Fluorescence “Turn On” Detection of Mercuric Ion Based on Bis(dithiocarbamato)copper(II) Complex Functionalized Carbon Nanodots

Abstract

A new "turn on" fluorescence nanosensor for selective Hg(2+) determination is reported based on bis(dithiocarbamato)copper(II) functionalized carbon nanodots (CuDTC2-CDs). The CuDTC2 complex was conjugated to the prepared amine-coated CDs by the condensation of carbon disulfide onto the nitrogen atoms in the surface amine groups, followed by the coordination of copper(II) to the resulting dithiocarbamate groups (DTC) and finally by the additional coordination of ammonium N-(dithicarbaxy) sarcosine (DTCS) to form the CuDTC2-complexing CDs. The CuDTC2 complex at surface strongly quenched the bright-blue fluorescence of the CDs by a combination of electron transfer and energy transfer mechanism. Hg(2+) could immediately switch on the fluorescence of the CuDTC2-CDs by promptly displacing the Cu(2+) in the CuDTC2 complex and thus shutting down the energy transfer pathway, in which the sensitive limit for Hg(2+) as low as 4 ppb was reached. Moreover, a paper-based sensor has been fabricated by printing the CuDTC2-CDs probe ink on a piece of cellulose acetate paper using a commercial inkjet printer. The fluorescence "turn on" on the paper provided the most conveniently visual detection of aqueous Hg(2+) ions by the observation with naked eye. The very simple and effective strategy reported here facilitates the development of portable and reliable fluorescence nanosensors for the determination of Hg(2+) in real samples.