High-Efficient Vacuum Ultraviolet-Ozone Assist-Deposited Polydopamine for Poly(lactic-co-glycolic acid)-Coated Pure Zn toward Biodegradable Cardiovascular Stent Applications.

Zinc is a prospective metal for biodegradable cardiovascular stent applications, but the excessively released Zn2+ during degradation remains a huge challenge in biocompatibility. Considerable efforts have been made to develop a high-efficient surface modification method, while maintaining adhesion strength, mechanical support, and vascular compatibility. Biomimetic polydopamine (PDA) can adhere to Zn tightly, subsequently achieving robust chemical bonds with poly(lactic-co-glycolic acid) (PLGA) coating. However, the deposition of PDA on Zn depends on the controlled conditions such as a sensitive pH and a long period of time. Herein, we introduce vacuum ultraviolet-ozone (VUV/O3) assist-deposition technology to accelerate the polymerization of PDA on pure Zn, which shortens the process to 40 min at a moderate pH of 8.5 and improves the deposition rate by 1-2 orders of magnitude under sufficient active oxygen species (ROS). Additionally, PLGA/PDA coating enhances the corrosion resistance, and their effective protection maintains the mechanical properties after long-term corrosion. Moreover, the controlled Zn2+ release contributes to the superior in vitro biocompatibility, which inhibits the hemolysis rate and smooth muscle cell (SMC) proliferation. The enhanced endothelial cell (EC) proliferation is promising to promote the re-endothelialization, avoiding in-stent restenosis and neointimal hyperplasia. Such modified Zn might be a viable candidate for the treatment of cardiovascular diseases.

Fabrication and characterization of silk fibroin coating on APTES pretreated Mg-Zn-Ca alloy.

To delay the degradation of magnesium alloys, silk fibroin as a natural organic polymer coating was fabricated on a 3-amino-propyltriethoxysilane (APTES) pretreated Mg-Zn-Ca alloy. APTES pretreatment coated the surface of magnesium alloys with amino groups, which can bond with functional groups in silk fibroin to form a compact coating/substrate interface. The influences of the APTES concentration and drying temperature on the coating adhesion and interface were investigated to explore the optimal parameters in the fabrication process. The nanoporous silk fibroin films completely covered the APTES pretreated Mg-Zn-Ca surface, which reached a thickness of ~7 µm. The chemical states for the coated Mg-Zn-Ca alloy were compared to those of the bare Mg-Zn-Ca alloy and the APTES pretreated Mg-Zn-Ca alloy to illustrate the coating mechanism. During in vitro degradation and electrochemical measurements in simulated body fluid (SBF), the samples with the silk fibroin coating showed remarkably improved corrosion resistance and a slower degradation rate compared to those of the bare samples, suggesting that the silk fibroin coating was an effective protection coating for the substrates and can delay the degradation of magnesium alloys. Moreover, a model for the in vitro degradation was proposed. In vitro cell experiments confirmed the excellent biocompatibility of silk fibroin coated Mg-Zn-Ca structure.

Silk fibroin film-coated MgZnCa alloy with enhanced in vitro and in vivo performance prepared using surface activation.

Magnesium and its alloys have generated considerable interest as one of the most promising biodegradable metals for biomedical bone implants. However, the enormous challenges are to improve their rapid corrosion excessively as well as to endow them with biocompatibility and biosafety. Herein, we introduce a natural silk fibroin protein coating to control the corrosion resistance and enhance the biocompatibility of MgZnCa alloy. To obtain a robust and reliable coated structure, different surface-activation processes are employed to increase the available functional groups on MgZnCa surfaces before coating. Compared to oxygen plasma activation, our unique vacuum ultraviolet-ozone (VUV/O3) activation method is effective in realizing uniform silk fibroin films as a protective barrier on MgZnCa alloy surfaces, and the nanoscratch test verified the superior adhesion strength of the silk fibroin-coated magnesium alloy structure. Long-term immersion results combined with electrochemical tests showed the preferable in vitro anticorrosion behavior and a low degradation rate of coated Mg alloy (1/8 times that of uncoated Mg alloy). Cell adhesion and cytotoxicity tests demonstrated that silk fibroin-coated MgZnCa presented improved biocompatibility with bone marrow mesenchymal stem cells. An animal study involving silk fibroin-coated MgZnCa implanted on one side of a rabbit spine for 180 days showed remarkably improved in vivo corrosion resistance, with 1/18 times the degradation rate of uncoated MgZnCa. These results not only comprehensively confirmed the validity of the VUV/O3-activation method as a coating strategy but also implied the tremendous potential of the modified Mg alloy for application as a degradable biomedical implant material. STATEMENT OF SIGNIFICANCE: MgZnCa alloy is a promising material in clinical implantation. Silk fibroin (SF) is a natural organic material with biocompatibility and biodegradability. To date, the combination of SF and MgZnCa alloy has exhibited considerable prospects for orthopedic applications. The realization of a direct coating is an enormous challenge because strong chemical bonds cannot be easily formed between organic and inorganic materials. To solve this bottleneck, we proposed a unique vacuum ultraviolet-ozone (VUV/O3) surface-activation method for the first time to modify the Mg alloy surface before SF coating, which significantly enhanced both in vitro and in vivo performance, such as superior biocompatibility and remarkably improved corrosion resistance of magnesium alloys (∼1/18 the in vivo degradation rate of uncoated MgZnCa).