Journal of Materials Science

, Volume 50, Issue 15, pp 5348–5361 | Cite as

Preparation of efficient magnetic biosorbents by clicking carbohydrates onto graphene oxide

  • Mina Namvari
  • Hassan Namazi
Original Paper


In this work, hydrophilic graphene nanosheets (GNS) and the related magnetic nanocomposites were prepared by first tethering alkyne-functionalized graphene oxide (GO) with azide-modified glucose followed by deposition of Fe3O4 nanoparticles on the functionalized GNS. For the preparation of nanohybrids, two approaches were designed: in the first one, after chlorination of GO with thionyl chloride, GO was reacted with propargyl alcohol and subsequently clicked with azide-glucoside. The resulted sweet GNS were easily dispersed in water and stable for 2 weeks. In the second approach, GO was functionalized with 3,4,5-tris(prop-2-yn-1-yloxy)benzoic acid via hydroxyl groups on its basal plane and finally treated with azide-glucoside. The obtained hydrophilic GNS were stable in water for 3 weeks. The results showed that both glucose-grafted GO sheets were reduced by sodium ascorbate during click-coupling reaction; this is one of the many advantages of click reaction. Finally, Fe3O4 nanoparticles were deposited on the sweet GNS and were superparamagnetic, responded quickly to an external magnetic field and exhibited efficient adsorption towards methylene blue, as a cationic dye. No leaching was observed even after a week of placing a magnet close to the vial containing the dispersion of magnetic sweet GNS.


Graphene Oxide Methylene Blue Biosorbents Graphene Nanosheets Sodium Ascorbate 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



Authors are pleased to acknowledge the University of Tabriz and Research Center for Pharmaceutical Nanotechnology (RCPN), Tabriz University of Medical Science for financial support of this work.


  1. 1.
    Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV (2004) Electric field effect in atomically thin carbon films. Science 306:666–669CrossRefGoogle Scholar
  2. 2.
    Liao L, Lin Y-C, Bao M, Cheng R, Bai J, Liu Y (2010) High-speed graphene transistors with a self-aligned nanowire gate. Nature 467:305–308CrossRefGoogle Scholar
  3. 3.
    Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F (2008) Macroscopic graphene membranes and their extraordinary stiffness. Nano Lett 8:902–907CrossRefGoogle Scholar
  4. 4.
    Chen C, Rosenblatt S, Bolotin KI, Kalb W, Kim P, Kymissis I (2009) Performance of monolayer graphene nanomechanical resonators with electrical readout. Nat Nanotechnol 4:861–867CrossRefGoogle Scholar
  5. 5.
    Mueller T, Xia F, Avouris P (2010) Graphene photodetectors for high-speed optical communications. Nat Photonics 4:297–301CrossRefGoogle Scholar
  6. 6.
    Bonaccorso F, Sun Z, Hasan T, Ferrari AC (2010) Graphene photonics and optoelectronics. Nat Photonics 4:611–622CrossRefGoogle Scholar
  7. 7.
    Ratinac KR, Yang W, Ringer SP, Braet F (2010) Toward ubiquitous environmental gas sensors-capitalizing on the promise of graphene. Environ Sci Technol 44:1167–1176CrossRefGoogle Scholar
  8. 8.
    Dan Y, Lu Y, Kybert NJ, Luo Z, Johnson ATC (2009) Intrinsic response of graphene vapor sensors. Nano Lett 9:1472–1475CrossRefGoogle Scholar
  9. 9.
    Schedin F, Geim AK, Morozov SV, Hill EW, Blake P, Katsnelson MI (2007) Detection of individual gas molecules adsorbed on graphene. Nat Mater 6:652–655CrossRefGoogle Scholar
  10. 10.
    Liu Y, Yu D, Zeng C, Miao Z, Dai L (2010) Biocompatible graphene oxide-based glucose biosensors. Langmuir 26:6158–6160CrossRefGoogle Scholar
  11. 11.
    Georgakilas V, Otyepka M, Bourlinos AB, Chandra V, Kim N, Kemp KC (2012) Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem Rev 112:6156–6214CrossRefGoogle Scholar
  12. 12.
    Choi EY, Han TH, Hong J, Kim JE, Lee SH, Kim HW (2010) Noncovalent functionalization of graphene with end-functional polymers. J Mater Chem 20:1907–1912CrossRefGoogle Scholar
  13. 13.
    Yang Q, Pan X, Huang F, Li K (2010) Fabrication of high-concentration and stable aqueous suspensions of graphene nanosheets by noncovalent functionalization with lignin and cellulose derivatives. J Phys Chem C 114:3811–3816CrossRefGoogle Scholar
  14. 14.
    Sharma R, Baik JH, Perera CJ, Strano MS (2010) Anomalously large reactivity of single graphene layers and edges toward electron transfer chemistries. Nano Lett 10:398–405CrossRefGoogle Scholar
  15. 15.
    Loh KP, Bao Q, Ang PK, Yang J (2010) The chemistry of graphene. J Mater Chem 20:2277–2289CrossRefGoogle Scholar
  16. 16.
    Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39:228–240CrossRefGoogle Scholar
  17. 17.
    Compton OC, Dikin DA, Putz KW, Brinson LC, Nguyen ST (2010) Electrically conductive “alkylated” graphene paper via chemical reduction of amine-functionalized graphene oxide paper. Adv Mater 22:892–896CrossRefGoogle Scholar
  18. 18.
    Meng F, Ishida H, Liu X (2014) Introduction of benzoxazine onto the graphene oxide surface by click chemistry and the properties of graphene oxide reinforced polybenzoxazine nanohybrids. RSC Adv 4:9471–9475CrossRefGoogle Scholar
  19. 19.
    Zhang X, Browne WR, Feringa BL (2012) Preparation of dispersible graphene through organic functionalization of graphene using a zwitterion intermediate cycloaddition approach. RSC Adv 2:12173–12176CrossRefGoogle Scholar
  20. 20.
    Veca LM, Lu FS, Meziani MJ, Cao L, Zhang PY, Qi G (2009) Polymer functionalization and solubilization of carbon nanosheets. Chem Commun 18:2565–2567CrossRefGoogle Scholar
  21. 21.
    Shen J, Hu Y, Li C, Qin C, Ye M (2009) Synthesis of amphiphilic graphene nanoplatelets. Small 5:82–85CrossRefGoogle Scholar
  22. 22.
    Chen Y, Zhang X, Yu P, Ma Y (2009) Stable dispersions of graphene and highly conducting graphene films: a new approach to creating colloids of graphene monolayers. Chem Commun 30:4527–4529CrossRefGoogle Scholar
  23. 23.
    Chandra V, Park J, Chun Y, Lee WJ, Hwang IC, Kim KS (2010) Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano 4:3979–3986CrossRefGoogle Scholar
  24. 24.
    Yang H, Shan C, Li F, Han D, Zhang Q, Niu L (2009) Covalent functionalization of polydisperse chemically-converted graphene sheets with amine-terminated ionic liquid. Chem Commun 26:3880–3882CrossRefGoogle Scholar
  25. 25.
    Yang Q, Pan X, Clarke K, Li K (2012) Covalent functionalization of graphene with polysaccharides. Ind Eng Chem Res 51:310–317CrossRefGoogle Scholar
  26. 26.
    Kolb HC, Finn MG, Sharpless KB (2004) Click chemistry: diverse chemical function from a few good reactions. Angew Chem Int Ed 40:2004–2021CrossRefGoogle Scholar
  27. 27.
    Golas PL, Matyjaszewski K (2010) Marrying click chemistry with polymerization: expanding the scope of polymeric materials. Chem Soc Rev 39:1338–1354CrossRefGoogle Scholar
  28. 28.
    Li N, Binder WH (2011) Click-chemistry for nanoparticle-modification. J Mater Chem 21:16717–16734CrossRefGoogle Scholar
  29. 29.
    Franc G, Kakkar AK (2010) ‘‘Click’’ methodologies: efficient, simple and greener routes to design dendrimers. Chem Soc Rev 39:1536–1544CrossRefGoogle Scholar
  30. 30.
    Millward SW, Agnew HD, Lai B, Lee SS, Lim J, Nag A (2013) In situ click chemistry: from small molecule discovery to synthetic antibodies. Integr Biol 5:87–95CrossRefGoogle Scholar
  31. 31.
    Thirumurugan P, Matosiuk D, Jozwiak K (2013) Click chemistry for drug development and diverse chemical–biology applications. Chem Rev 113:4905–4979CrossRefGoogle Scholar
  32. 32.
    Xi W, Scott TF, Kloxin CJ, Bowman CN (2014) Click chemistry in materials science. Adv Func Mater 24:2572–2590CrossRefGoogle Scholar
  33. 33.
    Pieters RJ, Rijkers DTS, Liskamp RMJ (2007) Application of the 1,3-dipolar cycloaddition reaction in chemical biology: approaches toward multivalent carbohydrates and peptides and peptide-based polymers. QSAR Comb Sci 26:1181–1190CrossRefGoogle Scholar
  34. 34.
    Chen Y, Star A, Vidal S (2013) Sweet carbon nanostructures: carbohydrate conjugates with carbon nanotubes and graphene and their applications. Chem Soc Rev 42:4532–4542CrossRefGoogle Scholar
  35. 35.
    Ryu HJ, Mahapatra SS, Yadav SK, Cho JW (2012) Synthesis of click-coupled graphene sheet with chitosan: effective exfoliation and enhanced properties of their nanocomposites. Eur Polym J 49:2627–2634CrossRefGoogle Scholar
  36. 36.
    Sun S, Cao Y, Feng J, Wu P (2010) Click chemistry as a route for the immobilization of well-defined polystyrene onto graphene sheets. J Mater Chem 20:5605–5607CrossRefGoogle Scholar
  37. 37.
    Pan Y, Bao H, Sahoo NG, Wu T, Li L (2011) Water-soluble poly(N-isopropylacrylamide)–graphene sheets synthesized via click chemistry for drug delivery. Adv Func Mater 21:2754–2763CrossRefGoogle Scholar
  38. 38.
    Cao Y, Lai Z, Feng J, Wu P (2011) Graphene oxide sheets covalently functionalized with block copolymers via click chemistry as reinforcing fillers. J Mater Chem 21:9271–9278CrossRefGoogle Scholar
  39. 39.
    Yang H, Kwon Y, Kwon T, Lee H, Kim BJ (2012) ‘Click’ preparation of CuPt nanorod-anchored graphene oxide as a catalyst in water. Small 8:3161–3168CrossRefGoogle Scholar
  40. 40.
    Yadav SK, Yoo HJ, Cho JW (2013) Click coupled graphene for fabrication of high-performance polymer nanocomposites. J Polym Sci B 51:39–47CrossRefGoogle Scholar
  41. 41.
    Devadoss A, Chidsey CED (2007) Azide-modified graphitic surfaces for covalent attachment of alkyne-terminated molecules by “click” chemistry. J Am Chem Soc 129:5370–5371CrossRefGoogle Scholar
  42. 42.
    Zhang W, Shi X, Zhang Y, Gu W, Li B, Xian Y (2013) Synthesis of water-soluble magnetic graphene nanocomposites for recyclable removal of heavy metal ions. J Mater Chem A 1:1745–1753CrossRefGoogle Scholar
  43. 43.
    Bustos-Ramírez K, Martínez-Hernández AL, Martínez-Barrera G, de Icaza M, Castaño VM, Velasco-Santos C (2013) Covalently bonded chitosan on graphene oxide via redox reaction. Materials 6:911–926CrossRefGoogle Scholar
  44. 44.
    Kabiri R, Namazi H (2014) Surface grafting of reduced graphene oxide using nanocrystalline cellulose via click reaction. J Nanopart Res 16:2474–2478CrossRefGoogle Scholar
  45. 45.
    Namvari M, Namazi H (2014) Sweet graphene I: fabrication of water- soluble graphene nanosheets by covalently attaching alkyne- terminated saccharides onto azide- modified graphene oxide by “click” chemistry. Carbohydr Res 396:1–8CrossRefGoogle Scholar
  46. 46.
    Zhang X, Liu X, Zheng W, Zhu J (2012) Regenerated cellulose/graphene nanocomposite films prepared in DMAC/LiCl solution. Carbohydr Polym 88:26–30CrossRefGoogle Scholar
  47. 47.
    Li R, Liu C, Ma M (2011) Studies on the properties of graphene oxide-reinforced starch biocomposites. Carbohyd Polym 84:631–637CrossRefGoogle Scholar
  48. 48.
    Kabiri R, Namazi H (2014) Nanocrystalline cellulose acetate (NCCA)/graphene oxide (GO) nanocomposites with enhanced mechanical properties and barrier against water vapor. Cellulose 21:3527–3539CrossRefGoogle Scholar
  49. 49.
    Namvari M, Namazi H (2014) Synthesis of magnetic citric acid-functionalized graphene oxide and its application in the removal of methylene blue from contaminated water. Polym Int 63:1881–1888CrossRefGoogle Scholar
  50. 50.
    Liu L, Li C, Bao C, Jia Q, Xiao P, Liu X (2012) Preparation and characterization of chitosan/graphene oxide composites for the adsorption of Au(III) and Pd(II). Talanta 93:350–357CrossRefGoogle Scholar
  51. 51.
    Yu J-G, Zhao X-H, Yang H, Liu Q, Chen X-H, Jiang X-Y, Chen X-Q, Jiao F-P (2014) Aqueous adsorption and removal of organic contaminants by carbon nanotubes. Sci Total Environ 482–483:241–251CrossRefGoogle Scholar
  52. 52.
    Yu J-G, Yu L-Y, Yang H, Liu Q, Chen X-H, Jiang X-Y, Chen X-Q, Jiao F-P (2015) Graphene nanosheets as novel adsorbents in adsorption, preconcentration and removal of gases, organic compounds and metal ions. Sci Total Environ 502:70–79CrossRefGoogle Scholar
  53. 53.
    Kui L, Xia ZG, Ke WX (2012) A brief review of graphene-based material synthesis and its application in environmental pollution management. Chin Sci Bull 57:1223–1234CrossRefGoogle Scholar
  54. 54.
    Yao Y, Miao S, Liu S, Ma LP, Sun H, Wang S (2012) Synthesis, characterization, and adsorption properties of magnetic Fe3O4@graphene nanocomposite. Chem Eng J 184:326–332CrossRefGoogle Scholar
  55. 55.
    Xie G, Xi P, Liu H, Chen F, Huang L, Shi Y, Hou F, Zeng Z, Shao C, Wang J (2012) A facile chemical method to produce superparamagnetic grapheme oxide–Fe3O4 hybrid composite and its application in the removal of dyes from aqueous solution. J Mater Chem 22:1033–1039CrossRefGoogle Scholar
  56. 56.
    Wang C, Feng C, Gao Y, Ma X, Wu Q, Wang Z (2011) Preparation of a graphene-based magnetic nanocomposite for the removal of an organic dye from aqueous solution. Chem Eng J 173:92–97CrossRefGoogle Scholar
  57. 57.
    Ai L, Zhang C, Chen Z (2011) Removal of methylene blue from aqueous solution by a solvothermal-synthesized graphene/magnetite composite. J Hazard Mater 192:1515–1524CrossRefGoogle Scholar
  58. 58.
    Geng Z, Lin Y, Yu X, Shen Q, Ma L, Li Z, Pan N, Wang X (2012) Highly efficient dye adsorption and removal: a functional hybrid of reduced graphene oxide–Fe3O4 nanoparticles as an easily regenerative adsorbent. J Mater Chem 22:3527–3535CrossRefGoogle Scholar
  59. 59.
    Sun H, Cao L, Lu L (2011) Magnetite/reduced graphene oxide nanocomposites: one step solvothermal synthesis and use as a novel platform for removal of dye pollutants. Nano Res 4:550–562CrossRefGoogle Scholar
  60. 60.
    Namvari M, Namazi H (2014) Clicking graphene oxide and Fe3O4 nanoparticles together: an efficient adsorbent to remove dyes from aqueous solutions. Int J Environ Sci Tech 11:1527–1536CrossRefGoogle Scholar
  61. 61.
    Zhang K, Zhang LL, Zhao XS, Wu J (2012) Graphene/polyaniline nanofiber composites as supercapacitor electrodes. J Chem Mater 22:1392–1401CrossRefGoogle Scholar
  62. 62.
    Roy B, Mukhopadhyay (2007) Sulfuric acid immobilized on silica: an excellent catalyst for Fischer type glycosylation. Tetrahedron Lett 48:3783–3787CrossRefGoogle Scholar
  63. 63.
    Geng J, Mantovani G, Tao L, Nicolas J, Chen G, Wallis R (2007) Site-directed conjugation of ‘click’ glycopolymers to from glycoprotein mimics: binding to mammalian lectin and induction of immunological function. J Am Chem Soc 129:15156–15163CrossRefGoogle Scholar
  64. 64.
    Dam HH, Caruso F (2012) Modular click assembly of degradable capsules using polyrotaxanes. ACS Nano 6:4686–4693CrossRefGoogle Scholar
  65. 65.
    Zhang J, Yang H, Shen G, Cheng P, Zhang J, Guo S (2010) Reduction of graphene oxide via L-ascorbic acid. Chem Commun 46:1112–1114CrossRefGoogle Scholar
  66. 66.
    Fernandez-Merino MJ, Guardia L, Paredes JI, Villar-Rodil S, SolisFernandez P, Martinez-Alonso A et al (2010) Vitamin C is an ideal substitute for hydrazine in the reduction of graphene oxide suspensions. J Phys Chem C 114:6426–6432CrossRefGoogle Scholar
  67. 67.
    Shen J, Shi M, Ma H, Yan B, Li N, Hu Y (2010) Synthesis of hydrophilic and organophilic chemically modified graphene oxide sheets. J Colloid Interface Sci 351:366–370CrossRefGoogle Scholar
  68. 68.
    Salvio R, Krabbenborg S, Naber WJM, Velders AH, Reinhoudt DN, van der Wiel WG (2009) The formation of large-area conducting graphene-like platelets. Chem Eur J 15:8235–8240CrossRefGoogle Scholar
  69. 69.
    Hong RY, Feng B, Liua G, Wang S, Li HZ, Ding JM, Zheng Y, Wei DG (2009) Preparation and characterization of Fe3O4/polystyrene composite particles via inverse emulsion polymerization. J Alloy Compd 476:612–618CrossRefGoogle Scholar
  70. 70.
    Chang PR, Yua J, Maa X, Anderson DP (2011) Polysaccharides as stabilizers for the synthesis of magnetic nanoparticles Carbohydr. Polym. 83:640–644Google Scholar
  71. 71.
    Juang RS, Wu FC, Tseng RL (2000) Mechanism of adsorption of dyes and phenols from water using activated carbons prepared from plum kernels. J Colloid Interface Sci 227:437–444CrossRefGoogle Scholar
  72. 72.
    Yang S-T, Chen S, Chang Y, Cao A, Liu Y, Wang H (2011) Removal of methylene blue from aqueous solution by graphene oxide. J Colloid Interface Sci 359:24–29CrossRefGoogle Scholar
  73. 73.
    Qu S, Huang F, Yu SN, Chen G, Kong JL (2008) Magnetic removal of dyes from aqueous solution using multi-walled carbon nanotubes filled with Fe2O3 particles. J Hazard Mater 160:643–647CrossRefGoogle Scholar
  74. 74.
    Thuy-Duong NP, Hung VP, Kim EJ, Oh ES, Hur SH, Chung JS (2012) Reduced graphene oxide–titanate hybrids: morphologic evolution by alkali-solvothermal treatment and applications in water purification. Appl Surf Sci 258:4551–4557CrossRefGoogle Scholar
  75. 75.
    Ai L, Jiang J (2012) Removal of methylene blue from aqueous solution with self-assembled cylindrical graphene–carbon nanotube hybrid. Chem Eng J 192:156–163CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  1. 1.Laboratory of Dendrimers and Nano-Biopolymers, Faculty of ChemistryUniversity of TabrizTabrizIran
  2. 2.Research Center for Pharmaceutical Nanotechnology (RCPN)Tabriz University of Medical ScienceTabrizIran

Personalised recommendations