Ligand-modulated aqueous synthesis of color-tunable copper nanoclusters for the photoluminescent assay of Hg(II)
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ORIGINAL PAPER
Ligand-modulated aqueous synthesis of color-tunable copper nanoclusters for the photoluminescent assay of Hg(II) Mingxia Jiao 1 & Yun Li 1 & Yuxiu Jia 1 & Le Xu 1 & Guiyun Xu 1 & Yingshu Guo 2 & Xiliang Luo 1 Received: 13 July 2020 / Accepted: 28 August 2020 # Springer-Verlag GmbH Austria, part of Springer Nature 2020
Abstract Water-soluble Cu nanoclusters (NCs) with tunable emission were synthesized through an eco-friendly one-pot aqueous method. Blue-, green-, and red-emitting NCs with the emission peaks at 420 nm, 505 nm, and 630 nm were obtained by employing ethanediamine, cysteine, and glutathione as surface ligands, respectively. The ligand effects on the optical properties of Cu NCs were studied by the single variable method. It has been revealed by systematic characterizations that the dependence of emission color on the structures of ligands was mainly attributed to their different size-tuning effects. Glutathione has the strongest chelating ability and it can significantly reduce the monomer reactivity and thus decrease the supersaturation degree of the reaction, which is favorable for modulating Cu precursor to grow into larger NCs. In contrast, ethanediamine ligand resulted in smaller nanoclusters due to its weaker binding capability. Because of the strong emission and terrific fluorescent stability, Cu NCs capped with ethanediamine, possessing an emission peak at 420 nm when excited at a wavelength of 350 nm, were directly used for probing Hg(II) with satisfying selectivity, presenting a linear range of 0.1–5.0 mM and a detection limit of 33 μM. The sensor showed good performance in real sample analysis with recoveries ranging from 99% to 103%, and comparable accuracy with atomic fluorescence spectroscopy, manifesting the reliability of the current strategy for sensing Hg(II).
Keywords Copper nanoclusters . Aqueous synthesis . Ligand effects . Tunable emission . Metal ion assay
Introduction
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00604-020-04539-6) contains supplementary material, which is available to authorized users. * Yingshu Guo [email protected] * Xiliang Luo [email protected] 1
Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, Shandong Key Laboratory of Biochemical Analysis, Key Laboratory of Analytical Chemistry for Life Science in Universities of Shandong, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
2
Collaborative Innovation Center of Tumor Marker Detection Technology, Equipment and Diagnosis-Therapy Integration in Universities of Shandong, Shandong Province Key Laboratory of Detection Technology for Tumor Markers, School of Chemistry and Chemical Engineering, Linyi University, Linyi 276005, China
Metal nanoclusters (NCs), which are tiny colloidal nanoparticles composed of a few to some hundreds of metal atoms, show great potential in the biomedical field, optoelectronics, and sensor development as sup
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