Abstract
A nanocomposite based on nanofibrillar cellulose (NFC) coated with gold–silver (core-shell) nanoparticles (Au@Ag NPs) was developed as a novel surface-enhanced Raman spectroscopy (SERS) substrate. SERS performance of NFC/Au@Ag NP nanocomposite was tested by 4-mercaptobenzoic acid. The cellulose nanofibril network was a suitable platform that allowed Au@Ag NPs to be evenly distributed and stabilized over the substrate, providing more SERS hotspots for the measurement. Two pesticides, thiram and paraquat, were successfully detected either individually or as a mixture in lettuce by SERS coupled with the nanocomposite. Strong Raman scattering signals for both thiram and paraquat were obtained within a Raman shift range of 400–2000 cm−1 and a Raman intensity ~ 8 times higher than those acquired by NFC/Au NP nanocomposite. Characteristic peaks were clearly observable in all SERS spectra even at a low concentration of 10 μg/L of pesticides. Limit of detection values of 71 and 46 μg/L were obtained for thiram and paraquat, respectively. Satisfactory SERS performance, reproducibility, and sensitivity of NFC/Au@Ag NP nanocomposite validate its applicability for real-world analysis to monitor pesticides and other contaminants in complex food matrices within a short acquisition time.
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References
Fenik J, Tankiewicz M, Biziuk M (2011) Properties and determination of pesticides in fruits and vegetables. TrAC Trends Anal Chem 30:814–826
Chang PL, Hsieh MM, Chiu TC (2016) Recent advances in the determination of pesticides in environmental samples by capillary electrophoresis. Int J Environ Res Public Health 13:409
Llorent-Martínez EJ, Ortega-Barrales P, Fernández-de Córdova ML, Ruiz-Medina A (2011) Trends in flow-based analytical methods applied to pesticide detection: a review. Anal Chim Acta 684:30–39
López-Paz JL, Catalá-Icardo M (2011) Analysis of pesticides by flow injection coupled with chemiluminescent detection: a review. Anal Lett 44:146–175
Mirceski V, Gulaboski R (2014) Recent achievements in square-wave voltammetry (a review). Maced J Chem Chem Eng 33:1–12
Pang S, Yang T, He L (2016) Review of surface enhanced Raman spectroscopic (SERS) detection of synthetic chemical pesticides. TrAC Trends Anal Chem 85:73–82
Aroca R (2006) Surface-enhanced vibrational spectroscopy. Chicheste, John Wiley & Sons, Ltd
Bantz KC, Meyer AF, Wittenberg NJ, Im H, Kurtuluş Ö, Lee SH, Lindquist NC, Oh SH, Haynes CL (2011) Recent progress in SERS biosensing. Phys Chem Chem Phys 13:11551–11567
Ji Y, Yang S, Guo S, Song X, Ding B, Yang Z (2010) Bimetallic Ag/Au nanoparticles: a low temperature ripening strategy in aqueous solution. Colloids Surfaces A Physicochem Eng Asp 372:204–209
Cortie MB, McDonagh AM (2011) Synthesis and optical properties of hybrid and alloy plasmonic nanoparticles. Chem Rev 111:3713–3735
Jana NR (2003) Silver coated gold nanoparticles as new surface enhanced Raman substrate at low analyte concentration. Analyst 128:954–956
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 136:8153–8156
Raveendran P, Fu J, Wallen SL (2006) A simple and “green” method for the synthesis of Au, Ag, and Au-Ag alloy nanoparticles. Green Chem 8:34–38
Wei H, Rodriguez K, Renneckar S, Vikesland PJ (2014) Environmental science and engineering applications of nanocellulose-based nanocomposites. Environ Sci Nano 1:302–316
Ogundare SA, van Zyl WE (2019) A review of cellulose-based substrates for SERS: fundamentals, design principles, applications. Cellulose 26:6489–6528
Ngo YH, Li D, Simon GP, Garnier G (2012) Gold nanoparticle-paper as a three-dimensional surface enhanced raman scattering substrate. Langmuir 28:8782–8790
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
Wei H, Rodriguez K, Renneckar S, Leng W, Vikesland PJ (2015) Preparation and evaluation of nanocellulose-gold nanoparticle nanocomposites for SERS applications. Analyst 140:5640–5649
Xiong Z, Lin M, Lin H, Huang M (2018) Facile synthesis of cellulose nanofiber nanocomposite as a SERS substrate for detection of thiram in juice. Carbohydr Polym 189:79–86
Zhang S, Xiong R, Mahmoud MA, Quigley EN, Chang H, el-Sayed M, Tsukruk VV (2018) Dual-excitation nanocellulose plasmonic membranes for molecular and cellular SERS detection. ACS Appl Mater Interfaces 10:18380–18389
Liou P, Nayigiziki FX, Kong F, Mustapha A, Lin M (2017) Cellulose nanofibers coated with silver nanoparticles as a SERS platform for detection of pesticides in apples. Carbohydr Polym 157:643–650
Jiang F, Hsieh Y-L (2014) Synthesis of cellulose nanofibril bound silver nanoprism for surface enhanced Raman scattering. Biomacromolecules 15:3608–3616
Frens G (1973) Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nat Phys Sci 241:20–22
Olson TY, Schwartzberg AM, Orme CA, Talley CE, O'Connell B, Zhang JZ (2008) Hollow gold−silver double-shell nanospheres: structure, optical absorption, and surface-enhanced Raman scattering. J Phys Chem C 112:6319–6329
Song L, Mao K, Zhou X, Hu J (2016) A novel biosensor based on Au@Ag core–shell nanoparticles for SERS detection of arsenic (III). Talanta 146:285–290
Liu B, Han G, Zhang Z, Liu R, Jiang C, Wang S, Han MY (2012) Shell thickness-dependent Raman enhancement for rapid identification and detection of pesticide residues at fruit peels. Anal Chem 84:255–261
Cheng Q, Wang S, Rials TG (2009) Poly(vinyl alcohol) nanocomposites reinforced with cellulose fibrils isolated by high intensity ultrasonication. Compos A Appl Sci Manuf 4:2387–2394
Jonoobi M, Oladi R, Davoudpour Y, Oksman K, Dufresne A, Hamzeh Y, Davoodi R (2015) Different preparation methods and properties of nanostructured cellulose from various natural resources and residues: a review. Cellulose 22:935–969
Zhang L, Li X, Ong L, Tabor RF, Bowen BA, Fernando AI, Nilghaz A, Garnier G, Gras SL, Wang X, Shen W (2015) Cellulose nanofibre textured SERS substrate. Colloids Surfaces A Physicochem Eng Asp 468:309–314
Haynes CL, McFarland AD, Van Duyne RP (2005) Surface-enhanced Raman spectroscopy. Anal Chem 77:338 A–346 A
Lu X, Samuelson DR, Xu Y, Zhang H, Wang S, Rasco BA, Xu J, Konkel ME (2013) Detecting and tracking nosocomial methicillin-resistant Staphylococcus aureus using a microfluidic SERS biosensor. Anal Chem 85:2320–2327
Zhang L, Wang B, Zhu G, Zhou X (2014) Synthesis of silver nanowires as a SERS substrate for the detection of pesticide thiram. Spectrochim Acta A Mol Biomol Spectrosc 133:411–416
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 136:527–532
Luo H, Wang X, Huang Y, Lai K, Rasco BA, Fan Y (2018) Rapid and sensitive surface-enhanced Raman spectroscopy (SERS) method combined with gold nanoparticles for determination of paraquat in apple juice. J Sci Food Agric 98:3892–3898
Fang H, Zhang X, Zhang SJ, Liu L, Zhao YM, Xu HJ (2015) Ultrasensitive and quantitative detection of paraquat on fruits skins via surface-enhanced Raman spectroscopy. Sensors Actuators B Chem 213:452–456
Wang C, Wu X, Dong P, Chen J, Xiao R (2016) Hotspots engineering by grafting Au@Ag core-shell nanoparticles on the Au film over slightly etched nanoparticles substrate for on-site paraquat sensing. Biosens Bioelectron 86:944–950
Group EW EWG’s 2019 Shopper’s Guide to Pesticides in Produce™. https://www.ewg.org/foodnews/summary.php
Kolberg DIS, Mack D, Anastassiades M et al (2012) Development and independent laboratory validation of a simplified. Sample preparation method for the determination of paraquat and diquat in food comodities. Anal Chim Acta 404:2465–2474
Sun H, Liu H, Wu Y (2017) A green, reusable SERS film with high sensitivity for in-situ detection of thiram in apple juice. Appl Surf Sci 416:704–709
EPA (2019) Electronic code of federal regulations
Bennett B, Workman T, Smith MN, Griffith WC, Thompson B, Faustman EM (2019) Longitudinal, seasonal, and occupational trends of multiple pesticides in house dust. Environ Health Perspect 127:17003
Etchegoin PG, Le Ru EC (2008) A perspective on single molecule SERS: current status and future challenges. Phys Chem Chem Phys 10:6079–6089
Funding
This research was financially supported by the Robert T. Marshall Scholarship, USDA National Institute of Food and Agriculture (2016-67021-24994 and 2018-67017-27880), and USDA NIFA Multi-state Project NC-1194.
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Asgari, S., Sun, L., Lin, J. et al. Nanofibrillar cellulose/Au@Ag nanoparticle nanocomposite as a SERS substrate for detection of paraquat and thiram in lettuce. Microchim Acta 187, 390 (2020). https://doi.org/10.1007/s00604-020-04358-9
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DOI: https://doi.org/10.1007/s00604-020-04358-9