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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >Water-soluble porphyrins as a dual-function molecular imaging platform for MRI and fluorescence zinc sensing
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Water-soluble porphyrins as a dual-function molecular imaging platform for MRI and fluorescence zinc sensing

机译：水溶性卟啉作为MRI和荧光锌感测的双重功能分子成像平台

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摘要

We report a molecular platform for dual-function fluorescence/MRI sensing of mobile zinc. Zinc-selective binding units were strategically attached to a water-soluble porphyrin template. The synthetic strategy for achieving the designed target ligand is flexible and convenient, and the key intermediates can be applied as general building blocks for the construction of other metal sensors based on a similar mechanism. The metal-free form, (DPA-C_2)_2-TPPS_3 (1), where DPA is dipicolylamine and TPPS_3 is 5-phenyl-10,15,20-tris(4-sulfonatophenyl)porphine, is an excellent fluorescent sensor for zinc. It has certain superior physical properties compared with earlier-generation zinc sensors including emission in the red and near-IR regions [λ_(em) = 645 nm (s) and 715 nm (m)], with a large Stokes shift of > 230 nm. The fluorescence intensity of 1 increases by > 10-fold upon zinc binding. The fluorescence "turn-on" is highly selective for zinc versus other divalent metal ions and is relatively pH-insensitive within the biologically relevant pH window. The manganese derivative, [(DPA-C_2)_2-TPPS_3Mn(Ⅲ)] (2), switches the function of the molecule to generate an MRI contrast agent. In the presence of zinc, the relaxivity of 2 in aqueous solution is significantly altered, which makes it a promising zinc MRI sensor. Both metal-free and Mn(lll)-inserted forms are efficiently taken up by live cells, and the intracellular zinc can be imaged by either fluorescence or MR, respectively. We anticipate that in vivo applications of the probes will facilitate a deeper understanding of the physiological roles of zinc and allow detection of abnormal zinc homeostasis for pathological diagnoses.
机译：我们报告了分子平台的移动锌双功能荧光/ MRI感应。锌选择性结合单元策略性地连接到水溶性卟啉模板上。用于实现设计的目标配体的合成策略既灵活又方便，并且基于类似的机理，关键中间体可以用作构建其他金属传感器的通用构件。无金属形式（DPA-C_2）_2-TPPS_3（1）（其中DPA为二聚烯丙基胺，TPPS_3为5-苯基-10,15,20-三（4-磺酰基苯基）卟啉）是一种出色的锌荧光传感器。与早期的锌传感器相比，它具有某些优越的物理性能，包括红色和近红外区域的发射[λ_（em）= 645 nm（s）和715 nm（m）]，斯托克斯位移大于230纳米锌结合后1的荧光强度增加> 10倍。荧光“开启”相对于其他二价金属离子对锌具有高度选择性，并且在生物学相关的pH窗口内对pH相对不敏感。锰衍生物[（DPA-C_2）_2-TPPS_3Mn（Ⅲ）]（2）转换分子的功能以产生MRI造影剂。在锌的存在下，水溶液中2的弛豫度显着改变，这使其成为很有前途的锌MRI传感器。不含金属和插入Mn（III）的形式均可被活细胞有效吸收，并且细胞内锌可分别通过荧光或MR成像。我们预期探针的体内应用将促进对锌的生理作用的更深了解，并允许检测异常的锌稳态以进行病理诊断。

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