Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Hochfeld-Magnetresonanzzentrum, Max-Planck-Institut für Biologische Kybernetik, Spemannstrasse 41, 72076 Tübingen, Germany.
J Colloid Interface Sci. 2012 Jan 15;366(1):70-79. doi: 10.1016/j.jcis.2011.09.053. Epub 2011 Oct 1.
Spherical, nonporous and monodisperse silica nanoparticles (NPs) with a diameter of about 100 nm were synthesized and covalently functionalized with lanthanoid(III) (Ln=Gd or Y) chelate complexes, which serve as contrast agents (CAs) for magnetic resonance imaging (MRI). The materials were fully characterized after each synthetic step by different analytical methods, such as dynamic light scattering, scanning electron microscopy, DRIFT and NMR spectroscopy, thermogravimetry and elemental analysis, as well as zetapotential measurements. High surface concentrations of Gd(III) complexes (up to 50 μmol g(-1)) were determined by ICP-AES and T(1)-measurements, respectively. MRI experiments show the typical concentration-dependent increase of the longitudinal relaxation rate. T(1)-weighted images of samples with more than 25 μg NPs per 100 μL agar display a clear contrast enhancement in the agar layer. The transverse relaxivities r(2) of the materials are significantly higher than r(2) of the corresponding free Gd(III) complexes in water and medium, whereas the longitudinal relaxivities r(1) are slightly increased. Due to the high loading of Gd(III) complexes, the relaxivities per particle are remarkably high (up to 2.78×10(5) mM(-1) s(-1) for r(1)). Thus, new hybrid materials, based on nonporous silica NPs with high local relaxivity values were synthesized, which can serve as very effective CAs for MRI.
合成了直径约为 100nm 的球形、无孔、单分散硅纳米颗粒(NPs),并用镧系(III)(Ln=Gd 或 Y)螯合物配合物进行了共价功能化,这些配合物可用作磁共振成像(MRI)的对比剂(CA)。在每个合成步骤后,通过不同的分析方法,如动态光散射、扫描电子显微镜、DRIFT 和 NMR 光谱、热重分析和元素分析以及等电位测量,对材料进行了充分的表征。通过 ICP-AES 和 T(1)-测量,分别确定了 Gd(III)配合物的高表面浓度(高达 50μmol g(-1))。MRI 实验表明,纵向弛豫率随浓度呈典型的依赖性增加。浓度超过 25μg NPs/100μL 琼脂的样品的 T(1)加权图像在琼脂层中显示出明显的对比度增强。材料的横向弛豫率 r(2)明显高于水和介质中相应的游离 Gd(III)配合物的 r(2),而纵向弛豫率 r(1)略有增加。由于 Gd(III)配合物的高负载,每个粒子的弛豫率非常高(对于 r(1),高达 2.78×10(5)mM(-1)s(-1))。因此,基于具有高局部弛豫率的无孔硅纳米颗粒,合成了新型的混合材料,可用作 MRI 的非常有效的 CA。