Novel insight on chemo-specific detection of toxic environmental chromium residues existing as recalcitrant Cr(III)-carboxyl complexes using plasmonic silver nanoplatform bi-functionalized with citrate and PVP

Chromium (Cr) is a toxic environmental pollutant that majorly exists in trivalent and hexavalent forms. Though Cr(VI) is more dangerous than Cr(III), the trivalent Cr forms complexes with environmentally-available organic molecules. This makes them potentially harmful and difficult to detect. In this study, we have designed an ultrasensitive plasmonic nanosensor using citrate and PVP functionalized Ag nanoparticles (Ag-citrate-PVPNPs) for the detection of trivalent chromium organic complexes such as Cr(III)-EDTA (Cr-E), Cr(III)-acetate (Cr-A), Cr(III)-citrate (Cr-C) and Cr(III)-tartrate (Cr-T). The nanoparticles (NPs) were structurally characterized by XRD, SEM, HRTEM, SAED, EDX and elemental mapping. The citrate and PVP molecules played a vital role in the detection mechanism and stability of the sensor. Upon detection, the yellow-colored Ag-citrate-PVP NPs turned into different shades of brown depending on the type of the Cr complex and concentration. It was accompanied by diminishing and/or shifting UV-Visible absorbance peaks due to the aggregation of Ag-citrate-PVP NPs. Further, a linear relationship was observed between absorbance reduction and analyte concentration. The selectivity tests showed that the sensor was non-functional to other metal ions and inorganic anions. The sensor was optimized using pH and temperature studies. The mechanism of detection was elucidated with the help of characterization techniques such as Raman spectroscopy, FTIR, XPS and UV-visible spectrophotometer. The limit of detection (LOD) was found to be 3.29, 4.87, 1.76 and 1.79 nM for Cr-E, Cr-A, Cr-C and Cr-T complexes respectively. This study provides a rapid and sensitive approach for the detection of multiple Cr(III)-organic complexes present in an aqueous solution.