Zn(II)-concentration dependent Raman spectra in the dithizone complex on gold nanoparticle surfaces in environmental water samples

Abstract

After the formation of dithizone with metal ion complexes, a selective Raman detection method for the Zn2+ ions in aqueous solutions was developed by observing the intensity change of the ring mode peaks at ∼1585cm−1 on gold nanoparticles (AuNPs). At high concentrations of Zn2+ ions, the conformation of the dithizone complex may have different orientations on AuNPs to yield the spectral changes at ca. ∼510 and ∼1585cm−1. The concentration dependent spectra changes indicated that a detection limit would be in the submicromolar region of Zn2+ ions. The other ions of Mg2+, K+, Fe3+, Hg2+, Co2+, Fe2+, Pb2+, Cu2+, Ni2+, Cr3+, NH4+, Cd2+, Na+, Ca2+, and Mn2+ at micromolar concentrations of 1μM did not produce such spectral changes. The detection limit based on the Raman band intensities was estimated to be as low as 500nM of Zn2+ ion in aqueous solutions. The three real samples of tap, river, and seawater were tested under the interference of the commonly existing interfering ions. Despite the presence of highly concentrated Na, Ca, Mg, and K, our interfacial spectroscopic methodology of Zn2+ determination could be applied in the environmental water samples.