Colorimetric and Fluorescent Sensing of Copper Ions in Water through o-Phenylenediamine-Derived Carbon Dots.

Fluorescent nitrogen and sulfur co-doped carbon dots (NSCDs) were synthesized using a simple one-step hydrothermal method starting from o-phenylenediamine (OPD) and ammonium sulfide. The prepared NSCDs presented a selective dual optical response to Cu(II) in water through the arising of an absorption band at 660 nm and simultaneous fluorescence enhancement at 564 nm. The first effect was attributed to formation of cuprammonium complexes through coordination with amino functional groups of NSCDs. Alternatively, fluorescence enhancement can be explained by the oxidation of residual OPD bound to NSCDs. Both absorbance and fluorescence showed a linear increase with an increase of Cu(II) concentration in the range 1-100 µM, with the lowest detection limit of 100 nM and 1 µM, respectively. NSCDs were successfully incorporated in a hydrogel agarose matrix for easier handling and application to sensing. The formation of cuprammonium complexes was strongly hampered in an agarose matrix while oxidation of OPD was still effective. As a result, color variations could be perceived both under white light and UV light for concentrations as low as 10 µM. Since these color changes were similarly perceived in tap and lake water samples, the present method could be a promising candidate for simple, cost-effective visual monitoring of copper onsite.

Tuning the Sensing Properties of N and S Co-Doped Carbon Dots for Colorimetric Detection of Copper and Cobalt in Water.

In this study, nitrogen and sulfur co-doped carbon dots (NS-CDs) were investigated for the detection of heavy metals in water through absorption-based colorimetric response. NS-CDs were synthesized by a simple one-pot hydrothermal method and characterized by TEM, STEM-coupled with energy dispersive X-ray analysis, NMR, and IR spectroscopy. Addition of Cu(II) ions to NS-CD aqueous solutions gave origin to a distinct absorption band at 660 nm which was attributed to the formation of cuprammonium complexes through coordination with amino functional groups of NS-CDs. Absorbance increased linearly with Cu(II) concentration in the range 1-100 µM and enabled a limit of detection of 200 nM. No response was observed with the other tested metals, including Fe(III) which, however, appreciably decreased sensitivity to copper. Increase of pH of the NS-CD solution up to 9.5 greatly reduced this interference effect and enhanced the response to Cu(II), thus confirming the different nature of the two interactions. In addition, a concurrent response to Co(II) appeared in a different spectral region, thus suggesting the possibility of dual-species multiple sensitivity. The present method neither requires any other reagents nor any previous assay treatment and thus can be a promising candidate for low-cost monitoring of copper onsite and by unskilled personnel.

Colorimetric Detection of Chromium(VI) Ions in Water Using Unfolded-Fullerene Carbon Nanoparticles.

Water pollution caused by hexavalent chromium (Cr(VI)) ions represents a serious hazard for human health due to the high systemic toxicity and carcinogenic nature of this metal species. The optical sensing of Cr(VI) through specifically engineered nanomaterials has recently emerged as a versatile strategy for the application to easy-to-use and cheap monitoring devices. In this study, a one-pot oxidative method was developed for the cage opening of C60 fullerene and the synthesis of stable suspensions of N-doped carbon dots in water-THF solutions (N-CDs-W-THF). The N-CDs-W-THF selectively showed variations of optical absorbance in the presence of Cr(VI) ions in water through the arising of a distinct absorption band peaking at 550 nm, i.e., in the transparency region of pristine material. Absorbance increased linearly, with the ion concentration in the range 1-100 µM, thus enabling visual and ratiometric determination with a limit of detection (LOD) of 300 nM. Selectivity and possible interference effects were tested over the 11 other most common heavy metal ions. The sensing process occurred without the need for any other reactant or treatment at neutral pH and within 1 min after the addition of chromium ions, both in deionized and in real water samples.