Micro-patterned hydroxyapatite/silk fibroin coatings on Mg--Zn--Y--Nd--Zr alloys for better corrosion resistance and cell behavior guidance

Abstract

In this study, a micro-patterned hydroxyapatite/silk fibroin (HA-SF) coating was firstly fabricated on the surface of Mg–Zn–Y–Nd–Zr alloy by template-assisted electrospraying technique coupling with spin coating technique. Two types of micro-patterns were achieved with high contour accuracy, namely HA-SF(line-pattern) and HA-SF(dot-pattern). The microstructure, composition, surface wettability and corrosion behaviors of the coatings were investigated by SEM, EDS, FTIR, XRD, water contact angle and potentiodynamic polarization test. The results revealed the hydrophilic nature of coatings and two orders of magnitude reduction of corrosion density (i_corr) as compared with that of the substrate. All the micro-patterned surfaces promoted the attachment of MC3T3-E1 cells with visible filopodia after 1 d incubation. In addition, coatings with line pattern exhibited the superior guidance to cell migration as compared to dot pattern, and the preference of cell attachment in the convex zone was observed. In summary, the obtained micro-patterned HA-SF coatings possessed the remarkably improvement of anticorrosion ability and good efficacy in guidance of cell attachment and alignment, which can serve as a promising strategy for cellular response modulation at the interface of magnesium-based implants and bone.

Keywords

magnesium alloy / silk fibroin / hydroxyapatite / micro-patterned surface / electrospraying technique

References

[1] Witte F. The history of biodegradable magnesium implants: A review. Acta Biomaterialia, 2010, 6(5): 1680–1692

[2] Wang J L, Xu J K, Hopkins C, . Biodegradable magnesium-based implants in orthopedics — A general review and perspectives. Advanced Science, 2020, 7(8): 1902443

[3] Zhao D, Witte F, Lu F, . Current status on clinical applications of magnesium-based orthopaedic implants: A review from clinical translational perspective. Biomaterials, 2017, 112: 287–302

[4] Zheng Y F, Gu X N, Witte F. Biodegradable metals. Materials Science and Engineering R: Reports, 2014, 77: 1–34

[5] Liu Y, Zheng Y F, Chen X H, . Fundamental theory of biodegradable metals-definition, criteria, and design. Advanced Functional Materials, 2019, 29(18): 1805402

[6] Li L, Zhang M, Li Y, . Corrosion and biocompatibility improvement of magnesium-based alloys as bone implant materials: a review. Regenerative Biomaterials, 2017, 4(2): 129–137

[7] Agarwal S, Curtin J, Duffy B, . Biodegradable magnesium alloys for orthopaedic applications: A review on corrosion, biocompatibility and surface modifications. Materials Science and Engineering C, 2016, 68: 948–963

[8] Dorozhkin S V. Calcium orthophosphate coatings on magnesium and its biodegradable alloys. Acta Biomaterialia, 2014, 10(7): 2919–2934

[9] Li L Y, Cui L Y, Zeng R C, . Advances in functionalized polymer coatings on biodegradable magnesium alloys — A review. Acta Biomaterialia, 2018, 79: 23–36

[10] Yin Z Z, Qi W C, Zeng R C, . Advances in coatings on biodegradable magnesium alloys. Journal of Magnesium and Alloys, 2020, 8(1): 42–65

[11] Wu G S, Ibrahim J M, Chu P K. Surface design of biodegradable magnesium alloys — A review. Surface and Coatings Technology, 2013, 233: 2–12

[12] Kannan M B. Electrochemical deposition of calcium phosphates on magnesium and its alloys for improved biodegradation performance: A review. Surface and Coatings Technology, 2016, 301: 36–41

[13] Wang H X, Zhu S J, Wang L G, . Formation mechanism of Ca-deficient hydroxyapatite coating on Mg–Zn–Ca alloy for orthopaedic implant. Applied Surface Science, 2014, 307: 92–100

[14] Song Y W, Shan D Y, Han E H. Electrodeposition of hydroxyapatite coating on AZ91D magnesium alloy for biomaterial application. Materials Letters, 2008, 62(17–18): 3276–3279

[15] Feng Y S, Ma X, Chang L, . Characterization and cytocompatibility of polydopamine on MAO-HA coating supported on Mg–Zn–Ca alloy. Surface and Interface Analysis, 2017, 49(11): 1115–1123

[16] Ma X, Zhu S J, Wang L G, . Synthesis and properties of a bio-composite coating formed on magnesium alloy by one-step method of micro-arc oxidation. Journal of Alloys and Compounds, 2014, 590: 247–253

[17] Wang Z, Wang X, Tian Y, . Degradation and osteogenic induction of a SrHPO₄-coated Mg–Nd–Zn–Zr alloy intramedullary nail in a rat femoral shaft fracture model. Biomaterials, 2020, 247: 119962

[18] Wang T L, Yang G Z, Zhou W C, . One-pot hydrothermal synthesis, in vitro biodegradation and biocompatibility of Sr-doped nanorod/nanowire hydroxyapatite coatings on ZK60 magnesium alloy. Journal of Alloys and Compounds, 2019, 799: 71–82

[19] Qiu X, Wan P, Tan L, . Preliminary research on a novel bioactive silicon doped calcium phosphate coating on AZ31 magnesium alloy via electrodeposition. Materials Science and Engineering C, 2014, 36: 65–76

[20] Feng Y, Zhu S, Wang L, . Characterization and corrosion property of nano-rod-like HA on fluoride coating supported on Mg–Zn–Ca alloy. Bioactive Materials, 2017, 2(2): 63–70

[21] Lu Y J, Wan P, Tan L L, . Preliminary study on a bioactive Sr containing Ca–P coating on pure magnesium by a two-step procedure. Surface and Coatings Technology, 2014, 252: 79–86

[22] Han J J, Wan P, Sun Y, . Fabrication and evaluation of a bioactive Sr–Ca–P contained micro-arc oxidation coating on magnesium strontium alloy for bone repair application. Journal of Materials Science & Technology, 2016, 32(3): 233–244

[23] Kim S M, Kang M H, Kim H E, . Innovative micro-textured hydroxyapatite and poly(l-lactic)-acid polymer composite film as a flexible, corrosion resistant, biocompatible, and bioactive coating for Mg implants. Materials Science and Engineering C, 2017, 81: 97–103

[24] Bao Q H, Zhao L Q, Jing H M, . Microstructure of hydroxyapatite/collagen coating on AZ31 magnesium alloy by a solution treatment. Journal of Biomimetics, Biomaterials and Biomedical Engineering, 2017, 30: 38–44

[25] Xiong P, Jia Z J, Li M, . Biomimetic Ca, Sr/P-doped silk fibroin films on Mg–1Ca alloy with dramatic corrosion resistance and osteogenic activities. ACS Biomaterials Science & Engineering, 2018, 4(9): 3163–3176

[26] Li M, Xiong P, Mo M S, . Electrophoretic-deposited novel ternary silk fibroin/graphene oxide/hydroxyapatite nanocomposite coatings on titanium substrate for orthopedic applications. Frontiers of Materials Science, 2016, 10(3): 270–280

[27] Zhu Y R, Chen Y Y, Xu G H, . Micropattern of nano-hydroxyapatite/silk fibroin composite onto Ti alloy surface via template-assisted electrostatic spray deposition. Materials Science and Engineering C, 2012, 32(2): 390–394

[28] Huang W, Ling S, Li C, . Silkworm silk-based materials and devices generated using bio-nanotechnology. Chemical Society Reviews, 2018, 47(17): 6486–6504

[29] Rockwood D N, Preda R C, Yücel T, . Materials fabrication from Bombyx mori silk fibroin. Nature Protocols, 2011, 6(10): 1612–1631

[30] Fang H, Wang C X, Zhou S C, . Enhanced adhesion and anticorrosion of silk fibroin coated biodegradable Mg–Zn–Ca alloy via a two-step plasma activation. Corrosion Science, 2020, 168: 108466

[31] Wang C, Fang H, Hang C, . Fabrication and characterization of silk fibroin coating on APTES pretreated Mg–Zn–Ca alloy. Materials Science and Engineering C, 2020, 110: 110742

[32] Wang C, Fang H, Qi X, . Silk fibroin film-coated MgZnCa alloy with enhanced in vitro and in vivo performance prepared using surface activation. Acta Biomaterialia, 2019, 91: 99–111

[33] Wang Y, Li X R, Wang Q, . Preliminary biocompatibility and neurotoxicity assessment of silk fibroin coated magnesium alloys for peripheral nerve repairs. Basic & Clinical Pharmacology & Toxicology, 2019, 124(S3): 46–47

[34] Wang S, Li J, Zhou Z, . Micro-/nano-scales direct cell behavior on biomaterial surfaces. Molecules, 2019, 24(1): 75

[35] Wu G, Li P, Feng H, . Engineering and functionalization of biomaterials via surface modification. Journal of Materials Chemistry B: Materials for Biology and Medicine, 2015, 3(10): 2024–2042

[36] Liu X Y, Chu P K, Ding C X. Surface nano-functionalization of biomaterials. Materials Science and Engineering R: Reports, 2010, 70(3–6): 275–302

[37] Zhao C, Wang X, Gao L, . The role of the micro-pattern and nano-topography of hydroxyapatite bioceramics on stimulating osteogenic differentiation of mesenchymal stem cells. Acta Biomaterialia, 2018, 73: 509–521

[38] Zhang F, Li G, Yang P, . Fabrication of biomolecule-PEG micropattern on titanium surface and its effects on platelet adhesion. Colloids and Surfaces B: Biointerfaces, 2013, 102: 457–465

[39] Klymov A, Song J, Cai X, . Increased acellular and cellular surface mineralization induced by nanogrooves in combination with a calcium-phosphate coating. Acta Biomaterialia, 2016, 31: 368–377

[40] Li M, Fu X, Gao H, . Regulation of an osteon-like concentric microgrooved surface on osteogenesis and osteoclastogenesis. Biomaterials, 2019, 216: 119269

[41] Huang Q, Elkhooly T A, Liu X, . Effects of hierarchical micro/nano-topographies on the morphology, proliferation and differentiation of osteoblast-like cells. Colloids and Surfaces B: Biointerfaces, 2016, 145: 37–45

[42] Mesquita-Guimarães J, Detsch R, Souza A C, . Cell adhesion evaluation of laser-sintered HAp and 45S5 bioactive glass coatings on micro-textured zirconia surfaces using MC3T3-E1 osteoblast-like cells. Materials Science and Engineering C, 2020, 109: 110492

[43] Holthaus M G, Stolle J, Treccani L, . Orientation of human osteoblasts on hydroxyapatite-based microchannels. Acta Biomaterialia, 2012, 8(1): 394–403

[44] Chen L, Wang D, Peng F, . Nanostructural surfaces with different elastic moduli regulate the immune response by stretching macrophages. Nano Letters, 2019, 19(6): 3480–3489

[45] Song X, Chang L, Wang J, . Investigation on the in vitro cytocompatibility of Mg–Zn–Y–Nd–Zr alloys as degradable orthopaedic implant materials. Journal of Materials Science: Materials in Medicine, 2018, 29(4): 44

[46] Wang J F, Zhou H B, Wang L G, . Microstructure, mechanical properties and deformation mechanisms of an as-cast Mg–Zn–Y–Nd–Zr alloy for stent applications. Journal of Materials Science & Technology, 2019, 35(7): 1211–1217

[47] Xie J W, Rezvanpour A, Wang C H, . Electric field controlled electrospray deposition for precise particle pattern and cell pattern formation. AIChE Journal, 2010, 56(10): 2607–2621

[48] Al-Milaji K N, Zhao H. Fabrication of superoleophobic surfaces by mask-assisted electrospray. Applied Surface Science, 2017, 396: 955–964

[49] Higashi K, Uchida K, Hotta A, . Micropatterning of silica nanoparticles by electrospray deposition through a stencil mask. Journal of Laboratory Automation, 2014, 19(1): 75–81

[50] Munir G, Koller G, Di Silvio L, . The pathway to intelligent implants: osteoblast response to nano silicon-doped hydroxyapatite patterning. Journal of the Royal Society Interface, 2011, 8(58): 678–688

[51] Cui W, Beniash E, Gawalt E, . Biomimetic coating of magnesium alloy for enhanced corrosion resistance and calcium phosphate deposition. Acta Biomaterialia, 2013, 9(10): 8650–8659

[52] He X L, Huang X W, Lu Q, . Nanoscale control of silks for regular hydroxyapatite formation. Progress in Natural Science: Materials International, 2012, 22(2): 115–119

[53] Xiong P, Jia Z, Zhou W, . Osteogenic and pH stimuli-responsive self-healing coating on biomedical Mg–1Ca alloy. Acta Biomaterialia, 2019, 92: 336–350

[54] Jia Z J, Zhou W H, Yan J L, . Constructing multilayer silk protein/nanosilver biofunctionalized hierarchically structured 3D printed Ti6Al4V scaffold for repair of infective bone defects. ACS Biomaterials Science & Engineering, 2019, 5(1): 244–261

[55] Feng W P, Feng S Y, Tang K Y, . A novel composite of collagen-hydroxyapatite/kappa-carrageenan. Journal of Alloys and Compounds, 2017, 693: 482–489

[56] Han F, Hu Y, Li J, . In situ silk fibroin-mediated crystal formation of octacalcium phosphate and its application in bone repair. Materials Science and Engineering C, 2019, 95: 1–10

[57] Chen J P, Chen S H, Lai G J. Preparation and characterization of biomimetic silk fibroin/chitosan composite nanofibers by electrospinning for osteoblasts culture. Nanoscale Research Letters, 2012, 7(1): 170 (11 pages)

[58] Zheng Z, Wei Y, Yan S, . Preparation of regenerated Antheraea yamamai silk fibroin film and controlled-molecular conformation changes by aqueous ethanol treatment. Journal of Applied Polymer Science, 2010, 116(1): 461–467

[59] You Q, Li Q, Zheng H, . Discerning silk produced by Bombyx mori from those produced by wild species using an enzyme-linked immunosorbent assay combined with conventional methods. Journal of Agricultural and Food Chemistry, 2017, 65(35): 7805–7812

[60] Agarwal R, García A J. Biomaterial strategies for engineering implants for enhanced osseointegration and bone repair. Advanced Drug Delivery Reviews, 2015, 94: 53–62

[61] Qiu Z M, Zhang F, Chu J T, . Corrosion resistance and hydrophobicity of myristic acid modified Mg–Al LDH/Mg(OH)₂ steam coating on magnesium alloy AZ31. Frontiers of Materials Science, 2020, 14(1): 96–107

[62] Fan X L, Li C Y, Wang Y B, . Corrosion resistance of an amino acid-bioinspired calcium phosphate coating on magnesium alloy AZ31. Journal of Materials Science & Technology, 2020, 49: 224–235

[63] Wang S, Zhu S J, Zhang X Q, . Effects of degradation products of biomedical magnesium alloys on nitric oxide release from vascular endothelial cells. Medical Gas Research, 2019, 9(3): 153–159

Acknowledgements

This study was supported by the National Natural Science Foundation of China (Grant Nos. 51601169, 51671175 and 51701184), the National Key Research and Development Program of China (2018YFC1106703) and the Key Projects of the Joint Fund of the National Natural Science Foundation of China (U1804251). Authors also would like to thank for the platform support from the Henan Key Laboratory of Advanced Magnesium Alloy and Key Laboratory of Materials Processing and Mold Technology (Ministry of Education).

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2020 Higher Education Press