Luminescent Rhenium and Ruthenium Complexes of an Amphoteric Poly(amidoamine) Functionalized with 1,10-Phenanthroline

A new amphoteric copolymer, PhenISA, has been obtained by copolymerization of 4-(4'-aminobutyl)-1,10-phenanthroline (BAP) with 2-methylpiperazine and bis(acrylamido)acetic acid (BAC) (6% of phenanthroline-containing repeating units). The copolymer showed excellent solubility in water, where it self-aggregated to give clear nanoparticle suspensions (hydrodynamic diameter = 21 +/- 2 nm, by dynamic light scattering (DLS) analysis). The phenanthroline pendants of the polymer stably coordinated either Re(CO)(3)(+) or Ru(phen)(2)(2+) fragments, affording luminescent Re-PhenISA, Re-Py-PhenISA, and Ru-PhenISA polymer complexes, emitting from triplet metal-to-ligand charge transfer ((MLCT)-M-3) excited states (with lambda(em) = 608, 571, and 614 nm, respectively, and photoluminescence quantum yields Phi(em) = 0.7%, 4.8%, and 4.1%, in aerated water solution, respectively). DLS analyses indicated that the polymer complexes maintained the nanosize of PhenISA. All the complexes were stable under physiological conditions (pH 7.4, 0.15 M NaCl) in the presence of an excess of the ubiquitous competitor cysteine. In vitro viability assays showed no toxicity of Re-Py-PhenISA and Ru-PhenISA complexes, at concentrations in the range of 0.5-50 mu M (calculated on the metal-containing unit), toward HEK-293 (human embryonic kidney) cells. A preliminary investigation of internalization in HEK-293 cells, by means of fluorescence confocal microscopy, showed that Ru-PhenISA enters cells via an endocytic pathway and, subsequently, homogeneously diffuse within the cytoplasm across the vesicle membranes.