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Supporting informationOxidase-mimicking activity of ultrathin MnO2 nanosheets in a colorimetric assay of chlorothalonil in food samplesEnze Sheng1a, Yuxiao Lu1a, Yuting Tanb, Yue Xiaoa, Zhenxi Lia, Zhihui Daiaa: Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of Biofunctional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210023, P. R. China.b: Department of Pesticide Science, College of Plant Protection, Nanjing Agricultural University, Nanjing 210095, P. R. China.*Tel./Fax: +86-25-85891051. E-mail: daizhihuii@njnu.. (Z. Dai)Cross-reactivityCross-reactivity (CR) was studied using the standards of chlorothalonil and interfering substances. The CR values were calculated as follows:CR% = (IC50 of chlorothalonil / IC50 of analogue) × 100Analysis of spiked samplesAll samples (wheat, rice, apple, pear, grape, tomato, and cucumber) were obtained from Walmart. All samples were verified without chlorothalonil before the spiking and recovery studies by GC.Real samples detection. The proposed fluorescence method was used for chlorothalonil detection in food and environmental samples, including wheat, rice, apple, pear, grape, tomato, cabbage and cucumber. All the samples (20 g) were mixed with 50 mL acetonitrile, ultrasonic extraction for 10 min and centrifuged for 10 min at 4000 rpm. Afterwards, the contents were filtered through anhydrous sodium. Afterwards, the contents were filtered through anhydrous sodium sulfate. The extraction procedure was repeated for three times, and the extract was combined. The organic phase evaporated to dryness. The remainder was dissolved with 2.0 mL Tris buffer solution containing 10% ethanol, and the chlorothalonil concentration in real sample was detected by using the current method based on calibration curve.Strip for quantification.The MnO2 NSs were dispersed in ultrapure water, then sprayed on a qualitative filter paper. Then, 50 ?L of the mixed buffer (containing PGAL, GAPD, TMB, and chlorothalonil (standard solution)) was dropped onto one prepared piece of test paper. Through the above steps, the standard color of paper-based MnO2-TMB for detecting different concentrations of standard chlorothalonil solution was obtained. Then according to the method of detecting the solution’s pH with a pH test strip, by comparing the color of the results of the samples detection with the color of the standard solution, the semi-quantitative and qualitative paper-based rapid detection of chlorothalonil residue could be achieved.Figure captionsFig. S1. (A) The effect of pH on the absorbance intensity ratio (A0 - A)/A0 of the MnO2 + TMB probe before and after the GAPD. (B) The effect of temperature on the absorbance intensity ratio. (C) The effect of time on the absorbance intensity of the MnO2 + TMB probe in the presence of 5, 10, 20 mU/mL. (D) The concentrations of GAPD sensing. (E) The color of the solution changed by the concentrations of GAPD.Fig. S2. Cross-reactivity of chlorothalonil and the interfering substances.Fig. S3. The matrix effect of samples (wheat, rice, apple, pear, grape, tomato, cucumber and cabbage) on the sensitivity of the chlorothalonil.Fig. S4. The correlation between the colorimetric assay and GC for analyses of samples with chlorothalonil.Fig. S1. (A) The effect of pH on the absorbance intensity ratio (A0 - A)/A0 of the MnO2 + TMB probe before and after the GAPD. (B) The effect of temperature on the absorbance intensity ratio. (C) The effect of time on the absorbance intensity of the MnO2 + TMB probe in the presence of 5 (black curve), 10 (red curve), 20 (blue curve) mU/mL. (D) The concentrations of GAPD sensing. (E) The color of the solution changed by the concentrations of GAPD.Fig. S2. (A) Absorbance intensity of the MnO2-TMB probe with different food samples (brown column) and MnO2-TMB- Chlorothalonil with food samples (green column). (B) The selectivity of the MnO2-TMB sensor to various pesticides, the concentrations of chlorothalonil were 5 ng/mL (yellow column), 50 ng/mL (green column) and 500 ng/mL (purple column).Fig. S3. The matrix effect of samples (wheat, rice, apple, pear, grape, tomato, cucumber and cabbage) on the sensitivity of the chlorothalonil.Fig. S4. The correlation between the colorimetric assay and GC for analyses of samples with chlorothalonil.Table captionsTable S1 Comparison of the proposed method with other methods for chlorothalonil detection. Table S2 The results of correlation between the colorimetric assay and GC for analyses of samples with chlorothalonil.Table S1 Comparison of the proposed method with other methods for chlorothalonil detection.MethodLOD(ng/mL)Reaction time(min)ReferencesGC5250ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1590/S0103-50532008000600012","ISSN":"16784790","abstract":"A new method to evaluate the levels of residue and the dissipation of chlorothalonil fungicide in tomatoes and cucumbers grown in experimental greenhouses was developed and validated. The vegetables were submitted to a single spraying with chlorothalonil at half, equal to and double of the recommended dose. Chlorothalonil residues were extracted in Ultra-Turrax system using ethyl acetate in the presence of anhydrous sodium sulphate and determined by gas chromatography with electron capture detection. The analytical curves were linear from 0.005 to 5.0 mg L -1 , with coefficient of determination higher then 0.995. The assays provide acceptable results with RSD values below 10.5% and recoveries were between 92.2 and 114.5% for tomatoes, and between 86.2 and 103.3% for cucumbers, both obtained from spiked samples at 0.028, 0.28, 2.8 and 5.0 mg kg -1 levels. Statistical interpretation of residue levels fitted to a first-order model for the dissipation behavior of chlorothalonil. The mean half-life after treatments at the recommended dose, in the two experimental years, was 8.8 days for tomatoes and 1.6 days for cucumbers. The higher decrease rate of chlorothalonil residues in cucumbers is mainly due to the higher growth rate of this vegetable relative to tomato. The developed method has proven to be efficient for the determination of chlorothalonil residues in tomatoes and cucumbers with a limit of quantification of 0.02 mg kg -1 level, permitting to evaluate the risk of consumer exposure to these residues. ? 2008 Sociedade Brasileira de Química.","author":[{"dropping-particle":"","family":"Kurz","given":"Márcia H.S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gon?alves","given":"Fábio F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Adaime","given":"Martha B.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Costa","given":"Ivan F.D.","non-dropping-particle":"Da","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Primel","given":"Ednei G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zanella","given":"Renato","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the Brazilian Chemical Society","id":"ITEM-1","issue":"6","issued":{"date-parts":[["2008"]]},"page":"1129-1135","title":"A gas chromatographic method for the determination of the fungicide chlorothalonil in tomatoes and cucumbers and its application to dissipation studies in experimental greenhouses","type":"article-journal","volume":"19"},"uris":[""]}],"mendeley":{"formattedCitation":"(Kurz et al., 2008)","plainTextFormattedCitation":"(Kurz et al., 2008)","previouslyFormattedCitation":"(Kurz et al., 2008)"},"properties":{"noteIndex":0},"schema":""}(Kurz et al., 2008)HPLC0.1894ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.foodchem.2017.06.080","ISSN":"18737072","abstract":"A green, simple, inexpensive, and sensitive ionic liquid immobilized fabric phase sorptive extraction method coupled with high performance liquid chromatography was developed for rapid screening and simultaneous determination of four fungicides (azoxystrobin, chlorothalonil, cyprodinil and trifloxystrobin) residues in tea infusions. This IL modified extraction fiber is capable of extracting target analytes directly from complicated tea water matrices with the addition of surfactant. A series of extraction conditions were investigated by one-factor-at-a-time approach and orthogonal test. After a series experiments, the optimum conditions were found to be 10% [HIMIM]NTf2 as coating solution, 2?min vortex time, 500?μL acetonitrile as dispersive solvent and 2?min desorption time. Under the above conditions, the proposed technique was applied to detect fungicides from real tea water samples with satisfactory results.","author":[{"dropping-particle":"","family":"Yang","given":"Miyi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gu","given":"Yihan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wu","given":"Xiaoling","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xi","given":"Xuefei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Xiaoling","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhou","given":"Wenfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zeng","given":"Haozhe","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Sanbing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Runhua","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gao","given":"Haixiang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Jing","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Food Chemistry","id":"ITEM-1","issued":{"date-parts":[["2018"]]},"page":"797-805","title":"Rapid analysis of fungicides in tea infusions using ionic liquid immobilized fabric phase sorptive extraction with the assistance of surfactant fungicides analysis using IL-FPSE assisted with surfactant","type":"article-journal","volume":"239"},"uris":[""]}],"mendeley":{"formattedCitation":"(Yang et al., 2018)","plainTextFormattedCitation":"(Yang et al., 2018)","previouslyFormattedCitation":"(Yang et al., 2018)"},"properties":{"noteIndex":0},"schema":""}(Yang et al., 2018)GC-MS5057ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1007/s12161-015-0228-1","ISSN":"1936976X","abstract":"? 2015, Springer Science+Business Media New York. Being susceptible to any matrix with pH > 5, taking cabbage as an example, the low recovery of chlorothalonil residues adsorbed onto the cabbage matrix was almost completely improved by extracting with 1/1 (v/v) acetonitrile (containing 5?% acetic acid)/toluene. Under the optimized conditions, the recoveries of chlorothalonil in cabbage fortified at three concentrations of 0.5 to 10?mg?kg ?1 were 71–93?% with relative standard deviations (RSDs) lower than 6?%. The limit of detection (LOD) and the limit of quantification (LOQ) of the gas chromatography–mass spectrometry (GC–MS) method for chlorothalonil were 0.05 and 0.5?mg?kg ?1 , respectively, which were much lower than the maximum residue limits (MRLs). The proposed analytical method demonstrated a potential for its application to monitor for chlorothalonil and to help assure food safety, especially base-sensitive-pesticide analysis.","author":[{"dropping-particle":"","family":"Hou","given":"Fan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhao","given":"Liuwei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Fengmao","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Food Analytical Methods","id":"ITEM-1","issue":"3","issued":{"date-parts":[["2016"]]},"page":"656-663","title":"Determination of Chlorothalonil Residue in Cabbage by a Modified QuEChERS-Based Extraction and Gas Chromatography–Mass Spectrometry","type":"article-journal","volume":"9"},"uris":[""]}],"mendeley":{"formattedCitation":"(Hou, Zhao, & Liu, 2016)","plainTextFormattedCitation":"(Hou, Zhao, & Liu, 2016)","previouslyFormattedCitation":"(Hou, Zhao, & Liu, 2016)"},"properties":{"noteIndex":0},"schema":""}(Hou, Zhao, & Liu, 2016)HPLC-MS/MS0.2120ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1007/s00216-016-9993-y","ISSN":"16182650","abstract":"? 2016, Springer-Verlag Berlin Heidelberg. This paper describes a novel and sensitive method for extraction, preconcentration, and determination of two important widely used fungicides, azoxystrobin, and chlorothalonil. The developed methodology is based on solid-phase extraction (SPE) using a polymeric material functionalized with gold nanoparticles (AuNPs) as sorbent followed by high-performance liquid chromatography (HPLC) with diode array detector (DAD). Several experimental variables that affect the extraction efficiency such as the eluent volume, sample flow rate, and salt addition were optimized. Under the optimal conditions, the sorbent provided satisfactory enrichment efficiency for both fungicides, high selectivity and excellent reusability ( > 120 re-uses). The proposed method allowed the detection of 0.05?μg?L ?1 of the fungicides and gave satisfactory recoveries (75–95?%) when it was applied to drinking and environmental water samples (river, well, tap, irrigation, spring, and sea waters).","author":[{"dropping-particle":"","family":"Catalá-Icardo","given":"Mónica","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gómez-Benito","given":"Carmen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Simó-Alfonso","given":"Ernesto Francisco","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Herrero-Martínez","given":"José Manuel","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Analytical and Bioanalytical Chemistry","id":"ITEM-1","issue":"1","issued":{"date-parts":[["2017"]]},"page":"243-250","publisher":"Analytical and Bioanalytical Chemistry","title":"Determination of azoxystrobin and chlorothalonil using a methacrylate-based polymer modified with gold nanoparticles as solid-phase extraction sorbent","type":"article-journal","volume":"409"},"uris":[""]}],"mendeley":{"formattedCitation":"(Catalá-Icardo, Gómez-Benito, Simó-Alfonso, & Herrero-Martínez, 2017)","plainTextFormattedCitation":"(Catalá-Icardo, Gómez-Benito, Simó-Alfonso, & Herrero-Martínez, 2017)","previouslyFormattedCitation":"(Catalá-Icardo, Gómez-Benito, Simó-Alfonso, & Herrero-Martínez, 2017)"},"properties":{"noteIndex":0},"schema":""}(Catalá-Icardo, Gómez-Benito, Simó-Alfonso, & Herrero-Martínez, 2017)ELISA0.052190ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acs.jafc.5b01980","ISSN":"15205118","abstract":"? 2015 American Chemical Society. An immunosensor based on surface plasmon resonance (SPR-sensor) was developed to analyze chlorothalonil residues and maximum residue limits (MRLs; 0.5-50 mg/kg) in vegetables in Japan. Conjugates of N-(pentachlorophenoxyacetyl)glycine and bovine serum albumin were covalently coated on the sensor chip. The SPR-sensor quantitatively determined chlorothalonil at concentrations ranging from 8.0 to 44 ng/mL, using TPN9A, a monoclonal antibody to chlorothalonil. The 50% inhibition concentration was 25 ng/mL. The reactivity was 10-fold lower than that of indirect competitive enzyme-linked immunosorbent assay (ic-ELISA). However, the SPR-sensor could determine chlorothalonil residues in vegetables at concentrations around the above MRLs. Chlorothalonil spiked in vegetables was recovered at 90-118% within 1 day and at 90-115% across 3 days, correlating with HPLC results. The sensor showed good performance for chlorothalonil residue analysis in vegetables with rapid determination, although the sensitivity and the cross-reactivity were less effective than with the ic-ELISA.","author":[{"dropping-particle":"","family":"Hirakawa","given":"Yuki","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yamasaki","given":"Tomomi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Watanabe","given":"Eiki","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Okazaki","given":"Fumiko","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Murakami-Yamaguchi","given":"Yukie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Oda","given":"Masayuki","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Iwasa","given":"Seiji","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Narita","given":"Hiroshi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Miyake","given":"Shiro","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Agricultural and Food Chemistry","id":"ITEM-1","issue":"28","issued":{"date-parts":[["2015"]]},"page":"6325-6330","title":"Development of an Immunosensor for Determination of the Fungicide Chlorothalonil in Vegetables, Using Surface Plasmon Resonance","type":"article-journal","volume":"63"},"uris":[""]}],"mendeley":{"formattedCitation":"(Hirakawa et al., 2015)","plainTextFormattedCitation":"(Hirakawa et al., 2015)","previouslyFormattedCitation":"(Hirakawa et al., 2015)"},"properties":{"noteIndex":0},"schema":""}(Hirakawa et al., 2015)Fluorescence assay4.3120ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.saa.2019.04.080","ISSN":"13861425","abstract":"A novel fluorescence application for simultaneous determination of two common fungicide pesticides (carbendazim and chlorothalonil)in peanut oil is presented. Using the strategy of combining excitation-emission matrix (EEM)fluorescence with three-way calibration methods, the proposed approach successfully achieved quantitative analysis of carbendazim and chlorothalonil pesticide residues in peanut oil, even with highly overlapped spectra. It needs little preparation, using “mathematical separation” instead of “analytical separation” to achieve concentration prediction of target analytes in complex systems. Each analyte was performed using fluorescence spectroscopy after instrument spectral correction and scatter removal. Then the data were modeled with two three-way calibration algorithms, including alternating trilinear decomposition (ATLD)and alternating penalty trilinear decomposition (APTLD). The results indicated that APTLD performed slightly better than ATLD for this system. The carbendazim and chlorothalonil can be recognized simultaneously with the correlation coefficients all above 0.96 between resolved spectra and actual spectra. Satisfactory results have been achieved with the average recoveries (mean ± standard deviation)of carbendazim and chlorothalonil being 100.2 ± 6.7% and 99.7 ± 6.7%, respectively. Moreover, as for carbendazim and chlorothalonil, the sensitivity (SENs)are 1.50 × 102 and 3.80 × 102 mL ng?1, the limits of detection (LODs)are 11 ng mL?1 and 4.3 ng mL?1, the limit of quantitation (LOQ)are 33.33 ng mL?1 and 13.03 ng mL?1, respectively. The above results demonstrated that the proposed method is sensitive, fast and accurate for direct quantitative analysis of multiple pesticide residues in complex matrix such as that of peanut oil.","author":[{"dropping-particle":"","family":"Yuan","given":"Yuan Yuan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Shu Tao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cheng","given":"Qi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kong","given":"De Ming","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Che","given":"Xian Ge","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy","id":"ITEM-1","issued":{"date-parts":[["2019"]]},"page":"117088","publisher":"Elsevier B.V.","title":"Simultaneous determination of carbendazim and chlorothalonil pesticide residues in peanut oil using excitation-emission matrix fluorescence coupled with three-way calibration method","type":"article-journal","volume":"220"},"uris":[""]}],"mendeley":{"formattedCitation":"(Yuan, Wang, Cheng, Kong, & Che, 2019)","plainTextFormattedCitation":"(Yuan, Wang, Cheng, Kong, & Che, 2019)","previouslyFormattedCitation":"(Yuan, Wang, Cheng, Kong, & Che, 2019)"},"properties":{"noteIndex":0},"schema":""}(Yuan, Wang, Cheng, Kong, & Che, 2019)Colorimetric assay0.02445This workPaper-based sensor145This work Table S2 The results of correlation between the colorimetric assay and GC for analyses of samples with chlorothalonil.Sample NumberColorimetric assay (ng/g)GC (ng/g)11.311.8222.132.3332.653.2343.787.5657.7410.23612.5414.65718.918.65821.6422.64924.6527.981033.9235.641142.5344.871254.3253.481360.3656.641468.3667.341592.3690.56ReferenceADDIN Mendeley Bibliography CSL_BIBLIOGRAPHY Hirakawa, Y., Yamasaki, T., Watanabe, E., Okazaki, F., Murakami-Yamaguchi, Y., Oda, M., Miyake, S. (2015). Development of an Immunosensor for Determination of the Fungicide Chlorothalonil in Vegetables, using Surface Plasmon Resonance. Journal of Agricultural and Food Chemistry, 63(28), 6325–6330. Hou, F., Zhao, L., & Liu, F. (2016). Determination of Chlorothalonil Residue in Cabbage by a Modified QuEChERS-based Extraction and Gas Chromatography–mass Spectrometry. Food Analytical Methods, 9(3), 656–663. Kurz, M. H. S., Gon?alves, F. F., Adaime, M. B., Da Costa, I. F. D., Primel, E. G., & Zanella, R. (2008). A Gas Chromatographic Method for the Determination of the Fungicide Chlorothalonil in Tomatoes and Cucumbers and its Application to Dissipation Studies in Experimental Greenhouses. Journal of the Brazilian Chemical Society, 19(6), 1129–1135. Yang, M., Gu, Y., Wu, X., Xi, X., Yang, X., Zhou, W., Li, J. (2018). Rapid Analysis of Fungicides in Tea Infusions using Ionic Liquid Immobilized Fabric Phase Sorptive Extraction with the Assistance of Surfactant Fungicides Analysis using IL-FPSE Assisted with Surfactant. Food Chemistry, 239, 797–805. Yuan, Y. Y., Wang, S. T., Cheng, Q., Kong, D. M., & Che, X. G. (2019). Simultaneous determination of Carbendazim and Chlorothalonil Pesticide Residues in Peanut Oil using Excitation-emission Matrix Fluorescence Coupled with Three-way Calibration Method. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 220, 117088. ................
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