In this contribution, we propose a novel functional surface-enhanced Raman spectroscopy (SERS) platform for the detection of one of the most hazardous heavy metal ions, Hg2+. The design of the proposed sensor is based on the combination of surface plasmon-polariton (SPP) supporting gold grating with the high homogeneity of the response and enhancement and mercaptosuccinic acid (MSA) based specific recognition layer. For the first time, diazonium grafted 4-ethynylphenyl groups have undergone the sunlight-induced thiol-yne reaction with MSA in the presence of Eosine Y. The developed SERS platform provides an extremely sensitive, selective, and convenient analytical procedure to detect mercury ions with limit of detection (LOD) as low as 10-10 M (0.027 µg/L) with excellent selectivity over other metals. The developed SERS sensor is compatible with a portable SERS spectrophotometer and does not require the expensive equipment for statistical methods of analysis.

Department of Solid State Engineering University of Chemistry and Technology 16628 Prague Czech Republic

ICMPE CNRS UPEC Université Paris Est F 94320 Thiais France

Research School of Chemistry and Applied Biomedical Sciences Tomsk Polytechnic University Tomsk 634050 Russian

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Li W.C., Tse H.F. Health Risk and Significance of Mercury in the Environment. Environ. Sci. Pollut. Res. 2015;22:192–201. doi: 10.1007/s11356-014-3544-x. PubMed DOI

Liang P., Feng X., Zhang C., Zhang J., Cao Y., You Q., Leung A.O.W., Wong M.-H., Wu S.-C. Human Exposure to Mercury in a Compact Fluorescent Lamp Manufacturing Area: By Food (Rice and Fish) Consumption and Occupational Exposure. Environ. Pollut. 2015;198:126–132. doi: 10.1016/j.envpol.2014.12.036. PubMed DOI

Yassa H.A. Autism: A Form of Lead and Mercury Toxicity. Environ. Toxicol. Pharmacol. 2014;38:1016–1024. doi: 10.1016/j.etap.2014.10.005. PubMed DOI

Walach H., Mutter J., Deth R. Inorganic Mercury and Alzheimer’s Disease—Results of a Review and a Molecular Mechanism. Diet Nutr. Dement. Cogn. Decline. 2015:593–601. doi: 10.1016/B978-0-12-407824-6.00055-0. DOI

Carocci A., Rovito N., Sinicropi M.S., Genchi G. Mercury Toxicity and Neurodegenerative Effects. Rev. Environ. Contam. Toxicol. 2014;229:1–18. doi: 10.1007/978-3-319-03777-6_1. PubMed DOI

Ha E., Basu N., Bose-O’Reilly S., Dórea J.G., McSorley E., Sakamoto M., Chan H.M. Current Progress on Understanding the Impact of Mercury on Human Health. Environ. Res. 2017;152:419–433. doi: 10.1016/j.envres.2016.06.042. PubMed DOI

Lemos V.A., dos Santos L.O. A New Method for Preconcentration and Determination of Mercury in Fish, Shellfish and Saliva by Cold Vapour Atomic Absorption Spectrometry. Food Chem. 2014;149:203–207. doi: 10.1016/j.foodchem.2013.10.109. PubMed DOI

Oliveira E.P., Yang L., Sturgeon R.E., Santelli R.E., Bezerra M.A., Willie S.N., Capilla R. Determination of Trace Metals in High-Salinity Petroleum Produced Formation Water by Inductively Coupled Plasma Mass Spectrometry Following on-Line Analyte Separation/Preconcentration. J. Anal. At. Spectrom. 2011;26:578–585. doi: 10.1039/c0ja00108b. DOI

Campanella B., Onor M., Ulivo A.D., Giannarelli S., Bramanti E. Impact of Protein Concentration on the Determination of Thiolic Groups of Ovalbumin: A Size Exclusion Chromatography–Chemical Vapor Generation–Atomic Fluorescence Spectrometry Study via Mercury Labeling. Anal. Chem. 2014;86:2251–2256. doi: 10.1021/ac4041795. PubMed DOI

Pietilä H., Perämäki P., Piispanen J., Majuri L., Starr M., Nieminen T., Kantola M., Ukonmaanaho L. Determination of methyl mercury in humic-rich natural water samples using N2-distillation with isotope dilution and on-line purge and trap GC-ICP-MS. Microchem. J. 2014;112:113–118. doi: 10.1016/j.microc.2013.10.002. DOI

Zhang Y., Liu Y., Zhen S.J., Huang C.Z. Graphene Oxide as an Efficient Signal-to-Background Enhancer for DNA Detection with a Long Range Resonance Energy Transfer Strategy. Chem. Commun. 2011;47:11718. doi: 10.1039/c1cc14491j. PubMed DOI

Guo Y., Zhang Y., Shao H., Wang Z., Wang X., Jiang X. Label-Free Colorimetric Detection of Cadmium Ions in Rice Samples Using Gold Nanoparticles. Anal. Chem. 2014;86:8530–8534. doi: 10.1021/ac502461r. PubMed DOI

Chen L., Zhao Y., Wang Y., Zhang Y., Liu Y., Han X.X., Zhao B., Yang J. Mercury Species Induced Frequency-Shift of Molecular Orientational Transformation Based on SERS. Analyst. 2016;141:4782–4788. doi: 10.1039/C6AN00945J. PubMed DOI

Wang Y., Wen G., Ye L., Liang A., Jiang Z. Label-Free SERS Study of Galvanic Replacement Reaction on Silver Nanorod Surface and Its Application to Detect Trace Mercury Ion. Sci. Rep. 2016;6:19650. doi: 10.1038/srep19650. PubMed DOI PMC

Guselnikova O., Postnikov P., Erzina M., Kalachyova Y., Švorčík V., Lyutakov O. Pretreatment-Free Selective and Reproducible SERS-Based Detection of Heavy Metal Ions on DTPA Functionalized Plasmonic Platform. Sensors Actuators B Chem. 2017;253:830–838. doi: 10.1016/j.snb.2017.07.018. DOI

Li M., Cushing S.K., Wu N. Plasmon-Enhanced Optical Sensors: A Review. Analyst. 2015;140:386–406. doi: 10.1039/C4AN01079E. PubMed DOI PMC

Fateixa S., Raposo M., Nogueira H.I.S., Trindade T. A General Strategy to Prepare SERS Active Filter Membranes for Extraction and Detection of Pesticides in Water. Talanta. 2018;182:558–566. doi: 10.1016/j.talanta.2018.02.014. PubMed DOI

Zapata F., López-López M., García-Ruiz C. Detection and Identification of Explosives by Surface Enhanced Raman Scattering. Appl. Spectrosc. Rev. 2016;51:227–262. doi: 10.1080/05704928.2015.1118637. DOI

Akanny E., Bonhommé A., Bois L., Minot S., Bourgeois S., Bordes C., Bessueille F. Development and Comparison of Surface-Enhanced Raman Scattering Gold Substrates for In Situ Characterization of ‘Model’ Analytes in Organic and Aqueous Media. Chem. Afr. 2019 doi: 10.1007/s42250-019-00053-2. DOI

Yuan Y., Panwar N., Yap S.H.K., Wu Q., Zeng S., Xu J., Tjin S.C., Song J., Qu J., Yong K.-T. SERS-Based Ultrasensitive Sensing Platform: An Insight into Design and Practical Applications. Coord. Chem. Rev. 2017;337:1–33. doi: 10.1016/j.ccr.2017.02.006. DOI

Alvarez-Puebla R.A., Liz-Marzán L.M. Traps and Cages for Universal SERS Detection. Chem. Soc. Rev. 2011;41:43–51. doi: 10.1039/C1CS15155J. PubMed DOI

Xu L., Yin H., Ma W., Kuang H., Wang L., Xu C. Ultrasensitive SERS Detection of Mercury Based on the Assembled Gold Nanochains. Biosens. Bioelectron. 2015;67:472–476. doi: 10.1016/j.bios.2014.08.088. PubMed DOI

Senapati T., Senapati D., Singh A.K., Fan Z., Kanchanapally R., Ray P.C. Highly Selective SERS Probe for Hg(Ii) Detection Using Tryptophan-Protected Popcorn Shaped Gold Nanoparticles. Chem. Commun. 2011;47:10326. doi: 10.1039/c1cc13157e. PubMed DOI

Han D., Lim S.Y., Kim B.J., Piao L., Chung T.D. Mercury(Ii) Detection by SERS Based on a Single Gold Microshell. Chem. Commun. 2010;46:5587. doi: 10.1039/c0cc00895h. PubMed DOI

Zhang L., Chang H., Hirata A., Wu H., Xue Q.-K., Chen M. Nanoporous Gold Based Optical Sensor for Sub-Ppt Detection of Mercury Ions. ACS Nano. 2013;7:4595–4600. doi: 10.1021/nn4013737. PubMed DOI

Si S., Liang W., Sun Y., Huang J., Ma W., Liang Z., Bao Q., Jiang L. Facile Fabrication of High-Density Sub-1-Nm Gaps from Au Nanoparticle Monolayers as Reproducible SERS Substrates. Adv. Funct. Mater. 2016;26:8137–8145. doi: 10.1002/adfm.201602337. DOI

Zhou Q., Kim T. Review of Microfluidic Approaches for Surface-Enhanced Raman Scattering. Sensors Actuators B Chem. 2016;227:504–514. doi: 10.1016/j.snb.2015.12.069. DOI

Guselnikova O., Postnikov P., Kalachyova Y., Kolska Z., Libansky M., Zima J., Svorcik V., Lyutakov O. Large-Scale, Ultrasensitive, Highly Reproducible and Reusable Smart SERS Platform Based on PNIPAm-Grafted Gold Grating. ChemNanoMat. 2017;3:135–144. doi: 10.1002/cnma.201600284. DOI

Kalachyova Y., Mares D., Lyutakov O., Kostejn M., Lapcak L., Švorčík V. Surface Plasmon Polaritons on Silver Gratings for Optimal SERS Response. J. Phys. Chem. C. 2015;119:9506–9512. doi: 10.1021/acs.jpcc.5b01793. DOI

Botasini S., Heijo G., Méndez E. Toward Decentralized Analysis of Mercury (II) in Real Samples. A Critical Review on Nanotechnology-Based Methodologies. Anal. Chim. Acta. 2013;800:1–11. doi: 10.1016/j.aca.2013.07.067. PubMed DOI

Kim H.N., Ren W.X., Kim J.S., Yoon J. Fluorescent and Colorimetric Sensors for Detection of Lead, Cadmium, and Mercury Ions. Chem. Soc. Rev. 2012;41:3210–3244. doi: 10.1039/C1CS15245A. PubMed DOI

Li L., Zhang Q., Ding Y., Cai X., Gu S., Cao Z. Application of l -Cysteine Capped Core–shell CdTe/ZnS Nanoparticles as a Fluorescence Probe for Cephalexin. Anal. Methods. 2014;6:2715–2721. doi: 10.1039/C4AY00094C. DOI

Ma Y., Jiang L., Mei Y., Song R., Tian D., Huang H. Colorimetric Sensing Strategy for Mercury(Ii) and Melamine Utilizing Cysteamine-Modified Gold Nanoparticles. Analyst. 2013;138:5338. doi: 10.1039/c3an00690e. PubMed DOI

Saikia D., Dutta P., Sarma N.S., Adhikary N.C. CdTe/ZnS Core/Shell Quantum Dot-Based Ultrasensitive PET Sensor for Selective Detection of Hg (II) in Aqueous Media. Sensors Actuators B Chem. 2016;230:149–156. doi: 10.1016/j.snb.2016.02.035. DOI

Wen G., Wen X., Choi M.M.F., Shuang S. Photoelectrochemical Sensor for Detecting Hg2+ Based on Exciton Trapping. Sensors Actuators B Chem. 2015;221:1449–1454. doi: 10.1016/j.snb.2015.07.103. DOI

Ke J., Li X., Zhao Q., Hou Y., Chen J. Ultrasensitive Quantum Dot Fluorescence Quenching Assay for Selective Detection of Mercury Ions in Drinking Water. Sci. Rep. 2015;4:5624. doi: 10.1038/srep05624. PubMed DOI PMC

Priyadarshini E., Pradhan N. Gold Nanoparticles as Efficient Sensors in Colorimetric Detection of Toxic Metal Ions: A Review. Sensors Actuators B Chem. 2017;238:888–902. doi: 10.1016/j.snb.2016.06.081. DOI

Escorihuela J., Marcelis A.T.M., Zuilhof H. Metal-Free Click Chemistry Reactions on Surfaces. Adv. Mater. Interfaces. 2015;2:1500135. doi: 10.1002/admi.201500135. DOI

Lowe A.B. Thiol-Ene “Click” Reactions and Recent Applications in Polymer and Materials Synthesis. Polym. Chem. 2010;1:17–36. doi: 10.1039/B9PY00216B. DOI

Bengamra M., Khlifi A., Ktari N., Mahouche-Chergui S., Carbonnier B., Fourati N., Kalfat R., Chehimi M.M. Silanized Aryl Layers through Thiol-Yne Photo-Click Reaction. Langmuir. 2015;31:10717–10724. doi: 10.1021/acs.langmuir.5b02540. PubMed DOI

Zalesskiy S.S., Shlapakov N.S., Ananikov V.P. Visible Light Mediated Metal-Free Thiol–yne Click Reaction. Chem. Sci. 2016;7:6740–6745. doi: 10.1039/C6SC02132H. PubMed DOI PMC

Filimonov V.D., Trusova M., Postnikov P., Krasnokutskaya E.A., Lee Y.M., Hwang H.Y., Kim H., Chi K.-W. Unusually Stable, Versatile, and Pure Arenediazonium Tosylates: Their Preparation, Structures, and Synthetic Applicability. Org. Lett. 2008;10:3961–3964. doi: 10.1021/ol8013528. PubMed DOI

Guselnikova O., Postnikov P., Chehimi M.M., Kalachyovaa Y., Svorcik V., Lyutakov O. Surface Plasmon-Polariton: A Novel Way To Initiate Azide–Alkyne Cycloaddition. Langmuir. 2019;35:2023–2032. doi: 10.1021/acs.langmuir.8b03041. PubMed DOI

Guselnikova O., Postnikov P., Elashnikov R., Trusova M., Kalachyova Y., Libansky M., Barek J., Kolska Z., Švorčík V., Lyutakov O. Surface Modification of Au and Ag Plasmonic Thin Films via Diazonium Chemistry: Evaluation of Structure and Properties. Colloids Surf. A Physicochem. Eng. Asp. 2017;516:274–285. doi: 10.1016/j.colsurfa.2016.12.040. DOI

Gam-Derouich S., Lamouri A., Redeuilh C., Decorse P., Maurel F., Carbonnier B., Beyazıt S., Yilmaz G., Yagci Y., Chehimi M.M. Diazonium Salt-Derived 4-(Dimethylamino)Phenyl Groups as Hydrogen Donors in Surface-Confined Radical Photopolymerization for Bioactive Poly(2-Hydroxyethyl Methacrylate) Grafts. Langmuir. 2012;28:8035–8045. doi: 10.1021/la300690d. PubMed DOI

Kalachyova Y., Erzina M., Postnikov P., Svorcik V., Lyutakov O. Flexible SERS Substrate for Portable Raman Analysis of Biosamples. Appl. Surf. Sci. 2018;458:95–99. doi: 10.1016/j.apsusc.2018.07.073. DOI

Guselnikova O., Kalachyova Y., Hrobonova K., Trusova M., Barek J., Postnikov P., Svorcik V., Lyutakov O. SERS Platform for Detection of Lipids and Disease Markers Prepared Using Modification of Plasmonic-Active Gold Gratings by Lipophilic Moieties. Sensors Actuators B Chem. 2018;265:182–192. doi: 10.1016/j.snb.2018.03.016. DOI

Guselnikova O., Postnikov P., Trelin A., Švorčík V., Lyutakov O. Dual Mode Chip Enantioselective Express Discrimination of Chiral Amines via Wettability-Based Mobile Application and Portable Surface-Enhanced Raman Spectroscopy Measurements. ACS Sesnors. 2019;4:1032–1039. doi: 10.1021/acssensors.9b00225. PubMed DOI

Ibrahim M., Haes H.E. Computational Spectroscopic Study of Copper, Cadmium, Lead and Zinc Interactions in the Environment. Int. J. Environ. Pollut. 2005;23:417. doi: 10.1504/IJEP.2005.007604. DOI

Sze Y.K., Davis A.R., Neville G.A. Raman and infrared studies of complexes of mercury(II) with cysteine, cysteine methyl ester and methionine. Inorg. Chem. 1975;14:1969–1974. doi: 10.1021/ic50150a045. DOI

Shindo H., Brown T.L. Infrared Spectra of Complexes of L-Cysteine and Related Compounds with Zinc(II), Cadmium(II), Mercury(II), and Lead(II)1. J. Am. Chem. Soc. 1965;87:1904–1908. doi: 10.1021/ja01087a013. PubMed DOI

United Nations Environment Programme Summary of the Assessment Report. Global Mercury Assessment. [(accessed on 6 May 2019)]; Available online: https://wedocs.unep.org/bitstream/handle/20.500.11822/11517/UNEP_GlobalAtmosphericMercuryAssessment_May2009.pdf.

Human Exposure International Mercury Assessment. United Nations Environment Programme. [(accessed on 6 May 2019)]; Available online: https://blogs.iit.edu/global-leaders/files/2012/06/IMA-Assessment_Part-1.pdf.

Ahmadivand A., Gerislioglu B., Manickam P., Kaushik A., Bhansali S., Nair M., Pala N. Rapid Detection of Infectious Envelope Proteins by Magnetoplasmonic Toroidal Metasensors. ACS Sensors. 2017;2:1359–1368. doi: 10.1021/acssensors.7b00478. PubMed DOI