Colorimetric detection of Cr3+ using gold nanoparticles functionalized with 4-amino hippuric acid Weiwei Jin, Pengcheng Huang, Yueji Chen, Fang-Ying Wu, Yiqun Wan Department of Chemistry, Nanchang University, Nanchang 330031, China E-mail:fywu@ncu.edu.cn Supplementary Material List of Contents page number Fig. S1 IR spectra of pure PAH and PAH-AuNPs. 2 Fig. S2 Particle size distribution histogram of PAH-AuNPs. 2 Fig. S3 Analytical stability of the PAH-AuNPs toward Cr3+. Intensity ratio (A635nm/A520nm) of PAH-AuNPs in the absence and presence of Cr3+ (A) for 10 days, and (B) for 5 batches. 3 Fig. S4 Intensity ratio of A635nm/A520nm in the presence of various concentrations PAH-AuNPs against upon adding Cr3+. 3 Fig. S5 Effect of PAH concentration on the detection of Cr3+. UV-vis spectra of PAH-AuNPs as a function of Cr3+ concentrations. Cr3+ concentrations increase from 0 to 120 μM with 5 μM as the interval in the first 70 μM and 10 μM as the interval in the last 50 μM. Fig. S6 Effects of pH on the detection of Cr3+. A635 nm/A520 nm 4 is the absorption ratio of the detection Cr3+ in the absence and presence of Cr3+, respectively. Cr3+ Concentration: 50 µM. Fig. S7 Effects of NaCl on the absorption ratio (A635nm/A520nm) of detection Cr3+ 4 5 Fig. S8 Plots of the time-dependent absorption ratio (A635nm/A520nm) over 10 min in the presence of varying concentrations of Cr3+. 5 Fig. S9 The plot of the the absorbance ratio (A635nm/A520nm) change of PAH-AuNPs upon addition of increasing concentration of Cr3+ in the absence (black) and presence of 0.2 mM EDTA (red). 5 Fig. S10 Relationship between the absorbance ratio (A635nm/A520nm) of PAH-AuNPs and the concentration of Cr3+ with deionized water (black), milk power (red), liquid milk (blue) and lake Corresponding authors: Department of Chemistry, Nanchang University, Nanchang 330031, China, Tel: + 86 79183969882; Fax: + 86 79183969514. E-mail address: fywu@ncu.edu.cn. 1 water (green) samples. 6 Table S1 Cr3+ Detection methods published 6 Table S2 The Calibration equations in the different matrix. 7 Fig. S1 IR spectra of pure PAH and PAH-AuNPs. Fig. S2 Particle size distribution histogram of PAH-AuNPs. 2 Fig. S3 Analytical stability of the PAH-AuNPs toward Cr3+. (A) Intensity ratio (A635nm/A520nm) of PAH-AuNPs in the absence and presence of Cr3+ for 10 days, (B) Intensity ratio (A635nm/A520nm) of PAH-AuNPs in the absence and presence of Cr3+ for 5 batches. Fig. S4 Intensity ratio of A635nm/A520nm in the presence of various concentrations PAH-AuNPs against upon adding Cr3+. 3 Fig. S5 Effect of PAH concentration on the detection of Cr3+. UV-vis spectra of PAH-AuNPs as a function of Cr3+ concentrations. Cr3+ concentrations increase from 0 to 120 μM with 5 μM as the interval in the first 70 μM and 10 μM as the interval in the last 50 μM. Fig. S6 Effects of pH on the detection of Cr3+. A635 nm/A520 nm is the absorption ratio of the detection Cr3+ in the absence and presence of Cr3+, respectively. Cr3+ Concentration: 50 µM. 4 Fig. S7 Effects of NaCl on the absorption ratio (A635nm/A520nm) of detection Cr3+. A635nm/A520nm is the absorption ratio of the detection Cr3+ in the absence and presence of Cr3+, respectively. Cr3+ Concentration: 50 µM. Fig. S8 Plots of the time-dependent absorption ratio (A635nm/A520nm) over 10 min in the presence of various concentrations of Cr3+. Fig. S9 The plot of the absorbance ratio (A635nm/A520nm) change of PAH-AuNPs upon addition of 5 increasing concentration of Cr3+ in the absence (black) and presence of 0.2 mM EDTA (red). Fig. S10 Relationship between the absorbance ratio (A635nm/A520nm) of PAH-AuNPs and the concentration of Cr3+ with deionized water (black), milk power (red), liquid milk (blue) and lake water (green) samples. Table S1 Cr3+ Detection Methods Published Method Colorimetric detection of Cr3+ using tripolyphosphate modified gold nanoparticles Xanthoceras sorbifoliatannin attached to gold nanoparticles Colorimetric speciation of Cr(III) and Cr(VI) with a gold nanoparticle probe Selective detection of Cr(III) in aqueous solution based on a gold nanoparticles Immunochromatographic assay for the rapid detection of chromium ions Fluorescent turn-on chemosensor for Fe3+ and Cr3+ Sensitive and selective SERS probe for trivalent chromium Fluorescence quenching method for determination Cr3+ based on Linearity range LOD μM Response to ions Ref. 0.22-22μM 0.10 Cr3+ 1 10-100 μM 3.0 Cr3+ 2 2-8μM 0.30 Cr3+ Cr6+ 3 0-0.4μM 0.4-0.8μM 0.12 Cr3+ 4 5–80 ng mL−1 0.018 Cr3+ Cr6+ 5 NA 2.57 Fe3+ Cr3 6 0-200 nM 0.05 Cr3+ 7 0.1-20μM 0.03 Cr3+ 8 6 CdSe QDs PAH modified AuNPs 5-120μM 1.17 Cr3+ This way 1. Xin, J.; Miao, L.; Chen, S.; Wu, A., Colorimetric detection of Cr3+ using tripolyphosphate modified gold nanoparticles in aqueous solutions. Anal. Methods 2012, 4, 1259-1264. 2. Ha, W.; Yu, J.; Wang, R.; Chen, J.; Shi, Y.-p., “Green” colorimetric assay for the selective detection of trivalent chromium based on Xanthoceras sorbifolia tannin attached to gold nanoparticles. Anal. Methods. 2014, 6, 5720-5726. 3. Liu, Y.; Wang, X., Colorimetric speciation of Cr(III) and Cr(VI) with a gold nanoparticle probe. Anal. Methods. 2013, 5, 1442-1448. 4. Zhao, L.; Jin, Y.; Yan, Z.; Liu, Y.; Zhu, H., Novel, highly selective detection of Cr(III) in aqueous solution based on a gold nanoparticles colorimetric assay and its application for determining Cr(VI). Anal. Chim. Acta 2012, 731, 75-81. 5. Liu, X.; Xiang, J.-J.; Tang, Y.; Zhang, X.-L.; Fu, Q.-Q.; Zou, J.-H.; Lin, Y., Colloidal gold nanoparticle probe-based immunochromatographic assay for the rapid detection of chromium ions in water and serum samples. Anal. Chim. Acta 2012, 745, 99-105. 6. Zhu, W.; Yang, L.; Fang, M.; Wu, Z.; Zhang, Q.; Yin, F.; Huang, Q.; Li, C., New carbazole-based Schiff base: Colorimetric chemosensor for Fe3+ and fluorescent turn-on chemosensor for Fe3+ and Cr3+. J. Lumin. 2015, 158, 38-43. 7. Ye, Y.; Liu, H.; Yang, L.; Liu, J., Sensitive and selective SERS probe for trivalent chromium detection using citrate attached gold nanoparticles. Nanoscale. 2012, 4, 6442-6448. 8. Sung, T.-W.; Lo, Y.-L.; Chang, I. L., Highly sensitive and selective fluorescence probe for Cr3+ ion detection using water-soluble CdSe QDs. Sensors and Actuators B: Chemical 2014, 202, 1349-1356. Table S2 The calibration equations in the different matrix Material Calibration equation Correlation coefficient (r) Deionized water y=0.00925 [C]/µM + 0.161 0.998 Milk power y=0.00943 [C]/µM + 0.161 0.999 Liquid milk y=0.0100 [C]/µM + 0.153 0.998 Lake water y=0.0102 [C]/µM + 0.139 0.999 7