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

Sensors (Basel). 2023 Mar 10;23(6):3029. doi: 10.3390/s23063029.

Abstract

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.

Keywords: agarose hydrogel; carbon dots; colorimetric; copper; fluorescence; o-Phenylenediamine; optical sensing.

Grants and funding

This work was supported by Regione Lazio through Progetto di Ricerca POR FESR LAZIO 2014–2020 Id: A0375-2020-36403 according to G09493 del 14 July 2021. M.A. has been supported by MIUR—Ministero dell’Istruzione Ministero dell’Università e della Ricerca (Ministry of Education, University and Research) under the national project FSE/FESR–PON Ricerca e Innovazione 2014–2020 (N° AIM1887574, CUP: E18H19000350007). This research was also supported by Fundação para a Ciência e Tecnologia, FCT/MCTES, through the Associate Laboratory for Green Chemistry—LAQV (grants UIDB/50006/2020 and UIDP/50006/2020).