Europium and terbium trisdipicolinate complexes are inkjet printed onto paper with commercially available desktop inkjet printers. Together with a commercial blue luminescent ink, the red‐emitting luminescent ink containing europium and the green‐emitting luminescent ink containing terbium are used to reproduce accurate full color images that are invisible under white light and appear under a 254 nm UV light. Such invisible luminescent images are attractive anti‐counterfeiting security features. The luminescent prints have a color range (gamut) nearly as wide as the gamut of a standard sRGB display. The gamut of the luminescent prints is determined by relying on a simple model predicting the relative spectral radiant emittances of any printed luminescent color halftone. The model is also used to establish the correspondence between the surface coverages of the printed luminescent inks and the emitted color of these luminescent halftones. The accuracy of the spectral prediction model is very good and can be rationalized by the absence of quenching when the luminescent lanthanide complexes are printed in superposition with the other luminescent materials.
The homoditopic ligand 6,6'-[methylenebis(1-methyl-1H-benzimidazole-5,2-diyl)]bis(4-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}pyridine-2-carboxylic acid) (H(2)L(C2)) has been tailored to self-assemble with lanthanide ions (Ln(III)), which results in the formation of neutral bimetallic helicates with the overall composition [Ln(2)(L(C2))(3)] and also provides a versatile platform for further derivatization. The grafting of poly(oxyethylene) groups onto the pyridine units ensures water solubility, while maintaining sizeable thermodynamic stability and adequate antenna effects for the excitation of both visible- and NIR-emitting Ln(III) ions. The conditional stability constants (log beta(23)) are close to 25 at physiological pH and under stoichiometric conditions. The ligand triplet state features adequate energy (0-phonon transition at approximately 21 900 cm(-1)) to sensitize the luminescence of Eu(III) (Q=21 %) and Tb(III) (11 %) in aerated water at pH 7.4. The emission of several other VIS- and NIR-emitting ions, such as Sm(III) (Q=0.38 %) or Yb(III) (0.15 %), for which in cellulo luminescence is evidenced for the first time, is also sensitized. The Eu(III) emission spectrum arises from a main species with pseudo-D(3) symmetry and without coordinated water. The cell viability of several cancerous cell lines (MCF-7, HeLa, Jurkat and 5D10) is unaffected if incubated with up to 500 microM [Eu(2)(L(C2))(3)] during 24 h. Bright Eu(III) emission is seen for incubation concentrations above 10 microM and after a 15-minute loading time; similar images are obtained with Tb(III) and Sm(III). The helicates probably permeate into the cytoplasm of HeLa cells by endocytosis. The described luminescent helical stains are robust chemical species which remain undissociated in the cell medium and in presence of other complexing agents, such as edta, dtpa, citrate or L-ascorbate. Their derivatization, which would open the way to the sensing of targeted in cellulo phenomena, is currently under investigation.
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