Synthesis and characterization of a Cu(ii) coordination-containing TAM radical as a nitroxyl probe.
Synthesis and characterization of a Cu(ii) coordination-containing TAM radical as a nitroxyl probe.
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DOI：
10.1039/d1ra07511j
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发表时间：
2022-05-23
期刊：
影响因子：
3.9
通讯作者：
Jiang, Dengzhao
中科院分区：
文献类型：
--
作者：
Liu, Wenbo;Tao, Ouyang;Chen, Li;Ling, Yun;Zeng, Ming;Jin, Hongguang;Jiang, Dengzhao
硝酰基（HNO）是生物系统中重要的信号分子，在许多生理过程中起着重要作用。然而，由于现有检测方法的灵敏度和/或特异性有限，其检测仍然具有挑战性。低频电子顺磁共振（EPR）光谱和成像，加上使用外源性顺磁探针，已成为不可缺少的技术，在体内测量各种生理参数，由于其特异性，非侵入性和良好的磁场穿透动物组织的深度。然而，由于需要改进的探针，通过EPR光谱和成像的HNO水平的体内检测是有限的。我们报告的第一个“打开响应”EPR探针HNO利用铜（二）配位含TAM自由基（表示为CuII[TD 1]）。在与HNO反应时，CuII[TD 1]显示EPR信号的16.1倍开启，低检测限为1.95 μM。此外，低温EPR光谱和ESI-MS研究表明，传感机制依赖于还原Cu（ii）的HNO。最后，CuII[TD 1]对HNO的选择性超过其他活性氮和氧物种，除了一些还原剂（Cys和Asc）。这种新的Cu（II）配位含TAM自由基在体内EPR HNO的应用程序中的还原剂的情况下，显示出巨大的潜力，并提供了深入了解开发改进的和有针对性的EPR HNO探针的生物医学应用。硝酰基（HNO）是生物系统中重要的信号分子，在许多生理过程中起着重要作用。
Nitroxyl (HNO) has been identified as an important signaling molecule in biological systems, and it plays critical roles in many physiological processes. However, its detection remains challenging because of the limited sensitivity and/or specificity of existing detection methods. Low-frequency electron paramagnetic resonance (EPR) spectroscopy and imaging, coupled with the use of exogenous paramagnetic probes, have been indispensable techniques for the in vivo measurement of various physiological parameters owing to their specificity, noninvasiveness and good depth of magnetic field penetration in animal tissues. However, the in vivo detection of HNO levels by EPR spectroscopy and imaging is limited due to the need for improved probes. We report the first “turn on-response” EPR probe for HNO utilizing a Cu(ii) coordination-containing TAM radical (denoted as CuII[TD1]). Upon reaction with HNO, CuII[TD1] shows a 16.1-fold turn-on in EPR signal with a low detection limit of 1.95 μM. Moreover, low-temperature EPR spectroscopic and ESI-MS studies showed that the sensing mechanism relies on the reduction of Cu(ii) by HNO. Lastly, CuII[TD1] is selective for HNO over other reactive nitrogen and oxygen species except for some reductants (Cys and Asc). This new Cu(ii) coordination-containing TAM radical shows great potential for in vivo EPR HNO applications in the absence of reducing agents and provides insights into developing improved and targeted EPR HNO probes for biomedical applications. Nitroxyl (HNO) has been identified as an important signaling molecule in biological systems, and it plays critical roles in many physiological processes.
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