KU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Heverlee, Belgium.
Dalton Trans. 2012 Sep 21;41(35):10549-56. doi: 10.1039/c2dt30605k. Epub 2012 Jul 25.
A ditopic DTPA monoamide derivative containing an 8-hydroxyquinoline moiety was synthesized and the corresponding gadolinium(III) complex (Gd(H5)(H(2)O)) was prepared. After adding aluminum(III), the 8-hydroxyquinoline part self-assembled into a heteropolymetallic triscomplex (Gd5)(3)Al(H(2)O)(3). The magnetic and optical properties of this metallostar compound were investigated in order to classify it as a potential in vitro bimodal contrast agent. The proton nuclear magnetic relaxation dispersion measurements indicated that the relaxivity r(1) of Gd(H5)(H(2)O) and (Gd5)(3)Al(H(2)O)(3) at 20 MHz and 310 K equaled 6.17 s(-1) mM(-1) and 10.9 s(-1) mM(-1) per Gd(III) ion respectively. This corresponds to a relaxivity value of 32.7 s(-1) mM(-1) for the supramolecular complex containing three Gd(III) ions. The high relaxivity value is prominently caused by an increase of the rotational tumbling time τ(R) by a factor of 2.7 and 5.5 respectively, in comparison with the commercially used MRI contrast agent Gd(III)-DTPA (Magnevist®). Furthermore, upon UV irradiation, (Gd5)(3)Al(H(2)O)(3) exposes green broad-band emission with a maximum at 543 nm. Regarding the high relaxivity and the photophysical properties of the (Gd5)(3)Al(H(2)O)(3) metallostar compound, it can be considered as a lead compound for in vitro bimodal applications.
合成了一种含有 8-羟基喹啉部分的双齿 DTPA 单酰胺衍生物,并制备了相应的钆(III)配合物[Gd(H5)(H2O)](-)。加入铝(III)后,8-羟基喹啉部分自组装成杂多金属三配合物[(Gd5)(3)Al(H2O)(3)](3-)。研究了该金属星化合物的磁学和光学性质,以将其归类为潜在的体外双模态对比剂。质子核磁共振弛豫色散测量表明,[Gd(H5)(H2O)](-)和[(Gd5)(3)Al(H2O)(3)](3-)在 20 MHz 和 310 K 下的弛豫率 r1分别为 6.17 s-1 mM-1和 10.9 s-1 mM-1每 Gd(III)离子。这对应于含有三个 Gd(III)离子的超分子配合物的弛豫率值为 32.7 s-1 mM-1。高弛豫率值主要是由于旋转翻滚时间τ(R)分别增加了 2.7 和 5.5 倍,与商业 MRI 对比剂 Gd(III)-DTPA(Magnevist®)相比。此外,[(Gd5)(3)Al(H2O)(3)](3-)在紫外光照射下会发出最大波长为 543 nm 的宽绿光带发射。鉴于[(Gd5)(3)Al(H2O)(3)](3-)金属星化合物的高弛豫率和光物理性质,它可以被认为是体外双模态应用的先导化合物。