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A molecularly imprinted nanoprobe incorporating Cu2O@Ag nanoparticles with different morphologies for selective SERS based detection of chlorophenols

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Abstract

In a new method for the determination of trace levels of chlorophenols in river waters, detection via surface-enhanced Raman scattering (SERS) is combined with recognition by a molecularly imprinted polymer (MIP). Nanoparticles of type Cu2O@Ag were synthesized by attaching silver particles to the surface of Cu2O nanoparticles. The Cu2O@Ag were then coated with a layer of a MIP that was obtained by atom transfer radical polymerization using from methacrylic acid as monomers and 2,6-dichlorophenol as the template. The morphology of Cu2O is found to be flower-like. The Cu2O@Ag-MIPs displays a strong SERS effect. Following removal of the template by rinsing with the mixture solution of methanol/acetic acid (9/1, v/v), the material was used to selectively bind 2,6-dichlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenol. The SERS peak intensity at 1580 cm−1 increases linearly with the concentration of the various chlorophenols in the range from 10 nM to 1 mM, and the detection limit is 5.8 nM. The imprinting factor is 4.62. The method was applied to the analysis of (spiked) river water, with recoveries ranging from 91.8 to 115.4% and relative standard deviations of <4.5%.

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References

  1. Virkutyte J, Varma RS (2014) Eco-friendly magnetic Iron oxide-pillared Montmorillonite for advanced catalytic degradation of Dichlorophenol. ACS Sustain 2:1545–1550

    Article  CAS  Google Scholar 

  2. Esfandiarnejad R, Sereshti H (2019) Designing an absolutely solvent-free binary extraction system as a green strategy for ultra-trace analysis of chlorophenols. Microchem J 146:701–707

    Article  CAS  Google Scholar 

  3. Gallego A, Soule JL, Napolitano H, Rossi SL, Vescina C, Korol SE (2018) Biodegradability of Chlorophenols in surface waters from the urban area of Buenos Aires. B Environ Contam Tox 100:541–547

    Article  CAS  Google Scholar 

  4. Liu W, Zha J, Meng XY, Wu JR, Sun C, Qiu PZ, Fizir M, He H (2017) Efficient removal and trace determination of chlorophenols from water using mixed hemi−/admicelle ionic liquid-coated magnetic graphene oxide and the adsorption mechanism. Anl Methods-UK 9:4581–4591

    Article  CAS  Google Scholar 

  5. De Paepe E, Wauters J, Claes J, Huysman S, Croubels S, Vanhaecke L (2019) Ultra-high-performance liquid chromatography coupled to quadrupole orbitrap high-resolution mass spectrometry for multi-residue screening of pesticides, (veterinary) drugs and mycotoxins in edible insects. Food Chem 293:187–196

    Article  Google Scholar 

  6. Martakidis K, Gavril D (2019) New inverse gas chromatographic methodology for studying mass transfer caused by the evaporation of volatile liquids. Instrum Sci Tchnol 47:389–409

    Article  CAS  Google Scholar 

  7. Hu Y, Cheng H, Zhao X (2017) Surface-enhanced Raman scattering-active gold nanoparticles with enzyme mimicking activities for measuring glucose and lactate in living tissue. ACS Nano 11:5558–5566

    Article  CAS  Google Scholar 

  8. Ai YJ, Liang P, Wu YX (2016) Rapid qualitative and quantitative determination of food colorants by both Raman spectra and surface-enhanced Raman scattering (SERS). Food Chem 241:427–433

    Article  Google Scholar 

  9. Keshavarz M, Tan B, Venkatakrishnan K (2018) Label-free SERS quantum semiconductor probe for molecular-level and in vitro cellular detection: a Noble-metal-free methodology. Acs Appl Mater Inter 41:34886–34904

    Article  Google Scholar 

  10. Li QQ, Gong SS, Zhang H, Huang FZ, Zhang LN, Li SK (2019) Tailorednecklace-like Ag@ ZIF-8 core/shell heterostructure nanowires for high-performance plasmonic SERS detection. Chem Eng J 371:26–33

    Article  CAS  Google Scholar 

  11. Zhou Y, Cheng X, Du D, Yang J, Zhao N, Ma S, Zhong T, Lin Y (2014) Graphene-silver Nanohybrids for ultrasensitive surface enhanced Raman spectroscopy size dependence of silver nanoparticles. J Mater Chem C 2:6850–6858

    Article  CAS  Google Scholar 

  12. Zhang MF, Zhao AW, Wang DP, Sun HH (2014) Hierarchically assembled NiCo@SiO2@Ag magnetic core-shell microspheres as highly efficient and recyclable 3D SERS substrate. Analyst 140:440–448

    Article  Google Scholar 

  13. Xu ZK, Luo YY, Duan GT (2019) Self-assembly of Cu2O Monolayer Colloidal Particle Film Allows the Fabrication of CuO nanoprobe with Superselectivity for Hydrogen Sulfide. Acs Appl Mat Interfaces 11:8164–8174

    Article  CAS  Google Scholar 

  14. Luo HQ, Zhou J, Zhong HH, Zhou L, Jia ZH, Tanc XL (2016) Polyhedron Cu2O@Ag composite microstructures:synthesis, mechanism analysis and structuredependent SERS properties. RSC Adv 6:101

    Google Scholar 

  15. Guo Y, Wang H, Ma XW, Jin J, Ji W, Wang X, Song W, Zhao B, He CY (2017) Fabrication of Ag-Cu2O/reduced Graphene oxide Nanocomposites as surface-enhanced Raman scattering substrates for in situ monitoring of peroxidase-like catalytic reaction and biosensing. Acs Appl Mater 9:19074–19081

    Article  CAS  Google Scholar 

  16. Lee YJ, Kim S, Park SH (2011) Morphology-dependent antibacterial activities of Cu2O. Mater Lett 65:818–820

    Article  CAS  Google Scholar 

  17. Jung HY, Seo Y, Park H, Huh YD (2015) Morphology-controlled synthesis of octahedral-to-rhombic dodecahedral Cu2O microcrystals and shape-dependent antibacterial activities. B Kor Chem Soc 36: 1828–1833

    Article  CAS  Google Scholar 

  18. Haynes CL, McFarland AD, Duyne RPV (2005) Surface-enhanced Raman spectroscopy. Anal Chem 77:338A–346A

    Article  CAS  Google Scholar 

  19. Li H, Jiang J, Wang Z (2017) A high performance and highly-controllable core-shell imprinted nanoprobe based on the surface-enhanced Raman scattering for detection of R6G in wate. J Colloid Interf Sci 501:86–93

    Article  CAS  Google Scholar 

  20. Wan YY, Wang M, Fu QF, Wang LJ, Wang DD, Zhang KL, Xia ZN, Gao D (2018) Novel dual functional monomers based molecularly imprinted polymers for selective extraction of myricetin from herbal medicines. J Chromatogr B 1097:1–9

    Article  Google Scholar 

  21. Lv YQ, Qin YT, Svec F, Tan TW (2016) Molecularly imprinted plasmonic nanonanoprobe for selective SERS detection of protein biomarkers. Biosens Bioelectron 80:433–441

    Article  CAS  Google Scholar 

  22. Hu R, Tang R, Xu JY, Lu F (2018) Chemical nanonanoprobe s based on molecularly-imprinted polymers doped with silver nanoparticles for the rapid detection of caffeine in wastewater. Anal Chim Acta 1034:176–183

    Article  CAS  Google Scholar 

  23. Guo Y, Dai MM, Zhu ZX, Chen YQ, He H, Qin TH (2019) Chitosan modified Cu2O nanoparticles with high catalytic activity for p-nitrophenol reduction. Appl Surf Sci 480:601–610

    Article  CAS  Google Scholar 

  24. Kumar S, Karfa P, Madhuri R, Madhuri R, Sharma PK (2018) Designing of fluorescent and magnetic imprinted polymer for rapid, selective and sensitive detection of imidacloprid via activators regenerated by the electron transfer-atom transfer radical polymerization (ARGET-ATRP) technique. J Phys Chem Solids 116:222–233

    Article  CAS  Google Scholar 

  25. Wu Y, Liu X, Meng M (2012) Bio-inspired adhesion: fabrication of molecularly imprinted nanocomposite membranes by developing a hybrid organic–inorganic nanoparticles composite structure. J Membrane Sci 490:169–178

    Article  Google Scholar 

  26. Sarfo DK, Izake EL, OMullane AP Ayoko GA (2019) fabrication of nanostructured SERS substrates on conductive solid platforms for environmental application. Crit Rev Env Sci Tec 49:1294–1329

    Article  CAS  Google Scholar 

  27. Xie YF, Zha MY, Hu Q, Cheng YL, Guo YH, Qian H, Yao WR (2017) Selective detection of chloramphenicol in milk based on a molecularly imprinted polymer–surface-enhanced Raman spectroscopic nanonanoprobe. J Raman Spectrosc 48:204–210

    Article  CAS  Google Scholar 

  28. Wu ZZ, He DY, Cui B, Jin ZY (2019) Ultrasensitive detection of microcystin-LR with gold immunochromatographi assay assisted by a molecular imprinting technique. Food Chem 283: 517–521

    Article  CAS  Google Scholar 

  29. Chang LM, Ding Y, Li X (2013) Surface molecular imprinting onto silver microspheres for surface enhanced Raman scattering applications. Biosens Bioelectron 50:106–110

    Article  CAS  Google Scholar 

  30. Liu BY, Zhang W, Lv HM (2012) Novel Ag decorated biomorphic SnO2 inspired by natural 3D nanostructures as SERS substrates. Mater Left 74:43–45

    Article  CAS  Google Scholar 

  31. Chen CF, Wang YZ, Ding SH, Hong CL, Wang ZJ (2019) A novel sensitive and selective electrochemical nanoprobe based on integration of molecularlyimprinted with hollow silver nanospheres for determination of carbamazepine. Microchem J 147:191–197

    Article  CAS  Google Scholar 

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Acknowledgements

This work is supported by the National Natural Science Foundation (No. 21576112), Natural Science Foundation Project of Jilin Province (20180623042TC, 20180101181JC, 20170520147JH). The Project of Department of Science & Technology of Jilin Province (20180623042TC, 20170520134JH), the Project of Education Department of Jilin Province (JJKH20191010KJ) and the Project of Human Resources and Social Security Department of Jilin Province (2017956).

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Authors and Affiliations

  1. College of Chemistry, Jilin Normal University, Siping, 136000, China

    Yue Li, Yan Wang & Qingwei Wang

  2. College of Physics, Jilin Normal University, Siping, 136000, China

    Mingchao Wang

  3. College of Environmental Science and Engineering, Jilin Normal University, Siping, 136000, People’s Republic of China

    Jinyue Zhang & Hongji Li

  4. Key Laboratory of Environmental Materials and Pollution Control, the Education Department of Jilin Province, Jilin Normal University, Siping, 136000, China

    Hongji Li

  5. Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, China

    Qingwei Wang & Hongji Li

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  1. Yue Li
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  2. Yan Wang
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  3. Mingchao Wang
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  4. Jinyue Zhang
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  5. Qingwei Wang
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  6. Hongji Li
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Correspondence to Qingwei Wang or Hongji Li.

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Li, Y., Wang, Y., Wang, M. et al. A molecularly imprinted nanoprobe incorporating Cu2O@Ag nanoparticles with different morphologies for selective SERS based detection of chlorophenols. Microchim Acta 187, 59 (2020). https://doi.org/10.1007/s00604-019-4052-y

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