Advertisement

Assembly of metal nanoparticles on regenerated fibers from wood sawdust and de-inked pulp: flexible substrates for surface enhanced Raman scattering (SERS) applications

  • 523 Accesses

  • 12 Citations

Abstract

We report on simple and low-cost active SERS substrates made using regenerated fibers from wood products. Glycidyltrimethylammonium chloride (GTAC) was used to graft ammonium groups on the fibers’ surfaces under strong alkaline conditions. After GTAC treatment, citrate-stabilized nanoparticles were assembled via electrostatic interaction. X-ray diffraction, Scanning electron microscopy images and optical photographs indicated that the surfaces of the fibers were conformally coated with metal nanoparticles. We also observed that after being cationized, the fibers experienced significant swelling and shrinking under dry and wet conditions. Rhodamine 6G was used as probe molecule to test the SERS performance of the substrates- concentrations as low as 10−9 M were detected. Furthermore, the modified fibers were used to detect melamine, illustrating their potential as viable substrates for applications such as markers for the quality and shelf-life of food products and detection of toxins.

This is a preview of subscription content, log in to check access.

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 199

This is the net price. Taxes to be calculated in checkout.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

References

  1. Abalde-Cela S, Ho S, Rodríguez-González B, Correa-Duarte MA, Álvarez-Puebla RA, Liz-Marzán LM, Kotov NA (2009) Loading of exponentially grown LBL films with silver nanoparticles and their application to generalized SERS detection. Angew Chem 121:5430–5433

  2. Castellanos L, Blanco-Tirado C, Hinestroza J, Combariza M (2012) In situ synthesis of gold nanoparticles using fique natural fibers as template. Cellulose 19:1933–1943

  3. Chen G, Wang Y, Yang M, Xu J, Goh SJ, Pan M, Chen H (2010) Measuring ensemble-averaged surface-enhanced Raman scattering in the hotspots of colloidal nanoparticle dimers and trimers. J Am Chem Soc 132:3644–3645

  4. 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: Mol Chem Phys 75:790–798

  5. da Silva Pinto M, Sierra-Avila CA, Hinestroza JP (2012) In situ synthesis of a Cu-BTC metal–organic framework (MOF 199) onto cellulosic fibrous substrates: cotton. Cellulose 19:1771–1779

  6. Driskell JD, Lipert RJ, Porter MD (2006) Labeled gold nanoparticles immobilized at smooth metallic substrates: systematic investigation of surface plasmon resonance and surface-enhanced Raman scattering. J Phys Chem B 110:17444–17451

  7. Hauru LK, Hummel M, Michud A, Sixta H (2014) Dry jet-wet spinning of strong cellulose filaments from ionic liquid solution. Cellulose 21:4471–4481

  8. Hauser PJ, Tabba AH (2001) Improving the environmental and economic aspects of cotton dyeing using a cationised cotton†. Color Technol 117:282–288

  9. Haynes CL, McFarland AD, Duyne RPV (2005) Surface-enhanced Raman spectroscopy. Anal Chem 77:338 A–346 A

  10. Isogai A, Atalla R (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319

  11. Kim N, Lin M, Hu Z, Li H (2009) Evaporation-controlled chemical enhancement of SERS using a soft polymer substrate. Chem Commun 7:6246–6248

  12. Kneipp K, Wang Y, Kneipp H, Perelman LT, Itzkan I, Dasari RR, Feld MS (1997) Single molecule detection using surface-enhanced Raman scattering (SERS). Phys Rev Lett 78:1667

  13. Kneipp K, Kneipp H, Itzkan I, Dasari RR, Feld MS (1999) Ultrasensitive chemical analysis by Raman spectroscopy. Chem Rev 99:2957–2976

  14. Kontturi E, Tammelin T, Österberg M (2006) Cellulose—model films and the fundamental approach. Chem Soc Rev 35:1287–1304

  15. Lahdetie A, Nousiainen P, Sipila J, Tamminen T, Jaaskelainen AS (2013) Laser-induced fluorescence (LIF) of lignin and lignin model compounds in Raman spectroscopy. Holzforschung 67:531–538

  16. Lee P, Meisel D (1982) Adsorption and surface-enhanced Raman of dyes on silver and gold sols. J Phys Chem 86:3391–3395

  17. Lee SJ, Guan Z, Xu H, Moskovits M (2007) Surface-enhanced Raman spectroscopy and nanogeometry: the plasmonic origin of SERS. J Phys Chem C 111:17985–17988

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

  19. Li X, Xu W, Zhang J, Jia H, Yang B, Zhao B, Li B, Ozaki Y (2004) Self-assembled metal colloid films: two approaches for preparing new SERS active substrates. Langmuir 20:1298–1304

  20. Lim D, Jeon K, Kim HM, Nam J, Suh YD (2010) Nanogap-engineerable Raman-active nanodumbbells for single-molecule detection. Nat Mater 9:60–67

  21. Marques PA, Nogueira HI, Pinto RJ, Neto CP, Trindade T (2008) Silver-bacterial cellulosic sponges as active SERS substrates. J Raman Spectrosc 39:439–443

  22. Martins NC, Freire CS, Pinto RJ, Fernandes SC, Neto CP, Silvestre AJ, Causio J, Baldi G, Sadocco P, Trindade T (2012) Electrostatic assembly of Ag nanoparticles onto nanofibrillated cellulose for antibacterial paper products. Cellulose 19:1425–1436

  23. McFarland AD, Van-Duyne RP (2003) Single silver nanoparticles as real-time optical sensors with zeptomole sensitivity. Nano Lett 3:1057–1062

  24. Moskovits M, Suh JS (1984) Surface selection rules for surface-enhanced Raman spectroscopy: calculations and application to the surface-enhanced Raman spectrum of phthalazine on silver. J Phys Chem 88:5526–5530

  25. Murphy CJ, Sau TK, Gole AM, Orendorff CJ, Gao J, Gou L, Hunyadi SE, Li T (2005) Anisotropic metal nanoparticles: synthesis, assembly, and optical applications. J Phys Chem B 109:13857–13870

  26. Nam S, Condon BD (2014) Internally dispersed synthesis of uniform silver nanoparticles via in situ reduction of [Ag (NH3)2] along natural microfibrillar substructures of cotton fiber. Cellulose 21:2963–2972

  27. 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

  28. Nie S, Emory SR (1997) Probing single molecules and single nanoparticles by surface-enhanced Raman scattering. Science 275:1102–1106

  29. Nikoobakht B, Wang J, El-Sayed MA (2002) Surface-enhanced Raman scattering of molecules adsorbed on gold nanorods: off-surface plasmon resonance condition. Chem Phys Lett 366:17–23

  30. Peng M, Gao J, Zhang P, Li Y, Sun X, Lee S (2011) Reductive self-assembling of Ag nanoparticles on germanium nanowires and their application in ultrasensitive surface-enhanced Raman spectroscopy. Chem Mater 23:3296–3301

  31. Pinto RJ, Marques PA, Martins MA, Neto CP, Trindade T (2007) Electrostatic assembly and growth of gold nanoparticles in cellulosic fibres. J Colloid Interface Sci 312:506–512

  32. Pönni R, Rautkari L, Hill CA, Vuorinen T (2014) Accessibility of hydroxyl groups in birch kraft pulps quantified by deuterium exchange in D2O vapor. Cellulose 21:1217–1226

  33. Ren W, Guo S, Dong S, Wang E (2011) A simple route for the synthesis of morphology-controlled and SERS-active Ag dendrites with near-infrared absorption. J Phys Chem C 115:10315–10320

  34. Schmit VL, Martoglio R, Scott B, Strickland AD, Carron KT (2011) Lab-on-a-bubble: synthesis, characterization, and evaluation of buoyant gold nanoparticle-coated silica spheres. J Am Chem Soc 134:59–62

  35. Schofield CL, Haines AH, Field RA, Russell DA (2006) Silver and Gold Glyconanoparticles for Colorimetric Bioassays. Langmuir 22:6707–6711

  36. Sun Y, Xia Y (2002) Shape-controlled synthesis of gold and silver nanoparticles. Science 298:2176–2179. doi:10.1126/science.1077229

  37. Surovtsev N, Adichtchev S, Duda T, Pokrovsky L, Sveshnikova L (2010) New surface-enhanced Raman scattering active substrate fabricated by use of the Langmuir–Blodgett technique. J Phys Chem C 114:4803–4807

  38. Tang W, Chase DB, Rabolt JF (2013) Immobilization of gold nanorods onto electrospun polycaprolactone fibers via polyelectrolyte decoration-A 3D SERS substrate. Anal Chem 85:10702–10709

  39. Tao A, Sinsermsuksakul P, Yang P (2007) Tunable plasmonic lattices of silver nanocrystals. Nat Nanotechnol 2:435–440

  40. Wei WY, White IM (2013) Inkjet-printed paper-based SERS dipsticks and swabs for trace chemical detection. Analyst 138:1020–1025

  41. Wei W, Li S, Millstone JE, Banholzer MJ, Chen X, Xu X, Schatz GC, Mirkin CA (2009) Surprisingly long-range surface-enhanced Raman scattering (SERS) on Au–Ni multisegmented nanowires. Angew Chem Int Ed 48:4210–4212

  42. Willets KA, Van Duyne RP (2007) Localized surface plasmon resonance spectroscopy and sensing. Annu Rev Phys Chem 58:267–297

  43. Wustholz KL, Henry A, McMahon JM, Freeman RG, Valley N, Piotti ME, Natan MJ, Schatz GC, Duyne RPV (2010) Structure–activity relationships in gold nanoparticle dimers and trimers for surface-enhanced raman spectroscopy. J Am Chem Soc 132:10903–10910

  44. Xu C, Wang X (2009) Fabrication of flexible metal-nanoparticle films using graphene oxide sheets as substrates. Small 5:2212–2217

  45. Xu W, Ling X, Xiao J, Dresselhaus MS, Kong J, Xu H, Liu Z, Zhang J (2012) Surface enhanced Raman spectroscopy on a flat graphene surface. Proc Natl Acad Sci USA 109:9281–9286. doi:10.1073/pnas.1205478109

  46. Yang M, Alvarez-Puebla R, Kim H, Aldeanueva-Potel P, Liz-Marzán LM, Kotov NA (2010) SERS-active gold lace nanoshells with built-in hotspots. Nano Lett 10:4013–4019

  47. Zavaleta CL, Smith BR, Walton I, Doering W, Davis G, Shojaei B, Natan MJ, Gambhir SS (2009) Multiplexed imaging of surface enhanced Raman scattering nanotags in living mice using noninvasive Raman spectroscopy. Proc Natl Acad Sci USA 106:13511–13516. doi:10.1073/pnas.0813327106

  48. Zhang YH, Cui JB, Lynd LR, Kuang LR (2006) A Transition from cellulose swelling to cellulose dissolution by o-phosphoric acid: evidence from enzymatic hydrolysis and supramolecular structure. Biomacromolecules 7:644–648

  49. Zhang X, Zou M, Qi X, Liu F, Zhu X, Zhao B (2010) Detection of melamine in liquid milk using surface-enhanced Raman scattering spectroscopy. J Raman Spectrosc 41:1655–1660

  50. Zhang C, Lv K, Cong H, Yu S (2012) Controlled assemblies of gold nanorods in PVA nanofiber matrix as flexible free-standing SERS substrates by electrospinning. Small 8:648–653

  51. Zhong L, Yin J, Zheng Y, Liu Q, Cheng X, Luo F (2014) Self-assembly of Au nanoparticles on PMMA template as flexible, transparent, and highly Active SERS substrates. Anal Chem 86:6262–6267

  52. Zhu Y, Kuang H, Xu L, Ma W, Peng C, Hua Y, Wang L, Xu C (2012) Gold nanorod assembly based approach to toxin detection by SERS. J Mater Chem 22:2387–2391

Download references

Acknowledgments

Ms. Rita Hatakka is gratefully acknowledged for her assistance with the experimental work.

Author information

Correspondence to Xian-Ming Kong.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 2 (MPG 7573 kb)

Supplementary material 1 (DOC 2450 kb)

Supplementary material 2 (MPG 7573 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Kong, X., Reza, M., Ma, Y. et al. Assembly of metal nanoparticles on regenerated fibers from wood sawdust and de-inked pulp: flexible substrates for surface enhanced Raman scattering (SERS) applications. Cellulose 22, 3645–3655 (2015). https://doi.org/10.1007/s10570-015-0743-7

Download citation

Keywords

  • Regenerated fibers
  • Wood sawdust
  • De-inked pulp
  • Ag nanoparticles
  • Flexible substrates
  • SERS