Adak Arup Kumar, Dutta Basudeb, Manna Saikat Kumar, Sinha Chittaranjan
Bidhannagar College, EB-2, Sector -1, Salt Lake, Kolkata 700064, West Bengal, India.
Department of Chemistry, Jadavpur University, Kolkata 700032, West Bengal, India.
ACS Omega. 2019 Nov 8;4(21):18987-18995. doi: 10.1021/acsomega.9b01860. eCollection 2019 Nov 19.
Designing a fluorogenic probe for the determination of Pd is a challenging analytical task. Pd is a potentially toxic and harmful substance even at a very low level of contamination in the end product. Herein, a promising spirolactam-functionalized chemosensor, rhodamine-appended benzophenone (HBR), is designed and characterized by spectroscopic (H NMR, C NMR, ESI-MS, and FT-IR) data along with the single-crystal X-ray diffraction technique. It acts as a highly sensitive and selective fluorogenic chemosensor for Pd ions over other environmentally relevant cations in aqueous ethanol (1:1, v/v) at pH 7.4. The limit of detection (LOD) is 34 nM that is far below the WHO recommended Pd uptake (47 μM). The plausible mechanism involves the specific binding of HBR with Pd and the formation of 1:1 stoichiometry of the complex, which has been supported by ESI-MS, FT-IR data, Job plot, and association constant data (Benesi-Hildebrand plot). The computation study has been attempted to explain the ring cleavage fluorescence enhancement scheme of HBR upon binding with Pd. Furthermore, this "turn-on" probe has successfully applied to image the Pd ion in cultured MDA-MB-231 cells.
设计一种用于测定钯的荧光探针是一项具有挑战性的分析任务。即使在最终产品中钯的污染水平非常低的情况下，它也是一种潜在的有毒有害物质。在此，设计了一种有前景的螺内酰胺功能化化学传感器——罗丹明连接的二苯甲酮（HBR），并通过光谱数据（氢核磁共振、碳核磁共振、电喷雾电离质谱和傅里叶变换红外光谱）以及单晶X射线衍射技术对其进行了表征。在pH 7.4的乙醇水溶液（1:1，v/v）中，它对钯离子的选择性高于其他环境相关阳离子，是一种高灵敏度和选择性的荧光化学传感器。检测限（LOD）为34 nM，远低于世界卫生组织推荐的钯摄入量（47 μM）。合理的机制涉及HBR与钯的特异性结合以及形成1:1化学计量比的配合物，这已得到电喷雾电离质谱、傅里叶变换红外光谱数据、乔布图和缔合常数数据（贝内西-希尔德布兰德图）的支持。已尝试通过计算研究来解释HBR与钯结合后环开裂荧光增强的机制。此外，这种“开启”探针已成功应用于对培养的MDA-MB-231细胞中的钯离子进行成像。
