Molecular MRI of Thrombosis.

This review focuses on recent approaches in using targeted MRI probes for noninvasive molecular imaging of thrombosis. Probe design strategies are discussed: choice of molecular target; nanoparticle versus small-molecule probe; and gadolinium versus iron oxide imaging reporter. Examples of these different design strategies are chosen from the recent literature.

Keys for unlocking photolabile metal-containing cages.

Photolabile metal-containing cages are metal complexes that undergo a change in coordination environment upon exposure to light of an appropriate wavelength. The light-responsive functionality can either be a component of the encapsulating ligand or a property of the metal complex itself. The altered coordination properties of light-responsive complexes can result in release of the coordinated metal ion into its surroundings, a differential reactivity of the metal center, or the liberation of a reactive molecule that had been passivated by binding to the metal center.

Development of next-generation photolabile copper cages with improved copper binding properties.

Seven new nitrogen-donor ligands that contain a photoactive nitrophenyl group within the ligand backbone have been prepared and evaluated for their binding affinity for copper(ii) and zinc(ii). Among this series, the ligand 3Gcage (pyridine-2-carboxylic acid {1-(2-nitro-phenyl)-3-[(pyridin-2-ylmethyl)-amino]-propyl}-amide) has the best affinity for copper(ii), with an apparent dissociation constant at pH 7.4 of 0.

Toward the detection of cellular copper(II) by a light-activated fluorescence increase.

A new type of Cu fluorescent sensor, coucage, has been prepared with a photosensitive nitrophenyl group incorporated into the backbone of a coumarin-tagged tetradentate ligand. Coucage provides a selective fluorescence response for Cu over other biologically relevant metal ions. Coordination of Cu dims the fluorescence output until irradiation with UV light cleaves the ligand backbone, which relieves the copper-induced quenching to provide a turn-on response.

A photolabile ligand for light-activated release of caged copper.

A photosensitive caged copper complex has been prepared from a tetradentate ligand (H2cage) composed of two pyridyl-amide arms connected by a photoreactive nitrophenyl group. H2cage binds Cu2+ in aqueous solution with a stability constant (log beta) of 10.8, which corresponds to a KD of 16 pM at pH 7.