An ultra-sensitive selective fluorescent sensor based on a 3D zinc-tetracarboxylic framework for the detection and enrichment of trace Cu2+ in aqueous media

Herein, a novel and fluorescent zinc-organic framework sensor [Zn-3(mu(3)-Hbptc)(2)(mu(2)-4,4 '-bpy)(2)(H2O)(4)](n)center dot 2nH(2)O (1) (H(4)bptc = 2,3,3 ',4 '-biphenyl tetracarboxylic acid, 4,4 '-bpy = 4,4 '-bipyridine) is synthesized and characterized, demonstrating its excellent fluorescence performance for Cu2+ detection and the enrichment of Cu2+ in aqueous media. The fluorescence intensity of 1 can be selectively quenched by Cu2+ in a linear range of Cu2+ concentrations of 0-0.7 mu M. The limit of detection (LOD) value is as low as 32.4 nM, which is superior to those of most of the fluorescent sensors based on metal-organic frameworks (MOFs). It is also far below the maximum allowable concentration of Cu2+ in drinking water as defined by the U.S. Environmental Protection Agency (EPA) and the World Health Organization (WHO), so it is employed for the detection of Cu2+ in actual water samples. More importantly, the nature of the interaction between the active coordination site (COO-) of 1 and Cu2+ determines the quenching mechanism, that is Cu2+ in the analyte is captured by MOF 1, which has been investigated by ICP, luminescence, UV-vis, XPS, and lifetime studies. Besides, the chemosensor shows regeneration performance without the loss of performance in five consecutive cycles. So MOF 1 is a simple and convenient probe used not only for the rapid detection but also for the enrichment of trace amounts of Cu2+ in aqueous media, and the application can be further extended to a variety of environmental and biological analysis processes.