Electronic Supplementary Material Copper nanoclusters as an on-off-on fluorescent probe for ascorbic acid Hanbing Rao a*, Hongwei Ge a, Zhiwei Lu a,Wei Liu a, Ziqi Chen a, Zhaoyi Zhanga, Xianxiang Wang a, Ping Zoua, Yanying Wang a*, Hua Heb, Xianying Zengc a College of Science, Sichuan Agricultural University, Ya’an 625014, P.R. China b Animal Genetics and Breeding Institute of Sichuan Agricultural University, Sichuan Ya’An 625014, P.R. China c College of Life Science, Sichuan Agricultural University, Ya’an 625014, P.R. China The authors wish it to be known that, in their opinions, Hanbing Rao and Hongwei Ge should be regarded as joint First Authors. *Corresponding author, Hanbing Rao, E-mail: rhb@sicau.edu.cn or rhbscu@gmail.com, Yanying Wang, E-mail: 43936939@qq.com Fig. S1 Fluorescence decays of TA-Cu NCs and TA-CuNCs/Fe(III). 1 Fig. S2 (a) Kinetic of reactions between TA-CuNCs and Fe(III) (black), TA-CuNC/Fe(III) and AA(red). (b) Dependence of ΔF/F0 of the prepared TA-Cu NCs and TA-Cu NCs/Fe(III) system on the dosage of TA-CuNCs. (c) Relative fluorescence intensities ΔF/F0 of solutions of TA-CuNCs in the presence of AA at different concentration of Fe(III) from 20-80μM. (d) Effects of solution pH on the fluorescence responses of TA-CuNCs in different systems: TA-CuNCs and Fe(III) (black); TA-CuNC/Fe(III) and AA(red). 2 Fig. S3 Fluorescence response of TA-CuNCs in the presence of variety of ions and molecules. Table S1. Nanosecond time-resolved luminescence transients of TA-CuNCs in different systems. The luminescence of TA-CuNCs(maximum wavelength, λmax=430 nm) was detected with a 355 nm excitation laser. system τ1 R2 (ns) τ (ns) TA-CuNCs 1.8369 1.091 1.84 TA-CuNCs + Fe(III) 1.8947 1.008 1.89 3 Table S2 The comparison of the determination of AA Methods Fluorescence method with graphene quantum dots Fluorescence method with Au nanoclusters Fluorescence method with CdTe quantum dots Fluorescent carbon dot nanosensor HPLC MnFe2O4@CNT-N electrochemical nanosensor Fluorescence method with TA-Cu NCs/Fe(III) Linear detection range Detection limit 0.3– 10μM 94 5-100μM 5 μM [2] 0.3-10μM 74 nM [3] Reference [1] 0.03-0.1mM [4] 0.2 [5] 2.0 × 10−6 -1.0 × 10− 4 M 1.8 × 10−6 M [6] 0.5-10μM 0.11 μM This work References [1] Liu J-J, Chen Z-T, Tang D-S, Wang Y-B, Kang L-T, Yao J-N (2015) Graphene quantum dots-based fluorescent probe for turn-on sensing of ascorbic acid. Sens. Actuators, B 212:214-219 [2] Hu L, Deng L, Alsaiari S, Zhang D, Khashab N M (2014) “Light-on” Sensing of Antioxidants Using Gold Nanoclusters. Anal. Chem. 86(10):4989-4994 [3] Chen Y J, Yan X P (2009) Chemical redox modulation of the surface chemistry of CdTe quantum dots for probing ascorbic acid in biological fluids. Small 5(17):2012-2018 [4] Zheng M, Xie Z, Qu D, Li D, Du P, Jing X, Sun Z (2013) On-off-on fluorescent carbon dot nanosensor for recognition of chromium(VI) and ascorbic acid based on the inner filter effect. ACS Appl Mater Interfaces 5(24):13242-13247 [5] Stan M, Soran M L, Marutoiu C (2014) Extraction and HPLC determination of the ascorbic acid content of three indigenous spice plants. J. Anal. Chem. 69(10):998-1002 [6] Fernandes D M, Silva N, Pereira C, Moura C, Magalhães J M C S, Bachiller-Baeza B, Rodríguez-Ramos I, Guerrero-Ruiz A, Delerue-Matos C, Freire C (2015) MnFe2O4@CNT-N as novel electrochemical nanosensor for determination of caffeine, acetaminophen and ascorbic acid. Sens. Actuators, B 218:128-136 4