Abstract
A highly sensitive and selective fluorometric method is described for determination of mercury(II). It is based on (a) the use of graphene oxide (GO) acting as a quencher of the fluoresence of the carboxy-fluorescein (FAM), and (b) of Hg(II)-triggered cleavage of the newly formed nucleic acid sequences harbored blunt 3′-hydroxyl termini by exonuclease III (Exo III) that leads to signal amplification. Two DNA probes are used, viz. a capture probe (CP) and a help probe; HP) that is partially complementary. In the absence of Hg(II), the FAM-labeled hairpin (signal probe, SP) is adsorbed onto the surface of GO via π-stacking interactions. CP blocks the release of the HP for binding to SP. This results in quenching of the green fluorescence of the label. Upon addition of Hg(II), the linear structure of CP is converted to a hairpin structure due to the formation of thymidine–Hg(II)–thymidine duplexes. HP is released from the CP/HP hybrids, and this causes SP to be released from from GO and fluorescence to be recovered. The signal is strongly amplified by using Exo III-assisted targeting and recycling of HP. Hence, Hg(II) can be detected via the strong increase in fluorescence. The method has a linear response in the 0.1 to 30 nM Hg(II) concentration range and a 10 pM detection limit. It was applied to the determination of Hg(II) in three (spiked) Chinese medicines.
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References
Eisler R (2003) Health risks of gold miners: a synoptic review. Environ Geochem Health 25:325–345
Korbas M, MacDonald TC, Pickering IJ, George GN, Krone PH (2011) Chemical form matters: differential accumulation of mercury following inorganic and organic mercury exposures in zebrafish larvae. ACS Chem Biol 7:411–420
Guzzi G, La Porta CA (2008) Molecular mechanisms triggered by mercury. Toxicology 244:1–12
Zalups RK (2000) Molecular interactions with mercury in the kidney. Pharmacol Rev 52:113–143
Park J, Zheng W (2012) Human exposure and health effects of inorganic and elemental mercury. J Prev Med Public Health 45:344–352
Gil S, Lavilla I, Bendicho C (2006) Ultrasound-promoted cold vapor generation in the presence of formic acid for determination of mercury by atomic absorption spectrometry. Anal Chem 78:6260–6264
Bernaus A, Gaona X, Esbri JM, Higueras P, Falkenberg G, Valiente M (2006) Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the mercury district of almadén in Spain. Environ Sci Technol 40:4090–4095
Hong YS, Rifkin E, Bouwer EJ (2011) Combination of diffusive gradient in a thin film probe and IC-ICP-MS for the simultaneous determination of CH3 Hg+ and Hg2+ in toxic water. Environ Sci Technol 45:6429–6436
Xie MH, Zhang K, Zhu FF, Wu H, Zou P (2017) Strategy for the detection of mercury ions by using exonuclease III-aided target recycling. RSC Adv 7:50420–50424
Hong MQ, Zeng BH, Li MY, Xu XQ, Chen GN (2017) An ultrasensitive conformation-dependent colorimetric probe for the detection of mercury(II) using exonuclease III-assisted target recycling and gold nanoparticles. Microchim Acta 185:72
Xie SB, Tang Y, Tang DY, Cai YH (2018) Highly sensitive impedimetric biosensor for Hg2+ detection based on manganese porphyrin-decorated DNA network for precipitation polymerization. Anal Chim Acta 1023:22–28
Cui X, Zhu L, Wu J, Hou Y, Wang PY, Wang ZN, Yang M (2015) A fluorescent biosensor based on carbon dots-labeled oligodeoxyribonucleotide and graphene oxide for mercury (II) detection. Biosens Bioelectron 63:506–512
Wang LL, Yao TM, Shi S, Cao YL, Sun WL (2014) A label-free fluorescent probe for Hg2+ and biothiols based on graphene oxide and Ru-complex. Sci Rep 4:5320
Li X, Ding XL, Fan J (2015) Nicking endonuclease-assisted signal amplification of split molecular aptamer beacon for biomolecules detection using graphene oxide as sensing platform. Analyst 140:7918–7925
Li Q, Wang YD, Shen GL, Tang H, Yu RQ, Jiang JH (2015) Split aptamer mediated endonuclease amplification for small-molecule detection. Chem Commun 51:4196–4199
Peng L, Zhu Z, Chen Y, Han D, Tan WH (2013) An exonuclease III and graphene oxide-aided assay for DNA detection. Biosens Bioelectron 35:475–478
Wang JK, Li TX, Gao XY, Lu ZH (2005) Exonuclease III protection assay with FRET probe for detecting DNA-binding proteins. Nucleic Acids Res 33:e23
Ning Y, Gao Q, Zhang XQ, Wei K, Chen LL (2016) A graphene oxide–based sensing platform for the determination of methicillin-resistant Staphylococcus aureus based on Strand-displacement polymerization recycling and synchronous fluorescent signal amplification. J Biomol Screen 21:851–857
Ling M, Peng ZH, Cheng LJ, Deng L (2015) Rapid fluorescent detection of Enterotoxigenic Escherichiacoli (ETEC) K88 based on graphene oxide-dependent Nanoquencher and Klenow fragment-triggered target cyclic amplification. Appl Spectrosc 69:1175–1181
Ning Y, Zou L, Gao Q, Hu J, Lu FG (2018) Graphene oxide-based fluorometric determination of methicillin-resistant Staphylococcus aureus by using target-triggered chain reaction and deoxyribonuclease-assisted recycling. Microchim Acta 185:183
Yan X, Li WK, Liu KY, Deng L (2015) Highly sensitive fluorescent aptasensor for Salmonella paratyphi a via DNase I-mediated cyclic signal amplification. Anal Methods 7:10243–10245
Wang WH, Kang TS, WaiHongChan P, Lu JJ, Chen XP, Leung CH, Ma DL (2015) A label-free G-quadruplex-based mercury detection assay employing the exonuclease III-mediated cleavage of T-Hg2+-T mismatched DNA. Sci Technol Adv Mater 16:065004
Yu LL, Lan W, Xu H, Chen H, Bai LJ, Wang WX (2017) Label-free detection of Hg2+ based on Hg2+-triggered toehold binding, exonuclease III assisted target recycling and hybridization chain reaction. Sensors Actuat B-Chem 248:411–418
Gan XR, Zhao HM, Chen S, Quan X (2015) Electrochemical DNA sensor for specific detection of picomolar Hg(II) based on exonuclease III-assisted recycling signal amplification. Analyst 140:2029–2036
Wang H, Sun K, Tao F, Stacchiola DJ, Hu YH (2013) 3D honeycomb-like structured graphene and its high efficiency as a CounterElectrode catalyst for dye-sensitized solar cells. Angew Chem Int Ed Eng 52:9210–9214
Gurunathan S, Kim JH (2016) Synthesis, toxicity, biocompatibility, and biomedical applications of graphene and graphene-related materials. Int J Nanomedicine 11:1927–1945
Duan YF, Ning Y, Song Y, Deng L (2014) Fluorescent aptasensor for the determination of Salmonella typhimurium based on a graphene oxide platform. Microchim Acta 181:647–653
Ning Y, Duan YF, Feng YY, Deng L (2014) Label-free fluorescent Aptasensor based on a graphene oxide self-assembled probe for the determination of adenosine triphosphate. Anal Lett 47:2350–2360
Zu FL, Yan FY, Bai ZJ, Xu JX, Wang YY, Huang YC, Zhou XJ (2017) The quenching of the fluorescence of carbon dots: a review on mechanisms and applications. Microchim Acta 184:1899–1914
Wang G, Xu G, Zhu Y, Zhang X (2014) A turn-on carbon nanotube-Ag nanoclusters fluorescent sensor for sensitive and selective detection of Hg2+ with cyclic amplification of exonuclease III activity. Chem Commun 50:747–750
Zhang Y, Tang L, Yang F, Sun Z, Zhang GJ (2015) Highly sensitive DNA-based fluorometric mercury(II) bioassay based on graphene oxide and exonuclease III-assisted signal amplification. Microchim Acta 182:1535–1541
Lu M, Xiao R, Zhang X, Niu J, Zhang X, Wang Y (2016) Novel electrochemical sensing platform for quantitative monitoring of Hg(II) on DNA-assembled graphene oxide with target recycling. Biosens Bioelectron 85:267–271
Li MK, Hu LY, Niu CG, Huang DW, Zeng GM (2018) A fluorescent DNA based probe for Hg(II) based on thymine-Hg(II)-thymine interaction and enrichment via magnetized graphene oxide. Microchim Acta 185:207
Bao T, Wei W, Zhang X, Xia Q, Wang S (2015) An exonuclease-assisted amplification electrochemical aptasensor for Hg2+ detection based on hybridization chain reaction. Biosens Bioelectron 70:318–323
Chen J, Zhou S, Wen J (2014) Disposable strip biosensor for visual detection of Hg(2+) based on Hg(2+) -triggered toehold binding and exonucleaseIII-assisted signal amplification. Anal Chem 86:3108–3114
Acknowledgments
We would like to thank National Natural Science Foundation (81774126, 81803964), Key Project Funded by Hunan traditional Chinese medicine administration (201711), Open Project Funded by Hunan Provincial Key Laboratory (20160214), Open Project Funded by Innovation Platform of Education department of Hunan Province (17 K067), Doctor start-up Foundation of Hunan University of Chinese Medicine (9982-1001019), Science and Technology Innovation Team in Colleges and Universities in Hunan Province《Chinese traditional medicine for treatment of infectious diseases》(No: 15) and Key Subjects of Hunan University of Chinese Medicine《Basic medicine》(NO.1) for the financial support. We also thank Gabrielle David, PhD, from Liwen Bianji, Edanz Group China (www.liwenbianji.cn/ac), for editing the English text of a draft of this manuscript.
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Ning, Y., Hu, J., Wei, K. et al. Fluorometric determination of mercury(II) via a graphene oxide-based assay using exonuclease III-assisted signal amplification and thymidine–Hg(II)–thymidine interaction. Microchim Acta 186, 216 (2019). https://doi.org/10.1007/s00604-019-3332-x
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DOI: https://doi.org/10.1007/s00604-019-3332-x