title: Synthesis and cell localization of self-assembled dinuclear lanthanide bioprobes.
abstract: Lanthanide bioprobes and bioconjugates are ideal luminescent stains in view of their low propensity to photobleaching, sharp emission lines and long excited state lifetimes permitting time-resolved detection for enhanced sensitivity. In this paper, we expand our previous work which demonstrated that self-assembled dinuclear triple-stranded helicates [Ln2(L(C2X))3] behave as excellent cell and tissue labels in immunocytochemical and immunohistochemical assays. The synthetic strategy of the hexadentate ditopic ligands incorporating dipicolinic acid, benzimidazole units and polyoxyethylene pendants is revisited in order to provide a more straightforward route and to give access to further functionalization of the polyoxyethylene arms by incorporating a terminal function X. Formation of the helicates [Ln2(L(C2X))3] (X=COOH, CH2OH, COEt, NH2, phthalimide) is ascertained by several experimental techniques and their stability tested against diethylenetriaminepentaacetate. Their photophysical properties (quantum yield, lifetime, radiative lifetime and sensitization efficiency) are presented and compared with those of the parent helicates [Ln2(L(C2))3]. Finally, the cellular uptake of five Eu(III) helicates is monitored by time-resolved luminescence microscopy and their localization in HeLa cells established by co-staining experiments.
authors.affiliation: Laboratory of Lanthanide Supramolecular Chemistry, École Polytechnique Fédérale de Lausanne, BCH 1404, 1015 Lausanne, Switzerland.
authors.forename: Anne-Sophie
authors.initials: AS
authors.lastname: Chauvin
authors.forename: Frédéric
authors.initials: F
authors.lastname: Thomas
authors.forename: Bo
authors.initials: B
authors.lastname: Song
authors.forename: Caroline D B
authors.initials: CD
authors.lastname: Vandevyver
authors.forename: Jean-Claude G
authors.initials: JC
authors.lastname: Bünzli
mesh_terms: D006367:HeLa Cells; D006801:Humans; D028581:Lanthanoid Series Elements / Q000138:chemical synthesis / Q000493:pharmacokinetics*; D008163:Luminescent Measurements / Q000379:methods*; D015336:Molecular Probe Techniques; D015335:Molecular Probes / Q000138:chemical synthesis / Q000493:pharmacokinetics; D013347:Subcellular Fractions / Q000378:metabolism*
chemical_list: D028581:Lanthanoid Series Elements; D015335:Molecular Probes
keywords: cell imaging; lanthanide; luminescent bioprobe; photophysical properties; self-assembly; time-resolved luminescence microscopy