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Fabrication of cube-like Fe3O4@SiO2@Ag nanocomposites with high SERS activity and their application in pesticide detection

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Abstract

The cube-like Fe3O4@SiO2@Ag (FSA) nanocomposites with great SERS activity have been successfully synthesized by a layer-by-layer procedure in this paper. The cube-like Fe3O4@SiO2 core–shell structures were prepared via a new route and Ag nanoparticles were introduced onto their surface through a one-pot hydrothermal reaction. By controlling the reaction time, the coverage rate of Ag on the FSA surface could be tuned, and then a series of FSA composites were obtained. The SERS properties of these FSA composites were investigated using p-aminothiophenol (p-ATP) as the probe molecule. It was found that the FSA composites synthesized with a reaction time of 6 h showed the best SERS performance, and the detection limit for p-ATP could reach 1 × 10−7 M. For practical application, the FSA composites were also used to detect thiram, one of the dithiocarbamate fungicides that has been widely used as a pesticide in agriculture. The detection limit is as low as 1 × 10−6 M (0.24 ppm), lower than the maximal residue limit of 7 ppm in fruit prescribed by the US Environmental Protection Agency. The resulting substrate with high SERS activity, stability and strong magnetic responsivity makes the FSA composite a perfect choice for practical SERS detection applications.

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References

  • Bruni S, Cariati F, Casu M, Lai A et al (1999) IR and NMR study of nanoparticle–support interactions in a Fe2O3–SiO2 nanocomposite prepared by a sol–gel method. Nano Struct Mater 11(5):573–586

    Article  Google Scholar 

  • Fleischmann M, Hendra PJ, McQuillan AJ (1974) Raman spectra of pyridine absorbed at a silver electrode. Chem Phys Lett 26(2):163–166

    Article  Google Scholar 

  • Gan ZB, Zhao AW, Zhang MF, Tao WY, Guo HY, Gao Q, Mao RR, Liu EH (2013) Controlled synthesis of Au-loaded Fe3O4@C composite microspheres with superior SERS detection and catalytic degradation abilities for organic dyes. Dalton T 42(24):8597–8605

    Article  Google Scholar 

  • Gao JH, Gu HW, Xu B (2009) Multifunctional magnetic nanoparticles: design, synthesis, and biomedical applications. Accounts Chem Res 42(8):1097–1107

    Article  Google Scholar 

  • Guo SJ, Dong SJ, Wang EK (2009) A general route to construct diverse multifunctional Fe3O4/metal hybrid nanostructures. Chem Eur J 15(10):2416–2424

    Article  Google Scholar 

  • Gupta B, Rani M, Kumar R (2012) Degradation of thiram in water, soil and plants: a study by high-performance liquid chromatography. Biomed Chromatogr 26(1):69–75

    Article  Google Scholar 

  • Han ZZ, Liu HL, Meng J, Yang LB, Liu J, Liu JH (2015) Portable kit for identification and detection of drugs in human urine using surface-enhanced Raman spectroscopy. Anal Chem 87(18):9500–9506

    Article  Google Scholar 

  • Hou CH, Hou SM, Hsueh YS, Lin J, Wu HC, Lin FH (2009) The in vivo performance of biomagnetic hydroxyapatite nanoparticles in cancer hyperthermal therapy. Biomaterials 30:3956–3960

    Article  Google Scholar 

  • Hu HB, Wang ZH, Pan L, Zhao SP, Zhu SY (2010) Ag-coated Fe3O4@SiO2 three-ply composite microspheres: synthesis, characterization, and application in detecting melamine with their surface-enhanced Raman scattering. J Phys Chem C 114(17):7738–7742

    Article  Google Scholar 

  • Innocenzi P (2003) Infrared spectroscopy of sol–gel derived silica-based films: a spectra-microstructure overview. J Non-Cryst Sol 316:309–319

    Article  Google Scholar 

  • Liu BH, Han GM, Zhang ZP, Liu RY, Jiang CL, Wang SH, Han MY (2012) Shell thickness-dependent Raman enhancement for rapid identification and detection of pesticide residues at Fruit Peels. Anal Chem 84(1):255–261

    Article  Google Scholar 

  • Liu M, Wang ZY, Zong SF, Chen H, Zhu D, Wu L, Hu GH, Cui YP (2014) SERS detection and removal of mercury(II)/silver(I) using oligonucleotide-functionalized core–shell magnetic silica sphere@Au nanoparticles. ACS Appl Mater Interfaces 6(10):7371–7379

    Article  Google Scholar 

  • Lv BL, Xu Y, Tian H, Wu D, Sun YH (2010) Synthesis of Fe3O4\SiO2\Ag nanoparticles and its application in surface-enhanced Raman scattering. J Sol State Chem 183(12):2968–2973

    Article  Google Scholar 

  • Ohmori M, Matijevic E (1993) Preparation and properties of uniform coated inorganic colloidal particles: 8 Silica on Iron. J Colloid Interf Sci 160(2):288–292

    Article  Google Scholar 

  • Pu ZF, Cao MH, Yang J, Huang KL, Hu CW (2006) Controlled synthesis and growth mechanism of hematite nanorhombohedra, nanorods and nanocubes. Nanotechnology 17(3):799–804

    Article  Google Scholar 

  • Queffelec AL, Boisde F, Larue JP, Haelters JP, Corbel B, Thouvenot D, Nodet P (2001) Development of an immunoassay (ELLSA) for the quantification of thiram in lettuce. J Agric Food Chem 49(4):1675–1680

    Article  Google Scholar 

  • Rastegarzadeh S, Pourreza N, Larki A (2013) Dispersive liquid-liquid microextraction of thiram followed by microvolume UV–Vis spectrophotometric determination. Spectrochim Acta, Part A 114:46–50

    Article  Google Scholar 

  • Schmidt-Nielsen K (1984) Scaling: why is animal size so important?. Cambridge University Press, New York

    Book  Google Scholar 

  • Stöber W, Fink A (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interf Sci 26:62–69

    Article  Google Scholar 

  • Su L, Jia WZ, Manuzzi DP, Zhang LC, Li XP, Gu ZY, Lei Y (2012) Highly sensitive surface-enhanced raman scattering using vertically aligned silver nanopetals. RSC Adv 2(4):1439–1443

    Article  Google Scholar 

  • Sugimoto T, Muramatsu A (1996) Formation mechanism of monodispersed α-Fe2O3 particles in dilute FeCl3 solutions. J Colloid Interf Sci 184:626–638

    Article  Google Scholar 

  • Tang XH, Dong RL, Yang LB, Liu JH (2015) Fabrication of Au nanorod-coated Fe3O4 microspheres as SERS substrate for pesticide analysis by near-infrared excitation. J Raman Spectrosc 46(5):470–475

    Article  Google Scholar 

  • Tao WY, Zhao AW, Sun HH, Gan ZB, Zhang MF, Li D, Guo HY (2014) Periodic silver nanodishes as sensitive and reproducible surface-enhanced Raman scattering substrates. RSC Adv 4(7):3487–3493

    Article  Google Scholar 

  • Vogel S (1988) Life’s devices: the physical world of animals and plants. Princeton University Press, Princeton

    Google Scholar 

  • Wang YS, Muramatsu A, Sugimoto T (1998) FTIR analysis of well-defined α-Fe2O3 particles. Colloid Surface A 34:281–297

    Article  Google Scholar 

  • Wang YQ, Zou BF, Gao T, Wu XP, Lou SY, Zhou SM (2012) Synthesis of orange-like Fe3O4/PPy composite microspheres and their excellent Cr(VI) ion removal properties. J Mater Chem 22(18):9034–9040

    Article  Google Scholar 

  • Wang JP, Yang L, Liu BH, Jiang HJ, Liu RY, Yang JW, Han GM, Mei QS, Zhang ZP (2014a) Inkjet-printed silver nanoparticle paper detects airborne species from crystalline explosives and their ultratrace residues in open environment. Anal Chem 86(7):338–3345

    Google Scholar 

  • Wang K, Zhang XL, Niu CY, Wang YQ (2014b) Template-activated strategy toward one-step coating silica colloidal microspheres with silver. ACS Appl Mater Interfaces 6(2):1272–1278

    Article  Google Scholar 

  • Waseem A, Yaqoob M, Nabi A (2010) Determination of thiram in natural waters using flow-injection with cerium (IV)-quinine chemiluminescence system. Luminescence 25(1):71–75

    Google Scholar 

  • Yang LB, Bao ZY, Wu YC, Liu JH (2012) Clean and reproducible SERS substrates for high sensitive detection by solid phase synthesis and fabrication of Ag-coated Fe3O4 microspheres. J Raman Spectrosc 43(7):848–856

    Article  Google Scholar 

  • Yang J, Wang ZY, Zong SF, Chen H, Zhang RH, Cui YP (2014) Dual-mode tracking of tumor-cell-specific drug delivery using fluorescence and label-free SERS techniques. Biosens Bioelectron 51:82–89

    Article  Google Scholar 

  • Ye YJ, Liu HL, Yang LB, Liu JH (2012) Sensitive and selective SERS probe for trivalent chromium detection using citrate attached gold nanoparticles. Nanoscale 4(20):6442–6448

    Article  Google Scholar 

  • Zhang L, Wang WZ, Zhou L, Shang M, Sun SM (2009) Fe3O4 coupled BiOCl: a highly efficient magnetic photocatalyst. Appl Catal B 90:458–462

    Article  Google Scholar 

  • Zhang XL, Niu HY, Yan JP, Cai YQ (2011) Immobilizing silver nanoparticles onto the surface of magnetic silica composite to prepare magnetic disinfectant with enhanced stability and antibacterial activity. Colloid Surf A 375:186–192

    Article  Google Scholar 

  • Zhang MF, Zhao AW, Wang DP, Sun HH (2015) Hierarchically assembled NiCo@SiO2@Ag magnetic core–shell microspheres as highly efficient and recyclable 3D SERS substrates. Analyst 140(2):440–448

    Article  Google Scholar 

  • Zhao WR, Chen HR, Li YS, Li L, Lang MD, Shi JL (2008) Uniform rattle-type hollow magnetic mesoporous spheres as drug delivery carries and their sustained-release property. Adv Funct Mater 18(18):2780–2788

    Article  Google Scholar 

  • Zhou JF, Meng LJ, Liu QH, Fu JW, Huang XB (2009) Superparamagnetic submicro-megranates: Fe3O4 nanoparticles coated with highly cross-linked organic/inorganic hybrids. Chem Comm 42:6370–6372

    Article  Google Scholar 

  • Zong SF, Wang ZY, Yang J, Wang CL, Xu SH, Cui YP (2012) A SERS and fluorescence dual mode cancer cell targeting probe based on silica coated Au@Ag core–shell nanorods. Talanta 97:368–375

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 61378038) and the State Key Laboratories of Transducer Technology for financial support.

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Authors and Affiliations

  1. Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, 230031, People’s Republic of China

    Lei Li, Aiwu Zhao, Dapeng Wang, Hongyan Guo, Henghui Sun & Qinye He

  2. Department of Chemistry, University of Science and Technology of China, Hefei, 230026, Anhui, People’s Republic of China

    Lei Li, Aiwu Zhao, Dapeng Wang, Hongyan Guo & Qinye He

  3. State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Hefei, 230031, People’s Republic of China

    Lei Li, Aiwu Zhao, Dapeng Wang, Hongyan Guo, Henghui Sun & Qinye He

Authors
  1. Lei Li
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  2. Aiwu Zhao
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  3. Dapeng Wang
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  4. Hongyan Guo
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  5. Henghui Sun
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Correspondence to Aiwu Zhao.

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Li, L., Zhao, A., Wang, D. et al. Fabrication of cube-like Fe3O4@SiO2@Ag nanocomposites with high SERS activity and their application in pesticide detection. J Nanopart Res 18, 178 (2016). https://doi.org/10.1007/s11051-016-3484-0

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  • DOI: https://doi.org/10.1007/s11051-016-3484-0

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