN. Oxidation to the corresponding pyrazole ligand creates a "turn on" fluorescent sensor now selective for Zn(2+) and able to distinguish it from Cd(2+).