Tributylhexadecylphosphonium Modification Strategy to Construct Gold Nanoprobes for the Detection of Aqueous Cr(III)-Organic Complexes.

Most metal probes based on gold nanoparticles (AuNPs) are designed for free metal ions in synthetic waters, and very few are applicable in the detection of metal-organic complexes ubiquitous in real water samples. In this study, we proposed a novel colorimetric nanoprobe strategy for complexed Cr(III) species based on the analyte-induced aggregation of AuNPs, as coated by a cationic surfactant tributylhexadecylphosphonium bromide (THPB) instead of traditional carboxyl modifiers. Such a detection system could be realized via both naked eye and/or UV-vis spectroscopy with detection limits of 8.0 and 0.29 μM, respectively, much lower than its allowable maximum level in industrial effluent as regulated by China EPA (1.5 mg Cr/L, ∼30 μM). The proposed detection system also exhibits high selectivity against various interfering substances including free ions, small organic molecules, and other metal-citrate complexes. The unique hydrolysis and extremely slow decomplexation of Cr(III) are believed to favor the formation of the specific interaction between Cr(III)-citrate and THPB-AuNPs, as verified by X-ray photoelectron spectroscopy characterization, thus endowing the nanoprobe with specific discrimination of the complexed Cr(III) via the aggregation of THPB-AuNPs. Also, the THPB-AuNPs could be stored at room temperature for 30 days and maintain constant detection performance. Moreover, the quantitative detection of Cr(III)-organic complexes with the background of various real water samples agreed well with that based on inductively coupled plasma atomic emission spectrometry, making it an attractive alternative for on-site detection of authentic samples containing Cr(III)-organic species.