Preparation and Performance of In-situ Deposition of Titanium Scaffolds with Polydopamine Passivated Europium-doped Black Phosphorus Nanosheets

WANG Bingqian; LI Meiting; CUI Yiyan; ZENG Hui; HUANG Shuo; GUO Fang; LIU Changkui

doi:10.16490/j.cnki.issn.1001-3660.2025.22.020

PDF(19945 KB)

Surface Technology ›› 2025, Vol. 54 ›› Issue (22) : 208-215. DOI: 10.16490/j.cnki.issn.1001-3660.2025.22.020

Preparation and Performance of In-situ Deposition of Titanium Scaffolds with Polydopamine Passivated Europium-doped Black Phosphorus Nanosheets

WANG Bingqian^1,2, LI Meiting², CUI Yiyan², ZENG Hui², HUANG Shuo², GUO Fang², LIU Changkui^1,2*

Author information +

History +

Abstract

The work aims to solve the defects of bioinertness on the surface of titanium alloy (Ti-6Al-4V) bone tissue engineering scaffold. The titanium alloy was modified by inserting a coating of strontium-doped black phosphorus nanoparticle with polydopamine on its surface, which improved the biological activity and bone integration ability of the Ti scaffold. Titanium alloy (Ti-6Al-4V) was designed and prepared as the substrate for the biological scaffold of bone tissue engineering. The black phosphorus nanosheets were covalently bonded with bioactive strontium by polyelectrolyte complex method. Through a simple oxidative self-polymerization reaction of dopamine (DA), polydopamine (PDA) was carried out on the surface of the scaffold, and a hierarchical structure with a composite monolayer of PDA was also obtained. At the same time, PDA@(BP+Sr) functional biological coating was successfully constructed on the surface of Ti-PDA through the secondary reaction function of PDA coating. The titanium surface before and after modification was characterized and analyzed by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectrometer (XPS), Zeta potentiometer and Raman spectrometer. The effects of the coating on mineralization ability and cell growth were evaluated by in vitro mineralization experiment and cell adhesion experiment. The prepared Ti scaffold coated with PDA@(BP+Sr) was tested, and the results showed that it had better biological activity and bone integration ability. SEM showed that the surface of the Ti scaffold was relatively smooth. Through oxidation and self-polymerization of PDA, spherical particle aggregates were uniformly distributed on the surface of the titanium PDA scaffold. After loading of BPNs and Sr²⁺, a large number of nanosheets were observed to be wrapped by PDA nanoparticles. EDS analysis and XPS analysis showed that P, Sr and N elements in the coating were obviously distributed. The zeta potentials of BPNs, BP+Sr and PDA@(BP+Sr) were (-20.30±1.64) mV, (-5.76±1.07) mV and (-12.73±0.42) mV, respectively, which indicated that the Ti-PDA@(BP+Sr) composite scaffold was successfully prepared. The Raman spectra of PDA@(BP+Sr) group showed characteristic Raman absorption peaks (A¹_g, B_2g, A²_g) in the two-dimensional material BPNs, indicating that the preparation of PDA@(BP+Sr) did not change the original lattice structure of BPNs, and retained its good characteristics as a carrier. In vitro mineralization experiments showed that the surface of Ti-PDA@BP and Ti-PDA@(BP+Sr) groups had more particle deposition and enriched some calcium salts, which proved that the combination of phosphate and calcium ions generated by BPNs degradation improved the mineralization ability of the scaffold. The surface of the scaffold was seeded with bone marrow mesenchymal stem cells (BMSCs) for 4 h. SEM showed that the number of cells on the surface of the scaffold treated with PDA@(BP+Sr) coating increased, the area of single cells spread larger, and the number of adherent cells extending out of the synapse was significantly better than that of the Ti group. The experimental results show that the PDA@(BP+Sr) coating on the surface of the Ti scaffold can effectively improve the biological activity of the scaffold and promote cell adhesion and proliferation, which will provide a new strategy for overcoming the common surface biological inertia of pure Ti scaffolds, so as to enhance its application potential in bone defect repair and reconstruction.

Key words

Ti alloy / Sr / black phosphorus nanosheet / polydopamine / surface modification / cell adhesion

Cite this article

EndNote

Ris (Procite)

Bibtex

Download Citations

WANG Bingqian, LI Meiting, CUI Yiyan, ZENG Hui, HUANG Shuo, GUO Fang, LIU Changkui. Preparation and Performance of In-situ Deposition of Titanium Scaffolds with Polydopamine Passivated Europium-doped Black Phosphorus Nanosheets[J]. Surface Technology. 2025, 54(22): 208-215 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.22.020

References

[1] GUPTA N K, SOMANI N, PRAKASH C, et al.Revealing the WEDM Process Parameters for the Machining of Pure and Heat-Treated Titanium (Ti-6Al-4V) Alloy[J]. Materials, 2021, 14(9): 2292.
[2] LIU W W, YANG D, WEI X H, et al.Fabrication of Piezoelectric Porous BaTiO(3) Scaffold to Repair Large Segmental Bone Defect in Sheep[J]. Journal of Biomaterials Applications, 2020, 35(4/5): 544-552.
[3] LIU W, LIU S F, WANG L Q.Surface Modification of Biomedical Titanium Alloy: Micromorphology, Microstructure Evolution and Biomedical Applications[J]. Coatings, 2019, 9(4): 249.
[4] CAO D, DING J D. Recent Advances in Regenerative Biomaterials[J]. Regenerative Biomaterials, 2022, 9: rbac098.
[5] ZHAI Y, ZHANG H, WANG J C, et al.Research Progress of Metal-Based Additive Manufacturing in Medical Implants[J]. Reviews on Advanced Materials Science, 2023, 62: 20230148.
[6] RAPHEL J, HOLODNIY M, GOODMAN S B, et al.Multifunctional Coatings to Simultaneously Promote Osseointegration and Prevent Infection of Orthopaedic Implants[J]. Biomaterials, 2016, 84: 301-314.
[7] SKALNY A V, ASCHNER M, SILINA E V, et al.The Role of Trace Elements and Minerals in Osteoporosis: A Review of Epidemiological and Laboratory Findings[J]. Biomolecules, 2023, 13(6): 1006.
[8] WANG B L, GUO H H, GENG T X, et al.The Effect of Strontium Ranelate on Titanium Particle-Induced Periprosthetic Osteolysis Regulated by WNT/β-Catenin Signaling in vivo and in vitro[J]. Bioscience Reports, 2021, 41(1)
[9] CHEN Y H, ZHENG Z W, ZHOU R P, et al.Developing a Strontium-Releasing Graphene Oxide-/Collagen-Based Organic-Inorganic Nanobiocomposite for Large Bone Defect Regeneration via MAPK Signaling Pathway[J]. ACS Applied Materials & Interfaces, 2019, 11(17): 15986-15997.
[10] CAUDRILLIER A, HURTEL-LEMAIRE A S, WATTEL A, et al. Strontium Ranelate Decreases Receptor Activator of Nuclear Factor-κB Ligand-Induced Osteoclastic Differentiation in Vitro: Involvement of the Calcium-Sensing Receptor[J]. Molecular Pharmacology, 2010, 78(4): 569-576.
[11] HUANG Y Z, WU C G, XIE H Q, et al.Strontium Promotes the Proliferation and Osteogenic Differentiation of Human Placental Decidual Basalis-and Bone Marrow-Derived MSCS in a Dose-Dependent Manner[J]. Stem Cells International, 2019, 2019(1): 4242178.
[12] AIMAITI A, MAIMAITIYIMING A, XU B Y, et al.Low-Dose Strontium Stimulates Osteogenesis but High-Dose Doses Cause Apoptosis in Human Adipose-Derived Stem Cells via Regulation of the ERK1/2 Signaling Pathway[J]. Stem Cell Research & Therapy, 2017, 8(1): 282.
[13] ZHANG F, PENG F F, QIN L, et al.PH/near Infrared Dual-Triggered Drug Delivery System Based Black Phosphorus Nanosheets for Targeted Cancer Chemo-Photothermal Therapy[J]. Colloids and Surfaces B: Biointerfaces, 2019, 180: 353-361.
[14] CAO J X, QI J Y, LIN X, et al.Biomimetic Black Phosphorus Nanosheet-Based Drug Delivery System for Targeted Photothermal-Chemo Cancer Therapy[J]. Frontiers in Bioengineering and Biotechnology, 2021, 9: 707208.
[15] SHAO J D, RUAN C S, XIE H H, et al.Photochemical Activity of Black Phosphorus for Near-Infrared Light Controlled in Situ Biomineralization[J]. Advanced Science, 2020, 7(14): 2000439.
[16] HUANG K Q, WU J, GU Z P.Black Phosphorus Hydrogel Scaffolds Enhance Bone Regeneration via a Sustained Supply of Calcium-Free Phosphorus[J]. ACS Applied Materials & Interfaces, 2019, 11(3): 2908-2916.
[17] ISLAND J O, STEELE G A, VAN DER ZANT H S J, et al. Environmental Instability of Few-Layer Black Phosphorus[J]. 2D Materials, 2015, 2(1): 011002.
[18] FAVRON A, GAUFRÈS E, FOSSARD F, et al. Photooxidation and Quantum Confinement Effects in Exfoliated Black Phosphorus[J]. Nature Materials, 2015, 14(8): 826-832.
[19] CHINCHULKAR S A, PATRA P, DEHARIYA D, et al.Polydopamine Nanocomposites and Their Biomedical Applications: A Review[J]. Polymers for Advanced Technologies, 2022, 33(12): 3935-3956.
[20] ZENG J K, WANG Y T, SUN Z Y, et al.A Novel Biocompatible PDA/IR820/DAP Coating for Antibiotic/Photodynamic/Photothermal Triple Therapy to Inhibit and Eliminate Staphylococcus Aureus Biofilm[J]. Chemical Engineering Journal, 2020, 394: 125017.
[21] LIU X, BAI Y F, XU J, et al.Robust Amphiphobic Few-Layer Black Phosphorus Nanosheet with Improved Stability[J]. Advanced Science, 2019, 6(23): 1901991.
[22] ZENG X W, LUO M M, LIU G, et al.Polydopamine-Modified Black Phosphorous Nanocapsule with Enhanced Stability and Photothermal Performance for Tumor Multimodal Treatments[J]. Advanced Science, 2018, 5(10): 1800510.
[23] LIU H W, ZOU Y Q, TAO L, et al.Sandwiched Thin-Film Anode of Chemically Bonded Black Phosphorus/Graphene Hybrid for Lithium-Ion Battery[J]. Small, 2017, 13(33): 1700758.
[24] WANG F Q, WU M F, ZHANG T, et al.Suppressing Self-Discharge of Vanadium Diboride by Zwitterionicity of the Polydopamine Coating Layer[J]. ACS Applied Materials & Interfaces, 2019, 11(5): 5123-5128.
[25] LU M, YU J.Mussel-Inspired Biomaterials for Cell and Tissue Engineering[M]//Novel Biomaterials for Regenerative Medicine. Singapore: Springer Nature Singapore, 2018: : 451-474.
[26] WU L, WANG J H, LU J, et al.Lanthanide-Coordinated Black Phosphorus[J]. Small, 2018, 14(29): 1801405.
[27] GUO Z N, ZHANG H, LU S B, et al.From Black Phosphorus to Phosphorene: Basic Solvent Exfoliation, Evolution of Raman Scattering, and Applications to Ultrafast Photonics[J]. Advanced Functional Materials, 2015, 25(45): 6996-7002.
[28] LIU H, NEAL A T, ZHU Z, et al.Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility[J]. ACS Nano, 2014, 8(4): 4033-4041.
[29] WANG H, YANG X Z, SHAO W, et al.Ultrathin Black Phosphorus Nanosheets for Efficient Singlet Oxygen Generation[J]. Journal of the American Chemical Society, 2015, 137(35): 11376-11382.
[30] WANG Z M, ZHAO J, TANG W Z, et al.Multifunctional Nanoengineered Hydrogels Consisting of Black Phosphorus Nanosheets Upregulate Bone Formation[J]. Small, 2019, 15(41): 1901560.
[31] 董利民, 王晨, 田杰谟, 等. 类骨磷灰石的结构分析与形成机制研究[C]//第五届中国功能材料及其应用学术会议论文集Ⅱ. 北京·秦皇岛, 2004: 261-264.
DONG L M, WANG C, TIAN J M, et al.Structural Analysis and Formation Mechanism of Osteoid Apatite[C]//Collected Papers of the 5th China Conference on Functional Materials and Their ApplicationsⅡ. Beijing·Qinhuangdao, 2004: 261-264.
[32] JIANG X W, JIN H, GUI R J.Visual Bio-Detection and Versatile Bio-Imaging of Zinc-Ion-Coordinated Black Phosphorus Quantum Dots with Improved Stability and Bright Fluorescence[J]. Biosensors and Bioelectronics, 2020, 165: 112390.
[33] 张涛, 高杰维, 屈树新, 等. 钙磷物质的量比对磷酸钙骨水泥性能的影响[J]. 无机化学学报, 2010, 26(6): 957-962.
ZHANG T, GAO J W, QU S X, et al.Influence of Ca/P Molar Ratio on Performance of Calcium Phosphate Cement[J]. Chinese Journal of Inorganic Chemistry, 2010, 26(6): 957-962.
[34] 王秀鹏, 叶建东, 王迎军. 钙磷摩尔比对新型PCCP+ DCPA体系骨水泥性能的影响[J]. 硅酸盐学报, 2007, 35(12): 1582-1586.
WANG X P, YE J D, WANG Y J.Influence of Calcium to Phosphate Molar Ratio on Performance of a Novel Calcium Phosphate Cement[J]. Journal of the Chinese Ceramic Society, 2007, 35(12): 1582-1586.

Funding

Key Research and Development Program of Department of Science and Technology of Shaanxi Province (2024SF-YBXM-271); Youth Innovation Team Project of Shaanxi Provincial Department of Education (24JP173); Xi'an Weiyang District Seience and Technology Bureau Project (202409); Innovative team for disease mechanism and prevention of oral and maxillofacial system (2022TD-54)