Octadentate Cages of Tb(III) 2-Hydroxyisophthalamides: A New Standard for Luminescent Lanthanide Labels

详细信息    查看全文

• 作者：Jide Xu ; Todd M. Corneillie ; Evan G. Moore ; Ga-Lai Law ; Nathaniel G. Butlin ; Kenneth N. Raymond
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：December 14, 2011
• 年：2011
• 卷：133
• 期：49
• 页码：19900-19910
• 全文大小：1085K
• 年卷期：v.133,no.49(December 14, 2011)
• ISSN：1520-5126

文摘

The synthesis, structure, and photophysical properties of several Tb(III) complexes with octadentate, macrotricyclic ligands that feature a bicapped topology and 2-hydroxyisophthalamide (IAM) chelating units are reported. These Tb(III) complexes exhibit highly efficient emission (桅_total 鈮?50%), large extinction coefficients (蔚_max 鈮?20,000 M^鈥? cm^鈥?), and long luminescence lifetimes (蟿_H2O 鈮?2.45 ms) at dilute concentrations in standard biological buffers. The structure of the methyl-protected ligand was determined by single-crystal X-ray diffraction and confirms the macrotricyclic structure of the parent ligand; the amide groups of the methyl-protected cage compound generate an anion binding cavity that complexes a chloride anion. Once the ligand is deprotected, a conformational change generates a similar cavity, formed by the phenolate and ortho amide oxygen groups that strongly bind lanthanide ions. The Tb(III) complexes thus formed display long-term stability, with little if any change in their spectral properties (including lifetime, quantum yield, and emission spectrum) over time or in different chemical environments. Procedures to prepare functionalized derivatives with terminal amine, carboxylate, and N-hydroxysuccinimide groups suitable for derivatization and protein bioconjugation have also been developed. These bifunctional ligands have been covalently attached to a number of different proteins, and the terbium complexes鈥?exceptional photophysical properties are retained. These compounds establish a new aqueous stability and quantum yield standard for long-lifetime lanthanide reporters.