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Nanoporous cellulose paper-based SERS platform for multiplex detection of hazardous pesticides

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Abstract

In this study, a nanoporous cellulose paper-based SERS platform was developed to analyze multiplex hazardous pesticides including thiram (T1), tricyclazole (T2), and carbaryl (C) by surface enhanced Raman scattering (SERS). Gold nanorods (AuNRs) with different aspect ratios were synthesized and compared to achieve the highest SERS signals on paper-based SERS substrates. The advantage of the nanoporous cellulose nanofiber (CNF) matrix with nanoscale surface roughness is that it allows actual nanofiltration, resulting in a uniform and well-controlled AuNR distribution on the top portion of the CNF matrix. The as-prepared CNF–AuNR-based SERS platform exhibited an enhancement factor of 1.4 × 107 as well as the ability to simultaneously detect T1, T2, and C at concentrations as low as 1 nM, 100 nM, and 1 μM, respectively. In addition to analyzing triplex pesticide mixtures in solution, the SERS platform allows for a paper-based SERS swab for rapid trace detection on real-world surfaces. The detection limits for T1, T2, and C residues in apple peels were 6, 60, and 600 ng cm−2, respectively, which are much lower than the maximum residue level requirement for apple peels (2000 ng cm−2). These results demonstrate that the low-cost, flexible, lightweight, paper-based SERS platform shows powerful potential for high SERS performance and on-site SERS analysis.

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References

  • Akhatova F, Danilushkina A, Kuku G, Saricam M, Culha M, Fakhrullin R (2018) Simultaneous intracellular detection of plasmonic and non-plasmonic nanoparticles using dark-field hyperspectral microscopy. Bull Chem Soc Jpn 91:1640–1645

    Article  CAS  Google Scholar 

  • Alsammarraie FK, Lin M (2017) Using standing gold nanorod arrays as surface-enhanced Raman spectroscopy (SERS) substrates for detection of carbaryl residues in fruit juice and milk. J Agric Food Chem 65:666–674

    Article  CAS  PubMed  Google Scholar 

  • Araújo A et al (2017) Direct growth of plasmonic nanorod forests on paper substrates for low-cost flexible 3D SERS platforms. Flex Print Electron 2:014001

    Article  CAS  Google Scholar 

  • Baldi I et al (2003) Association between Parkinson’s disease and exposure to pesticides in southwestern France. Neuroepidemiology 22:305

    Article  PubMed  Google Scholar 

  • Bin T, Zeng T, Liu J, Zhou J, Ye Y, Wang X (2017) Waste fiber powder functionalized with silver nanoprism for enhanced Raman scattering analysis. Nanoscale Res Lett 12:341

    Article  CAS  Google Scholar 

  • Cheng D, He M, Ran J, Cai G, Wu J, Wang X (2018) Depositing a flexible substrate of triangular silver nanoplates onto cotton fabrics for sensitive SERS detection. Sens Actuators B Chem 270:508–517

    Article  CAS  Google Scholar 

  • Dutta S et al (2016) Cellulose framework directed construction of hierarchically porous carbons offering high-performance capacitive deionization of brackish water. ACS Sustain Chem Eng 4:1885–1893

    Article  CAS  Google Scholar 

  • Dutta S et al (2017) 3D network of cellulose-based energy storage devices and related emerging applications. Mater Horiz 4:522–545

    Article  CAS  Google Scholar 

  • Elbaz A et al (2009) Professional exposure to pesticides and Parkinson disease. Ann Neurol 66:494

    Article  PubMed  Google Scholar 

  • Ge F, Chen Y, Liu A, Guang S, Cai Z (2019) Flexible and recyclable SERS substrate fabricated by decorated TiO2 film with Ag NPs on the cotton fabric. Cellulose. https://doi.org/10.1007/s10570-018-2209-1

    Article  Google Scholar 

  • Hormozi-Nezhad MR, Robatjazia H, Jalali-Heravi M (2013) Thorough tuning of the aspect ratio of gold nanorods using response surface methodology. Anal Chim Acta 779:14–21

    Article  CAS  PubMed  Google Scholar 

  • Hossain T et al (2017) Electrochemical biosensing strategies for DNA methylation analysis. Biosens Bioelectron 94:63–73

    Article  CAS  PubMed  Google Scholar 

  • Jiang L, Qian J, Cai F, He S (2011) Raman reporter-coated gold nanorods and their applications in multimodal optical imaging of cancer cells. Anal Bioanal Chem 400:2793–2800

    Article  CAS  PubMed  Google Scholar 

  • Joshi P, Santhanam V (2016) Paper-based SERS active substrates on demand. RSC Adv 6:68545

    Article  CAS  Google Scholar 

  • Joshia P, Santhanam V (2016) Paper-based SERS active substrates on demand. RSC Adv 6:68545–68552

    Article  CAS  Google Scholar 

  • Jung H, Park M, Kang M, Jeong K (2016) Silver nanoislands on cellulose fibers for chromatographic separation and ultrasensitive detection of small molecules. Light Sci Appl 5:e16009

    Article  PubMed  PubMed Central  Google Scholar 

  • Kalachyova Y et al (2016) The effect of silver grating and nanoparticles grafting for LSP–SPP coupling and SERS response intensification. J Phys Chem C 120:10569–10577

    Article  CAS  Google Scholar 

  • Kiguchi M, Fujii S (2017) Governing the metal-molecule interface: towards new functionality in single-molecule junctions. Bull Chem Soc Jpn 90:1–11

    Article  CAS  Google Scholar 

  • Kim W, Kim Y, Park H, Choi S (2015) Facile fabrication of a silver nanoparticle immersed, surface-enhanced Raman scattering imposed paper platform through successive ionic layer absorption and reaction for on-site bioassays. ACS Appl Mater Interfaces 7:27910–27917

    Article  CAS  PubMed  Google Scholar 

  • Kim D, Ko Y, Kwon G, Choo Y, You J (2018) Low-cost, high-performance plasmonic nanocomposites for hazardous chemical detection using surface enhanced Raman scattering. Sens Actuators B Chem 274:30–36

    Article  CAS  Google Scholar 

  • Lee D, Yoon S (2016) Effect of nanogap curvature on SERS: a finite-difference time-domain study. J Phys Chem C 120:20642–20650

    Article  CAS  Google Scholar 

  • Lee CH, Hankus ME, Tian L, Pellergrino PM, Singamaneni S (2011) Highly sensitive surface enhanced Raman scattering substrates based on filter paper loaded with plasmonic nanostructures. Anal Chem 83:8953–8958

    Article  CAS  PubMed  Google Scholar 

  • Lee H et al (2018) Gold nanoparticle-coated ZrO2-nanofiber surface as a SERS-active substrate for trace detection of pesticide residue. Nanomaterials 8:402

    Article  CAS  PubMed Central  Google Scholar 

  • Lin KQ et al (2016) Size effect on SERS of gold nanorods demonstrated via single nanoparticle spectroscopy. J Phys Chem C 120:20806–20813

    Article  CAS  Google Scholar 

  • Ma C, Gao Q, Hong W, Fan J, Fang J (2017) Real-time probing nanopore-in-nanogap plasmonic coupling effect on silver supercrystals with surface-enhanced Raman spectroscopy. Adv Funct Mater 27:1603233

    Article  CAS  Google Scholar 

  • Mostafalou S, Abdollahi M (2017) Pesticides: an update of human exposure and toxicity. Arch Toxicol 91:549–599

    Article  CAS  PubMed  Google Scholar 

  • Orendorff CJ, Gearheart L, Jana NR, Murphy CJ (2006) Aspect ratio dependence on surface enhanced Raman scattering using silver and gold nanorod substrates. Phys Chem Chem Phys 8:165–170

    Article  CAS  PubMed  Google Scholar 

  • Ou Y, Wang X, Lai K, Huang Y, Rasco BA, Fan Y (2018) Gold nanorods as surface-enhanced Raman spectroscopy substrates for rapid and sensitive analysis of allura red and sunset yellow in beverages. J Agric Food Chem 66:2954–2961

    Article  CAS  PubMed  Google Scholar 

  • Park M, Jung H, Jeong Y, Jeong K (2017) Plasmonic Schirmer strip for human tear-based gouty arthritis diagnosis using surface-enhanced Raman scattering. ACS Nano 11:438–443

    Article  CAS  PubMed  Google Scholar 

  • Pérez-Juste J, Pastoriza-Santosa I, Liz-Marzána LM, Mulvaneyb P (2005) Gold nanorods: synthesis, characterization and applications. Coord Chem Rev 249:1870–1901

    Article  CAS  Google Scholar 

  • Polavarapu L, Liz-Marzán LM (2013) Towards low-cost flexible substrates for nanoplasmonic sensing. Phys Chem Chem Phys 15:5288

    Article  CAS  PubMed  Google Scholar 

  • Ros I et al (2014) SERS Properties of gold nanorods at resonance with molecular, transverse, and longitudinal plasmon excitations. Plasmonics 9:581–593

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Sai-Anand G et al (2019) Recent progress on the sensing of pathogenic bacteria using advanced nanostructures. Bull Chem Soc Jpn 92:216–244

    Article  CAS  Google Scholar 

  • Su J et al (2017) Multicolor gold–silver nano-mushrooms as ready-to-use SERS probes for ultrasensitive and multiplex DNA/miRNA detection. Anal Chem 89:2531–2538

    Article  CAS  PubMed  Google Scholar 

  • Tang H et al (2012) Determination of tricyclazole content in paddy rice by surface enhanced Raman spectroscopy. J Food Sci 77:T105–T109

    Article  CAS  PubMed  Google Scholar 

  • Tian L, Jiang Q, Liu K, Luan J, Naik RR, Singamaneni S (2016) Bacterial nanocellulose-based flexible surface enhanced Raman scattering substrate. Adv Mater Interfaces 3:1600214

    Article  CAS  Google Scholar 

  • Vianna PG et al (2016) Graphene oxide/gold nanorod nanocomposite for stable surface-enhanced Raman spectroscopy. ACS Photonics 3:1027–1035

    Article  CAS  Google Scholar 

  • Vigderman L, Manna P, Zubarev ER (2012) Quantitative replacement of cetyl trimethylammonium bromide by cationic thiol ligands on the surface of gold nanorods and their extremely large uptake by cancer cells. Angew Chem 124:660–665

    Article  Google Scholar 

  • Wang Y, Wang Y, Wang W, Sun K, Chen L (2016) Reporter-embedded SERS tags from gold nanorod seeds: selective immobilization of reporter molecules at the tip of nanorods. ACS Appl Mater Interfaces 8:28105–28115

    Article  CAS  PubMed  Google Scholar 

  • Wang Y et al (2018) Flexible, transparent and highly sensitive SERS substrates with cross-nanoporous structures for fast on-site detection. Nanoscale 10:15195

    Article  CAS  PubMed  Google Scholar 

  • Wei H, Rodriguex K, Renneckar S, Leng W, Vikesland PJ (2015) Preparation and evaluation of nanocellulose–gold nanoparticle nanocomposites for SERS applications. Analyst 140:5640

    Article  CAS  PubMed  Google Scholar 

  • Xin W, Yang J, Li C, Goorsky MS, Carlson L, Rosa IMD (2017) Novel strategy for one-pot synthesis of gold nanoplates on carbon nanotube sheet as an effective flexible SERS substrate. ACS Appl Mater Interfaces 9:6246–6254

    Article  CAS  PubMed  Google Scholar 

  • Xiong Z, Chen X, Liou P, Lin M (2017) Development of nanofibrillated cellulose coated with gold nanoparticles for measurement of melamine by SERS. Cellulose 24:2801–2811

    Article  CAS  Google Scholar 

  • Xu Q et al (2017) Template-free synthesis of SERS-active gold nanopopcorn for rapid detection of chlorpyrifos residues. Sens Actuators B 241:1008–1013

    Article  CAS  Google Scholar 

  • Xue Y, Li X, Li H, Zhang W (2014) Quantifying thiol–gold interactions towards the efficient strength control. Nat Commun 5:4348

    Article  CAS  PubMed  Google Scholar 

  • Yang J et al (2014) Single-step and rapid growth of silver nanoshells as SERS-active nanostructures for label-free detection of pesticides. ACS Appl Mater Interfaces 6:12541–12549

    Article  CAS  PubMed  Google Scholar 

  • Yu WW, White IM (2013) Inkjet-printed paper-based SERS dipsticks and swabs for trace chemical detection. Analyst 138:1020

    Article  CAS  PubMed  Google Scholar 

  • Yu Q et al (2018) Multi-functional regenerated cellulose fibers decorated with plasmonic Au nanoparticles for colorimetry and SERS assays. Cellulose 25:6041–6053

    Article  CAS  Google Scholar 

  • Zhang Y, Wang Z, Wu L, Pei Y, Chen P, Cui Y (2014) Rapid simultaneous detection of multi-pesticide residues on apple using SERS technique. Analyst 139:5148–5154

    Article  CAS  PubMed  Google Scholar 

  • Zhang C, Zhu J, Li J, Zhao J (2017) Small and sharp triangular silver nanoplates synthesized utilizing tiny triangular nuclei and their excellent SERS activity for selective detection of thiram residue in soil. ACS Appl Mater Interfaces 9:17387–17398

    Article  CAS  PubMed  Google Scholar 

  • Zhang S et al (2018) Dual-excitation nanocellulose plasmonic membranes for molecular and cellular SERS detection. ACS Appl Mater Interfaces 10:18380–18389

    Article  CAS  PubMed  Google Scholar 

  • Zhu Z, Espulgar WV, Yoshikawa H, Masato Saito M, Fan B, Dou X, Tamiya E (2018) Electrochemically modulated surface-enhanced Raman spectra of aminoglutethimide (AGI) on the Ag-sputtered electrode. Bull Chem Soc Jpn 91:1579–1585

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This study was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (No. 2018R1D1A1B07047874) and a Cooperative Research Program for Agriculture Science and Technology Development (Project No. PJ01279701) Rural Development Administration, Republic of Korea.

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Correspondence to Jungmok You.

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Kwon, G., Kim, J., Kim, D. et al. Nanoporous cellulose paper-based SERS platform for multiplex detection of hazardous pesticides. Cellulose 26, 4935–4944 (2019). https://doi.org/10.1007/s10570-019-02427-8

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