Department of Chemistry, Chung-Ang University, Seoul 06974, Republic of Korea.
Analyst. 2019 Dec 2;144(24):7263-7269. doi: 10.1039/c9an01884k.
A novel hypochlorous-acid-selective signaling probe based on the carbonodithioate derivative of resorufin (RT-1) was developed. Probe RT-1 showed prominent colorimetric and turn-on type fluorescence signaling behavior exclusively toward hypochlorous acid, induced by oxidative hydrolysis, to regenerate resorufin dye. Hypochlorous acid signaling was not affected by the presence of common metal ions and anions as background, except for the redox active bromide and iodide anions. The detection limit of RT-1 for hypochlorous acid was found to be 2.18 × 10-9 M (0.11 ppb), and the signaling was completed within 3 min. It was also confirmed that hypochlorous acid signaling by the carbonodithioate-based probe RT-1 was superior to that of the closely related carbonothioate derivative RT-2. This was rationalized by density functional theory calculations, which demonstrated that the C[double bond, length as m-dash]S sulfur atom of the former is more negatively charged than that of the latter. Finally, as a biological application of the probe, visualization of hypochlorous acid in RAW 264.7 murine macrophages and HeLa cells was successfully conducted to detect the cellular response to hypochlorous acid.
一种基于碳二硫代酯衍生的 Resorufin（RT-1）的新型次氯酸选择性信号探针被开发出来。探针 RT-1 表现出显著的比色和开启型荧光信号行为，仅对次氯酸有响应，次氯酸通过氧化水解作用来再生 Resorufin 染料。次氯酸信号不受常见金属离子和阴离子的存在影响，除了具有氧化还原活性的溴化物和碘化物阴离子。发现 RT-1 对次氯酸的检测限为 2.18 × 10-9 M（0.11 ppb），信号在 3 分钟内完成。还证实了基于碳二硫代酯的探针 RT-1 的次氯酸信号优于密切相关的碳硫代酯衍生物 RT-2。这可以通过密度泛函理论计算来合理化，该计算表明前者的 C[双键，长度 as m-dash]S 硫原子比后者的带负电荷更多。最后，作为探针的生物应用，成功地在 RAW 264.7 小鼠巨噬细胞和 HeLa 细胞中可视化次氯酸，以检测细胞对次氯酸的反应。
