硝酮氟化物：一种基于硫醇的荧光探针，用于活细胞中硝酮的成像。
NitroxylFluor: A Thiol-Based Fluorescent Probe for Live-Cell Imaging of Nitroxyl.
机构信息
Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign , Urbana, Illinois 61801, United States.
出版信息
J Am Chem Soc. 2017 Dec 27;139(51):18476-18479. doi: 10.1021/jacs.7b11471. Epub 2017 Dec 14.
Detection of nitroxyl (HNO), the transient one-electron reduced form of nitric oxide, is a significant challenge owing to its high reactivity with biological thiols (with rate constants as high as 10 M s). To address this, we report a new thiol-based HNO-responsive trigger that can compete against reactive thiols for HNO. This process forms a common N-hydroxysulfenamide intermediate that cyclizes to release a masked fluorophore leading to fluorescence enhancement. To ensure that the cyclization step is rapid, our design capitalizes on two established physical organic phenomena; the alpha-effect and the Thorpe-Ingold effect. Using this new trigger, we developed NitroxylFluor, a selective HNO-responsive fluorescent probe. Treatment of NitroxylFluor with an HNO donor results in a 16-fold turn-on. This probe also exhibits excellent selectivity over various reactive nitrogen, oxygen, and sulfur species and efficacy in the presence of thiols (e.g., glutathione in mM concentrations). Lastly, we successfully performed live cell imaging of HNO using NitroxylFluor.
检测亚硝酰自由基（HNO），即一氧化氮的单电子还原形式，是一项重大挑战，因为其与生物硫醇（反应速率常数高达 10 M s）的高反应性。为了解决这个问题，我们报告了一种新的基于硫醇的 HNO 响应触发物，它可以与反应性硫醇竞争 HNO。这个过程形成了一个常见的 N-羟磺酰胺中间体，它环化释放出一个被掩蔽的荧光团，导致荧光增强。为了确保环化步骤快速进行，我们的设计利用了两个已确立的物理有机现象；alpha 效应和 Thorpe-Ingold 效应。使用这种新的触发物，我们开发了 NitroxylFluor，一种选择性的 HNO 响应荧光探针。用 HNO 供体处理 NitroxylFluor 会导致 16 倍的开启。该探针还表现出对各种活性氮、氧和硫物种的优异选择性，以及在硫醇存在下的功效（例如，在 mM 浓度下的谷胱甘肽）。最后，我们成功地使用 NitroxylFluor 进行了活细胞内 HNO 的成像。
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