Supporting Information Cascade Signal Amplification Based on Copper Nanoparticle-Reported Rolling Circle Amplification for Ultrasensitive Electrochemical Detection of the Prostate Cancer Biomarker Ye Zhu a, Huijuan Wang b, Lin Wang c, Jing Zhu a, Wei Jiang a * a Key Laboratory of Colloid and Interface Chemistry of Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China. b School of Pharmaceutical Sciences, Shandong University, Jinan 250012, China. c Department of Radiation Oncology, Qilu Hospital, Shandong University, Jinan 250012, China. Corresponding Author: * E-mail: wjiang@sdu.edu.cn. Tel: +86-531-88362588. Fax: +86-531-88564464. S1
Table S1. Comparison of the Analytical Methods Using Poly(thymine)-templated CuNPs for Signal Generation. Templates for CuNPs Techniques target Linear range Detection limit Refs fluorescence S1 nuclease 0.005-2 U/mL 0.0005U/m L S1 Terminal deoxynucleotidyl transferase catalyzed fluorescence T4 PNK 0.25-25 U/mL fluorescence T4 PNK 0.012-0.175 U/mL 0.25 U/mL S2 0.01 U/mL S3 fluorescence Cu 2+ - 20 μm S4 (40 bases) fluorescence Hg 2+ 0.5-100 nm 0.1 nm. S5 fluorescence H 2 O 2 0.55-110 μm 0.55 μm. S6 (40 bases) glucose 0.05-1.6 mm 0.05 mm fluorescence melamine 0.1-6 mm 95 nm S7 fluorescence cysteine 0-1000 nm 12.5 nm S8 (25 bases) fluorescence N- acetylcysteine 0.2-100 mm 50 nm S9 fluorescence streptavidin 0.5-100 nm 0.1 nm S10 S2
fluorescence trypsin 0.01 41 μm 1.75 nm S11 Terminal deoxynucleotidyl transferase catalyzed fluorescence DNA 0.1-10 nm 98.2 pm S12 RCA product containing thousands of repeats electrochemical PSA 0.05-500 fg/ml (0.001-14.7 fm) 0.020 fg/ml (0.59 am) This work Figure S1. TEM image of fifty-thymine sequence-templated CuNPs. S3
Figure S2. (A) DPSV responses of the method using aptamer-t50-templated CuNPs toward varying PSA concentrations (from a to k: 0, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, 100, and 500 ng/ml); (B) The corresponding calibration curve. Figure S3. (A) DPSV responses of the developed method toward spiked PSA in 10 6 times diluted serum samples (from a to m: 0, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, 100, 500, and 1000 fg/ml PSA); (B) The corresponding calibration curve. REFERENCES (S1) Qing, Z.; He, X.; Qing, T.; Wang, K.; Shi, H.; He, D.; Zou, Z.; Yan, L.; Xu, F.; Ye, X.; Mao, Z. Poly(Thymine)-Templated Fluorescent Copper Nanoparticles for Ultrasensitive Label-Free Nuclease Assay and Its Inhibitors Screening. Anal. Chem. 2013, 85, 12138-12143. S4
(S2) Dong, Z.-Z.; Zhang, L.; Qiao, M.; Ge, J.; Liu, A.-L.; Li, Z.-H. A Label-Free Assay for T4 Polynucleotide Kinase/Phosphatase Activity and Its Inhibitors Based on Poly(Thymine)- Templated Copper Nanoparticles. Talanta 2016, 146, 253-258. (S3) Ye, T.; Li, C.; Su, C.; Ji, X.; Zheng, J.; Tinnefeld, P.; He, Z. Enzymatic Polymerization of Poly(Thymine) for the Synthesis of Copper Nanoparticles with Tunable Size and Their Application in Enzyme Sensing. Chem. Commun. 2015, 51, 8644-8647. (S4) Qing, Z.; Mao, Z.; Qing, T.; He, X.; Zou, Z.; He, D.; Shi, H.; Huang, J.; Liu, J.; Wang, K. Visual and Portable Strategy for Copper(II) Detection Based on a Striplike Poly(Thymine)- Caged and Microwell-Printed Hydrogel. Anal. Chem. 2014, 86, 11263-11268. (S5) Wang, H.-B.; Chen, Y.; Li, Y.; Zhang, H.-D.; Cao, J.-T. A Rapid, Sensitive and Label-Free Sensor for Hg(Ii) Ion Detection Based on Blocking of Cysteine-Quenching of Fluorescent Poly(Thymine)-Templated Copper Nanoparticles. RSC Adv. 2015, 5, 94099-94104. (S6) Mao, Z.; Qing, Z.; Qing, T.; Xu, F.; Wen, L.; He, X.; He, D.; Shi, H.; Wang, K. Poly(thymine)-Templated Copper Nanoparticles as a Fluorescent Indicator for Hydrogen Peroxide and Oxidase-Based Biosensing. Anal. Chem. 2015, 87, 7454-7460. (S7) Zhu, H.-W.; Dai, W.-X.; Yu, X.-D.; Xu, J.-J.; Chen, H.-Y. Poly Thymine Stabilized Copper Nanoclusters as a Fluorescence Probe for Melamine Sensing. Talanta 2015, 144, 642-647. (S8) Zhang, L.; Cai, Q.-Y.; Li, J.; Ge, J.; Wang, J.-Y.; Dong, Z.-Z.; Li, Z.-H. A Label-Free Method for Detecting Biothiols Based on Poly(Thymine)-Templated Copper Nanoparticles. Biosens. Bioelectron. 2015, 69, 77-82. (S9) Wang, H.-B.; Zhang, H.-D.; Chen, Y.; Ou, L.-J.; Liu, Y.-M. Poly(thymine)-Templated Fluorescent Copper Nanoparticles for Label-Free Detection of N-Acetylcysteine in Pharmaceutical Samples. Anal. Methods 2015, 7, 6372-6377. (S10) Wang, H.-B.; Zhang, H.-D.; Chen, Y.; Liu, Y.-M. A Fluorescent Biosensor for Protein Detection Based on Poly(Thymine)-Templated Copper Nanoparticles and Terminal Protection of Small Molecule-Linked DNA. Biosens. Bioelectron. 2015, 74, 581-586. S5
(S11) Ou, L.-J.; Li, X.-Y.; Li, L.-J.; Liu, H.-W.; Sun, A.-M.; Liu, K.-J. A Sensitive Assay for Trypsin Using Poly(Thymine)-Templated Copper Nanoparticles as Fluorescent Probes. Analyst 2015, 140, 1871-1875. (S12) Hu, W.; Ning, Y.; Kong, J.; Zhang, X. Formation of Copper Nanoparticles on Poly(Thymine) through Surface-Initiated Enzymatic Polymerization and Its Application for DNA Detection. Analyst 2015, 140, 5678-5684. S6