Selective Fluorescence Turn-On and Ratiometric Detection of Organophosphate Using Dual-Emitting Mn-Doped ZnS Nanocrystal Probe

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1 Supporting Information for Selective Fluorescence Turn-On and Ratiometric Detection of Organophosphate Using Dual-Emitting Mn-Doped ZnS Nanocrystal Probe Kui Zhang,, Tao Yu,, Fei Liu, Mingtai Sun, Huan Yu, Bianhua Liu, Zhongping Zhang, Hui Jiang*, and Suhua Wang*, * Corresponding author. shwang@iim.ac.cn; jiangtide@sina.cn Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 2331, China Beijing Institute of Pharmaceutical Chemistry, State Key Laboratory of NBC Protection for Civilian, Beijing, 125, China Fujian Inspection and Research Institute for Product Quality, Fuzhou, Fujian 352, China These two authors contributed equally to this work. S1

2 Normalized PL intensity h 3 h 4 h 5 h. Figure S1. Normalized PL spectra of dual-emission ZnS:Mn nanocrystals by controlling refluxing time with 2 h, 3 h, 4 h, and 5 h, respectively. Normalized PL intensity a b. Figure S2. The fluorescence emission spectra of dual-emission ZnS:Mn nanocrystals solution (a) before and (b) after being stored in dark room for 6 months. S2

3 PL intensity (a.u.) min min 3 min min 5 min 6 min 7 min 8 min 9 min I 6 /I Time (min) Figure S3. Stability of the fluorescence intensity of the dual-emitting probe. The change of the relative intensity ratio (I 6 /I 435 ) is not significant (< 5%) in 1.5 hours. I 6 /I I 6 /I 435 = [DEP] R = Concentration (µm) Figure S4. Changes of fluorescence emission ratio of the dual-emitting probe solution upon different concentrations of DEP in lake water. S3

4 C DEP (µm) PL C DEP (µm) PL PL C DEP (µm) Figure S5. The fluorescence spectra changes of different dual-emitting probe samples upon the exposure to different concentrations of DEP. S4

5 Table S1. Comparison of different DEP detection approaches Detection Method LOD Reference gas chromatography-mass spectrometry 1 µg/l (S1-S3) gas chromatography (GC) coupled with flame/ionisation detector 2 ng/ml (S4-S5) liquid chromatography quadrupole time-of-flight mass spectrometry a mass spectrometry-based method to measure degradation products organophosphorous insecticides 5 ng/ml (S6).2-.4 ng/ml (S7) liquid chromatography-mass spectrometry 1 µg/l (S8-S1) biological effect monitoring by measurement of the reduction of blood cholinesterase activity 72µmol/mol creatinine (S11) the reactivation of organophosphorus hydrolase and 1 µg/ml (S12) diethylphosphoryl-ache (DEP-AChE) conjugates a semi-quantitative exposure assessment method based on visual mg/l (S13-S15) observations of fluorescence images fluorescence turn-on detection by hydrolyzing of organophosphate.1 nm (S16) pesticide in a basic medium Other methods / (S17-S18) As shown in Table S1, these common techniques are usually time-consuming with employment of cumbersome and expensive gas chromatography, liquid chromatography, mass spectrometer, and/or coupled to different detectors (reference S1-S1). Although they meet the extremely sensitivity requirements, the operation often requires tedious and strict sample extraction procedure, apparently not suitable for rapid screening of high concentration samples because clean-up of the column and detectors are very difficult. The biological monitoring methods (reference S11-S12) based on the measurement of blood cholinesterase activity are also suitable for low concentration levels of DEP, but they are usually used in special scenario such as human blood and urine. The method in reference S13-S15 uses Visual Scoring System to visualize dermal exposure of organophosphate metabolite and is only suitable for high concentration detection due to its poor LOD ( mg/l). In comparison with these methods, the present method can be applied in many scenarios with median and high concentration of DEP like farms, surface water S5

6 contamination, and etc. Such a probe method and the further test strips are very simple and low cost, and the detection of analyte is easy-operation and independent on large/expensive equipments. References (S1) Margariti, M. G.; Tsatsakis, A. M. Biomarkers 9, 14, ; (S2) Hardt, L.; Angerer, J. J. Anal. Toxicol., 24, ; (S3) De Alwis, G. K. H.; Needham, L. L.; Barr, D. B. J. Anal. Toxicol. 8, 32, (S4) Bavcon M.; Trebse, P.; Zupancic-Kralj L. Chemosphere, 3, 5, ; (S5) Moate T. F.; Lu C.; Fenske R. A.; Hahne R. M.; Kalman D. A. J. Anal. Toxicol. 1999, 23, (S6) Ibanez M.; Sancho J. V.; Pozo O. J.; Hernandez F. Anal. Bioanal. Chem. 6, 384, (S7) Weerasekera, G.; Smith, K. D.; Quiros-Alcala, L.; Fernandez, C.; Bradman, A.; Eskenazi, B.; Needham, L. L.; Barr, D. B. J. Environ. Monit. 9, 11, (S8) John, H.; Worek, F.; Thiermann, H. Anal. Bioanal. Chem. 8, 391, ; (S9) Sun, X. W.; Xu, W.; Zeng, Y.; Hou, Y. R.; Guo, L.; Zhao, X. J.; Sun, C. H. J. Appl. Toxicol. 14, 34, ; (S1) Hernandez, F.; Sancho, J. V.; Pozo, O. J. Rapid Commun. Mass Spectrom. 2, 16, (S11) Cocker, J.; Mason, H. J.; Garfitt, S. J.; Jones, K. Toxicol. Lett. 2, 134, (S12) Ashani, Y.; Leader, H.; Rothschild, N.; Dosoretz, C. Biochem. Pharmacol. 1998, 55, (S13) Fenske R. A. Am. Ind. Hyg. Assoc. J. 1988, 49, ; (S14) Aragon, A.; Blanco, L.; Lopez, L.; Liden, C.; Nise, G.; Wesseling, C. Ann. Occup. Hyg. 4, 48, 61-66; (S15) Aragon, A.; Blanco, L.; Funez, A.; Ruepert, C.; Liden, C.; Nise, G.; Wesseling, C. Ann. Occup. Hyg. 6, 5, (S16) Zhang, K.; Mei, Q. S.; Guan, G. J.; Liu, B. H.; Wang, S. H.; Zhang, Z. P. Anal. Chem. 1, 82, (S17) Andreu, V.; Picó, Y. TrAC Trends Anal. Chem. 4, 23, ; (S18) Martínez Vidal, J. L.; Plaza-Bolaños, P.; Romero-González, R.; Garrido Frenich, A. J. Chromatogr. A 9, 1216, S6