Banik Dipanjan, Banerjee Shilpita, Halder Satyajit, Ganguly Rajdeep, Karak Anirban, Ghosh Pintu, Jana Kuladip, Mahapatra Ajit Kumar
Molecular Sensor and Supramolecular Chemistry Laboratory, Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Howrah-711103, West Bengal, India.
Division of Molecular Medicine, Bose Institute, P 1/12, CIT Scheme VIIM, Kolkata 700054, India.
Anal Methods. 2025 Apr 17;17(16):3290-3304. doi: 10.1039/d5ay00153f.
Hypochlorite (ClO), a potent oxidizer and disinfectant, and hydrazine, a powerful reducing agent, are widely used in daily life and various industries. However, their extensive use comes with significant risks, as they are highly toxic to both the environment and human health. They have been associated with various health issues and even linked to cancer. Therefore, the simultaneous detection of hypochlorite and hydrazine is crucial for assessing their impact and monitoring the onset and progression of related diseases. A phenanthroimidazole-indandione based colorimetric and ratiometric fluorescent probe PIID was designed and synthesized for dual channel detection of hypochlorite and hydrazine in environmental and biological samples. Probe PIID, which showed a strong yellow-orange emission at 640 nm with a massive Stokes shift of 220 nm, exhibited excellent fluorescence change from yellow-orange to green (526 nm) in the presence of ClO and from yellow-orange to blue (424 nm) in the presence of hydrazine in an aqueous-THF solvent system. A strong ICT effect, which was acting in probe PIID, gets weakened through ClO - mediated cleavage of the CC bridge bond to produce aldehyde PIB with a blue shift of 114 nm and hydrazine-induced hydrazinolysis of the indanedione moiety to form hydrazone compound PIBH with a blue shift of 216 nm and that was also confirmed by DFT studies. Not only that, the probe exhibits excellent selectivity over other ROS (reactive oxygen species) and amines with a very fast response time of 40 seconds for hypochlorite and 90 seconds for hydrazine, and high sensitivity was observed with detection limits of 32.75 nM for hypochlorite and 92 nM for hydrazine. Moreover, PIID was employed to monitor both the analytes successfully in environmental water samples and in a solid-state TLC strip study. Hypochlorite was monitored in commercial disinfectants, and by exogenous bioimaging in human breast cancer cells (MDA-MB 231) and endogenous bioimaging in RAW 264.7 macrophage cells with very low cytotoxicity and good cell viability. Meanwhile, hydrazine was tracked in soil samples, and confocal imaging was performed on onion tissue.
次氯酸盐（ClO）是一种强效氧化剂和消毒剂，肼是一种强还原剂，它们在日常生活和各种工业中被广泛使用。然而，它们的广泛使用伴随着重大风险，因为它们对环境和人类健康都具有高毒性。它们与各种健康问题相关，甚至与癌症有关。因此，同时检测次氯酸盐和肼对于评估它们的影响以及监测相关疾病的发生和发展至关重要。设计并合成了一种基于菲咯咪唑 - 茚二酮的比色和比率荧光探针PIID，用于在环境和生物样品中双通道检测次氯酸盐和肼。探针PIID在640 nm处显示出强烈的黄橙色发射，具有220 nm的大斯托克斯位移，在水 - 四氢呋喃溶剂体系中，在存在ClO时表现出从黄橙色到绿色（526 nm）的优异荧光变化，在存在肼时表现出从黄橙色到蓝色（424 nm）的荧光变化。在探针PIID中起作用的强ICT效应通过ClO介导的CC桥键断裂而减弱，产生蓝移114 nm的醛PIB，以及肼诱导的茚二酮部分的肼解反应，形成蓝移216 nm的腙化合物PIBH，这也通过密度泛函理论（DFT）研究得到证实。不仅如此，该探针对其他活性氧（ROS）和胺类具有优异的选择性，对次氯酸盐的响应时间非常快，为40秒，对肼的响应时间为90秒，并且观察到高灵敏度，次氯酸盐的检测限为32.75 nM，肼的检测限为92 nM。此外，PIID成功用于监测环境水样和固态薄层色谱条研究中的两种分析物。在商业消毒剂中监测次氯酸盐，并通过人乳腺癌细胞（MDA - MB 231）中的外源性生物成像和RAW 264.7巨噬细胞中的内源性生物成像进行监测，具有非常低的细胞毒性和良好的细胞活力。同时，在土壤样品中追踪肼，并对洋葱组织进行共聚焦成像。
