Anion Receptor Chemistry

The principles of the design of responsive luminescent probes and sensors based on lanthanide emission are summarised, based on a mechanistic understanding of their mode of action. Competing kinetic pathways for deactivation of the excited states that occur are described, highlighting the need to consider each of the salient quenching processes. Such an analysis dictates the choice of both the ligand and its integral sensitising moiety for the particular application. The key aspects of quenching involving electron transfer and vibrational and electronic energy transfer are highlighted and exemplified. Responsive systems for pH, pM, pX and pO2 and selected biochemical analytes are distinguished, according to the nature of the optical signal observed. Signal changes include both simple and ratiometric intensity measurements, emission lifetime variations and the unique features associated with the observation of circularly polarised luminescence (CPL) for chiral systems. A classification of responsive lanthanide probes is introduced. Examples of the operation of probes for reactive oxygen species, citrate, bicarbonate, α1-AGP and pH are used to illustrate reversible and irreversible transformations of the ligand constitution, as well as the reversible changes to the metal primary and secondary coordination sphere that sensitively perturb the ligand field. Finally, systems that function by modulation of dynamic quenching of the ligand or metal excited states are described, including real time observation of endosomal acidification in living cells, rapid urate analysis in serum, accurate temperature assessment in confined compartments and high throughput screening of drug binding to G-protein coupled receptors.

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The design of responsive luminescent lanthanide probes and sensors.

Synthesis and Photoluminescence Characterization of the Complexes of Samarium Dibenzoylmethanates with 1,10-Phenanthroline Derivatives

Biomolecules play critical roles in biological activities and are closely related to various disease conditions. The reliable, selective and sensitive detection of biomolecules holds much promise for specific and rapid biosensing. In recent years, luminescent lanthanide probes have been widely used for monitoring the activity of biomolecules owing to their long luminescence lifetimes and line-like emission which allow time-resolved and ratiometric analyses. In this review article, we concentrate on recent advances in the detection of biomolecule activities based on lanthanide luminescent systems, including upconversion luminescent nanoparticles, lanthanide-metal organic frameworks, and lanthanide organic complexes. We also introduce the latest remarkable accomplishments of lanthanide probes in the design principles and sensing mechanisms, as well as the forthcoming challenges and perspectives for practical achievements.

Lanthanide upconversion and downshifting luminescence for biomolecules detection

Luminescent Lanthanide Metal Organic Frameworks (LnMOFs): A Versatile Platform towards Organomolecule Sensing

Luminescent lanthanide complexes have been actively studied as selective anion receptors for the past two decades. Ln(iii) complexes, particularly of europium(iii) and terbium(iii), offer unique photophysical properties that are very valuable for anion sensing in biological media, including long luminescence lifetimes (milliseconds) that enable time-gating methods to eliminate background autofluorescence from biomolecules, and line-like emission spectra that allow ratiometric measurements. By careful design of the organic ligand, stable Ln(iii) complexes can be devised for rapid and reversible anion binding, providing a luminescence response that is fast and sensitive, offering the high spatial resolution required for biological imaging applications. This review focuses on recent progress in the development of Ln(iii) receptors that exhibit sufficiently high anion selectivity to be utilised in biological or environmental sensing applications. We evaluate the mechanisms of anion binding and sensing, and the strategies employed to tune anion affinity and selectivity, through variations in the structure and geometry of the ligand. We highlight examples of luminescent Ln(iii) receptors that have been utilised to detect and quantify specific anions in biological media (e.g. human serum), monitor enzyme reactions in real-time, and visualise target anions with high sensitivity in living cells.

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Advances in anion binding and sensing using luminescent lanthanide complexes

Organic redox flow batteries are currently the focus of intense scientific interest because they have the potential to be developed into low-cost, environmentally sustainable solutions to the energ...

Samantha E. Bodman

Papers

Advances in anion binding and sensing using luminescent lanthanide complexes

Experimental Validation of a Computational Screening Approach to Predict Redox Potentials for a Diverse Variety of Redox-Active Organic Molecules