Porphyrins as Versatile, Aggregation-Tolerant, and Biocompatible Polarizing Agents for Triplet Dynamic Nuclear Polarization of Biomolecules
Porphyrins as Versatile, Aggregation-Tolerant, and Biocompatible Polarizing Agents for Triplet Dynamic Nuclear Polarization of Biomolecules
复制标题
卟啉作为生物分子三重态动态核极化的多用途、耐聚集和生物相容性极化剂
DOI：
10.1021/acs.jpclett.1c00294
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发表时间：
2021-03-10
影响因子：
5.7
通讯作者：
Yanai, Nobuhiro
中科院分区：
文献类型：
--
作者：
Hamachi, Tomoyuki;Nishimura, Koki;Yanai, Nobuhiro
三重态动态核极化(Triplet-DNP)是利用光激发的三重态电子的自旋极化实现中温核自旋极化。三重态DNP在生物分子中的应用一直受到阻碍，因为到目前为止使用的唯一极化剂-烯往往在生物分子基质中聚集并失去极化。在这里，我们首次报道了使用卟啉作为三重态DNP的极化剂，并提出了一种新的聚集容忍极化剂的概念。四(4-羧基苯基)卟啉钠盐(TCPPNa)可以分散在非晶态和晶态的生物分子基质中，重要的是，它即使在轻微聚集的状态下也能产生极化的三重态电子。含有轻微聚集的TCPPNa的结晶赤藓糖醇的三重-DNP可以实现120倍以上的信号增强。由于TCPPNa也是第一个生物相容的三重DNP偏振剂，这项工作为三重DNP的生物和医学应用向前迈出了关键的一步。
Triplet dynamic nuclear polarization (triplet-DNP) achieves nuclear spin polarization at moderate temperatures by using spin polarization of photoexcited triplet electrons. The applications of triplet-DNP for biomolecules have been hampered because acenes, the only polarizing agents used so far, tend to aggregate and lose their polarization in biomolecular matrices. Here, we report for the first time use of porphyrins as polarizing agents of triplet-DNP and propose a new concept of aggregation-tolerant polarizing agents. Sodium salts of tetrakis(4-carboxyphenyl)porphyrin (TCPPNa) can be dispersed in amorphous as well as crystalline biomolecular matrices, and importantly, it can generate polarized triplet electrons even in a slightly aggregated state. Triplet-DNP of crystalline erythritol containing slightly aggregated TCPPNa can achieve more than 120-fold signal enhancement. Because TCPPNa is also the first biocompatible triplet-DNP polarizing agent, this work provides a crucial step forward for the biological and medical applications of triplet-DNP.