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Cellulose

pp 1–12 | Cite as

Construction of cellulose/ZnO composite microspheres in NaOH/zinc nitrate aqueous solution via one-step method

  • Sen Wang
  • Yiwen Yang
  • Ang LuEmail author
  • Lina ZhangEmail author
Original Paper
  • 46 Downloads

Abstract

In the present paper, NaOH/zinc nitrate aqueous solution was successfully developed as a novel solvent to dissolve cellulose from cotton linter pulp via cooling. The 13C NMR result proved that the dissolution was a physical process without derivatization. Dynamic light scattering, viscometry and rheology measurements were used to investigate the solution properties of cellulose in different concentration regimes. The rheological test results proved that cellulose dissolved in NaOH/zinc nitrate solution was relatively stable at room temperature, which benefits commercial scale production of cellulose materials. Interestingly, single cellulose chains tended to aggregate in the solution, which facilitated their self-assembly into regenerated cellulose microspheres (CM). During the regeneration, the precursor zinc salts in the solution precipitated as ZnO nanoparticles, which were further embedded in the porous structure of CM. Thus, composite microspheres (CMZ) consisted of cellulose and ZnO with an average size of about 12 nm were facilely fabricated via one-step method, and mean diameter of the CMZ microspheres was 60 μm. The results of FT-IR, scanning electron microscope, X-ray diffraction, and thermo gravimetric analysis demonstrated that ZnO having hexagonal wurtzite structure were evenly embedded in the cellulose microspheres, leading to the formation of cellulose/ZnO composite. Antimicrobial tests indicated that cellulose/ZnO microspheres displayed good antibacterial properties. This work provided new pathway to utilize a water-based and eco-friendly solvent of cellulose to construct environmentally friendly and sustainable organic/inorganic hybrid materials.

Graphical abstract

Keywords

Cellulose solvent ZnO Microspheres Antibacterial properties 

Notes

Acknowledgments

This work was supported by the Major Program of National Natural Science Foundation of China (21334005), the Major International (Regional) Joint Research Project (21620102004) and the National Natural Science Foundation of China (51573143) and the Fundamental Research Funds for the Central Universities (2042018kf0042).

References

  1. Abe M, Kuroda K, Sato D et al (2015) Effects of polarity, hydrophobicity, and density of ionic liquids on cellulose solubility. Phys Chem Chem Phys 17:32276–32282.  https://doi.org/10.1039/C5CP05808B CrossRefPubMedGoogle Scholar
  2. Ashoka S, Nagaraju G, Tharamani CN, Chandrappa GT (2009) Ethylene glycol assisted hydrothermal synthesis of flower like ZnO architectures. Mater Lett 63:873–876.  https://doi.org/10.1016/j.matlet.2009.01.054 CrossRefGoogle Scholar
  3. Aydin Sevinç B, Hanley L (2010) Antibacterial activity of dental composites containing zinc oxide nanoparticles. J Biomed Mater Res B Appl Biomater 94B:22–31.  https://doi.org/10.1002/jbm.b.31620 CrossRefGoogle Scholar
  4. Bagheri M, Rabieh S (2013) Preparation and characterization of cellulose–ZnO nanocomposite based on ionic liquid ([C4mim] Cl). Cellulose 20:699–705CrossRefGoogle Scholar
  5. Bergmann M, Tekman MB, Gutow L (2017) Sea change for plastic pollution. Nature 544:297CrossRefGoogle Scholar
  6. Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548.  https://doi.org/10.1002/mabi.200400222 CrossRefPubMedPubMedCentralGoogle Scholar
  7. Cai J, Zhang L (2006) Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules 7:183–189.  https://doi.org/10.1021/bm0505585 CrossRefPubMedGoogle Scholar
  8. Cai J, Zhang L, Liu S et al (2008) Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules 41:9345–9351CrossRefGoogle Scholar
  9. Cen L, Neoh K, Kang E (2003) Surface functionalization technique for conferring antibacterial properties to polymeric and cellulosic surfaces. Langmuir 19:10295–10303CrossRefGoogle Scholar
  10. Chang H-C, Zhang R-L, Hsu D-T (2015) The effect of pressure on cation–cellulose interactions in cellulose/ionic liquid mixtures. Phys Chem Chem Phys 17:27573–27578.  https://doi.org/10.1039/C5CP04607F CrossRefPubMedGoogle Scholar
  11. Costa SV, Gonçalves AS, Zaguete MA et al (2013) ZnO nanostructures directly grown on paper and bacterial cellulose substrates without any surface modification layer. Chem Commun 49:8096–8098.  https://doi.org/10.1039/C3CC43152E CrossRefGoogle Scholar
  12. Daneshvar N, Salari D, Khataee A (2004) Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2. J Photochem Photobiol Chem 162:317–322.  https://doi.org/10.1016/S1010-6030(03)00378-2 CrossRefGoogle Scholar
  13. Fink HP, Weigel P, Purz HJ, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Prog Polym Sci 26:1473–1524CrossRefGoogle Scholar
  14. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896.  https://doi.org/10.1007/s10570-013-0030-4 CrossRefGoogle Scholar
  15. Gimenez AJ, Yanez-Limon JM, Seminario JM (2013) ZnO–cellulose composite for UV sensing. IEEE Sens J 13:1301–1306.  https://doi.org/10.1109/JSEN.2012.2231067 CrossRefGoogle Scholar
  16. Gonçalves G, Marques PAAP, Neto CP et al (2009) Growth, structural, and optical characterization of ZnO-coated cellulosic fibers. Cryst Growth Des 9:386–390.  https://doi.org/10.1021/cg800596z CrossRefGoogle Scholar
  17. Huang Z, Zheng X, Yan D et al (2008) Toxicological effect of ZnO nanoparticles based on bacteria. Langmuir 24:4140–4144.  https://doi.org/10.1021/la7035949 CrossRefPubMedGoogle Scholar
  18. Inphonlek S, Pimpha N, Sunintaboon P (2010) Synthesis of poly(methyl methacrylate) core/chitosan-mixed-polyethyleneimine shell nanoparticles and their antibacterial property. Colloids Surf B Biointerfaces 77:219–226.  https://doi.org/10.1016/j.colsurfb.2010.01.029 CrossRefPubMedGoogle Scholar
  19. Isogai A (1997) NMR analysis of cellulose dissolved in aqueous NaOH solutions. Cellulose 4:99–107.  https://doi.org/10.1023/A:1018471419692 CrossRefGoogle Scholar
  20. Isogai A, Atalla RH (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319CrossRefGoogle Scholar
  21. Jia B, Mei Y, Cheng L et al (2012) Preparation of copper nanoparticles coated cellulose films with antibacterial properties through one-step reduction. ACS Appl Mater Interfaces 4:2897–2902CrossRefGoogle Scholar
  22. John A, Ko H-U, Kim D-G, Kim J (2011) Preparation of cellulose–ZnO hybrid films by a wet chemical method and their characterization. Cellulose 18:675–680.  https://doi.org/10.1007/s10570-011-9523-1 CrossRefGoogle Scholar
  23. Jouault N, Xiang Y, Moulin E et al (2012) Hierarchical supramolecular structuring and dynamical properties of water soluble polyethylene glycol-perylene self-assemblies. Phys Chem Chem Phys 14:5718–5728.  https://doi.org/10.1039/C2CP23786E CrossRefPubMedGoogle Scholar
  24. Katepetch C, Rujiravanit R, Tamura H (2013) Formation of nanocrystalline ZnO particles into bacterial cellulose pellicle by ultrasonic-assisted in situ synthesis. Cellulose 20:1275–1292CrossRefGoogle Scholar
  25. Khatri V, Halász K, Trandafilović LV et al (2014) ZnO-modified cellulose fiber sheets for antibody immobilization. Carbohydr Polym 109:139–147.  https://doi.org/10.1016/j.carbpol.2014.03.061 CrossRefPubMedGoogle Scholar
  26. Kondo T (1997) The assignment of IR absorption bands due to free hydroxyl groups in cellulose. Cellulose 4:281–292.  https://doi.org/10.1023/A:1018448109214 CrossRefGoogle Scholar
  27. Kumar A, Gullapalli H, Balakrishnan K et al (2011) Flexible ZnO–cellulose nanocomposite for multisource energy conversion. Small 7:2173–2178.  https://doi.org/10.1002/smll.201100458 CrossRefPubMedGoogle Scholar
  28. Lue A, Liu Y, Zhang L, Potthast A (2011) Light scattering study on the dynamic behaviour of cellulose inclusion complex in LiOH/urea aqueous solution. Polymer 52:3857–3864.  https://doi.org/10.1016/j.polymer.2011.06.034 CrossRefGoogle Scholar
  29. MacArthur E (2017) Beyond plastic waste. Science 358:843.  https://doi.org/10.1126/science.aao6749 CrossRefPubMedGoogle Scholar
  30. Mary G, Bajpai S, Chand N (2009) Copper(II) ions and copper nanoparticles-loaded chemically modified cotton cellulose fibers with fair antibacterial properties. J Appl Polym Sci 113:757–766CrossRefGoogle Scholar
  31. Matsumoto T, Tatsumi D, Tamai N, Takaki T (2001) Solution properties of celluloses from different biological origins in LiCl·DMAc. Cellulose 8:275–282.  https://doi.org/10.1023/A:1015162027350 CrossRefGoogle Scholar
  32. McCormick CL, Callais PA, Hutchinson BH (1985) Solution studies of cellulose in lithium chloride and N,N-dimethylacetamide. Macromolecules 18:2394–2401.  https://doi.org/10.1021/ma00154a010 CrossRefGoogle Scholar
  33. Morgenstern B, Kammer H-W (1996) Solvation in cellulose–LiCl–DMAc solutions. Trends Polym Sci 4:87–92Google Scholar
  34. Nagarkar S, Nicolai T, Chassenieux C, Lele A (2010) Structure and gelation mechanism of silk hydrogels. Phys Chem Chem Phys 12:3834–3844.  https://doi.org/10.1039/B916319K CrossRefPubMedGoogle Scholar
  35. Özgür Ü, Alivov YI, Liu C et al (2005) A comprehensive review of ZnO materials and devices. J Appl Phys 98:041301.  https://doi.org/10.1063/1.1992666 CrossRefGoogle Scholar
  36. Rochman CM, Browne MA, Halpern BS et al (2013) Classify plastic waste as hazardous. Nature 494:169CrossRefGoogle Scholar
  37. Rosenau T, Potthast A, Sixta H, Kosma P (2001) The chemistry of side reactions and byproduct formation in the system NMMO/cellulose (Lyocell process). Prog Polym Sci 26:1763–1837CrossRefGoogle Scholar
  38. Rosenau T, Potthast A, Adorjan I et al (2002) Cellulose solutions in N-methylmorpholine-N-oxide (NMMO)—degradation processes and stabilizers. Cellulose 9:283–291CrossRefGoogle Scholar
  39. Sangeetha G, Rajeshwari S, Venckatesh R (2011) Green synthesis of zinc oxide nanoparticles by aloe barbadensis miller leaf extract: structure and optical properties. Mater Res Bull 46:2560–2566.  https://doi.org/10.1016/j.materresbull.2011.07.046 CrossRefGoogle Scholar
  40. Sirelkhatim A, Mahmud S, Seeni A et al (2015) Review on zinc oxide nanoparticles: antibacterial activity and toxicity mechanism. Nano Micro Lett 7:219–242.  https://doi.org/10.1007/s40820-015-0040-x CrossRefGoogle Scholar
  41. Swatloski RP, Spear SK, Holbrey JD, Rogers Robin D (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975CrossRefGoogle Scholar
  42. Wang S, Lu A, Zhang L (2016) Recent advances in regenerated cellulose materials. Prog Polym Sci 53:169–206.  https://doi.org/10.1016/j.progpolymsci.2015.07.003 CrossRefGoogle Scholar
  43. Wang S, Lyu K, Sun P et al (2017a) Influence of cation on the cellulose dissolution investigated by MD simulation and experiments. Cellulose 24:4641–4651.  https://doi.org/10.1007/s10570-017-1456-x CrossRefGoogle Scholar
  44. Wang S, Sun P, Liu M et al (2017b) Weak interactions and their impact on cellulose dissolution in an alkali/urea aqueous system. Phys Chem Chem Phys 19:17909–17917.  https://doi.org/10.1039/C7CP02514A CrossRefPubMedGoogle Scholar
  45. Wang S, Sun P, Zhang R et al (2017c) Cation/macromolecule interaction in alkaline cellulose solution characterized with pulsed field-gradient spin-echo NMR spectroscopy. Phys Chem Chem Phys 19:7486–7490.  https://doi.org/10.1039/C6CP08744B CrossRefPubMedGoogle Scholar
  46. Xia T, Kovochich M, Liong M et al (2008) Comparison of the mechanism of toxicity of zinc oxide and cerium oxide nanoparticles based on dissolution and oxidative stress properties. ACS Nano 2:2121–2134.  https://doi.org/10.1021/nn800511k CrossRefPubMedPubMedCentralGoogle Scholar
  47. Yang Q, Qin X, Zhang L (2011) Properties of cellulose films prepared from NaOH/urea/zincate aqueous solution at low temperature. Cellulose 18:681–688CrossRefGoogle Scholar
  48. Zhang C, Liu R, Xiang J et al (2014) Dissolution mechanism of cellulose in N,N-dimethylacetamide/lithium chloride: revisiting through molecular interactions. J Phys Chem B 118:9507–9514.  https://doi.org/10.1021/jp506013c CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.College of Chemistry and Molecular SciencesWuhan UniversityWuhanChina

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