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1 Supporting Information Electrochemiluminescent Pb 2+ -Driven Circular Etching Sensor Coupled to a DNA Micronet-Carrier Wen-Bin Liang,, Ying Zhuo, Ying-Ning Zheng, Cheng-Yi Xiong, Ya-Qin Chai, *, and Ruo Yuan *, Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing , PR China Department of Clinical Biochemistry, Laboratory Sciences, Southwest Hospital, Third Military Medical University, 30 Gaotanyan Street, Shapingba District, Chongqing , PR China * Corresponding Author yqchai@swu.edu.cn (Yaqin Chai), yuanruo@swu.edu.cn (Ruo Yuan). Tel.: ; Fax: S-1

2 Scheme S1 Schematic illustration for the mechanism of the ECL reactions on the proposed biosensor surface. Figure S1 The schematic diagram of the equivalent circuit with model impedance data. S-2

3 Figure S2 Polyacrylamide gel electrophoresis characterization of the generation of DNA micronet-carrier. Figure S3 The ECL performance (blue line) associated with electrochemical (red line) response of the proposed biosensor. S-3

4 Figure S4 The characterization of ECL biosensor with different layers. S-4

5 Figure S5 The investigation of the repeatability of the proposed ECL biosensor via intra- and inter-assay. A, the investigation of the repeatability via intra-assay by 15 different ECL biosensors without reaction of Pb 2+ ; B, the investigation of the repeatability via inter-assay by 15 different ECL biosensors without reaction of Pb 2+ ; C, the investigation of the repeatability via intra-assay by 15 different ECL biosensors with reaction of 400 nm Pb 2+ ; D, the investigation of the repeatability via inter-assay by 15 different ECL biosensors with reaction of 400 nm Pb 2+. S-5

6 Figure S6 The concentration range for the concentration of Pb 2+ in the applicability evaluation by the standard addition method (A) and comparison with the inductively coupled plasma mass spectrometry (B) in a box chart (box, 25% 75% value range;, mean value;, 1% to 99% percentile; ICP, inductively coupled plasma mass spectrometry). S-6

7 Table S1 Comparison of the developed ECL strategy with other methods from the literature. Methods Linear Range Detection Limit Ref. ECL nm 70 nm Ref. S1 ECL nm 0.35 pm Ref. S2 EC nm 300 nm Ref. S3 EC nm 34 pm Ref. S4 EC nm 21 nm Ref. S5 FL nm 5 nm Ref. S6 FL 1 pm-3 µm 0.3 pm Ref. S7 SERS 10 pm-1 µm 8.9 pm Ref. S8 ICPMS µg/l 3 ng/l Ref. S9 ECL 50 pm-500 µm 4.73 pm This work Abbreviations: EC, electrochemistry; ECL, electrochemiluminescence; FL, fluorescence; ICPMS, inductively coupled plasma mass spectrometry; SERS, surface enhanced Raman scattering. S-7

8 REFERENCES S1. Dong, Y.; Tian, W.; Ren, S.; Chi, Y.; Chen, G. Graphene Quantum Dots/L-cysteine Coreactant Electrochemiluminescence System and Its Application in Sensing Lead (II) Ions. ACS Appl. Mater. Interfaces 2014, 6, S2. Lei, Y. M.; Huang, W. X.; Zhao, M.; Chai, Y. Q.; Yuan, R.; Zhuo, Y. Electrochemiluminescence Resonance Energy Transfer System: Mechanism and Application in Ratiometric Aptasensor for Lead Ion. Anal. Chem. 2015, 87, S3. Xiao, Y.; Rowe, A. A.; Plaxo, K. W. Electrochemical Detection of Parts-per-billion Lead via an Electrode-bound DNAzyme Assembly. J. Am. Chem. Soc. 2007, 129, S4. Cui, L.; Wu, J.; Li, J.; Ju, H. X. Electrochemical Sensor for Lead Cation Sensitized with a DNA Functionalized Porphyrinic Metal-organic Framework. Anal. Chem. 2015, 87, S5. Kang, W. J.; Pei, X.; Rusinek, C. A.; Bange, A.; Haynes, E. N.; Heineman, W. R.; Papautsky, I. Determination of Lead with a Copper-based Electrochemical Sensor. Anal. Chem. 2017, 89, S6. Li, T.; Dong, S.; Wang, E. A Lead (II)-driven DNA Molecular Device for Turn-on Fluorescence Detection of Lead (II) Ion with High Selectivity and Sensitivity. J. Am. Chem. Soc. 2010, 132, S7. Liang, L. L.; Lan, F. F.; ge, S. G.; Yu, J. H.; Ren, N.; Yan, M. Metal-enhanced Ratiometric Fluorescence/Naked Eye Bimodal Biosensor for Lead Ions Analysis with Bifunctional Nanocomposite Probes. Anal. Chem. 2017, 89, S8. Shi, Y.; Wang, H. Y.; Jiang, X. X.; Sun, B.; Song, B.; Su, Y. Y.; He, Y. Ultrasensitive, Specific, Recyclable, and Reproducible Detection of Lead Ions in Real Systems Through a S-8

9 Polyadenine-assisted, Surface-enhanced Raman Scattering Silicon Chip. Anal. Chem. 2016, 88, S9. Liu, X.; Zhu, Z. L.; Li, H. L.; He, D.; Li, Y. T.; Zheng, H. T.; Gan, Y. Q.; Li, Y. X.; Belshaw, N. S.; Hu, S. H. Liquid Spray Dielectric Barrier Discharge Induced Plasma-chemical Vapor Generation for the Determination of Lead by ICP-MS. Anal. Chem. 2017, 89, S-9

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