Jean-Claude Bunzli - Lanthanide bimetallic helicates for in vitro imaging and sensing

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  Bunzli,J.C.G., Chauvin,A.S., Vandevyver,C.D.B., Bo,S., Comby,S.   Fluorescence Methods and Applications: Spectroscopy, Imaging,   and Probes 2008 1130 97-105

  Abstract: As the need for targeting luminescent   biolabels increases, for mapping selected analytes, imaging of   cells and organs, and tracking in cellulo processes, lanthanide   bimetallic helicates are emerging as versatile bioprobes. The   wrapping of three ligand strands around two metallic centers by   self-assembly affords robust molecular edifices with tunable   chemical and photophysical properties. In addition,   heterometallic helical chelates can be assembled leading to   bioprobes with inherent chiral properties. In this paper, we   review the literature demonstrating that neutral [Ln(2)(L-CX)(3)]   (x = 1-3) helicates represent a viable alternative to existing   chelating agents for bio-analyses, while featuring specific   enhanced properties. These bimetallic chelates self-assemble in   water, and at physiological pH the 2:3 (Ln:L-CX) complex is by   far the dominant species, conditional stability constants log   beta(23) being in the range 23-30. The metal ions are   9-coordinate and lie in sites with slightly distorted D-3   symmetry. Efficient protection from water interaction by the   tightly wrapped ligand strands results in sizeable photophysical   properties, with quantum yields up to 24% for Eu-III and 11 % for   Tb-III, while the luminescence of several other visible and/or   near-infrared emitting Ln(III) ions is also sensitized.   Noncytotoxicity for all the helicates is established for several   living cell lines including HeLa, HaCat, MCF-7, 5D10, and Jurkat.   We present new data pertaining to the live cell imaging ability   of [Eu-2(L-C1)(3)] and compare the three systems with x = 1-3   with respect to thermodynamic stability, photophysics,   cell-permeation ability, and targeting capability for sensing in   cellulo processes. Prospects of derivatization for characterizing   specific biological interactions are discussed

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