Polyelectrolytes fabrication on magnesium alloy surface by layer-by-layer assembly technique with antiplatelet adhesion and antibacterial activities

  • Mengke Peng
  • Xiaodan Zhang
  • Xiao Xiao
  • Mengjin Dong
  • Guowei Zhao
  • Peng Liu
  • Yashao ChenEmail author
  • Changhao WangEmail author


Magnesium alloy (MgA) was widely used in biomedical field owing to its good biocompatibility and degradability. The surface of MgA was usually modified to improve its corrosion resistance, biocompatibility, and biological properties. Herein, we employed a layer-by-layer assembly technique to assemble both polyanionic and polycationic electrolytes onto the microarc oxidation-treated MgA surface to yield MgA-MgO-PEI-[Ge(HANPs)/Lzm]50, where the gelatin-conjugated hydroxyapatite nanoparticles [Ge(HANPs)] are the polyanionic electrolyte, lysozyme (Lzm) is the polycationic electrolyte, and polyethyleneimine (PEI) is the transition layer. The morphology and chemical composition of MgA-MgO-PEI-[Ge(HANPs)/Lzm]50 were characterized by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy, indicating that [Ge(HANPs)/Lzm]50 were successfully fabricated on the surface of MgA-MgO. The surface of MgA-MgO-PEI-[Ge(HANPs)/Lzm]50 exhibited good hydrophilicity as evidenced by the low water contact angle of 24.5°. Excellent corrosion resistance of MgA-MgO-PEI-[Ge(HANPs)/Lzm]50 was obtained since it can decrease about four orders of magnitude of corrosive current (Icorr) compared to pristine MgA. The biological assay for MgA-MgO-PEI-[Ge(HANPs)/Lzm]50 showed good antiplatelet adhesion and excellent antibacterial activities against both E. coli and S. aureus.

Graphical abstract


Magnesium alloy Polyelectrolytes LbL assembly Antiplatelet adhesion Antibacterial activities 



This work was financially supported by the National Natural Science Foundation of China (Nos. 21773149, 21273142, 21703132), State Key Project of Research and Development (No. 2016YFC1100300), and Program for Changjiang Scholars and Innovative Research Team in University (IRT_14R33).


  1. 1.
    Staiger, MP, Pietak, AM, Huadmai, J, Dias, G, “Magnesium and its Alloys as Orthopedic Biomaterials: A Review.” Biomaterials, 27 1728–1734 (2006)CrossRefGoogle Scholar
  2. 2.
    Chen, YJ, Xu, ZG, Smith, C, Sankar, J, “Recent Advances on the Development of Magnesium Alloys for Biodegradable Implants.” Acta Biomater., 10 45–61 (2014)Google Scholar
  3. 3.
    Zhao, DW, Witte, F, Lu, FQ, Wang, JL, Li, JL, Qin, L, “Current Status on Clinical Applications of Magnesium-Based Orthopaedic Implants: A Review from Clinical Translational Perspective.” Biomaterials, 112 287–302 (2017)CrossRefGoogle Scholar
  4. 4.
    Witte, F, Hort, N, Vogt, C, Cohen, S, Kainer, KU, Willumeit, R, Feyerabend, F, “Degradable Biomaterials Based on Magnesium Corrosion.” Curr. Opin. Solid State Mater. Sci., 12 63–72 (2008)CrossRefGoogle Scholar
  5. 5.
    Li, Y, Cai, S, Shen, SB, Xu, GH, Zhang, FY, Wang, FW, “Self-Healing Hybrid Coating of Phytic Acid/Silane for Improving the Corrosion Resistance of Magnesium Alloy.” J. Coat. Technol. Res., 15 (3) 571–581 (2018)CrossRefGoogle Scholar
  6. 6.
    Jamesh, M, Kumar, S, Sankara Narayanan, TSN, “Electrodeposition of Hydroxyapatite Coating on Magnesium for Biomedical Applications.” J. Coat. Technol. Res., 9 (4) 495–502 (2012)CrossRefGoogle Scholar
  7. 7.
    Chen, S, Zhang, J, Chen, YQ, Zhao, S, Chen, MY, Li, X, Maitz, MF, Wang, J, Huang, N, “Application of Phenol/Amine Copolymerized Film Modified Magnesium Alloys: Anticorrosion and Surface Biofunctionalization.” ACS Appl. Mater. Interfaces, 7 24510–24522 (2015)CrossRefGoogle Scholar
  8. 8.
    Zhang, M, Cai, S, Zhang, FY, Xu, GH, Wang, FW, Yu, N, Wu, XD, “Preparation and Corrosion Resistance of Magnesium Phytic Acid/Hydroxyapatite Composite Coatings on Biodegradable AZ31 Magnesium Alloy.” J Mater Sci: Mater Med., 28 (6) 1–9 (2017)Google Scholar
  9. 9.
    Uma Rani, R, Shalini, VM, Thota, HK, Sharma, AK, “Comparison of Corrosion Performance of Various Conversion Coatings on Magnesium Alloy Using Electrochemical Techniques.” J. Coat. Technol. Res., 10 (5) 707–715 (2013)CrossRefGoogle Scholar
  10. 10.
    Zhong, YX, Hu, J, Zhang, YF, Tang, SW, “The One-Step Electroposition of Superhydrophobic Surface on AZ31 Magnesium Alloy and its Time-Dependence Corrosion Resistance in NaCl Solution.” Appl. Surf. Sci., 427 1193–1201 (2018)CrossRefGoogle Scholar
  11. 11.
    Shi, P, Niu, B, Shanshan, E, Chen, Y, Li, Q, “Preparation and Characterization of PLA Coating and PLA/MAO Composite Coatings on AZ31 Magnesium Alloy for Improvement of Corrosion Resistance.” Surf. Coat. Technol., 262 26–32 (2015)CrossRefGoogle Scholar
  12. 12.
    Zhou, B, Li, Y, Deng, HB, Hu, Y, Li, B, “Antibacterial Multilayer Films Fabricated by Layer-by-Layer Immobilizing Lysozyme and Gold Nanoparticles on Nanofibers.” Colloid. Surface. B, 116 432–438 (2014)CrossRefGoogle Scholar
  13. 13.
    Richardson, JJ, Cui, JW, Björnmalm, M, Braunger, JA, Hirotaka, E, Caruso, F, “Innovation in Layer-by-Layer Assembly.” Chem. Rev., 116 14828–14867 (2016)CrossRefGoogle Scholar
  14. 14.
    Fujita, S, Shiratori, S, “Waterproof Anti Reflection Films Fabricated by Layer-by-Layer Adsorption Process.” Jpn. J. Appl. Phys., 43 2346–2351 (2004)CrossRefGoogle Scholar
  15. 15.
    Kim, JH, Kim, SH, Shiratori, S, “Fabrication of Nanoporous and Hetero Structure Thin Film via a Layer-by-Layer Self Assembly Method for a Gas Sensor.” Sens. Actuators. B, 102 241–247 (2004)CrossRefGoogle Scholar
  16. 16.
    Decher, G, “Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites.” Science, 277 1232–1237 (1997)CrossRefGoogle Scholar
  17. 17.
    Decher, G, Hong, J, Schmitt, J, “Buildup of Ultrathin Multilayer Films by a Self-Assembly Process: III. Consecutively Alternating Adsorption of Anionic and Cationic Polyelectrolytes on Charged Surfaces.” Thin Solid Films, 210–211 831–835 (1992)CrossRefGoogle Scholar
  18. 18.
    Decher, G, Hong, JD, “Buildup of Ultrathin Multilayer Films by a Self-Assembly Process, 1 Consecutive Adsorption of Anionic and Cationic Bipolar Amphiphiles on Charged Surfaces.” Makromol. Chem. Macromol. Symp., 46 321–327 (1991)CrossRefGoogle Scholar
  19. 19.
    Decher, G, Hong, JD, “Buildup of Ultrathin Multilayer Films by a Self-Assembly Process: II. Consecutive Adsorption of Anionic and Cationic Bipolar Amphiphiles and Polyelectrolytes on Charged Surfaces.” Berich. Bunsen. Gesell., 95 1430–1434 (1991)CrossRefGoogle Scholar
  20. 20.
    Zhao, YB, Liu, HP, Li, CY, Chen, Y, Li, SQ, Zeng, RC, Wang, ZL, “Corrosion Resistance and Adhesion Strength of a Spin-Assisted Layer-by-Layer Assembled Coating on AZ31 Magnesium Alloy.” Appl. Surf. Sci., 434 787–795 (2018)CrossRefGoogle Scholar
  21. 21.
    Zhang, XD, Yi, JH, Zhao, GW, Huang, LL, Yan, GJ, Chen, YS, Liu, P, “Layer-by-Layer Assembly of Silver Nanoparticles Embedded Polyelectrolyte Multilayer on Magnesium Alloy with Enhanced Antibacterial Property.” Surf. Coat. Technol., 286 103–112 (2016)CrossRefGoogle Scholar
  22. 22.
    Bakhsheshi-Rad, HR, Hamzah, E, Ismail, AF, Azizc, M, Kasiri-Asgarani, M, Akbari, E, Jabbarzare, S, Najafinezhad, A, Hadisi, Z, “Synthesis of a Novel Nanostructured Zinc Oxide/Baghdadite Coating on Mg Alloy for Biomedical Application: In-Vitro Degradation Behavior and Antibacterial Activities.” Ceram. Int., 43 14842–14850 (2017)CrossRefGoogle Scholar
  23. 23.
    Tian, JH, Ding, S, Zhou, CR, Li, LH, Zhang, P, Jiao, YP, Li, H, “A Study on Degradation about Biomimetic Mineralized AZ91 Magnesium Alloy and its Antibacterial Activity Against S.aureus.” J. Funct. Mater., 44 (5) 640–644 (2013)Google Scholar
  24. 24.
    Tian, JH, Shen, S, Zhou, CR, Dang, XL, Jiao, YP, Li, LH, Ding, S, Li, H, “Investigation of the Antibacterial Activity and Biocompatibility of Magnesium Alloy Coated with HA and Antibacterial Peptide.” J Mater Sci: Mater Med., 26 (2) 1–12 (2015)Google Scholar
  25. 25.
    Kiristi, M, Singh, VV, Esteban-Fernández, DÁB, Uygun, M, Soto, F, Uygun, DA, Wang, J, “Lysozyme-Based Antibacterial Nanomotors.” ACS Nano, 9 (9) 9252–9259 (2015)CrossRefGoogle Scholar
  26. 26.
    Mine, Y, Ma, F, Lauriau, S, “Antibacterial Peptides Released by Enzymatic Hydrolysis of Hen Egg White Lysozyme.” J. Agric. Food Chem., 52 1088–1094 (2004)CrossRefGoogle Scholar
  27. 27.
    Visan, A, Cristescu, R, Stefan, N, Miroiu, M, Nita, C, Socol, M, Florica, C, Rasoga, O, Zgura, I, Sima, LE, Chiritoiu, M, Chifiriuc, MC, Holban, AM, Mihailescu, IN, Socol, G, “Antibacterial Polycaprolactone/Polyethylene Glycol Embedded Lysozyme Coatings of Ti Implants for Osteoblast Functional Properties in Tissue Engineering.” Appl. Surf. Sci., 417 234–243 (2017)CrossRefGoogle Scholar
  28. 28.
    Caro, A, Humblot, V, Méthivier, C, Minier, M, Salmain, M, Pradier, CM, “Grafting of Lysozyme and/or Poly(ethylene glycol) to Prevent Biofilm Growth on Stainless Steel Surfaces.” J. Phys. Chem. B, 113 (7) 2101–2109 (2009)CrossRefGoogle Scholar
  29. 29.
    Eby, DM, Luckarift, HR, Johnson, GR, “Hybrid Antibacterial Enzyme and Silver Nanoparticle Coatings for Medical Instruments.” ACS Appl. Mater. Interfaces, 1 (7) 1553–1560 (2009)CrossRefGoogle Scholar
  30. 30.
    Dutta, P, Ray, N, Roy, S, Dasgupta, AK, Bouloussa, O, Sarkar, A, “Covalent Immobilization of Active Lysozyme on Si/Glass Surface Using Alkoxy Fischer Carbene Complex on SAM.” Org. Biomol. Chem., 9 5123–5128 (2011)CrossRefGoogle Scholar
  31. 31.
    Yu, WZ, Zhang, YZ, Liu, XM, Xiang, YM, Li, ZY, Wu, SL, “Synergistic Antibacterial Activity of Multi Components in Lysozyme/Chitosan/Silver/Hydroxyapatite Hybrid Coating.” Mater. Des., 139 351–362 (2018)CrossRefGoogle Scholar
  32. 32.
    Agarwal, S, Riffault, M, Hoey, D, Duffy, B, Curtin, J, Jaiswal, S, “Biomimetic Hyaluronic Acid-Lysozyme Composite Coating on AZ31 Mg Alloy with Combined Antibacterial and Osteoinductive Activities.” ACS Biomater. Sci. Eng., 3 3244–3253 (2017)CrossRefGoogle Scholar
  33. 33.
    Bella, ED, Parrilli, A, Bigi, A, Panzavolta, S, Amadori, S, Giavaresi, G, Martini, L, Borsari, V, Fini, M, “Osteoinductivity of Nanostructured Hydroxyapatite-Functionalized Gelatin Modulated by Human and Endogenous Mesenchymal Stromal Cells.” J. Biomed. Mater. Res. A, 106 914–923 (2018)CrossRefGoogle Scholar
  34. 34.
    Ran, JB, Hu, JX, Chen, L, Shen, XY, Tong, H, “Preparation and Characterization of Gelatin/Hydroxyapatite Nanocomposite for Bone Tissue Engineering.” Polym Compos., 52 71–81 (2015)Google Scholar
  35. 35.
    Song, SL, Liu, HY, Guo, XH, Hu, NF, “Comparative Electrochemical Study of Myoglobin Loaded in Different Polyelectrolyte Layer-by-Layer Films Assembled by Spin-Coating.” Electrochim. Acta., 54 5851–5857 (2009)CrossRefGoogle Scholar
  36. 36.
    Salarian, M, Solati-Hashjin, M, Shafiei, SS, Salarian, R, Nemati, ZA, “Template-Directed Hydrothermal Synthesis of Dandelion-Like Hydroxyapatite in the Presence of Cetyltrimethylammonium Bromide and Polyethylene Glycol.” Ceram. Int., 35 2563–2569 (2009)CrossRefGoogle Scholar
  37. 37.
    Li, OL, Tsunakawa, M, Shimada, Y, Nakamura, K, Nishinaka, K, Ishizaki, T, “Corrosion Resistance of Composite Oxide Film Prepared on Ca-added Flameresistant Magnesium Alloy AZCa612 by Micro-arc Oxidation.” Corros. Sci., 125 99–105 (2017)CrossRefGoogle Scholar
  38. 38.
    Chen, YS, Yan, GJ, Wang, XD, Qian, HM, Yi, JH, Huang, LL, Liu, P, “Bio-functionalization of Micro-arc Oxidized Magnesium Alloys via Thiol-ene Photochemistry.” Surf. Coat. Technol., 269 191–199 (2015)CrossRefGoogle Scholar
  39. 39.
    Song, GL, Shi, ZM, “Corrosion Mechanism and Evaluation of Anodized Magnesium Alloys.” Corros. Sci., 85 126–140 (2014)CrossRefGoogle Scholar
  40. 40.
    Andreeva, DV, Fix, D, Möhwald, H, Shchukin, DG, “Buffering Polyelectrolyte Multilayers for Active Corrosion Protection.” J. Mater. Chem., 18 1738–1740 (2008)CrossRefGoogle Scholar
  41. 41.
    Yang, Y, Qi, PK, Wen, F, Li, XY, Xia, Q, Maitz, MF, Yang, ZL, Shen, R, Tu, QF, Huang, N, “Mussel-Inspired One-Step Adherent Coating Rich in Amine Groups for Covalent Immobilization of Heparin: Hemocompatibility, Growth Behaviors of Vascular Cells, and Tissue Response.” ACS Appl. Mater. Interfaces, 6 14608–14620 (2014)CrossRefGoogle Scholar
  42. 42.
    Wei, YL, Chen, YS, Liu, P, Gao, Q, Sun, Y, Huang, CZ, “Surface Modification of Hydrophobic PMMA Intraocular Lens by the Immobilization of Hydroxyethyl Methacrylate for Improving Application in Ophthalmology.” Plasma Chem. Plasma Process., 31 811–825 (2011)CrossRefGoogle Scholar
  43. 43.
    Venault, A, Huang, CW, Zheng, J, Chinnathambi, A, Alharbi, SA, Chang, Y, Chang, Y, “Hemocompatible Biomaterials of Zwitterionic Sulfobetaine Hydrogels Regulated with pH-Responsive DMAEMA Random Sequences.” Int. J. Polym. Mater., 65 65–74 (2016)CrossRefGoogle Scholar
  44. 44.
    Yao, K, Huang, XD, Huang, XJ, Xu, ZK, “Improvement of the Surface Biocompatibility of Silicone Intraocular Lens by the Plasma-Induced Tethering of Phospholipid Moieties.” J. Biomed. Mater. Res. A, 78 684–692 (2006)CrossRefGoogle Scholar
  45. 45.
    Huang, XJ, Xu, ZK, Wan, LS, Wang, ZG, “Surface Modification of Polyacrylonitrile-Based Membranes by Chemical Reactions to Generate Phospholipid Moieties.” Langmuir, 21 2941–2947 (2005)CrossRefGoogle Scholar
  46. 46.
    Wetzels, G, Koole, LH, “Photoimmobilisation of Poly(N-vinylpyrrolidinone) as a Means to Improve Haemocompatibility of Polyurethane Biomaterials.” Biomaterials, 20 1879–1887 (1999)CrossRefGoogle Scholar
  47. 47.
    Xi, M, Jin, J, Zhang, BY, “Surface Modification of Poly(propylene carbonate) by Layer-by-Layer Assembly and its Hemocompatibility.” RSC Adv., 4 38943–38950 (2014)CrossRefGoogle Scholar

Copyright information

© American Coatings Association 2019

Authors and Affiliations

  • Mengke Peng
    • 1
  • Xiaodan Zhang
    • 1
  • Xiao Xiao
    • 1
  • Mengjin Dong
    • 1
  • Guowei Zhao
    • 1
  • Peng Liu
    • 2
  • Yashao Chen
    • 1
    Email author
  • Changhao Wang
    • 1
    Email author
  1. 1.Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical EngineeringShaanxi Normal UniversityXi’anChina
  2. 2.Key Laboratory of Biorheological Science and Technology (Ministry of Education), College of BioengineeringChongqing UniversityChongqingChina

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