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Rapid and scalable preparation of flexible Ag nanoparticle-decorated nanocellulose SERS sensors by magnetron sputtering for trace detection of toxic materials

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Abstract

Cellulose-based surface-enhanced Raman scattering (SERS) platforms have attracted extensive attention as a flexible, sustainable, eco-friendly and ultrasensitive sensor for trace detection of chemical and biological molecules. However, preparation of cellulose-based SERS substrates usually suffers from high cost, complicated fabrication step, time-consuming process and poor signal reproducibility. In this research, the flexible Ag nanoparticle-coated bacterial nanocellulose (AgNP@BNC) SERS substrates are successfully developed by a facile, low-cost, efficient and scalable magnetron sputtering technology. Taking advantage of the characteristics of magnetron sputtering technology, silver nanoparticles are rapidly and uniformly deposited onto the surface of BNC membrane. In addition, due to the large specific surface area, excellent permeability and adsorption properties of hydrophilic nanocellulose, the target molecules are also uniformly distributed on the surface of nanocellulose membrane. As a result, the optimal AgNP-120@BNC SERS substrate exhibits high sensitivity of 10–9 M for crystal violet, remarkable signal homogeneity and excellent storage stability. The flexible AgNP-120@BNC SERS substrate also exhibits ultra-sensitive pesticide detection with a detection limit of 7.8 × 10–8 M for lambda-cyhalothrin on irregular fruit surfaces by a feasible paste-and-read way. This research demonstrates promising application of magnetron sputtering technology in the development of flexible, low-cost and large-scale nanocellulose-based SERS sensors for trace detection of toxic materials.

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References

  • Abolfotouh D, Hassan MA, Shokry H, Roig A, Azab MS, Kashyout AE (2020) Bacterial nanocellulose from agro-industrial wastes: low-cost and enhanced production by Komagataeibacter saccharivorans MD1. Sci Rep 10:1–14

    Google Scholar 

  • Agarwal UP, Ralph SA, Baez C, Reiner RS (2021) Contributions of crystalline and noncrystalline cellulose can occur in the same spectral regions: evidence based on Raman and IR and its implication for crystallinity measurements. Biomacromol 22:1357–1373

    Article  CAS  Google Scholar 

  • Atanasov PA, Nedyalkov NN, Fukata N, Jevasuwan W (2021) Advanced silver and gold substrates for surface-enhanced Raman spectroscopy of pesticides. Spectrosc Lett 54:528–538

    Article  CAS  Google Scholar 

  • Basir A, Khan A, Mustafa R, Zargham KM, Rizvi F, Mahmood F, Yousaf A (2011) Toxicopathological effects of lambda-cyhalothrin in female rabbits (Oryctolagus cuniculus). Hum Exp Toxicol 30:591–602

    Article  CAS  PubMed  Google Scholar 

  • Bian X, Xu J, Yang J, Kl C, Jiang S (2021) Flexible Ag SERS substrate for non-destructive and rapid detection of toxic materials on irregular surface. Surf Interfaces 23:100995

    Article  CAS  Google Scholar 

  • Botta R, Eiamchai P, Horprathum M, Limwichean S, Chananonnawathorn C, Patthanasettakul V, Nuntawong N (2018) Investigation of silver nanorods as reusable SERS-active substrates for trace level detection of 2-MIB volatile organic compound. Sensor Actuat B Chem 271:122–127

    Article  CAS  Google Scholar 

  • Botta R, Eiamchai P, Horprathum M, Limwichean S, Chananonnawathorn C, Patthanasettakul V, Maezono R, Jomphoak A, Nuntawong N (2020) 3D structured laser engraves decorated with gold nanoparticle SERS chips for paraquat herbicide detection in environments. Sensor Actuat B-Chem 304:127327

    Article  CAS  Google Scholar 

  • Botta R, Limwichean S, Limsuwan N, Moonlek C, Horprathum M, Eiamchai P, Chananonnawathorn C, Patthanasettakul V, Chindaudom P, Nuntawong N, Ngernsutivorakul T (2022) An efficient and simple SERS approach for trace analysis of tetrahydrocannabinol and cannabinol and multi-cannabinoid detection. Spectrochim Acta A 281:121598

    Article  CAS  Google Scholar 

  • Çelik A, Mazmanci B, Çamlica Y, Çömelekoğlu Ü, Aşkin A (2005) Evaluation of cytogenetic effects of lambda-cyhalothrin on Wistar rat bone marrow by gavage administration. Ecotox Environ Safe 61:128–133

    Article  Google Scholar 

  • Chen J, Huang M, Kong L, Lin M (2019) Jellylike flexible nanocellulose SERS substrate for rapid in-situ non-invasive pesticide detection in fruits/vegetables. Carbohyd Polymers 205:596–600

    Article  CAS  Google Scholar 

  • Chen J, Huang M, Kong L (2020) Flexible Ag/nanocellulose fibers SERS substrate and its applications for in-situ hazardous residues detection on food. Appl Surf Sci 533:147454

    Article  CAS  Google Scholar 

  • Deshmukh AR, Dikshit PK, Kim BS (2022) Green in situ immobilization of gold and silver nanoparticles on bacterial nanocellulose film using Punica granatum peels extract and their application as reusable catalysts. Int J Biol Macromol 205:169–177

    Article  CAS  PubMed  Google Scholar 

  • Du J, Jing C (2011) Preparation of Fe3O4@Ag SERS substrate and its application in environmental Cr (VI) analysis. J Colloid Interf Sci 358:54–61

    Article  CAS  Google Scholar 

  • Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mater Today 16:220–227

    Article  CAS  Google Scholar 

  • Fan X, Zhao S, Hu J (2019) Dissipation behavior and dietary risk assessment of lambda-cyhalothrin, thiamethoxam and its metabolite clothianidin in apple after open field application. Regul Toxicol Pharm 101:135–141

    Article  CAS  Google Scholar 

  • Gomez M, Lazzari M (2014) Reliable and cheap SERS active substrates. Mater Today 7:358–359

    Article  Google Scholar 

  • Gu J, Dichiara A (2020) Hybridization between cellulose nanofibrils and faceted silver nanoparticles used with surface enhanced Raman scattering for trace dye detection. Int J Biol Macromol 143:85–92

    Article  CAS  PubMed  Google Scholar 

  • Gullace S, Montes-García V, Martín V, Larios D, Girelli Consolaro V, Obelleiro F, Calogero G, Casalini S, Samorì P (2021) Universal fabrication of highly efficient plasmonic thin-films for label-free SERS detection. Small 17:2100755

    Article  CAS  Google Scholar 

  • Hu H, Gao W, Zang R, Gao J, Tang S, Li X, Liang L, Zhang H, Cao H (2020) Direct growth of vertically orientated nanocavity arrays for plasmonic color generation. Adv Funct Mater 30:2002287

    Article  CAS  Google Scholar 

  • Huang F, Ma G, Liu J, Lin J, Wang X, Guo L (2016) High-yield synthesis of hollow octahedral silver nanocages with controllable pack density and their high-performance sers application. Small 12:5442–5448

    Article  CAS  PubMed  Google Scholar 

  • Huang X, Wang A, Luo J, Gao Y, Guan L, Zhang P, Liu F, Mu W, Li B (2022) Lambda-cyhalothrin-loaded nanocapsules pose an unacceptable acute toxicological risk to zebrafish (Danio rerio) at the adult and larval stages but present an acceptable risk to embryos. J Hazard Mater 422:126853

    Article  CAS  PubMed  Google Scholar 

  • Huo D, Chen B, Meng G, Huang Z, Li M, Lei Y (2020) Ag-nanoparticles@ bacterial nanocellulose as a 3D flexible and robust surface-enhanced Raman scattering substrate. ACS Appl Mater Interfaces 12:50713–50720

    Article  CAS  PubMed  Google Scholar 

  • Kavkler K, Demšar A (2011) Examination of cellulose textile fibres in historical objects by micro-Raman spectroscopy. Spectrochim Acta A 78:740–746

    Article  Google Scholar 

  • Kelly PJ, Arnell RD (2000) Magnetron sputtering: a review of recent developments and applications. Vacuum 56:159–172

    Article  CAS  Google Scholar 

  • Kim D, Kim J, Henzie J, Ko Y, Lim H, Kwon G, Na J, Kim HJ, Yamauchi Y, You J (2021) Mesoporous Au films assembled on flexible cellulose nanopaper as high-performance SERS substrates. Chem Eng J 419:129445

    Article  CAS  Google Scholar 

  • Klemm D, Cranston ED, Fischer D, Gama M, Kedzior SA, Kralisch D, Kramer F, Kondo T, Lindström T, Nietzsche S (2018) Nanocellulose as a natural source for groundbreaking applications in materials science: today’s state. Mater Today 21:720–748

    Article  CAS  Google Scholar 

  • Li L, Chin WS (2020) Rapid fabrication of a flexible and transparent Ag nanocubes@PDMS film as a SERS substrate with high performance. ACS Appl Mater Interfaces 12:37538–37548

    Article  CAS  PubMed  Google Scholar 

  • Li C, Huang Y, Li X, Zhang Y, Chen Q, Ye Z, Alqarni Z, Bell S, Xu Y (2021) Towards practical and sustainable SERS: a review of recent developments in the construction of multifunctional enhancing substrates. J Mater Chem C 9:11517–11552

    Article  CAS  Google Scholar 

  • Li X, Zhang T, Chen Z, Yu J, Cao A, Liu D, Cai W, Li Y (2022) Au polyhedron array with tunable crystal facets by PVP-assisted thermodynamic control and its sharp shape as well as high-energy exposed planes co-boosted SERS activity. Small 18:2105045

    Article  CAS  Google Scholar 

  • Liang J, Liu Q, Li T, Luo Y, Lu S, Shi X, Zhang F, Asiri AM, Sun X (2021) Magnetron sputtering enabled sustainable synthesis of nanomaterials for energy electrocatalysis. Green Chem 23:2834–2867

    Article  CAS  Google Scholar 

  • Liu DY, Sui G, Bhattacharyya D (2014) Synthesis and characterisation of nanocellulose-based polyaniline conducting films. Compos Sci Technol 99:31–36

    Article  CAS  Google Scholar 

  • Luo Y, Xing L, Hu C, Zhang W, Lin X, Gu J (2022) Facile synthesis of nanocellulose-based Cu2O/Ag heterostructure as a surface-enhanced Raman scattering substrate for trace dye detection. Int J Biol Macromol 205:366–375

    Article  CAS  PubMed  Google Scholar 

  • Mohammadkazemi F, Faria M, Cordeiro N (2016) In situ biosynthesis of bacterial nanocellulose-CaCO3 hybrid bionanocomposite: one-step process. Mater Sci Eng C 65:393–399

    Article  CAS  Google Scholar 

  • Peng Y, Lin C, Long L, Masaki T, Tang M, Yang L, Liu J, Huang Z, Li Z, Luo X, Lombardi JR, Yang Y (2021) Charge-transfer resonance and electromagnetic enhancement synergistically enabling mxenes with excellent SERS sensitivity for SARS-CoV-2 S protein detection. Nano-Micro Lett 13:52

    Article  Google Scholar 

  • Sharma KK, Tripathy V, Mohapatra S, Matadha NY, Pathan ARK, Sharma BN, Dubey JK, Katna S, George T, Tayade A (2021) Dissipation kinetics and consumer risk assessment of novaluron+ lambda-cyhalothrin co-formulation in cabbage. Ecotox Environ Safe 208:111494

    Article  CAS  Google Scholar 

  • Shen Y, Wu X, Wu B, Tan Y, Liu J (2021) Qualitative analysis of lambda-cyhalothrin on chinese cabbage using mid-infrared spectroscopy combined with fuzzy feature extraction algorithms. Agriculture 11:275

    Article  CAS  Google Scholar 

  • Shi Y, Li Y, Zhang J, Yu Z, Yang D (2015) Electrospun polyacrylonitrile nanofibers loaded with silver nanoparticles by silver mirror reaction. Mater Sci Eng C 51:346–355

    Article  CAS  Google Scholar 

  • Sivashanmugan K, Liao JD, You JW, Wu CL (2013) Focused-ion-beam-fabricated Au/Ag multilayered nanorod array as SERS-active substrate for virus strain detection. Sensor Actuat B Chem 181:361–367

    Article  CAS  Google Scholar 

  • Song Y, Huang HC, Lu W, Li N, Su J, Cheng SB, Lai Y, Chen J, Zhan J (2021) Ag@WS2 quantum dots for Surface Enhanced Raman Spectroscopy: enhanced charge transfer induced highly sensitive detection of thiram from honey and beverages. Food Chem 344:128570

    Article  CAS  PubMed  Google Scholar 

  • Sutter P, Lahiri J, Zahl P, Wang B, Sutter E (2013) Scalable synthesis of uniform few-layer hexagonal boron nitride dielectric films. Nano Lett 13:276–281

    Article  CAS  PubMed  Google Scholar 

  • Thomas B, Raj MC, Joy J, Moores A, Drisko GL, Sanchez C (2018) Nanocellulose, a versatile green platform: from biosources to materials and their applications. Chem Rev 118:11575–11625

    Article  CAS  PubMed  Google Scholar 

  • Tian Y, Liu H, Chen Y, Zhou C, Jiang Y, Gu C, Jiang T, Zhou J (2019) Seedless one-spot synthesis of 3D and 2D Ag nanoflowers for multiple phase SERS-based molecule detection. Sensor Actuat B- Chem 301:127142

    Article  CAS  Google Scholar 

  • Trache D, Tarchoun AF, Derradji M, Hamidon TS, Masruchin N, Brosse N, Hussin MH (2020) Nanocellulose: from fundamentals to advanced applications. Front Chem 8:392

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Wang Y, Wang M, Sun X, Shi G, Zhang J, Ma W, Ren L (2018) Grating-like SERS substrate with tunable gaps based on nanorough Ag nanoislands/moth wing scale arrays for quantitative detection of cypermethrin. Opt Exp 26:22168–22181

    Article  CAS  Google Scholar 

  • Wang K, Sun DW, Pu H, Wei Q (2019) Surface-enhanced Raman scattering of core-shell Au@Ag nanoparticles aggregates for rapid detection of difenoconazole in grapes. Talanta 191:449–456

    Article  CAS  PubMed  Google Scholar 

  • Wen P, Yang F, Ge C, Li S, Xu Y, Chen L (2021) Self-assembled nano-Ag/Au@ Au film composite SERS substrates show high uniformity and high enhancement factor for creatinine detection. Nanotechnology 32:395502

    Article  CAS  Google Scholar 

  • Wu J, Du Y, Wang C, Bai S, Zhang T, Chen T, Hu A (2019) Reusable and long-life 3D Ag nanoparticles coated Si nanowire array as sensitive SERS substrate. Appl Surf Sci 494:583–590

    Article  CAS  Google Scholar 

  • Wu D, Hu M, Zhang Y, Zhou J, Wang Z (2020a) Long-range ordered silver nanoflower array structure for surface enhanced Raman scattering detecting. Appl Surf Sci 505:144520

    Article  CAS  Google Scholar 

  • Wu L, Zhang W, Liu C, Foda MF, Zhu Y (2020b) Strawberry-like SiO2/Ag nanocomposites immersed filter paper as SERS substrate for acrylamide detection. Food Chem 328:127106

    Article  CAS  PubMed  Google Scholar 

  • Wu J, Xi J, Chen H, Li S, Zhang L, Li P, Wu W (2022) Flexible 2D nanocellulose-based SERS substrate for pesticide residue detection. Carbohyd Polym 277:118890

    Article  CAS  Google Scholar 

  • Xing C, Liu D, Chen J, Fan Y, Zhou F, Kaur K, Cai W, Li Y (2021a) Convective self-assembly of 2D nonclose-packed binary Au nanoparticle arrays with tunable optical properties. Chem Mater 33:310–319

    Article  CAS  Google Scholar 

  • Xing C, Zhong S, Liu D, Zhang T, Cao A, Zeng P, Men D, Li C, Cai W, Li Y (2021b) Hydrogel film@Au nanoparticle arrays based on self-assembly co-assisted by electrostatic attraction and hydrogel-shrinkage for SERS detection with active gaps. Adv Mater Interfaces 8:2101055

    Article  CAS  Google Scholar 

  • Xu J, Li X, Wang Y, Guo R, Shang S, Jiang S (2019) Flexible and reusable cap-like thin Fe2O3 film for SERS applications. Nano Res 12:381–388

    Article  CAS  Google Scholar 

  • Xu Y, Kutsanedzie FYH, Hassan M, Zhu J, Ahmad W, Li H, Chen Q (2020) Mesoporous silica supported orderly-spaced gold nanoparticles SERS-based sensor for pesticides detection in food. Food Chem 315:126300

    Article  CAS  PubMed  Google Scholar 

  • Xu D, Zhang Y, Zhang S, Yang W, Chen J (2021) Ultrasensitive SERS detection of crystal violet and malachite green based on high surface roughness copper nanocorns prepared via solid-state ionics method. Sensor Actuat A-Physl 331:113042

    Article  CAS  Google Scholar 

  • Xu D, Zhang Y, Zhang S, Yang W, Wang Z, Li J (2022) Copper nanoleaves SERS substrates with high surface roughness for sensitive detection crystal violet and rhodamine 6G. Opt Laser Technol 145:107502

    Article  CAS  Google Scholar 

  • Yan X, Wang M, Sun X, Wang Y, Shi G, Ma W, Hou P (2019) Sandwich-like Ag@Cu@CW SERS substrate with tunable nanogaps and component based on the plasmonic nanonodule structures for sensitive detection crystal violet and 4-aminothiophenol. Appl Surf Sci 479:879–886

    Article  CAS  Google Scholar 

  • Yang L, Peng Y, Yang Y, Liu J, Huang H, Yu B, Zhao J, Lu Y, Huang Z, Li Z (2019) A novel ultra-sensitive semiconductor SERS substrate boosted by the coupled resonance effect. Adv Sci 6:1900310

    Article  Google Scholar 

  • Zeng M, Laromaine A, Roig A (2014) Bacterial cellulose films: influence of bacterial strain and drying route on film properties. Cellulose 21:4455–4469

    Article  CAS  Google Scholar 

  • Zhai J, Zhang Y, Cui C, Li A, Wang W, Guo R, Qin W, Ren E, Xiao H, Zhou M (2021) Flexible waterborne polyurethane/cellulose nanocrystal composite aerogels by integrating graphene and carbon nanotubes for a highly sensitive pressure sensor. ACS Sustain Chem Eng 9:14029–14039

    Article  CAS  Google Scholar 

  • Zhang S, Sun G, He Y, Fu R, Gu Y, Chen S (2017) Preparation, characterization, and electrochromic properties of nanocellulose-based polyaniline nanocomposite films. ACS Appl Mater Interfaces 9:16426–16434

    Article  CAS  PubMed  Google Scholar 

  • Zhang T, Li X, Li C, Cai W, Li Y (2021) One-pot synthesis of ultrasmooth, precisely shaped gold nanospheres via surface self-polishing etching and regrowth. Chem Mater 33:2593–2603

    Article  CAS  Google Scholar 

  • Zheng J, Huang Z, Zeng Y, Liu W, Wei B, Qi Z, Wang Z, Xia C, Liang H (2022) Electrostatic shielding regulation of magnetron sputtered Al-based alloy protective coatings enables highly reversible zinc anodes. Nano Lett 22:1017–1023

    Article  CAS  PubMed  Google Scholar 

  • Zhong F, Wu Z, Guo J, Jia D (2018) Porous silicon photonic crystals coated with Ag nanoparticles as efficient substrates for detecting trace explosives using SERS. Nanomaterials 8:872

    Article  PubMed Central  Google Scholar 

  • Zhou X, Hu Z, Yang D, Xie S, Jiang Z, Niessner R, Haisch C, Zhou H, Sun P (2020) Bacteria detection: from powerful SERS to its advanced compatible techniques. Adv Sci 7:2001739

    Article  CAS  Google Scholar 

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Acknowledgments

We would like to thank the Hong Kong Innovation & Technology Commission and China Resources Co., Ltd. for financial support.

Funding

This work is financially supported by the Hong Kong Innovation and Technology Funding (No. PRP/104/20TI).

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Authors and Affiliations

  1. School of Fashion and Textiles, The Hong Kong Polytechnic University, Hung Hom, Kowloon, 999077, Hong Kong, China

    Sihang Zhang, Jiangtao Xu, Zhichao Liu, Yingying Huang & Shouxiang Jiang

  2. Research Institute for Intelligent Wearable Systems, The Hong Kong Polytechnic University, Hung Hom, Kowloon, 999077, Hong Kong, China

    Shouxiang Jiang

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  1. Sihang Zhang
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  2. Jiangtao Xu
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  3. Zhichao Liu
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Contributions

S.J. supervised this study. S.Z. and S.J. conceived this idea and designed the experiment. S.Z. wrote the main original manuscript and carried out the main experiment. S.Z. and J.X. performed the FDTD simulations. S.Z., J.X., Z.L. and Y.H. analyzed the experimental data. All the authors reviewed and revised the manuscript.

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Correspondence to Shouxiang Jiang.

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Zhang, S., Xu, J., Liu, Z. et al. Rapid and scalable preparation of flexible Ag nanoparticle-decorated nanocellulose SERS sensors by magnetron sputtering for trace detection of toxic materials. Cellulose 29, 9865–9879 (2022). https://doi.org/10.1007/s10570-022-04871-5

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