A novel strategy for the design of 8-hydroxyquinolinate-based lanthanide bioprobes that emit in the near infrared range
A novel strategy for the design of 8-hydroxyquinolinate-based lanthanide bioprobes that emit in the near infrared range
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DOI：
10.1002/chem.200600964
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Bunzli, Jean-Claude G.
中科院分区：
文献类型：
--
作者：
Comby, Steve;Imbert, Daniel;Bunzli, Jean-Claude G.
利用三齿8-羟基喹啉亚基的螯合作用，合成了一种新的多齿三足配体T2soxMe。电位滴定和分光光度滴定显示 7 个 pK(a) 值介于 3.7 和 10.2 之间。在水中，使用 T2soxMe 可在生理 pH 值下生成热力学稳定且可溶的 Ln(III) 复合物，条件稳定常数范围为 log beta(11) = 7.8-8.6。这些螯合物具有抗水解性，并显示出令人感兴趣的光物理性质，特别是在近红外 (NIR) 范围内。在 D2O 和 H2O 中记录的 Nd-III 和 Yb-III 配合物的发射寿命表明金属离子的第一配位层中不存在水分子。此外，三线态的低能量允许从配体到金属离子的有效能量转移：在pH 7.4的水中，Nd-III和Yb-III的近红外发光的敏化效率分别达到75和接近100%，导致总量子产率为0.027和0.13%；还检测到 Er-III 发光。根据WST-1测试，在孵育24小时后，浓度高达250μm的Yb-III Podate对Jurkat细胞没有表现出相当大的细胞毒性。最后，相同的足爪与人血清白蛋白偶联，导致近红外发光强度增加 50%。
A new polydentate tripodal ligand T2soxMe was synthesized to take advantage of the chelating effect of tridentate 8-hydroxyquinolinate subunits. Potentiometric and spectrophotometric titrations reveal seven pK(a) values of between 3.7 and 10.2. In water, the use of T2soxMe leads to thermodynamically stable and soluble Ln(III) complexes at physiological pH, with conditional stability constants in the range log beta(11) = 7.8-8.6. The chelates are resistant toward hydrolysis and show interesting photophysical properties, particularly in the near infrared (NIR) range. The emission lifetimes of the Nd-III and Yb-III complexes recorded in D2O and H2O suggest the absence of water molecules in the first coordination sphere of the metal ions. Moreover, the low energy of the triplet state allows efficient energy transfer from the ligand to the metal ions: in water at pH 7.4, the sensitization efficacy of the NIR luminescence reaches 75 and approximate to 100% for Nd-III and Yb-III, respectively, leading to overall quantum yields of 0.027 and 0.13%; Er-III luminescence is also detected. According to the WST-1 test, the Yb-III podate at concentrations of up to 250 mu m does not display sizeable cytotoxicity for Jurkat cells after 24 h of incubation. Finally, the same podate is shown to couple to human serum albumin, leading to an increase of 50% in the NIR-luminescence intensity.