Gd3+-Based Magnetic Resonance Imaging Contrast Agent Responsive to Zn2+

被引:29
作者
Regueiro-Figueroa, Martin [1 ,2 ]
Guenduez, Serhat [3 ]
Patinec, Veronique [4 ]
Logothetis, Nikos K. [5 ,6 ]
Esteban-Gomez, David [1 ,2 ]
Tripier, Raphael [4 ]
Angelovski, Goran [3 ]
Platas-Iglesias, Carlos [1 ,2 ]
机构
[1] Univ A Coruna, Ctr Invest Cient Avanzadas, Grp QUICOOR, La Coruna 15008, Spain
[2] Univ A Coruna, Dept Quim Fundamental, La Coruna 15008, Spain
[3] Max Planck Inst Biol Cybernet, MR Neuroimaging Agents, D-72076 Tubingen, Germany
[4] Univ Bretagne Occidentale, UMR CNRS 6521, UFR Sci & Tech, F-29238 Brest 3, France
[5] Max Planck Inst Biol Cybernet, Physiol Cognit Proc, D-72076 Tubingen, Germany
[6] Univ Manchester, Dept Imaging Sci & Biomed Engn, Manchester, Lancs, England
关键词
LANTHANIDE(III) COMPLEXES; METAL-IONS; ZINC IONS; MRI; GADOLINIUM; ACID; DESIGN; PROBES; EQUILIBRIUM; STABILITY;
D O I
10.1021/acs.inorgchem.5b01719
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
We report the heteroditopic ligand H5L, which contains a DO3A unit for Gd3+ complexation connected to an NO2A moiety through a N-propylacetamide linker. The synthesis of the ligand followed a convergent route that involved the preparation of 1,4-bis(tert-butoxycarbonylmethyl)-1,4,7-triazacyclononane following the orthoamide strategy. The luminescence lifetimes of the Tb(D-5(4)) excited state measured for the TbL complex point to the absence of coordinated water molecules. Density functional theory calculations and H-1 NMR studies indicate that the EuL complex presents a square antiprismatic coordination in aqueous solution, where eight coordination is provided by the seven donor atoms of the DO3A unit and the amide oxygen atom of the N-propylacetamide linker. Addition of Zn2+ to aqueous solutions of the TbL complex provokes a decrease of the emission intensity as the emission lifetime becomes shorter, which is a consequence of the coordination of a water molecule to the Tb3+ ion upon Zn2+ binding to the NO2A moiety. The relaxivity of the GdL complex recorded at 7 T (25 degrees C) increases by almost 150% in the presence of 1 equiv of Zn2+, while Ca2+ and Mg2+ induced very small relaxivity changes. In vitro magnetic resonance imaging experiments confirmed the ability of GdL to provide response to the presence of Zn2+.
引用
收藏
页码:10342 / 10350
页数:9
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