Abstract
A sponge inspired three dimensional flexible aluminum foil based ZnO nanosheet array substrate is described for use in real-world surface enhanced Raman spectroscopic detection. Gold and silver nanoparticles were employed to form numerous hot spots on uniformly grown ZnO nanosheets on the substrate. This flexible spongy substrate can extract analytes (such as the fungicide thiram) from various complex sample surfaces by physical swabbing. Specifically, this substrate was applied to detect thiram on the surface of fruits and vegetables. Non-destructive recycling detection with a relative standard deviation of 6.1% was accomplished by monitoring the characteristic Raman peak at 1382 cm−1. This modified substrate has a low detection limit (0.2 ng cm−2 of thiram for apple and tomato), outstanding uniformity (relative standard deviation = 8.9%) and thermal stability (relative standard deviation = 0.9%).
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Schematic representation of using a aluminum foil modified with ZnO nanosheets as a flexible and recyclable substrate for SERS analysis of pollutants. The substrate can be cleaned after use by UV irradiation.
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References
Fleischmann M, Hendra PJ, McQuillan AJ (1974) Raman spectra of pyridine adsorbed at a silver electrode. Chem Phys Lett 26(2):163–166
Zhang L, Liu T, Liu K, Han L, Yin Y, Gao C (2015) Gold Nanoframes by nonepitaxial growth of au on AgI nanocrystals for surface-enhanced Raman spectroscopy. Nano Lett 15(7):4448–4454
Sykes EA, Chen J, Zheng G, Chan WCW (2014) Investigating the impact of nanoparticle size on active and passive tumor targeting efficiency. ACS Nano 8(6):5696–5706
Gong Z, Du H, Cheng F, Wang C, Wang C, Fan M (2014) Fabrication of SERS swab for direct detection of trace explosives in fingerprints. ACS Appl Mater Interfaces 6(24):21931–21937
Zhang C, Gao Y, Yang N, You T, Chen H, Yin P (2018) Direct determination of the tumor marker AFP via silver nanoparticle enhanced SERS and AFP-modified gold nanoparticles as capturing substrate. Microchim Acta 185(2):90
Fu C, Wang Y, Chen G, Yang L, Xu S, Xu W (2015) Aptamer-based surface-enhanced Raman scattering-microfluidic sensor for sensitive and selective polychlorinated biphenyls detection. Anal Chem 87(19):9555–9558
Creighton JA, Blatchford CG, Albrecht MG (1979) Plasma resonance enhancement of Raman scattering by pyridine adsorbed on silver or gold sol particles of size comparable to the excitation wavelength. J Chem Soc Faraday Trans 2 75(0):790–798
Ren W, Zhu C, Wang E (2012) Enhanced sensitivity of a direct SERS technique for Hg2+ detection based on the investigation of the interaction between silver nanoparticles and mercury ions. Nanoscale 4(19):5902–5909
Jensen L, Aikens CM, Schatz GC (2008) Electronic structure methods for studying surface-enhanced Raman scattering. Chem Soc Rev 37(5):1061–1073
Y-e S, Wang W, Zhan J (2016) A positively charged silver nanowire membrane for rapid on-site swabbing extraction and detection of trace inorganic explosives using a portable Raman spectrometer. Nano Res 9(8):2487–2497
Li JF, Huang YF, Ding Y, Yang ZL, Li SB, Zhou XS, Fan FR, Zhang W, Zhou ZY, Wu DY, Ren B, Wang ZL, Tian ZQ (2010) Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464:392-395.https://www.nature.com/articles/nature08907#supplementary-information
Martín A, Wang JJ, Iacopino D (2014) Flexible SERS active substrates from ordered vertical au nanorod arrays. RSC Adv 4(38):20038–20043
Fan M, Zhang Z, Hu J, Cheng F, Wang C, Tang C, Lin J, Brolo AG, Zhan H (2014) Ag decorated sandpaper as flexible SERS substrate for direct swabbing sampling. Mater Lett 133:57–59
Li D, Duan H, Wang Y, Zhang Q, Cao H, Deng W, Li D (2017) On-site preconcentration of pesticide residues in a drop of seawater by using electrokinetic trapping, and their determination by surface-enhanced Raman scattering. Microchim Acta 185(1):10
Duan N, Shen M, Wu S, Zhao C, Ma X, Wang Z (2017) Graphene oxide wrapped Fe3O4@au nanostructures as substrates for aptamer-based detection of Vibrio parahaemolyticus by surface-enhanced Raman spectroscopy. Microchim Acta 184(8):2653–2660
Wang J, Yang L, Liu B, Jiang H, Liu R, Yang J, Han G, Mei Q, Zhang Z (2014) Inkjet-printed silver nanoparticle paper detects airborne species from crystalline explosives and their Ultratrace residues in open environment. Anal Chem 86(7):3338–3345
Chen J, Huang Y, Kannan P, Zhang L, Lin Z, Zhang J, Chen T, Guo L (2016) Flexible and adhesive surface enhance Raman scattering active tape for rapid detection of pesticide residues in fruits and vegetables. Anal Chem 88(4):2149–2155
Wang P, Wu L, Lu Z, Li Q, Yin W, Ding F, Han H (2017) Gecko-inspired Nanotentacle surface-enhanced Raman spectroscopy substrate for sampling and reliable detection of pesticide residues in fruits and vegetables. Anal Chem 89(4):2424–2431
Zhu Y, Li M, Yu D, Yang L (2014) A novel paper rag as ‘D-SERS’ substrate for detection of pesticide residues at various peels. Talanta 128:117–124
Barbillon G, Sandana VE, Humbert C, Bélier B, Rogers DJ, Teherani FH, Bove P, McClintock R, Razeghi M (2017) Study of au coated ZnO nanoarrays for surface enhanced Raman scattering chemical sensing. J Mater Chem C 5(14):3528–3535
Yang Y, Liu J, Fu Z-W, Qin D (2014) Galvanic replacement-free deposition of au on ag for Core–Shell Nanocubes with enhanced chemical stability and SERS activity. J Am Chem Soc 136(23):8153–8156
Ansar SM, Ameer FS, Hu W, Zou S, Pittman CU, Zhang D (2013) Removal of molecular adsorbates on gold nanoparticles using sodium borohydride in water. Nano Lett 13(3):1226–1229
Zhou Y, Lee C, Zhang J, Zhang P (2013) Engineering versatile SERS-active nanoparticles by embedding reporters between au-core/ag-shell through layer-by-layer deposited polyelectrolytes. J Mater Chem C 1(23):3695–3699
Liu B, Tan H, Chen Y (2013) Visual detection of silver(I) ions by a chromogenic reaction catalyzed by gold nanoparticles. Microchim Acta 180(5):331–339
Yang L, Wang W, Jiang H, Zhang Q, Shan H, Zhang M, Zhu K, Lv J, He G, Sun Z (2017) Improved SERS performance of single-crystalline TiO2 nanosheet arrays with coexposed {001} and {101} facets decorated with ag nanoparticles. Sensors Actuators B Chem 242:932–939
Saute B, Narayanan R (2011) Solution-based direct readout surface enhanced Raman spectroscopic (SERS) detection of ultra-low levels of thiram with dogbone shaped gold nanoparticles. Analyst 136(3):527–532
Markina NE, Markin AV, Zakharevich AM, Goryacheva IY (2017) Calcium carbonate microparticles with embedded silver and magnetite nanoparticles as new SERS-active sorbent for solid phase extraction. Microchim Acta 184(10):3937–3944
Bu Y, Liu K, Hu Y, Kaneti YV, Brioude A, Jiang X, Wang H, Yu A (2017) Bilayer composites consisting of gold nanorods and titanium dioxide as highly sensitive and self-cleaning SERS substrates. Microchim Acta 184(8):2805–2813
Kang JS, Hwang SY, Lee CJ, Lee MS (2002) SERS of Dithiocarbamate pesticides adsorbed on silver surface; Thiram. Bull Kor Chem Soc 23:1604–1610
Chao YC, Chen CY, Lin CA, He JH (2011) Light scattering by nanostructured anti-reflection coatings. Energy Environ Sci 4(9):3436–3441
Qiu B, Xing M, Yi Q, Zhang J (2015) Chiral carbonaceous nanotubes modified with Titania nanocrystals: Plasmon-free and recyclable SERS sensitivity. Angew Chem Int Ed 54(36):10643–10647
Alessandri I, Ferroni M (2009) Exploiting optothermal conversion for nanofabrication: site-selective generation of au/TiO2 inverse opals. J Mater Chem 19(42):7990–7994
Acknowledgements
This work was supported by the financial support from the National Natural Science Foundation of China (NSFC 21575077, 21750110438, 21876099), the Science and Technology Development Plans of Shandong Province (ZR2017ZC0227) and the Fundamental Research Funds of Shandong University (2016JC030).
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Wang, Y., Yu, X., Chang, Y. et al. A 3D spongy flexible nanosheet array for on-site recyclable swabbing extraction and subsequent SERS analysis of thiram. Microchim Acta 186, 458 (2019). https://doi.org/10.1007/s00604-019-3579-2
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DOI: https://doi.org/10.1007/s00604-019-3579-2