Self-assembled Ln(III) cyclen-based micelles and AuNPs conjugates as candidates for luminescent and magnetic resonance imaging (MRI) agents

Abstract

ABSTRACT The tetra-substituted heptadentate cyclen (1,4,7,10-tetraazacyclododecane) based Eu(III)/Tb(III)/Gd(III)-complexes 1.Ln and 2.Ln were developed. 1.Eu/Tb and 2.Eu/Tb were employed in the formation of luminescent self-assembling ternary structures, and we demonstrate that only in the presence of appropriate sensitizing antennae, was the lanthanide-emission of 1.Eu/Tb and 2.Eu/Tb ‘switched on’. 1.Gd/2.Gd were developed as potential MIR contrast agents, and employed in NMRD-measurements, where their relaxivity was investigated, and their (relatively high) r1 values determined. The formation of a self-assembled micelle-type structure was clearly observed for 2.Gd. The functionalised gold nanoparticles 1.Ln-AuNP were also synthesized from 1.Ln. As for the free complexes, the Ln-emission was ‘switched on’ for 1.Eu/Tb-AuNP in the presence of the antennae. NMRD measurements indicated that the relaxivity for the 1.Gd-AuNP systems was very high, with a value of 445 s-1mM-1 (at 400 MHz), demonstrating the cumulative effect of the relatively high number of 1.Gd complexes on the surface of the AuNP.