Mandal Sandip, Banerjee Arnab, Ghosh Debasree, Mandal Dipak Kumar, Safin Damir A, Babashkina Maria G, Robeyns Koen, Mitoraj Mariusz P, Kubisiak Piotr, Garcia Yann, Das Debasis
Department of Chemistry, The University of Burdwan, Burdwan, 713104, West Bengal, India.
Dalton Trans. 2015 Aug 7;44(29):13186-95. doi: 10.1039/c5dt01854d.
3',6'-Bis(diethylamino)-2-(pyridin-2-ylmethyl)spiro[isoindoline-1,9'-xanthen]-3-one () was synthesized for the selective fluorescence and colorimetric recognition of Hg(2+) at pH 6.0. In addition, was useful for imaging Hg(2+) in fish kidney and liver tissues using a fluorescence microscope. Spirolactam ring opening of for Hg(2+) recognition is strongly influenced by the nature of the mercury salt and found to be NO3(-)-induced. Other mercury salts such as HgCl2, Hg(CH3COO)2 and Hg(ClO4)2 failed to induce fluorescence and colorimetric response of under the same experimental conditions. For instance, the former salt does not exhibit spirolactam ring opening but forms a new ionic compound (H3L)2[Hg6Cl18]·2H2O (), whose structure has been elucidated by single crystal X-ray diffraction. This might be explained by (1) the higher covalent nature of Hg(2+) and, hence, the lower acidity of the metal center and its inability to induce the ring opening reaction, and (2) the bulky anion, in the case of Hg(ClO4)2, which is also ionic, faces steric hindrance to accommodate within the N(Et)2 group upon spirolactam ring opening.
合成了3',6'-双(二乙氨基)-2-(吡啶-2-基甲基)螺[异吲哚啉-1,9'-呫吨]-3-酮(),用于在pH 6.0时对Hg(2+)进行选择性荧光和比色识别。此外,它还可用于使用荧光显微镜对鱼肾和肝组织中的Hg(2+)进行成像。用于Hg(2+)识别的螺内酰胺环开环受到汞盐性质的强烈影响,发现是由NO3(-)诱导的。其他汞盐如HgCl2、Hg(CH3COO)2和Hg(ClO4)2在相同实验条件下未能诱导的荧光和比色响应。例如,前一种盐不表现出螺内酰胺环开环,而是形成一种新的离子化合物(H3L)2[Hg6Cl18]·2H2O(),其结构已通过单晶X射线衍射阐明。这可能是由于(1)Hg(2+)的较高共价性质,因此金属中心的酸性较低,无法诱导开环反应,以及(2)在Hg(ClO4)2的情况下,庞大的阴离子也是离子性的,在螺内酰胺环开环时面临空间位阻,无法容纳在N(Et)2基团内。