Naha Sanay, Thirumalaivasan Natesan, Garai Somenath, Wu Shu-Pao, Velmathi Sivan
Department of Chemistry, National Institute of Technology Tiruchirappalli, Tiruchirappalli 620015, India.
Department of Applied Chemistry, National Chiao Tung University, Hsinchu 30010, Taiwan.
ACS Omega. 2020 Aug 3;5(31):19896-19904. doi: 10.1021/acsomega.0c02963. eCollection 2020 Aug 11.
The homeostasis of short-lived reactive species such as hydrogen sulfide/hypochlorous acid (HS/HOCl) in biological systems is essential for maintaining intercellular balance. An unchecked increase in biological HS concentrations impedes homeostasis. In this report, we present a molecular probe pyrene-based sulfonyl hydrazone derived from pyrene for the selective detection of HS endogenously as well as exogenously through a "turn-off" response in water. The structure of the receptor is confirmed by Fourier-transform infrared spectroscopy, H and C nuclear magnetic resonance spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction studies. The receptor shows excellent green emission in both the aqueous phase and solid state. Quenching of green emission of the receptor is observed only when HS is present in water with a detection limit of 18 nM. Other competing anions and cations do not have any influence on the receptor's optical properties. The efficiency of HS detection is not negatively impacted by other reactive sulfur species too. The sensing mechanism of HS follows a chemodosimetric reductive elimination of sulfur dioxide, which is supported by product isolation. The receptor is found to be biocompatible, as evident by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, and its utility is extended to endogenous and exogenous fluorescence imaging of HeLa cells and zebrafish.
生物系统中硫化氢/次氯酸（HS/HOCl）等短寿命活性物质的稳态对于维持细胞间平衡至关重要。生物体内HS浓度不受控制的增加会破坏稳态。在本报告中，我们展示了一种基于芘的磺酰腙分子探针，该探针通过水中的“关闭”响应选择性地检测内源性和外源性的HS。通过傅里叶变换红外光谱、H和C核磁共振光谱、电喷雾电离质谱以及单晶X射线衍射研究确定了受体的结构。该受体在水相和固态中均表现出出色的绿色发射。仅当水中存在HS时才观察到受体绿色发射的猝灭，检测限为18 nM。其他竞争性阴离子和阳离子对受体的光学性质没有任何影响。HS的检测效率也不会受到其他活性硫物种的负面影响。HS的传感机制遵循二氧化硫的化学计量还原消除，产物分离对此提供了支持。通过3-(4,5-二甲基噻唑-2-基)-2,5-二苯基四氮唑溴盐试验证明该受体具有生物相容性，其应用扩展到了HeLa细胞和斑马鱼的内源性和外源性荧光成像。
