A molecular chemodosimeter to probe "closed shell" ions in kidney cells.

Two quinidine-functionalized coumarin molecular probes have been synthesized and have been found to bind metal cations (Cd2+, Co2+, Cu2+, Fe2+, Hg2+, Ni2+, and Zn2+) with high affinity in organic-aqueous media (DMSO-HEPES). The chemodosimeters coordinate with the Zn2+ ions in a two-to-one ratio (molecular probe : Zn2+) with a log ß of 10.0 M-2. Upon the addition of the closed-shell metal ions studied, a fluorescence turn-on via an excimer formation is seen at 542 nm due to the quinaldine moiety adopting a syn arrangement when coordinated to the metal Zn2+ ions. Confocal microscopy monitored free Zn2+ ions in the Human Embryonic Kidney cell line HEK293 by coordinating with the chemodosimter.

Structural Features of a Family of Coumarin-Enamine Fluorescent Chemodosimeters for Ion Pairs.

A family of coumarin-enamine chemodosimeters is evaluated for their potential use as fluorescent molecular probes for multiple analytes [cadmium(II), cobalt(II), copper(II), iron(II), nickel(II), lead(II), and zinc(II)], as their chloride and acetate salts. These fluorophores displayed excellent optical spectroscopic modulation when exposed to ion pairs with different Lewis acidic and basic properties in dimethyl sulfoxide (DMSO). The chemodosimeters were designed to undergo excited-state intramolecular proton transfer (ESIPT), which leads to significant Stokes shifts (ca. 225 nm) and lower-energy fluorescence emission (ca. 575 nm). A more basic anion, e.g., acetate, inhibited the ESIPT mechanism by deprotonation of the enol, producing a binding pocket (N^O- chelate) that can coordinate to an appropriate metal ion. Coordination of the metal ions enhances the fluorescent intensity via the chelation-enhanced fluorescence emission mechanism. Subjecting the spectroscopic data to linear discriminant analysis provided insights into the source of these systems' markedly different behavior toward ion pairs, despite the subtle structural differences in the organic framework. These compounds are examples of versatile, low-molecular-weight, dual-channel fluorescent sensors for ion-pair recognition. This study paves the way for using these probes as practical components of a sensing array for different metal ions and their respective anions.