pp 1–12 | Cite as

Fabrication of stable copper nanoparticles embedded in nanocellulose film as a bionanocomposite plasmonic sensor and thereof for optical sensing of cyanide ion in water samples

  • Mehran Pouzesh
  • Shahram NekoueiEmail author
  • Mohammad Ali Ferdosi Zadeh
  • Farzaneh Keshtpour
  • Shaobin Wang
  • Farzin NekoueiEmail author
Original Research


Herein, an optical plasmonic chemosensor was fabricated via in situ embedding of stable copper nanoparticles (Cu NPs) within flexible nanocellulose film (ECNPs-NC film) utilized for optical sensing of cyanide (CN). Glycerol, as a plasticizer, was added to the nanocellulose suspension to improve ductility of nanocellulose-based film. In addition, to enhance the stability of Cu NPs against oxidizing and corrosion, the fabricated ECNPs-NC film was immersed and coated by benzotriazole solution. The Cu NPs were stable for 4 months. The fabricated ECNPs-NC film was characterized by various methods such as field emission scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopic, dynamic light scattering, thermo-gravimetric analysis, and energy-dispersive X-ray spectroscopy. Analytical parameters influencing the efficiency of ECNPs-NC film fabrication were investigated and optimum conditions were stablished. The fabricated ECNPs-NC film was applied as a novel optical sensor for CN detection in water samples. By changing in CN concentration, surface plasmon resonance absorption intensity was changed and it was linear in the range of 0.25–0.40 µg mL−1 with a detection limit of 0.015 µg mL−1.


Nanocellulose film Optical sensor Copper nanoparticles Cyanide Chemosensor Bionanocomposite 



The financial support from Yasuj University of Medical Sciences, Yasuj, Iran, is gratefully acknowledged.

Supplementary material

10570_2019_2405_MOESM1_ESM.docx (956 kb)
Supplementary material 1 (DOCX 956 kb)


  1. Abbaspour A, Asadi M, Ghaffarinejad A, Safaei E (2005) A selective modified carbon paste electrode for determination of cyanide using tetra-3, 4-pyridinoporphyrazinatocobalt (II). Talanta 66:931–936CrossRefGoogle Scholar
  2. Abdul Khalil HPS, Bhat AH, Ireana Yusra AF (2012) Green composites from sustainable cellulose nanofibrils: a review. Carbohydr Polym 87:963–979. CrossRefGoogle Scholar
  3. Agnihotri S, Mukherji S, Mukherji S (2014) Size-controlled silver nanoparticles synthesized over the range 5–100 nm using the same protocol and their antibacterial efficacy. RSC Adv 4:3974–3983CrossRefGoogle Scholar
  4. Asfaram A, Ghaedi M, Agarwal S, Tyagi I, Gupta VK (2015) Removal of basic dye Auramine-O by ZnS: Cu nanoparticles loaded on activated carbon: optimization of parameters using response surface methodology with central composite design. RSC Adv 5:18438–18450CrossRefGoogle Scholar
  5. Batley GE, Kirby JK, McLaughlin MJ (2012) Fate and risks of nanomaterials in aquatic and terrestrial environments. Acc Chem Res 46:854–862CrossRefGoogle Scholar
  6. Cai J, Kimura S, Wada M, Kuga S (2008) Nanoporous cellulose as metal nanoparticles support. Biomacromolecules 10:87–94CrossRefGoogle Scholar
  7. Chetty R, Xia W, Kundu S, Bron M, Reinecke T, Schuhmann W, Muhler M (2009) Effect of reduction temperature on the preparation and characterization of Pt–Ru nanoparticles on multiwalled carbon nanotubes. Langmuir 25:3853–3860CrossRefGoogle Scholar
  8. Dang TMD, Le TTT, Fribourg-Blanc E, Dang MC (2011) Synthesis and optical properties of copper nanoparticles prepared by a chemical reduction method. Adv Natl Sci Nanosc Nanotechnol 2:015009CrossRefGoogle Scholar
  9. Das S, Srivastava VC (2015) Copper succinate nanoparticles synthesis by electrochemical method: effect of pH on structural, thermal and textural properties. Mater Lett 150:130–134CrossRefGoogle Scholar
  10. Dufresne A, Thomas S, Pothan LA (2013) Bionanocomposites: state of the art, challenges, and opportunities. Wiley, HobokenGoogle Scholar
  11. Edwards JV, Prevost N, French A, Concha M, DeLucca A, Wu Q (2013) Nanocellulose-based biosensors: design, preparation, and activity of peptide-linked cotton cellulose nanocrystals having fluorimetric and colorimetric elastase detection sensitivity. Engineering 5:20CrossRefGoogle Scholar
  12. Eivazihollagh A et al (2017) One-pot synthesis of cellulose-templated copper nanoparticles with antibacterial properties. Mater Lett 187:170–172CrossRefGoogle Scholar
  13. Golmohammadi H, Morales-Narváez E, Naghdi T, Merkoçi A (2017) Nanocellulose in (bio) sensing. Chem Mater 29(13):5426–5446CrossRefGoogle Scholar
  14. Gupta VK, Ganjali M, Norouzi P, Khani H, Nayak A, Agarwal S (2011a) Electrochemical analysis of some toxic metals by ion–selective electrodes. Crit Rev Anal Chem 41:282–313CrossRefGoogle Scholar
  15. Gupta VK, Nayak A, Agarwal S, Singhal B (2011b) Recent advances on potentiometric membrane sensors for pharmaceutical analysis. Comb Chem High Throughput Screen 14:284–302CrossRefGoogle Scholar
  16. Gupta VK, Sethi B, Sharma R, Agarwal S, Bharti A (2013) Mercury selective potentiometric sensor based on low rim functionalized thiacalix [4]-arene as a cationic receptor. J Mol Liq 177:114–118CrossRefGoogle Scholar
  17. Gupta VK, Kumar S, Singh R, Singh L, Shoora S, Sethi B (2014a) Cadmium (II) ion sensing through p-tert-butyl calix [6] arene based potentiometric sensor. J Mol Liq 195:65–68CrossRefGoogle Scholar
  18. Gupta VK, Singh AK, Kumawat LK (2014b) Thiazole Schiff base turn-on fluorescent chemosensor for Al3 + ion. Sens Actuators B Chem 195:98–108CrossRefGoogle Scholar
  19. Gupta VK, Mergu N, Kumawat LK, Singh AK (2015a) A reversible fluorescence “off–on–off” sensor for sequential detection of aluminum and acetate/fluoride ions. Talanta 144:80–89CrossRefGoogle Scholar
  20. Gupta VK, Mergu N, Kumawat LK, Singh AK (2015b) Selective naked-eye detection of magnesium (II) ions using a coumarin-derived fluorescent probe. Sens Actuators B Chem 207:216–223CrossRefGoogle Scholar
  21. Haghighi FH, Hadadzadeh H, Farrokhpour H (2016) Investigation of the in situ generation of oxide-free copper nanoparticles using pulsed-laser ablation of bulk copper in aqueous solutions of DNA bases. RSC Adv 6:109885–109896CrossRefGoogle Scholar
  22. He J, Kunitake T, Nakao A (2003) Facile in situ synthesis of noble metal nanoparticles in porous cellulose fibers. Chem Mater 15:4401–4406CrossRefGoogle Scholar
  23. Jiang F, Hsieh Y-L (2015) Cellulose nanocrystal isolation from tomato peels and assembled nanofibers. Carbohydr Polym 122:60–68CrossRefGoogle Scholar
  24. Jonoobi M, Harun J, Mathew AP, Hussein MZB, Oksman K (2010) Preparation of cellulose nanofibers with hydrophobic surface characteristics. Cellulose 17:299–307CrossRefGoogle Scholar
  25. Kaushik M, Moores A (2016) Review: nanocelluloses as versatile supports for metal nanoparticles and their applications in catalysis. Green Chem 18:622–637CrossRefGoogle Scholar
  26. Khanna P, Gaikwad S, Adhyapak P, Singh N, Marimuthu R (2007) Synthesis and characterization of copper nanoparticles. Mater Lett 61:4711–4714CrossRefGoogle Scholar
  27. Lai L et al (2012) Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ Sci 5:7936–7942CrossRefGoogle Scholar
  28. Lavoine N, Desloges I, Dufresne A, Bras J (2012) Microfibrillated cellulose—its barrier properties and applications in cellulosic materials: a review. Carbohydr Polym 90:735–764. CrossRefGoogle Scholar
  29. Li Z, Gu L (2011) Effects of mass ratio, pH, temperature, and reaction time on fabrication of partially purified pomegranate ellagitannin–gelatin nanoparticles. J Agric Food Chem 59:4225–4231CrossRefGoogle Scholar
  30. Li X, Wang H, Robinson JT, Sanchez H, Diankov G, Dai H (2009) Simultaneous nitrogen doping and reduction of graphene oxide. J Am Chem Soc 131:15939–15944CrossRefGoogle Scholar
  31. Lin N, Dufresne A (2014a) Nanocellulose in biomedicine: current status and future prospect. Eur Polym J 59:302–325CrossRefGoogle Scholar
  32. Lin N, Dufresne A (2014b) Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradiented sulfation degrees. Nanoscale 6:5384–5393CrossRefGoogle Scholar
  33. Liu J et al (2015) Design of a heterogeneous catalyst based on cellulose nanocrystals for cyclopropanation: synthesis and solid-state NMR characterization. Chem A Eur J 21:12414–12420CrossRefGoogle Scholar
  34. Lin SM, Geng S, Li N, Liu SG, Li NB, Luo HQ (2017) l-histidine-protected copper nanoparticles as a fluorescent probe for sensing ferric ions. Sens Actuators B Chem 252:912–918CrossRefGoogle Scholar
  35. Matsumoto M, Kitaoka T (2016) Ultraselective gas separation by nanoporous metal- organic frameworks embedded in gas-barrier nanocellulose films. Adv Mater (Weinheim, Ger) 28:1765–1769CrossRefGoogle Scholar
  36. Momeni S, Ahmadi R, Safavi A, Nabipour I (2017) Blue-emitting copper nanoparticles as a fluorescent probe for detection of cyanide ions. Talanta 175:514–521CrossRefGoogle Scholar
  37. Mondal P, Sinha A, Salam N, Roy AS, Jana NR, Islam S (2013) Enhanced catalytic performance by copper nanoparticle–graphene based composite. RSC Adv 3:5615–5623CrossRefGoogle Scholar
  38. Morales-Narváez E et al (2015) Nanopaper as an optical sensing platform. ACS Nano 9:7296–7305CrossRefGoogle Scholar
  39. Nekouei F, Kargarzadeh H, Nekouei S, Tyagi I, Agarwal S, Gupta VK (2016a) Preparation of Nickel hydroxide nanoplates modified activated carbon for Malachite Green removal from solutions: kinetic, thermodynamic, isotherm and antibacterial studies. Process Saf Environ Prot 102:85–97CrossRefGoogle Scholar
  40. Nekouei F, Nekouei S (2017a) Comparative study of photocatalytic activities of Zn5(OH) 8Cl2·H2O and ZnO nanostructures in ciprofloxacin degradation: response surface methodology and kinetic studies. Sci Total Environ 601:508–517CrossRefGoogle Scholar
  41. Nekouei F, Nekouei S (2017b) Enhanced enzymatic and ex situ biodegradation of petroleum hydrocarbons in solutions using Alcanivorax borkumensis enzymes in the presence of nitrogen and phosphorus co-doped reduced graphene oxide as a bacterial growth enhancer. J Mater Chem A 5:24462–24471CrossRefGoogle Scholar
  42. Nekouei F, Noorizadeh H, Nekouei S, Asif M, Tyagi I, Agarwal S, Gupta VK (2016b) Removal of malachite green from aqueous solutions by cuprous iodide–cupric oxide nano-composite loaded on activated carbon as a new sorbent for solid phase extraction: Isotherm, kinetics and thermodynamic studies. J Mol Liq 213:360–368CrossRefGoogle Scholar
  43. Nekouei F, Nekouei S, Keshtpour F, Noorizadeh H, Wang S (2017) Cr (OH) 3-NPs-CNC hybrid nanocomposite: a sorbent for adsorptive removal of methylene blue and malachite green from solutions. Environ Sci Poll Res 24:25291–25308CrossRefGoogle Scholar
  44. Nekouei F, Nekouei S, Jashnsaz O, Pouzesh M (2018a) Green approach for in situ growth of highly-ordered 3D flower-like CuS hollow nanospheres decorated on nitrogen and sulfur co-doped graphene bionanocomposite with enhanced peroxidase-like catalytic activity performance for colorimetric biosensing of glucose. Mater Sci Eng C 90:576–588CrossRefGoogle Scholar
  45. Nekouei F, Nekouei S, Kargarzadeh H (2018b) Enhanced adsorption and catalytic oxidation of ciprofloxacin on hierarchical CuS hollow nanospheres@ N-doped cellulose nanocrystals hybrid composites: kinetic and radical generation mechanism studies. Chem Eng J 335:567–578CrossRefGoogle Scholar
  46. Nekouei F, Nekouei S, Noorizadeh H (2018c) Enhanced adsorption and catalytic oxidation of ciprofloxacin by an Ag/AgCl@ N-doped activated carbon composite. J Phys Chem Solids 114:36–44CrossRefGoogle Scholar
  47. Nekouei S, Nekouei F, Ferdosi Zadeh MA (2018d) Fast and green separation of malachite green in water samples by micro-dispersion scanometry method without heating, cooling and organic solvents at room temperature. Chem Eng Res Design 134:198–211. CrossRefGoogle Scholar
  48. Pourreza N, Golmohammadi H, Naghdi T, Yousefi H (2015) Green in situ synthesized silver nanoparticles embedded in bacterial cellulose nanopaper as a bionanocomposite plasmonic sensor. Biosens Bioelectron 74:353–359CrossRefGoogle Scholar
  49. Rajesh K, Ajitha B, Reddy YAK, Suneetha Y, Reddy PS (2016) Synthesis of copper nanoparticles and role of pH on particle size control. Mater Today Proc 3:1985–1991CrossRefGoogle Scholar
  50. Rauf M, Meetani M, Hisaindee S (2011) An overview on the photocatalytic degradation of azo dyes in the presence of TiO2 doped with selective transition metals. Desalination 276:13–27CrossRefGoogle Scholar
  51. Roy N, Gaur A, Jain A, Bhattacharya S, Rani V (2013) Green synthesis of silver nanoparticles: an approach to overcome toxicity. Environ Toxicol Pharmacol 36:807–812. CrossRefGoogle Scholar
  52. Ruiz-Palomero C, Soriano ML, Valcárcel M (2017) Nanocellulose as analyte and analytical tool: opportunities and challenges. TrAC Trends Anal Chem 87:1–18CrossRefGoogle Scholar
  53. Salas C, Nypelö T, Rodriguez-Abreu C, Carrillo C, Rojas OJ (2014) Nanocellulose properties and applications in colloids and interfaces. Curr Opin Colloid Interface Sci 19:383–396CrossRefGoogle Scholar
  54. Segal L, Creely J, Martin A Jr, Conrad C (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794CrossRefGoogle Scholar
  55. Shimizu M, Saito T, Fukuzumi H, Isogai A (2014) Hydrophobic, ductile, and transparent nanocellulose films with quaternary alkylammonium carboxylates on nanofibril surfaces. Biomacromolecules 15:4320–4325CrossRefGoogle Scholar
  56. Siqueira G, Bras J, Dufresne A (2009) New process of chemical grafting of cellulose nanoparticles with a long chain isocyanate. Langmuir 26:402–411CrossRefGoogle Scholar
  57. Soomro RA, Nafady A, Memon N, Sherazi TH, Kalwar NH (2014a) L-cysteine protected copper nanoparticles as colorimetric sensor for mercuric ions. Talanta 130:415–422CrossRefGoogle Scholar
  58. Soomro RA, Sherazi SH, Memon N, Shah M, Kalwar N, Hallam KR, Shah A (2014b) Synthesis of air stable copper nanoparticles and their use in catalysis. Adv Mater Lett 5:191–198CrossRefGoogle Scholar
  59. Spoljaric S, Salminen A, Luong ND, Seppälä J (2015) Ductile nanocellulose-based films with high stretchability and tear resistance. Eur Polym J 69:328–340CrossRefGoogle Scholar
  60. Sreeju N, Rufus A, Philip D (2016) Microwave-assisted rapid synthesis of copper nanoparticles with exceptional stability and their multifaceted applications. J Mol Liq 221:1008–1021CrossRefGoogle Scholar
  61. Srivastava SK, Gupta VK, Dwivedi MK, Jain S (1995) Caesium PVC—crown (dibenzo-24-crown-8) based membrane sensor. Anal Proc Incl Anal Commun 32:21–23CrossRefGoogle Scholar
  62. Susman MD, Feldman Y, Vaskevich A, Rubinstein I (2012) Chemical deposition and stabilization of plasmonic copper nanoparticle films on transparent substrates. Chem Mater 24:2501–2508CrossRefGoogle Scholar
  63. Tokarek K, Hueso JL, Kuśtrowski P, Stochel G, Kyzioł A (2013) Green synthesis of chitosan-stabilized copper nanoparticles. Eur J Inorg Chem 2013:4940–4947Google Scholar
  64. Vainio U, Pirkkalainen K, Kisko K, Goerigk G, Kotelnikova N, Serimaa R (2007) Copper and copper oxide nanoparticles in a cellulose support studied using anomalous small-angle X-ray scattering. Eur Phys J D 42:93–101CrossRefGoogle Scholar
  65. Wang M, Tian X, Ras RH, Ikkala O (2015) Sensitive humidity-driven reversible and bidirectional bending of nanocellulose thin films as bio-inspired actuation. Adv Mater Interfaces 2:1500080CrossRefGoogle Scholar
  66. Xie J, Zhang X, Wang H, Zheng H, Huang Y (2012) Analytical and environmental applications of nanoparticles as enzyme mimetics. TrAC Trends Anal Chem 39:114–129CrossRefGoogle Scholar
  67. Yola ML, Gupta VK, Eren T, Şen AE, Atar N (2014) A novel electro analytical nanosensor based on graphene oxide/silver nanoparticles for simultaneous determination of quercetin and morin. Electrochim Acta 120:204–211CrossRefGoogle Scholar
  68. Zhang D, Yang H (2013) Gelatin-stabilized copper nanoparticles: synthesis, morphology, and their surface-enhanced Raman scattering properties. Phys B Condens Matter 415:44–48CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Social Determinants of Health Research CenterYasuj University of Medical SciencesYasujIran
  2. 2.Young Researchers and Elites Club, Central Tehran BranchIslamic Azad UniversityTehranIran
  3. 3.Department of Chemical EngineeringCurtin UniversityPerthAustralia

Personalised recommendations