Signaling Recognition Events with Fluorescent Sensors and Switches.

In the last century the production and application of halides assumed an ever greater importance. In the fields of medicine, dentistry, plastics, pesticides, food, photography etc many new halogen containing compounds have come into everyday use. In an analogous manner many techniques for the detection and determination of halogen compounds and ions have been developed with scientific journals reporting ever more sensitive methods. The 19th century saw the discovery of what is now thought of as a classical method for halide determination, namely the quenching of fluorescence. However, little analytically was done until over 100 years after its discovery, when the first halide sensors based on the quenching of fluorescence started to emerge. Due to the typical complexity of fluorescence quenching kinetics of optical halide sensors and their lack of selectivity, they have found little if any place commercially, despite their sensitivity, where other techniques such as ion-selective electrodes, x-ray fluorescence spectroscopy and colorimetry have dominated the analytical market. In this review article the author summarizes the relevant theory and work to date for halide sensing using fluorescence quenching methods and outlines the future potential that fluorescence quenching based optical sensors have to offer in halide determination.

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Optical halide sensing using fluorescence quenching: theory, simulations and applications - a review

http://www.molekulare-physiologie.de/publication/pdf/Cl_Rev_2000.pdf

Neuronal Ca2+-activated Cl− channels — homing in on an elusive channel species

Chloride movement across cell plasma and internal membranes, is of central importance for regulation of cell volume and pH, vectorial salt movement in epithelia, and, probably, intracellular traffic. Quinolinium-based chloride-sensitive fluorescent indicators provide a new approach to study chloride transport mechanisms and regulation that is complementary to 36Cl tracer methods, intracellular microelectrodes, and patch clamp. Indicator fluorescence is quenched by chloride by a collisional mechanism with Stern-Volmer constants of up to 220 M-1. Fluorescence is quenched selectively by chloride in physiological systems and responds to changes in chloride concentration in under 1 ms. The indicators are nontoxic and can be loaded into living cells for continuous measurement of intracellular chloride concentration by single-cell fluorescence microscopy. In this review, the structure-activity relationships for chloride-sensitive fluorescent indicators are described. Methodology for measurement of chloride transport in isolated vesicle and liposome systems and in intact cells is evaluated critically by use of examples from epithelial cell physiology. Future directions for synthesis of tailored chloride-sensitive indicators and new applications of indicators for studies of transport regulation and intracellular ion gradients are proposed.

Development and biological applications of chloride-sensitive fluorescent indicators

Once the Cinderella amongst the Platinum Group Metals at the Photochemistry Ball, iridium has become of intense interest since the beginning of the decade. Complexes of iridium(III) can be prepared that are highly luminescent, with emission wavelengths tuneable over the whole of the visible region. Whilst most studies have focused on tris-bidentate complexes, a rich and varied chemistry is also possible using tridentate ligands. In this review, we discuss the synthesis and excited-state properties of such complexes, exploring in particular how the number of cyclometallating carbon atoms in the coordination sphere of the metal ion influences the luminescence. Moving from [IrN6]3+ to [IrN3X3] coordination via [IrN5X]2+ and cis/trans-[IrN4X2]+ complexes, where N is a heterocyclic nitrogen and X is an anionic ligand or cyclometallated carbon, a whole range of luminescence efficiencies are encountered, ranging from the barely detectable to room temperature quantum yields approaching unity. We consider the extent to which these profound differences, arising as a result of subtle changes in molecular structure, can be rationalised in terms of the nature of the frontier orbitals.

Hsien C. Tseng

Papers

Structure-activity relationships of chloride-sensitive fluorescent indicators for biological application.