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. Graphical Abstract

中文翻译：

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自组装的基于 Ln(III) 循环的胶束和 AuNPs 偶联物作为发光和磁共振成像 (MRI) 试剂的候选物

摘要 开发了基于 Eu(III)/Tb(III)/Gd(III)-配合物 1.Ln 和 2.Ln 的四取代七齿环烯（1,4,7,10-四氮杂环十二烷）。1.Eu/Tb 和 2.Eu/Tb 用于形成发光自组装三元结构，我们证明只有在适当的敏化天线存在的情况下，1.Eu/Tb 和 2 的镧系元素发射.Eu/Tb '开启'。1.Gd/2.Gd 被开发为潜在的 MIR 造影剂，并用于 NMRD 测量，其中研究了它们的弛豫度，并确定了它们的（相对较高的）r1 值。对于 2.Gd，可以清楚地观察到自组装胶束型结构的形成。功能化的金纳米粒子 1.Ln-AuNP 也由 1.Ln 合成。至于自由配合物，Ln 发射被“开启”为 1。Eu/Tb-AuNP 存在触角。NMRD 测量表明 1.Gd-AuNP 系统的弛豫率非常高，值为 445 s-1mM-1（在 400 MHz 时），表明相对较高数量的 1.Gd 配合物对AuNP 的表面。图形概要