Supporting Information

Transcription

1 Supporting Information Graphene Quantum Dot-MnO 2 Nanosheet-Based Optical Sensing Platform: a Sensitive Fluorescence Turn Off-On Nanosensor for Glutathione Detection and Intracellular Imaging Xu Yan 1,2,, Yang Song 2,, Chengzhou Zhu 2, Junhua Song 2, Dan Du *,1,3, Xingguang Su *,2 and Yuehe Lin *,1 1 School of Mechanical and Materials Engineering, Washington State University, Pullman, Washington 99164, United States 2 Department of Analytical Chemistry, College of Chemistry, Jilin University, Changchun, , China 3 Key Laboratory of Pesticide and Chemical Biology of the Ministry of Education, P. R. China and College of Chemistry, Central China Normal University, Wuhan, , P. R. China AUTHOR INFORMATION Corresponding Author * dan.du@mail.ccnu.edu.cn (D Du) * yuehe.lin@wsu.edu (YH Lin) * suxg@jlu.edu.cn (XG Su) S-1

2 Figure S1. (A) TEM of uniform MnO2 nanosheets. (B) XPS spectra and (C) Raman spectrum of MnO2 nanosheets. S-2

3 Figure S2. UV-vis absorption of MnO 2 nanosheet and the fluorescence excitation spectra of GQDs. S-3

4 Figure S3. (A) TEM image of the GQDs/MnO 2 mixture; (B) The lifetime of GQDs in absence and presence of MnO 2 nanosheets. S-4

5 Figure S4. (A) The effect of the ph value on the FL intensity ratio of GQDs-MnO 2 probe in the presence of 10 µmol L -1 GSH; (B) The effect of reaction time on the FL intensity of GQDs-MnO 2 system in the absence (black) and presence (red) of GSH (10 µmol L -1 ). F 0 and F were the FL intensity of the GQDs-MnO 2 system in the absence and presence of GSH, respectively. S-5

6 Figure S5. The UV vis absorption spectra of MnO 2-10 µmol L -1 GSH for 8 min. S-6

7 Figure S6. (A) Fluorescence spectra of GQDs-50 µg ml -1 MnO 2 sensing probe with different concentrations of GSH. The concentrations of GSH were 0, 1.0, 2.0, 5.0, 10.0, 20.0, 50.0 and 100 µmol L -1, respectively. The inset was the change trend of FL intensity ratio with different GSH concentrations. (B) Relationship between the FL intensity ratio and the logarithm of the GSH concnentration. F and F 0 are fluorescence intensities of GQDs-MnO 2 sensing probe in the presence and absence of GSH, respectively. S-7

8 A 1.2 B 1.2 C 1.2 Cell Viability (%) Cell Viability (%) Cell Viability (%) Concentration (µg ml -1 ) Concentration (µg ml -1 ) Concentration (µg ml -1 ) 50 Figure S7. Relative viabilities of MCF-7 cells after treated with (A) MnO 2 nanosheets, (B) GQDs, and (C) MnO 2 /GQDs nanoprobe, respectively. In this experiment, MCF-7 cells were incubated with different concentration of MnO 2 nanosheets, GQDs, and MnO 2 /GQDs nanoprobe for 1 h. Afterwards cells were washed with PBS, placed into fresh cell medium, re-incubated for additional 24 h before the MTT assay. S-8

9 Figure S8. Confocal imaging of MCF-7 cells treated with GQDs only, GQDs with NMM and GQDs with BSO for 2 and 4 h. S-9

10 Figure S9. Confocal fluorescence microscope images showing MCF-7 cells pretreated with NMM, BSO and LPA for 1 h followed by incubation with the nanoprobes. S-10

11 Table S1. Comparison of the proposed method with other methods for GSH detection Method Linear range Detection Limit React time (µmol L -1 ) (µmol L -1 ) (min) Reference HPLC / 1 Surface Enhanced Raman Scattering Surface Enhanced Raman Scattering Colorimetry Colorimetry Colorimetry / 5 6 Electrochemiluminescence / 7 Electrochemiluminescence / 8 Electrochemiluminescence / 9 Fluorometry / 10 Fluorometry / Fluorometry / / 12 Fluorometry / 13 Fluorometry Fluorometry Fluorometry Fluorometry Fluorometry / 0.9 / 18 Fluorometry / 19 Fluorometry Fluorometry This work S-11

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