pp 1–13 | Cite as

Preparation, characterization and antibacterial properties of cellulose membrane containing N-halamine

  • Shengli ZhangEmail author
  • Chengcheng Kai
  • Bofang Liu
  • Silue Zhang
  • Wei Wei
  • Xiaoling Xu
  • Zuowan ZhouEmail author
Original Research


Polyethylenimine (PEI), a type of water-soluble chain polymer containing a great number of primary, secondary and tertiary amine groups in the molecule, was used as an N-halamine precursor. It was grafted onto dialdehyde cellulose membrane (DCM) followed by chlorination to prepare a novel N-halamine antibacterial cellulose membrane (Cl–PEI–DCM). The appropriate conditions affecting the aldehyde content of DCM and the active chlorine (Cl+) content of Cl–PEI–DCM were systematically studied at oxidation, grafting and chlorination stages, respectively. The structure and properties of the samples were investigated by SEM, ATR–FTIR, XRD, XPS, light transmittance measurements and tensile tests. The stability and rechargeability of the Cl–PEI–DCM were evaluated, and its antibacterial activity was tested against S. aureus and E. coli. Results showed that the Cl+ content of the chlorinated samples was strongly dependent on the aldehyde content of DCM and PEI concentration. Under the optimum testing condition, the Cl+ content of the Cl–PEI–DCM reached 1.30 wt%. The hydroxyl groups on the cellulose membrane were changed to aldehyde groups and the successful introduction of PEI and N–Cl bond were confirmed. The 1.30 wt% Cl–PEI–DCM exhibited high antibacterial activity against both S. aureus and E. coli, which can completely inactivate two bacterial pathogens within 5 min even after 15 days of storage. Moreover, the Cl–PEI–DCM membrane displayed good stability, rechargeability, transparency and high mechanical strength. These results demonstrated that the Cl–PEI–DCM can be considered as a visualized wound dressing material or antibacterial shoe insole.

Graphical abstract


Periodate oxidation Dialdehyde cellulose Polyethylenimine (PEI) Antibacterial cellulose membrane N-chloramine 



The present work financially supported by Science and Technology Pillar Program of Sichuan Province (2016GZ0222).


  1. Bastarrachea LJ, Goddard JM (2013) Development of antimicrobial stainless steel via surface modification with N-halamines: characterization of surface chemistry and N-halamine chlorination. J Appl Polym Sci 127:821–831CrossRefGoogle Scholar
  2. Buket D, Roy B, Mingyu Q, Tung-Shi H, Worley S (2017) N-halamine biocidal materials with superior antimicrobial efficacies for wound dressings. Molecules 22(10):1582–1598CrossRefGoogle Scholar
  3. Cao J, Wei W, Gou GJ, Jiang M, Cui YH, Zhang SL, Wang Y, Zhou ZW (2018) Cellulose films from the aqueous DMSO/TBAH-system. Cellulose 25:1975–1986CrossRefGoogle Scholar
  4. Chen YX, Li JN, Li QQ, Shen YY, Ge ZC, Zhang WW, Chen SG (2016) Novel water-soluble, antibacterial, and biocompatible quaternized chitosan by introducing sulfobetaine. Carbohydr Polym 143:246–253CrossRefGoogle Scholar
  5. Chen SG, Zhang SB, Galluzzi M, Li F, Zhang XC, Yang XH, Liu XY, Cai XH, Zhu XL, Du B, Li JN, Huang P (2019) Insight into multifunctional polyester fabrics finished by one-step ecofriendly strategy. Chem Eng J 358:634–642CrossRefGoogle Scholar
  6. Cheung RCF, Ng TB, Wong JH, Chan WY (2015) Chitosan: an update on potential biomedical and pharmaceutical applications. Mar Drugs 13(8):5156–5186CrossRefGoogle Scholar
  7. Ciofani G, Raffa V, Menciassi A, Cuschieri A (2008) Cytocompatibility, interactions, and uptake of polyethyleneimine-coated boron nitride nanotubes by living cells: confirmation of their potential for biomedical applications. Biotechnol Bioeng 101:850–858CrossRefGoogle Scholar
  8. Deborde M, von Gunten U (2008) Reactions of chlorine with inorganic and organic compounds during water treatment—kinetics and mechanisms: a critical review. Water Res 42(1–2):13–51CrossRefGoogle Scholar
  9. Demir B, Broughton RM, Huang TS, Bozack MJ, Worley SD (2017) Polymeric antimicrobial N-halamine-surface modification of stainless steel. Ind Eng Chem Res 56:11773–11781CrossRefGoogle Scholar
  10. Demircan D, Zhang BZ (2017) Facile synthesis of novel soluble cellulose-grafted hyperbranched polymers as potential natural antimicrobial materials. Carbohydr Polym 157:1913–1921CrossRefGoogle Scholar
  11. Dong A, Wang YJ, Gao YY, Gao TY, Gao G (2017) Chemical insights into antibacterial N-halamines. Chem Rev 117:4806–4862CrossRefGoogle Scholar
  12. Gerba CP (2015) Quaternary ammonium biocides: efficacy in application. Appl Environ Microbiol 81(2):464–469CrossRefGoogle Scholar
  13. Gu JW, Yuan LJ, Zhang Z, Yang XH, Luo JX, Gui ZF, Chen SG (2018) Non-leaching bactericidal cotton fabrics with well-preserved physical properties, no skin irritation and no toxicity. Cellulose 25:5415–5426CrossRefGoogle Scholar
  14. Hou SH, Dong X, Zhu JH, Zheng JF, Bi WH, Li SH, Zhang SB (2017) Preparation and characterization of an antibacterial ultrafiltration membrane with N-chloramine functional groups. J Colloid Interface Sci 496:391–400CrossRefGoogle Scholar
  15. Hui F, Debiemme-Chouvy C (2013) Antimicrobial N-halamine polymers and coatings: a review of their synthesis, characterization, and applications. Biomacromolecules 14(3):585–601CrossRefGoogle Scholar
  16. Jin LQ, Li WG, Xu QH, Sun QC (2015) Amino-functionalized nanocrystalline cellulose as an adsorbent for anionic dyes. Cellulose 22:2443–2456CrossRefGoogle Scholar
  17. Kang ZZ, Zhang B, Jiao YC, Xu YH, He QZ, Liang J (2013) High-efficacy antimicrobial cellulose grafted by a novel quaternarized N-halamine. Cellulose 20(2):885–893CrossRefGoogle Scholar
  18. Kang B, Li YD, Liang J, Yan X, Chen J, Lang WZ (2016) Novel PVDF hollow fiber ultrafiltration membranes with antibacterial and antifouling properties by embedding N-halamine functionalized multiwalled carbon nanotubes (MWNTs). RSC Adv 6:1710–1721CrossRefGoogle Scholar
  19. Kim UJ, Kuga S, Wada M, Okano T, Kondo T (2000) Periodate oxidation of crystalline cellulose. Biomacromolecules 1:488–492CrossRefGoogle Scholar
  20. Li HL, Wu B, Mu CD, Lin W (2011) Concomitant degradation in periodate oxidation of carboxymethyl cellulose. Carbohydr Polym 84:881–886CrossRefGoogle Scholar
  21. Li L, Puhl S, Meinel L, Germershaus O (2014) Silk fibroin layer-by-layer microcapsules for localized gene delivery. Biomaterials 35:7929–7939CrossRefGoogle Scholar
  22. Li XL, Liu Y, Jiang ZM, Li R, Ren XH, Huang TS (2015) Synthesis of an N-halamine monomer and its application in antimicrobial cellulose via an electron beam irradiation process. Cellulose 22(6):3609–3617CrossRefGoogle Scholar
  23. Lindh J, Carlsson DO, Strømme M, Mihranyan A (2014) Convenient one-pot formation of 2,3-dialdehyde cellulose beads via periodate oxidation of cellulose in water. Biomacromolecules 15:1928–1932CrossRefGoogle Scholar
  24. Liu Y, Li J, Cheng X, Ren X, Huang TS (2015) Self-assembled antibacterial coating by N-halamine polyelectrolytes on a cellulose substrate. J Mater Chem B 3:1446–1454CrossRefGoogle Scholar
  25. Parhiz H, Hashemi M, Hatefi A, Shier WT, Farzad SA, Ramezani M (2013) Arginine-rich hydrophobic polyethylenimine: potent agent with simple components for nucleic acid delivery. Int J Biol Macromol 60:18–27CrossRefGoogle Scholar
  26. Qi KZ, Cheng B, Yu JG, Ho WK (2017) Review on the improvement of the photocatalytic and antibacterial activities of ZnO. J Alloys Compd 27:792–820CrossRefGoogle Scholar
  27. Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Chem Soc Rev 38(7):2046–2064CrossRefGoogle Scholar
  28. Shankar S, Rhim JW (2018) Antimicrobial wrapping paper coated with a ternary blend of carbohydrates (alginate, carboxymethyl cellulose, carrageenan) and grapefruit seed extract. Carbohydr Polym 196:92–101CrossRefGoogle Scholar
  29. Sheppard NC, Brinckmann SA, Gartlan KH, Puthia M, Svanborg C, Krashias G, Eisenbarth SC, Flavell RA, Sattentau QJ, Wegmann F (2014) Polyethyleneimine is a potent systemic adjuvant for glycoprotein antigens. Int Immunol 26:531–538CrossRefGoogle Scholar
  30. Soice NP, Maladono AC, Takigawa DY, Norman AD, Krantz WB, Greenberg AR (2003) Oxidative degradation of polyamide reverse osmosis membranes: studies of molecular model compounds and selected membranes. J Appl Polym Sci 90(5):1173–1184CrossRefGoogle Scholar
  31. Sun YY, Chen TY, Worley SD, Sun G (2001) Novel refreshable N-halamine polymeric biocides containing imidazolidin-4-one derivatives. J Polym Sci Polym Chem 39(18):3073–3084CrossRefGoogle Scholar
  32. Toure Y, Genet MJ, Dupont-Gillain CC, Sindic M, Rouxhet PG (2014) Conditioning materials with biomacromolecules: composition of the adlayer and influence on clean ability. J Colloid Interface Sci 432:158–169CrossRefGoogle Scholar
  33. Varma AJ, Kokane SP, Pathak G, Pradhan SD (1997) Thermal behavior of galactomannan guar gum and its periodate oxidation products. Carbohydr Polym 32(2):111–114CrossRefGoogle Scholar
  34. Wang H, Wang ZM, Yan X, Chen J, Lang WZ, Guo YJ (2017a) Novel organic-inorganic hybrid polyvinylidene fluoride ultrafiltration membranes with antifouling and antibacterial properties by embedding N-halamine functionalized silica nanospheres. J Ind Eng Chem 52:295–304CrossRefGoogle Scholar
  35. Wang LL, Hu C, Shao LQ (2017b) The antimicrobial activity of nanoparticles: present situation and prospects for the future. Int J Nanomed 12:1227–1249CrossRefGoogle Scholar
  36. Zhang XY, Shen GY, Sun SY, Shen YM, Zhan CXG, Xiao AG (2014) Direct immobilization of antibodies on dialdehyde cellulose film for convenient construction of an electrochemical immunosensor. Sens Actuators B Chem 200:304–309CrossRefGoogle Scholar
  37. Zhang SL, Wang ZK, Chen HY, Kai CC, Jiang M, Wang Q, Zhou ZW (2018) Polyethylenimine functionalized Fe3O4/steam-exploded rice straw composite as an efficient adsorbent for Cr(VI) removal. Appl Surf Sci 440:1277–1285CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.School of Geosciences and Environmental EngineeringSouthwest Jiaotong UniversityChengduChina
  2. 2.School of Materials Science and EngineeringSouthwest Jiaotong UniversityChengduChina

Personalised recommendations